JPS6160425B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention provides water-insoluble dye images for color diffusion transfer.
Regarding the dispersion method of donor material (hereinafter referred to as CPM)
It is something that In the color diffusion transfer method, CPM is a hydrophilic buffer.
It is exposed to light while being distributed in the form of fine particles in the inder.
Provided as a component of the element, but CPM itself
Silver halide emulsion with colored body and combination
When there is strong absorption in the photosensitive region (hereinafter simply referred to as
When the CPM itself is colored), the halogen
In the layer on the opposite side of the exposure direction with respect to the silver oxide emulsion layer.
The halogen as CPM-containing hydrophilic binder layer
Provided in combination with a silver oxide emulsion layer, and also CPM
Silver halide itself colorless or combined
It does not have strong absorption in the photosensitive region of the emulsion (hereinafter simply referred to as
(in other words, the CPM itself is colorless), so the halo
When the sensitivity of the silver germide emulsion is not significantly impaired
is distributed in the form of fine particles in the silver halide emulsion.
Provided as a silver halide emulsion layer containing CPM
You can also CPM is an alkaline process in which it follows imagewise exposure.
Diffusible color under any condition due to liquid treatment
Diffusion transfers from the photosensitive element to the image-receiving layer and dyes it.
It is classified according to whether it is done. The first typical type is the so-called dye developer.
(hereinafter referred to as [A] type CPM)
It has a pigment part (colored parts) in its molecular structure.
It is essentially colorless and becomes colored by hydrolysis etc.
) and the silver halide development area.
It is a compound that has This compound is essentially a
It is diffusive in alkali processing liquids, but is related to imagewise exposure.
The silver halide is developed as a result of the development
Because it was oxidized in the area where it occurred,
Or even more so-called due to local PH decrease.
Substantial in alkaline processing solutions for tanning properties
It becomes non-diffusible. The second typical type is CPM, which is alkaline.
A halo that is non-diffusive in the processing solution but imagewise exposed.
CPM reacts with the products oxidized by silver
As a result, it becomes diffusive in the alkaline processing solution.
It releases the dye obtained. This type will be added later.
As mentioned above, it is classified into four types, and each
There are [B], [C], [D], and [E] types of CPM. The third typical type is CPM, which is alkaline.
It is cleaved in the processing solution and becomes diffusible in the alkaline processing solution.
Releases possible dye, but oxidized developer
If present, cleavage will not occur in alkaline processing solution.
It continues to maintain non-proliferation properties, and it is important to expand this.
Dispersible dye-releasing hydrolyzable compound (hereinafter referred to as [F] type)
CPM). Regardless of the type of CPM mentioned above, imagewise exposure
Before light, there is virtually no diffusion in the photosensitive element.
After imagewise exposure, the
When processing with a lukewarm treatment liquid,
Crabs release diffusible pigments or diffusible colors
It is necessary to transfer it to the image-receiving layer as an element. Furthermore, when CPM is provided on the photosensitive element,
The substantial performance of the photosensitive element may be impaired due to storage, etc.
It is necessary that there be no. These requirements must be met.
Various CPM distribution methods have been proposed. Dispersion of CPM, which has been actively researched
The method is normal, not the color diffusion transfer method.
Dispersion method of color couplers in color photography
The so-called oil protection content, also known as
There is a method using the dispersion method, for example, U.S. Patent No.
3345163, 3438775, etc.
Ru. This method renders CPM virtually water-immiscible.
High-boiling organic solvents (e.g. tricresyl phosphate)
G, NN-diethyl laurylamide, dibutylph
tallate, etc.) and co-solvents (e.g. ethyl acetate).
4-methylcyclohexanone, methyl isoprol, 4-methylcyclohexanone,
of gelatin aqueous solution after dissolving it in
A method of finely dispersing it in a hydrophilic colloid solution such as
It is. This dispersion method uses minute amounts of high-boiling organic matter in the dispersed state.
With CPM dissolved in a molecular state in a solvent droplet,
It is thought that it is dispersed in a hydrophilic colloid solution.
Therefore, the combination of CPM and high boiling point organic solvent is optimal.
In the case of , the coating state has excellent light transmittance.
This results in a beautiful coating film. However, in the color diffusion transfer method, the photosensitive layer
The applied CPM is treated with an alkaline treatment liquid.
Since it becomes a diffusible dye, it has good diffusion transferability to the image-receiving layer.
and the dyeing state in the image-receiving layer.
You have to judge whether the CPM distribution method is good or bad.
stomach. According to our research results, oil protect
Products made using the light dispersion method have excellent light transmittance.
Even the most beautiful coatings cannot absorb diffusible dyes.
The diffusion transfer speed to the image layer takes too much time, and the
The density of the diffusible dye transferred to the image layer is not sufficient.
It was found that it had the following drawbacks. Even more so
Photosensitive with CPM dispersed in LeProtect
The photographic element with the sexual layer is left in a cool dark place for about 6 months.
The one left on the surface of the photosensitive layer is a high boiling point solvent.
oozes out, for example, spots appear on the image-receiving layer, etc.
It has been determined that there are defects that significantly impede performance.
I made it clear. In addition, the colloidal solution containing the dispersion is
During the manufacturing process, there is a need for long-term storage, so
It is desirable that the product be stable during long-term storage. but
However, in general, while keeping the particle size small,
Furthermore, it can be stored for a long time without causing CPM crystallization.
It is difficult to form CPM crystals after application and drying.
It is also said to be difficult to prevent precipitation.
Ru. Therefore, the stability of the oil protect dispersion can be improved.
For example, Japanese Patent Application Laid-open No. 17637/1983 and JP-A No. 50-
Disclosed in Publication No. 34233, US Patent No. 3287133, etc.
It is shown. However, these techniques
Stability of oil protect dispersion, high boiling point
The bleeding of the medium onto the surface of the photosensitive element is improved to some extent.
Although improvements have been made, the diffusion transfer of diffusible dyes to the image-receiving layer
Transfer speed, completeness of diffusible dye transferred to image-receiving layer
There was almost no improvement in transfer density under
Not done. On the other hand, methods other than the above-mentioned oil protect dispersion method
CPM distribution methods are also being actively researched.
There is. For example, in U.S. Patent No. 3,438,775,
ball mill, sand grinding, ultrasonic etc.
Technique to obtain CPM dispersion using mechanical energy
The technique has been revealed. This method refines the CPM
A lot of energy is consumed to do so. This many
Because of the amount of energy, heat accumulation or localized
This creates a heating condition that causes decomposition and deterioration of CPM.
There are drawbacks to this, and there is also a limit to the ability to make CPM into fine particles.
Most of them are 1 to 0.5 μm. like this
For large particles, the rate of diffusion transfer of diffusible dye to the image-receiving layer
is extremely slow, and the diffusion that is stained in the image-receiving layer
The disadvantage is that the maximum concentration of the sex pigment is small. The same specification also states that CPM is dissolved in a suitable solvent.
and disperse the resulting solution in a polymeric binder.
It describes the CPM method. Furthermore, the same specification states that CPM can be dissolved in acetone.
Filter the solution to remove acetone-insoluble substances.
and drop the solution into about 5 times the volume of water,
It describes how to disperse CPM in water.
Ru. CPM dispersion obtained by the dispersion method
is flocculated and precipitated, so the precipitate
is collected by filtration and a surfactant is added to the precipitate.
Form an aqueous slurry by adding
Restore gelatin matrices using an ultrasonic homogenizer
It is necessary to distribute it throughout the tree. These two
The two dispersion methods are relatively simple to operate and are readily available to those skilled in the art.
A dispersion method that has traditionally been used as a conventional technique for
It is. However, this method disperses
However, the speed of diffusion transfer of the diffusible dye to the image-receiving layer is extremely high.
of the diffusible dye transferred to the image-receiving layer.
The disadvantage is that the transfer density in the completed state is low.
It had Yet another CPM dispersion method is described in U.S. Patent No.
3832173. This method is
Nitrogen CPM and polymer in a strongly alkaline solution
Dissolve in an elementary gas atmosphere and add hydrochloric acid to the solution.
How to make dispersed particles of CPM by neutralization
It is. In this method, the salts produced by neutralization are permeated through water.
Strong alkali must be removed by analysis, etc.
CPM is easily decomposed or oxidized due to
In addition, it is insoluble in alkali.
Groups that can be hydrolyzed by CPM or alkaline
It is said that this method cannot be applied to CPM that exists in the molecular structure.
There is a big drawback. As mentioned above, various methods of distributing CPM are known.
However, both dispersion methods are
It is clear that this is not a fully satisfactory dispersion method.
It became brighter. The first object of the present invention is to make CPM into fine particles and
A new product that does not cause agglomeration or precipitation even during long-term storage.
The purpose is to provide a method for distributing CPM. The second object of the present invention is to provide a dispersion of CPM to a photosensitive material.
What is coated inside the base is a photosensitive silver halide emulsion.
It does not impede the sensitivity of CPM and does not cause crystal precipitation of CPM.
Also, when treated with an alkaline treatment solution, all
Produces diffusible dyes quickly, or
Maximum density without causing speckled noise on the image-receiving layer.
to quickly form large, clear dye images.
A novel dispersion method to obtain a dispersion of CPM that can
The goal is to provide the following. The third object of the present invention is to
The dispersion of CPM obtained by
Color expansion using a silver halide emulsion layer as one of its constituents
An object of the present invention is to provide a scatter transfer photographic element. Other objects of the invention can be found in the following detailed description and
It will become clear from the examples. As a result of intensive research, the inventors have found that the above purpose is (a)
The dispersion of CPM consisting of steps (b) and (b) is
Step (a) and step (b) have a number average molecular weight of 2000 or more.
by conducting in the substantial absence of the polymer
I found that it can be achieved by (a); dissolving the CPM in a water-miscible organic solvent; (b); containing the solution formed in step (a) and a surfactant;
Mix the water with the CPM and the surfactant
A process in which the agent is dispersed in water containing the agent. The CPM that can be applied to the dispersion method of the present invention is
- CPM that can be used in diffusion transfer method
It is virtually insoluble in pure water at 25°C.
be. These CPMs are also completed in the molecular structure
It may already contain a pigment part.
color during development and subsequent processes that occur simultaneously.
It may be something in which an elementary part is formed, or there may be
In other words, the essential ingredients for pigment formation are treated with an alkaline processing solution.
It becomes diffusible, moves to the image-receiving layer, and is stained on the image-receiving layer.
Even if the pigment is formed there,
stomach. That is, various types applicable to the dispersion method of the present invention
The pigment part of CPM is azo dye, azomethine
Pigments, anthraquinone dyes, azine dyes, India
Various types such as phenol dyes can be mentioned.
In addition, the precursors of these dyes, leuco
co-dye, shift-type dye with acylated auxochrome, or
Diazonium compounds, oxidized products of color developing agents, etc.
Couplers that can react to form dyes are listed below.
I can do it. It is a CPM that can be applied to the dispersion method of the present invention.
[A] type CPM includes, for example, U.S. Patent No.
No. 2983606, No. 3345163, No. 3255001, No. 3255001, No.
No. 3218164, No. 3453107, No. 3551406,
Same No. 3135605, Same No. 3421892, Same No. 3563739
No. 3482972, No. 3415644, No. 3415644, No. 3482972, No. 3415644, No.
What is stated in each specification etc. of No. 3594165
can give. It also introduces hydrolyzable groups into the dye developer.
hydrolyzable dye developer and short wavelength shift
Dye developers can also be used. Representatives of these
Specific examples include U.S. Patent No. 3,230,082;
3329670, 3307947, 3230083, 3307947, 3230083,
No. 3230084, No. 3230085, No. 3579334,
Same No. 3295973, Same No. 3196014, Same No. 3336287
U.S. Application No. 709548, July 28, 1976
No., July 29, 1976, U.S. Application No. 709936, Tokukosho
No. 36-379, No. 36-12393, and No. 37-2241.
U.S. Pat. No. 3,312,682 and U.S. Pat. No. 3,826,801
Can you list the compounds listed in the specifications, etc.?
Wear. Furthermore, the pigment part is reduced to leuco bodies.
Enables temporarily converted leuco dye developer
It can be used for. These representative examples and
U.S. Patent No. 2909430, U.S. Patent No. 3320063,
Specifications of No. 2892710 and No. 2992105, JP-A
Described in publications such as No. 48-66440 and No. 48-66441
Examples include compounds that have been [A] A typical example of type CPM is: etc. The above representative examples applicable to the dispersion method of the present invention
Type 2 CPM is oxidized by silver halide.
This product releases a diffusible dye when it reacts with the product.
For details, type [B], [C], [D] and
and [E] type. Among these, [B] type
is an antidote that can couple with oxidized developing agent.
It is a reactive CPM and is a reactive CPM that
Color that is soluble and diffusible in alkaline processing solutions
It can separate and release elements. This type of CPM
is a so-called diffusible dye-releasing coupler.
The ring reaction site is released by the oxidized developing agent.
is replaced by a residue. released
The electronic conjugation system of the dye is pre-incorporated into the coupler.
It can also be shaped by a coupling reaction.
may be made. The former coupler is emitted
Shows spectral absorption similar to that of dyes. On the contrary, the latter
Couplers are substantially colorless and colored
But its absorption is directly related to the absorption of the released pigment.
is temporary regardless. Above [B] type CPM
As US Patent No. 3227550, US Patent No. 3880658
British Patent No. 840731, British Patent No. 3765886, British Patent No. 840731, British Patent No.
Specifications of No. 904364, No. 904365, No. 1038331
Calligraphy, Special Publication No. 15471, Special Application No. 50-
Described in No. 133879 and Specification No. 50-113480, etc.
I can list things that have been done. A specific example of type B CPM is: etc. The above [C] type CPM is an oxidized developing agent.
Next to the reaction point that occurs following the coupling reaction with
Due to the intramolecular ring-closing reaction with the substituent in the tangential position,
It is a CPM that releases dye residues contained in substituents.
Ru. Especially for phenolic or aniline compounds.
Aromatic primary amino developer is oxidized to the 4th position
After scanning, the strip containing the dye part located at the 3rd position is
forms an azine ring with the fluoronamide group,
Releases a diffusible dye containing sulfinic acid
It is. As this [C] type CPM, the US patent
In the specifications of No. 3443940 and No. 3734726, etc.
These include those listed. Here are some typical examples of type CPM: etc. The [D] type CPM was oxidized as a result of development.
Oxidized by developing agent and decomposed by alkaline processing solution
It releases a diffusible dye, so-called diffusible dye.
It is called a dispersive dye-releasing redox compound.
be. A typical example of [D] type CPM is disclosed in U.S. Patent No.
3725062, 3698897, 3728113, 3725062, 3698897, 3728113,
No. 3928312, No. 3844785, No. 3942987,
Same No. 3932380, Same No. 3932381, Same No. 3931144
No. 3929760, No. 3245789 and France
Specifications of Patent No. 2284140, U.S. Published Patent No.
No. 351673, JP-A No. 50-118723, No. 51-104343
No. 52-7727, No. 52-8827, No. 51-113624
No. 50-115528 and No. 51-114930,
Patent application No. 51-78057, No. 51-125857, No. 51-
No. 78428, No. 51-78777, and No. 51-125860.
Application specification and research date closure
It is described in magazine 15162 etc. Preferred specific examples of [D] type CPM are: The [E] type CPM was oxidized as a result of development.
Intramolecular ring closure reaction that occurs following oxidation by the developing agent
As a result of the reaction, it is a CPM that releases a diffusible dye.
Regarding this [E] type CPM, U.S. Patent No.
No. 3443943, No. 3443939, No. 3443940 and
It is described in each specification such as No. 3751406. Here are some typical examples of [E] type CPM: etc. can be mentioned. [F] type CPM is Research Discrow.
14432, 14447 and Japanese Unexamined Patent Application Publication No. 1973-111628
No. 51-63618, No. 52-4819, etc.
has been done. Specific representative compounds of this [F] type CPM are
If you give it to me, etc. The CPM to which the dispersion method of the present invention can be applied is as follows.
It is not limited to the CPM that is specifically described.
do not have. However, the dispersion method of the present invention can be advantageously
Preferred applicable CPMs are [A] type CPM, [D]
Type CPM and [F] type CPM. Water-miscible organic solvents applicable to the dispersion method of the present invention
As a medium, it is freely miscible with water at room temperature (25℃).
For example, acetone, methyl alcohol, etc. are preferable.
alcohol, ethyl alcohol, isopropyl alcohol
, tetrahydrofuran, dimethylformamide
dioxane, N-methyl-2-pyrrolidone,
Acetonitrile, ethylene glycol monoethyl
Ether, ethylene glycol monobutyl ether
alcohol, diacetone alcohol, etc. this
These may be used alone or in combination of two or more.
You can also be there. The amount of CPM dissolved in a water-miscible organic solvent is
Solubility of CPM in water-miscible organic solvents and
Can be arbitrarily selected depending on the melting temperature.
but preferably per 100 ml of water-miscible organic solvent.
However, the CPM is 50gr to 0.1gr, particularly preferably 20gr.
~1gr. Dissolve CPM in a water-miscible organic solvent
If necessary, regular stirring equipment can be used in
You can use it and stir it, or you can further heat it to dissolve it.
It is also possible to tighten. The solution then formed
If there are insoluble substances mixed in, use excessive means.
It is better to remove it. The water according to the present invention is deionized.
Water used in the photographic field is preferred;
Can be used effectively. Surface activity that can be used in the dispersion method of the present invention
As a sex agent, for example, dodecylbenzene sulfur
Sodium salt of phosphoric acid, tetradecylbenzenesulfonate
Sodium salt of acid, di-t-butylnaphthalene sulfur
Sodium salt of phosphoric acid, triisopropylnaphthalene sulfate
Foonic acid sodium salt, mononaphthalene sulfonic acid
Na salt, P-nonylphenoxypropylsulf
Na salt of onic acid, Na salt of dodecyl sulfonic acid,
Sodium salt of perfluorooctane sulfonic acid, vinyl
Sodium 2-ethylhexylsulfosuccinate
salt, diisooctylsulfosuccinic acid Na salt, di
(1,1,7-trihydro-perfluorohepti
) Sodium salt of sulfosuccinic acid, Sodium stearic acid
salt of 2-methyl-hexanol sulfonic acid
Na salt, heptadecenylbenzimidazole sulfate
Foonic acid Na salt, N-methyloleyltaurai
Sodium salt, N-perfluorooctyl sulfur
K salt of nyl-N-propylglycine, sorbitan
lauryl monoester, etc. These surfactants may be used alone or in combination of two or more.
It can also be used by using Amount of surfactant used in the dispersion method of the invention
can vary over a wide range, which makes the CPM
Usually 5 to 200% by weight based on the amount, but preferably
The percentage is 10 to 100% by weight. In the dispersion method of the present invention, CPM is
The amount of polymer that should have a protective colloidal effect on
The presence of surfactant-containing CPM solution
This prevents uniform dispersion of CPM into the aqueous solution.
A photosensitive halo is a photosensitive element coated with a dispersion.
The drawback is that it impedes the sensitivity of silver germide emulsions.
Ru. As a result of various studies, we found that the properties of individual polymers
Therefore, it is difficult to set particularly strict standards.
However, polymers with a number average molecular weight of 2000 or more are generally applicable.
I guess. However, the number average molecular weight is 2000 or more
Even if the polymer is present in trace amounts, it may cause
No sound is recognized. The limit amount showing the above disadvantages is individual
Similar to the above, it depends on the properties of the polymer.
However, in general, the polymer content is 0.01g or more per 1g of CPM.
and an aqueous solution containing a surfactant.
Total volume of mixed system of solution containing CPM (25℃)
The amount was 0.1g or more per 100ml. Therefore, when carrying out the dispersion method of the present invention,
In this case, the steps (a) and (b) above are performed using a number-average molecule.
carried out in the substantial absence of polymer in an amount of 2000 or more
It is necessary to become Number average molecular weight of 2000 or more
Examples of polymers include gelatin, agar, and arabic.
Agum, Albumin, Sodium Alginate, Dex
Natural polymers such as transulfate, polyvinyl
alcohol, polyvinylpyrrolidone, polyac
Rylamide, polyethylene sulfonate, poly
Sodium acrylate, polymethacrylic acid
Ammonium salt, polyvinylbenzyltrimethyla
Synthetic polymers such as ammonium chloride, etc.
Ru. In the present invention, in order to perform the step (b),
Usually, the solution formed in step (a) above is used as a surfactant.
If added gradually while stirring to water containing
good. The method of addition is arbitrary, but preferably pressure
Apply force to the nozzle at the tip of the cylindrical container.
There is a method of adding surfactants to an aqueous solution.
In this case, the inner diameter of the nozzle is preferably 0.05 to 0.5 mmφ.
stomach. Another preferred method is to
0.01~0.1mmφ hole 1cm ² having 10-100 pieces per
Pressure is applied to the cylindrical container to make the solution surface active.
Another method is to add it to an aqueous solution of the sex agent. Furthermore, the main issue
In bright light, it is more preferable to perform the step (b) above.
As a method, the solution formed in step (a) above is
The first stream is water containing surfactant, and the water containing surfactant is the second stream.
, and the first flow and the second flow are
At least at the starting point, they are separate;
At least while the first flow is present, the second flow
While the flow continues, the first flow and the
This is a method of mixing the second stream. Use this method
It is said that the particle size distribution of CPM becomes narrower when
It has advantages and is even easier to carry out on a large scale industrially.
Capable of continuous production and therefore suitable for mass production
Ru. For example, this method is schematically shown in Figure 1.
The liquid containing the surfactant stored in the first liquid storage tank 1 is
The water 2 is supplied by a water feed pump 4 inserted into a conduit 3.
A second flow is formed from the nozzle 5 by the suction force of
The liquid is supplied to the container 6, while the liquid is stored in the second liquid storage tank 7.
The CPM solution 8 that was
The suction force of the pump 10 causes the first
The liquid is supplied to the container 6 by forming a flow of . And no
The liquid supply from nozzle 5 and the liquid supply from nozzle 11 are mutually
The nozzles 5 and 11 intersect obliquely so that they collide with each other.
Orient yourself as follows. Note that the diameter of the nozzle 5 is
Make it thicker than the diameter of the hole 11. Supply from nozzle 5
It is preferable to maintain the aqueous solution 2 below 10°C.
Therefore, the liquid storage tank 1, conduit 3, and nozzle 5 are
Is it possible to install a cooling device (not shown)?
put. Furthermore, the CPM supplied from the nozzle 11
Solution 8 is preferably maintained at a temperature of 30°C or higher.
The liquid storage tank 7, conduit 9 and nozzle 11 are each
A heating device (not shown) is installed. another
As a method, as shown schematically in Figure 2,
Solution 2 and CPM solution 8 are in the nozzle 12.
so that the liquid is mixed and supplied from the nozzle 12 to the container 6.
You may do so. In addition, the mixing efficiency is increased in the nozzle 12.
Attach static mixer 17 to
put. Also, a temperature control device is installed as shown in Figure 1.
put. (Not shown) Yet another method is to
of aqueous solution 2 and CPM as schematically shown in the figure.
The solution 8 is mixed in the suction type mixer 13 and sent to the nozzle 1.
4 to the container 6. In addition, inside the nozzle 14
Static mixer 17 to increase mixing efficiency
Attach it. Also, as in Figure 1, a temperature control device is installed.
Install the stand. (Not shown) Furthermore, this person
In the method, the second flow is caused by the suction force of the water feed pump 4.
On the other hand, the first flow is formed by the second flow.
As the flow builds up, the suction mixer 13
It is formed naturally through work. Ma
The diameter of the nozzle 11 at the tip of the first flow conduit 9
and adjusting the valve 15 provided in the conduit 9.
The quantity ratio of the first flow and the second flow is always kept constant by
The particle size distribution of CPM can be made very
It can be made narrower, and the particle size of CPM can also be changed arbitrarily.
This is an excellent method for In addition, the valve 16
This is to adjust the amount of liquid supplied to the second flow.
Ru. Formed in step (a) above with water containing a surfactant
The ratio of the amount of the solution to 1 volume of the solution is
The water containing the sex agent preferably has a volume of 2 or more.
more preferably 3 volumes or more. In the dispersion method of the present invention, the step (b) above is performed.
When the solution formed in step (a) above is heated to 30℃ or higher,
condition and water containing surfactant is 10
By performing the step (b) above at a temperature below ℃,
very favorable results can be obtained. As described above, obtained according to the dispersion method of the present invention.
Most of the CPM dispersion produced has a particle size of 0.01 μm.
or less, and even if stored for a long period of time, aggregation, precipitation, etc. will not occur.
First, it has extremely excellent stability. CPM fraction obtained according to the dispersion method of the present invention
Sansan is a color diffusion transfer photosensitive material using various methods.
It can be applied to CPM fraction obtained according to the dispersion method of the present invention
In order for the scatter to be a constituent layer of the photosensitive element, it is usually necessary to
A hydrophilic binder such as gelatin as an inder.
mixed with a silver halide emulsion layer and combined with a silver halide emulsion layer.
It may be applied on the support. At that time, disperse
Mixing ratio of hardened CPM and hydrophilic binder
can be arbitrarily determined depending on the purpose, but usually
CPM is 0.1g to 1g of hydrophilic binder
5g, preferably 0.3g to 2g. coating
The cloth film thickness should be 0.5μm to 3.0μm in dry state.
stomach. The water-miscible organic solvent used in the dispersion method of the present invention is
Mixed with a hydrophilic binder and coated on a support
After that, remove it by natural drying or hot air drying.
good. Another method is to use an evaporator etc.
It is also possible to evaporate under reduced pressure using
The hydrophilic buffer is removed after the water-miscible organic solvent is removed.
It may be mixed with an inder and coated on the support.
Yet another method is to use a hydrophilic buffer such as gelatin.
After mixing with indah, let it cool and form into noodles.
After removing the water-miscible organic solvent by washing with water,
Heat it to 40°C to 80°C, make it into a sol again, and place it on the support.
It can also be painted on. Mixed with CPM obtained according to the dispersion method of the present invention.
Hydrophilic binders that can be combined include, for example,
Gelatin modified with gelatin, acylating agents, etc.
Chin, grafted by vinyl polymer
Proteins such as gelatin, casein, and albumin
quality, hydroxyethyl cellulose, hydroxyl
Lopyl cellulose, carboxymethyl cellulose
cellulose derivatives such as methylcellulose,
Part of polyvinyl alcohol or polyvinyl acetate
Partial hydrolyzate, polyvinylpyrrolidone, polyac
Lylamides, polyvinyl ethers, e.g.
Polymeric non-electrolytes such as methyl vinyl ether,
Partial hydrolysis of lyacrylic acid and polyacrylamide
Decomposition product, copolymer of vinyl methyl ether and maleic acid
Anionic synthetic polymers such as compounds can be used.
Ru. These hydrophilic binders may be used alone or in combination.
can be used. Furthermore, these hydrophilic binders and alkyl alkyl
Latex polymerization of hydrophobic monomers such as rylates
A body dispersion may also be used. Furthermore, these hydrophilic
Inders, especially amino groups, hydroxyl groups,
Various polymers with functional groups such as boxyl groups are
Insoluble without loss of treatment agent permeability due to hardening agent
can be converted into Name a particularly useful hardening agent.
Formaldehyde, glyoxal, gluta
Aldehydes such as raldehyde, N-hydroxy
Dimethylphthalimide, 1-hydroxymethylbenzene
N-methylol compounds such as zotriazole,
2,5-hexadione, 1,2-cyclopentadi
Ketones such as on, N-polymethylols,
Methylol compounds such as xammethylolmelamine
1,4-bis(2,3-epoxypropoxy)
c) Epoxy compounds such as diethyl ether,
Aziridine compounds such as lyethylene phosphamide
3-Hydroxy-5-chloro-8-triazide
High-molecular materials such as nylated gelatin are
can be given. Furthermore, these hydrophilic binders
- In addition to the hardening agent, a hardening accelerator such as carbonate is used.
You can stay there. CPM fraction obtained according to the dispersion method of the present invention
Application of a mixture of powder and hydrophilic binder
Various application aids or thickeners can be used to facilitate
Use is optional. Examples of coating aids include saponin and alkyl esters.
etherified sucrose, monoalkyl etherified
Glycerin, ethoxy of p-nonylphenol
There are ethylene adducts, etc. Examples of thickeners include
For example, poly-p-sulfostyrene potassium salt,
Lulose sulfate, polyacrylamide, rice
Acrylic acid polyester described in National Patent No. 3655407
There are Mah et al. CPM fraction obtained according to the dispersion method of the present invention
If the dispersion is colorless, remove the CPM dispersion.
Mixed with a silver halide emulsion and coated on a support.
Both are possible. At that time, it was dispersed
The mixing ratio of CPM and hydrophilic binder depends on the purpose.
Although it can be arbitrarily determined depending on the
CPM per mole of silver oxide is 5×10 ^-3 mole ~ 5 mole
preferably 1×10 ^-2 Mol~5×10 ^-1 Mo
It is le. Coating film thickness is 1.0μm to 4.0μm in dry state
It should be m. The photosensitive element according to the present invention is provided on a support.
at least one silver halide emulsion layer
in combination with silver halide in a silver halide emulsion layer of
It has a built-in CPM layer. 1 set of this combination
Or by using two sets, you can create a single color or
It is also possible to obtain two-color dye images for pseudocolor photography.
Ru. Also, for example, color photography using multicolor subtraction method.
When used in a method, blue sensitivity is applied to the support from the exposed side.
Emulsion layer, green-sensitive emulsion layer and red-sensitive emulsion layer sequentially
It is preferable to layer the emulsions and
Yellow CPM, Magenta CPM and Cyan
It is desirable to have CPM. Or, if necessary, JP-A No. 50-79333
and as described in Publication No. 50-79334.
At least one of the green-sensitive emulsion layer or the red-sensitive emulsion layer
One part combined with CPM, blue sensitive milk
It may be located closer to the exposure side with respect to the agent layer.
In addition, if necessary, yellow filter layer, Halley
Provide layers such as an anti-shock layer, an intermediate layer, and a protective layer.
be able to. Moreover, Special Publication No. 49-6207
To improve light source suitability as described in
The following measures may be taken. Silver halide emulsions include, for example, silver chloride, silver bromide,
Silver chlorobromide, silver iodobromide, silver chloroiodobromide or these
It may consist of a colloidal dispersion of a mixture or the like. this
Silver halide emulsions can be either fine-grained or coarse-grained.
The average particle size may range from about 0.1 microns to about 2 microns.
Useful is the micron range. Also this
Silver halide emulsions are prepared by any known method.
For example, single-jet emulsion, lip
Mann emulsion, thiocyanate or thioether ripening
Emulsion, U.S. Patent No. 2222264, U.S. Patent No. 3320069 and
and the specifications of the same No. 3271157.
It includes things like Substantial surface photosensitivity
An emulsion containing silver halide grains with
In addition, halogenated particles have substantial photosensitivity inside the particles.
Emulsions containing silver particles are also used, and these halogen
Silver oxide emulsions are disclosed in, for example, U.S. Pat.
In the specifications of No. 3206313 and No. 3447927, etc.
Are listed. In the present invention, negative emulsion
Rui is U.S. Patent No. 2184013, U.S. Patent No. 2541472, U.S. Patent No.
No. 3367778, British Patent No. 723019, French Patent No.
Patent No. 1520821, U.S. Patent No. 2563785, U.S. Patent No.
No. 2456953, No. 3761276 and No. 2861885
Use a direct positive emulsion as described in the specification etc.
You can also do it. These silver halide emulsions are contained in gelatin.
Natural sensitizers or chemical sensitizers such as reduced
agent, sulfur, selenium or tellurium compounds, gold, white
Gold or palladium compounds, or combinations thereof
It can be sensitized by A suitable sensitization method is rice
National Patent No. 1623499, National Patent No. 2399083, National Patent No.
3297447 and 3297446.
It is listed. Silver halide emulsions also have speed-increasing properties.
compounds such as polyalkylene glycols, cations
surfactants and thioethers or their
combinations, such as U.S. Pat. No. 2,886,437;
No. 3046132, No. 2944900 and No. 3294540
You can use those listed in each specification etc.
Wear. Furthermore, silver halide emulsions may cause fog.
It can be protected against
It can be stabilized against a decrease in temperature. Alone
or a suitable antifoggant used in combination.
and stabilizers as described in U.S. Patent No. 2,131,038 and
Thiazoli as described in each specification etc. of No. 2694716
Um salt, U.S. Patent Nos. 2,886,437 and 2,444,605
Azaindenes as described in each specification, etc.,
Mercury salts as described in Patent No. 2728663, US
Urazol as described in Patent No. 3287135
series, as described in U.S. Pat. No. 3,236,652.
Luhocatechol, described in British Patent No. 623448
Oxime nitrones and nitroindazoes as listed
as described in U.S. Pat. No. 2,403,927.
Mercaptotetrazoles, US Patent No. 3266897
No. 3397987, as stated in the specifications, etc.
Mercaptotetrazoles, U.S. Patent No.
Polyvalent metal salts as described in US Pat. No. 2,839,405
Chiuroniu as described in Patent No. 3220839
Salt, U.S. Patent Nos. 2,566,263 and 2,597,915
Palladium, platinum and
and gold salts. These silver halide emulsions also have additional sensitivity.
Optical sensitizing dyes can be used to give photosensitivity.
Wear. For example, a silver halide emulsion can be used as an organic sensitizing dye.
The dye can be treated with a solvent or in the form of a dispersion.
In addition to the description in National Patent No. 1154781,
Additional optical sensitization can be achieved. optimal
For best results, dyes must be added in the final step or
It is desirable to add it to the emulsion somewhat earlier in the process.
stomach. Sensitization useful for sensitizing such silver halide emulsions
Dyes are described, for example, in U.S. Pat. No. 2,526,632;
No. 2503776, No. 2493748 and No. 3384486
It is stated in each specification etc. can be used effectively
Optical sensitizers include cyanines, merocyanines,
Styryls, hemicyanines (e.g. enamines)
mycyanin), oxonol and hemioxonol
This includes tools, etc. Cyanine dyes are examples.
For example, thiazoline, oxazoline, pyrroline, piri
Gin, oxazole, thiazole, selenazole
and basic core-containing substances such as imidazole.
is desirable. Such a nucleus is an alkyl group, an alkylene
group, hydroxyalkyl group, sulfoalkyl group
group, carboxyalkyl group, aminoalkyl group or
or enamine groups, and may also contain carbocyclic
It may be attached to a ring or a heterocyclic ring, which
These rings are halogen, phenyl group, alkyl group,
Substituted with a loalkyl group, cyano group or alkoxy group
It may or may not be replaced. this
These dyes can be symmetrically or asymmetrically dyed with methylene or
has an alkyl group, a phenyl group, and an enamel group in the polymethine chain.
May have a min group or a heterocyclic substituent.
stomach. Merocyanine dyes are basic dyes such as those mentioned above.
Nuclei, e.g. thiohydantoin, rhodanine, oki
Sazolidenedione, Thiazolidenedione, Parvi
such as tar acid, thiazolinone, and malononitrile.
Contains an acidic core. This acid nucleus is an alkyl group,
Kylene group, phenyl group, carboxyalkyl group,
Sulfoalkyl group, hydroxyalkyl group, alkaline
Coxyalkyl group, alkylamino group or hetero
Optionally substituted with a cyclic nucleus. Above if desired
Combinations of dyes can also be used. Moreover,
In addition, the silver halide emulsion may absorb visible light if desired.
supersensitizing additives, such as ascorbic acid, that do not
Derivatives, azaindenes, cadmium salts or rice
Specifications of National Patent No. 2933390 and National Patent No. 2937089
Containing organic sulfonic acids as described in books etc.
can be made to have The support of the photosensitive element is treated with a processing composition.
Planar material that does not undergo significant dimensional changes over time
It is desirable that Depending on the purpose, glass
Although rigid supports such as
supports are useful. and as a flexible support
It is preferable to use materials used in general photographic materials.
For example, cellulose nitrate film,
Cellulose acetate film, polyvinyl acetate
Tar film, polystyrene film, police
Tylene terephthalate film, polycarbonate
Thin films and the like are advantageously used. Also, expanded
The water in the alkaline treatment composition is supported after treatment.
US Patented to help radiate through the body
In the specifications of No. 3573044 and No. 3690879, etc.
Use a water vapor permeable support as described
It is advantageous to do so. Also, the support is transparent
Whether it is opaque or opaque depends on the layer structure of the photosensitive element and image-receiving layer.
composition, direction of exposure, or processed in light or dark.
The selection is made based on various conditions such as whether it will be processed locally.
Ru. When using a transparent support and processing in a bright place.
from the edge of the transparent support to the silver halide emulsion layer.
Transparent support to prevent light leakage during exposure
It does not interfere with observation, but it prevents light from passing through the surface.
It is desirable that it be colored to the extent that it can be seen. Also, an opaque support is used for the purpose of blocking light.
For example, carbon black, oxidized
Even if pigments such as titanium are contained in the support,
Optionally use a binder on the support.
You can also apply it after cleaning. The support optionally contains various photographic additives.
For example, phosphoric acid esters, phthalic acid esters, etc.
Plasticizers such as Stell, 2-(2-hydroxy-4
-t-butylphenyl)benztriazole
UV absorbers, hindered phenols, etc.
It may also contain an antioxidant. coated with support
Provide an undercoat layer to maintain adhesion with the underlying layer.
Or corona discharge treatment or ultraviolet irradiation treatment on the surface of the support.
It is advantageous to carry out preliminary treatments such as cleaning and flame treatment.
Ru. The thickness of the support is not limited, but is usually 20~
It is desirable to have a thickness of 300μ. Layer containing CPM dispersion, silver halide emulsion layer
For example, as a method of coating a support with
National Patent No. 2761791, National Patent No. 2761417, National Patent No.
2761418 and 2761419
Ritthopper method, U.S. Patent Nos. 3513017 and 3513017;
In addition to the curtain method described in specification No. 3508947, the day
There are various methods such as roll method, roller method, and air knife method.
However, the multi-slit hopper method
It is preferable to apply multiple layers simultaneously. CPM fraction obtained according to the dispersion method of the present invention
Photosensitive elements containing scattering materials cannot be obtained using conventional dispersion methods.
It has various excellent properties that are unique to the world. For example, the prior art polymer and
Adding a strong acid to a strong alkaline solution containing CPM
The method of dispersing CPM by neutralization is salt by neutralization.
can be obtained by the dispersion method of the present invention because
When compared to photosensitive elements containing dispersions of CPM.
In some cases, the binder properties according to the present invention are much better.
is excellent. Also, the aforementioned U.S. Patent No. 3438775
When compared with the CPM distribution method described in the specification of the
In some cases, colored particles obtained by the dispersion method of the present invention
The photosensitive element containing the dispersion of CPM is halogenated
The desensitization of silver has been significantly improved, and the spectral sensitivity has also been improved.
It has excellent color reproducibility and no color confounding.
It was recognized that Furthermore, CPM obtained according to the dispersion method of the present invention
The dispersion is prepared using a hydrophilic binder or a halogen
It can be mixed compactly with silver oxide emulsion.
The thickness of the coating film can be reduced, allowing for faster processing.
This will make a major contribution. Also oil protection
Contains a dispersion of CPM obtained by the dispersion method.
Solvent bleed onto the surface often seen in optical elements
However, no crystal precipitation of CPM was observed at all. The CPM applied to the photosensitive element is the above [A] and
If type [F], negative silver halide emulsion layer
A positive diffusion transfer dye can be developed using
give an image. On the contrary, the representative
[B] [C] [D] [E] type CPM is a negative type.
If development is performed using a silver halide emulsion layer,
Gives a diffusion transfer dye image of the moth. Therefore, the types of [B], [C], [D] and [E]
In order to obtain a positive diffusion transfer dye image in CPM,
requires an inversion method, and various inversion methods are used.
By doing this, it is possible to obtain a positive diffusion transfer dye.
Wear. For example, U.S. Pat. No. 3,227,552;
Specification No. 2592250, Specification No. 2005837, Specification No.
Specification No. 3367778, Specification No. 3761276, British Patent
Specification No. 1011062, Japanese Patent Publication No. 41-17184,
As described in Japanese Patent Application Laid-open No. 50-8524, etc.
There is a method using a direct positive silver halide emulsion.
British Patent No. 904364, Japanese Unexamined Patent Publication No. 1983-325
There is a method using physical development described in the publication No.
Japanese Patent Publication No. 43-21778, U.S. Patent No. 3227554
No. 3632345 specification etc.
Add CPM into the fogged emulsion layer as if
As a contact layer, it reacts with the oxidized form of the developing agent and develops it.
Negative-tone halogen containing compounds that release inhibitors
can be obtained by methods such as using a silver emulsion layer.
can. As mentioned above, in order to obtain a positive diffusion transfer dye image,
Various methods can be used, but preferably
The method using direct positive silver halide emulsions is preferred.
stomach. Examples of direct positive silver halide emulsions include
The entire surface can be developed by pre-exposure or chemical treatment.
It is now in a state where it can be developed imagewise through imagewise exposure.
There are some silver halide emulsions that become impossible to image.
It can be done. Also, as another direct positive silver halide emulsion
mainly has photosensitivity inside the silver halide grains.
Examples include direct positive silver halide emulsions. CPM fraction obtained according to the dispersion method of the present invention
Scatter to obtain positive color diffusion transfer dye images
As a silver halide emulsion, the latter direct positive type silver halide emulsion is
Silver halide emulsions are preferred. This direct positive halo
When exposed imagewise, silver germide emulsions primarily contain
A latent image is formed inside the silver halide grains, causing fog.
A positive silver image is formed when the surface is developed under these conditions.
It is something that There are various development processes under such fogging conditions.
There is a method. For example, West German Patent No. 850383
and U.S. Patent No. 2497875, etc.
A so-called air fog developer may be used, or
Also, even if flash exposure is applied to the entire surface during development,
good. This method is described in West German Patent No. 854888.
Specification, US Patent No. 2,592,298, British Patent
No. 1150553, No. 1195838 and No. 1187029
It is stated in the specification of the No. Furthermore, the presence of fogging agents
Development processing may be carried out while the film is still in use. A card that can be used for this
Hydrazine compounds and N-substituted quaternary
grade ammonium salts, etc., and these can be used alone or
They can also be used together. These fogging agents include
U.S. Patent No. 2588982, U.S. Patent No. 3227552, U.S. Patent No.
No. 3615615, No. 3719494, No. 3734738, No. 3719494, No. 3734738, No.
It is described in the specification of No. 3718470, etc. cabri
The amount of agent can vary widely depending on the purpose
However, when added to the processing solution, it is generally
The amount is 0.01 to 2.0 g per 1 processing solution, and the photosensitive element
1m when adding inside ² 0.001~0.5g per
Ru. Containing photosensitive silver halide emulsion and CPM
A photosensitive element having a layer having various layers may have various layer configurations.
obtain. The preferred layer structure is a multilayer structure, starting from the exposed side.
Coating in the order of blue-sensitive emulsion, green-sensitive emulsion, and red-sensitive emulsion.
It is a combination of blue-sensitive emulsion and green-sensitive emulsion.
A yellow filter layer may be placed in between. or,
A protective layer may be placed adjacent to the blue-sensitive emulsion layer.
stomach. Combination of photosensitive silver halide emulsion and CPM
For example, add it to separate adjacent layers.
However, leuco type CPM, short wavelength shift type
Does not have a pigment structure during CPM or exposure.
CPM, i.e. virtually colorless to visible light.
CPM does not reduce the sensitivity of the emulsion, so
It can be added into the silver germide emulsion layer. Also, for example, US Pat. No. 2,800,458, etc.
silver halide emulsion by the mixed packet method described in
It can also be used by applying and CPM in one layer.
Ru. CPM fraction obtained according to the dispersion method of the present invention
Scattered objects are used in multicolor subtractive color photography
An intermediate layer may be used in the photosensitive element if
It's advantageous. The intermediate layer is between emulsion layer units with different color sensitivities.
to prevent undesirable interactions between
In addition, pigments and pigments that can be diffusible in alkaline processing solutions are
Adjusting the diffusivity of the composition in the alkaline processing solution
It also has functions. This middle layer consists of gelatin, calcium alginate
or as described in U.S. Pat. No. 3,384,483.
Any item, as described in Special Publication No. 18435/1973
Vinyl acetate-crotonic acid copolymer, isopropyl
Cellulose, hydroxypropyl methylcellulose
Polyvinyl vinyl as described in Special Publication No. 47-47606
Ruamides, as described in U.S. Pat. No. 3,575,700
Gotoku polyvinylamide graft copolymer, Tokukosho
Publication No. 49-20972 and US Patent No. 3756816
A system of latex liquid and penetrant is useful as described in the book.
It is. This intermediate layer is dependent on the CPM used and the alkaline
Interlayer arbitrarily selected depending on the type of processing liquid composition
It may also contain an interaction inhibitor. For example, developing
Diffusible in alkaline processing liquids due to the oxide of the agent
A second type of CPM that releases a dye that can be
is a reducing agent such as a non-diffusible hydroquinone derivative.
A non-containing agent that can react with and fix the oxidation products of the developer.
Diffusive coupler, described in JP-A-48-15532
Amidrazone compound or German patent No. 2123268
The hydrazone compounds described in the publication are used as emulsion layer units.
prevents undesirable exchange of developer oxidation products between
used to prevent After imagewise exposure of the above photosensitive element, alkaline treatment
When processed with liquid, it becomes alkaline for imagewise exposure.
The dye that can become diffusible in the processing solution is used in the photosensitive element mentioned above.
Diffusion to the image-receiving layer placed in superimposed relationship with
The layer is then dyed to form a dye image.
will be accomplished. The image receiving layer preferably contains a mordant.
Yes. A suitable mordant for the image-receiving layer is diffusion transfer.
It is preferable for diffusible dyes or their precursors.
Any material can be used as long as it has a desirable mordant effect.
For example, poly-4-vinyl pin
Lysine, poly-4-vinyl-N-benzylpyridi
Ni-paratoluenesulfonate, cetyltri
Methylammonium bromide and the like are useful.
Also US Patent No. 2882156, Belgian Patent
No. 729202, U.S. Patent No. 3488706
Specification No. 3859096, Specification No. 3788855
Specification No. 3227148, Specification No. 3271147
, Specification No. 3709690, Specification No. 3625694
, Specification No. 3770493, Specification No. 3756814
Mordant described in Japanese Patent Publication No. 50-61228
can also be used advantageously. The above mordant is usually gelatin, polyvinyl alcohol
Polyvinylpyrrolidone, fully or partially
Various parents such as cellulose esters hydrolyzed into
It is used in combination with an aqueous binder, for example,
Poly-N-methyl-2-vinylpyridine, N-methyl
Toxy-methyl-poly-hexylmethyleneadipah
Vinyl alcohol and N-vinylpyrrolidone
copolymer or mixture of polymers, partially hydrolyzed
Polyvinyl acetate, acetyl cellulose
gelatin, polyvinyl alcohol, acyl
such as guanylhydrazone derivatives of styrene polymers.
Uni, with just a hydrophilic binder that has a mordant effect.
It is also possible to constitute an image-receiving layer. in the image receiving layer
The mordant content is preferably in the range of 10 to 100% by weight.
Yes. Also, as a special example, Japanese Patent Application Laid-Open No. 50-47626
Treat the mordant with alkaline as described in the report.
It can also be included in the physical solution. The image-receiving layer is further coated with UV absorbers, fluorescent brighteners, etc.
Contains various additives commonly used in photographic technology
You can also do that. The diffusible dye that is diffusely transferred to the image-receiving layer is a dye.
It is not a leuco dye or a dye precursor.
For example, in order to change these into pigments,
oxidizing agent, color developing agent or diazonium
It is advantageous to include a compound or the like. these acids
coloring agent, color developing agent, or diazonium compound
As an image-receiving layer containing substances, etc., US Patent No.
Specification No. 2647049, Specification No. 3676124, Specification No.
Specification No. 2698798, Japanese Unexamined Patent Publication No. 1983-80131, France
Patent No. 2232776 specification, Patent No. 2232777 specification, etc.
Those listed can be used. The above image-receiving layer is
may be in a superimposed relationship with the photosensitive element,
They may exist separately before processing, or both may exist separately.
may be combined together. Also, processing
After that, the photosensitive element and the image-receiving layer may be integrated.
It is also easy to peel off the photosensitive element and image-receiving layer.
stomach. The photosensitive element and image-receiving layer are separated before processing.
or after processing, the photographic element and image-receiving layer are separated.
When removing the image-receiving layer, the image-receiving layer is usually provided on a separate support from the photosensitive element.
placed on the body. Also, the image receiving layer is the same as the photosensitive element.
It can also be provided on a support. Various materials can be used as the support for the image-receiving layer.
Can be for example baryta paper, polyethylene
Paper laminated with resin such as diacetate cell
Loin, cellulose triacetate, cellulose acetate butyrate
etc. cellulose organic acid ester sheets, e.g.
For example, inorganic acid esters such as cellulose nitrate etc.
such as polyethylene terephthalate, etc.
Eel polyester sheet, polyvinyl acetate
Polyvinyl ester sheets such as
Polyvinyl acetal such as ribinyl acetal etc.
sheet of polystyrene, polypropylene, etc.
Polyalkylene such as pyrene, polyethylene, etc.
It can be used depending on the purpose, such as a sheet.
The support for the image-receiving layer may also be transparent or non-transparent depending on the purpose.
May be transparent. The silver halide emulsion layer, image-receiving layer, and storage layer described above
alkaline processing liquid such as a protective layer or intermediate layer.
The binders used in the permeable layer include those mentioned above.
mixed with CPM obtained according to the dispersion method of the present invention.
Using various hydrophilic binders that can be
can be used. Alkaline is removed by treatment with an alkaline treatment solution.
Pigments that can become diffusible in a caustic processing solution are used in the image-receiving layer.
The formation of the dye image is substantially completed.
After that, lower the pH in the system to around neutrality, and then
Greater dye image shape with increased stability
changes in the pigment image that occur at high pH
It is necessary to prevent color and contamination. For this reason, within the system
Using a neutralizing layer containing a neutralizing agent that lowers the pH of
Ru. As a material used as a neutralizing agent, one
or more carboxyl group, sulfonic group or hydrolysis
has a group that produces a carboxyl group by
Preferred are film-forming polymeric acids such as
Use any suitable polymeric acid.
be able to. The polymeric acid preferably has a molecular weight of about 10,000 to about
It has a molecular weight of 100,000, for example in the United States.
As described in Patent No. 3362819
A model of a 1:1 copolymer of maleic anhydride and ethylene.
Butyl ester, maleic anhydride and methyl vinyl
Monobutyl ester of 1:1 copolymer of ether
1:1 copolymerization of maleic anhydride and ethylene
Monoethyl ester, monopropyl ester in the body
monopentyl ester and monohexyl ester
Stell, maleic anhydride and methyl vinyl ether
Monoethyl ester of 1:1 copolymer of
Lopyle ester, monopentyl ester and monopentyl ester
Nohexyl ester, polyacrylic acid, polymeth
Acrylic acid and varieties of acrylic acid and methacrylic acid
Other copolymers with a ratio of acrylic acid and methacrylic acid
copolymers with various ratios of vinyl monomers, i.e.
For example, acrylic esters, methacrylic acid
Esters, vinyl ethers, etc., at least
30 mol%, preferably 50-90 mol% acrylic
Copolymers containing acid or methacrylic acid, etc.
can be used. Also, special application No. 1978-78774
Polymer acids and the like described in the specification can be used advantageously.
I can do it. In addition, research desk closure
(Research Disclosure) 12331
Metal salts, monomer acids, ballasted organics
Acids, alkyl phosphates, polyalkyl phosphates
Suphate, poly(1-acryloyl-2,2,
2-trimethylhydradium, p-toluenesul
phonate), etc., can be used alone or as needed.
Can be used in combination with under polymer
I can do it. Additionally, polymer acids and monomers can be added as needed.
Using acids or polymer acids in combination with organic amines
It's okay. These polymer acids, monomer acids,
The organic amines and binder polymers are e.g.
Methanol, ethanol, propanol, butano
Alcohols such as alcohols, e.g. acetone, metal
Thyl ethyl ketone, diethyl ketone, cyclohexane
Ketones such as Sanone, e.g. methyl acetate
ethyl acetate, isopropyl acetate, butyl acetate
esters or mixtures thereof, such as
It can be dissolved in and applied. Also, rice
As described in National Patent No. 3576625
It can also be microencapsulated. The thickness of the neutralization layer depends on the alkaline processing liquid used.
Composition and materials contained in the neutralization layer used
It is not possible to make a general decision as it varies depending on
Generally speaking, a range of 5 to 30 μm is suitable.
Ru. The above neutralizing layer is based on the layer structure of the photographic material for diffusion transfer.
It can be provided at any location depending on the situation. for example
U.S. Patent No. 3415644, U.S. Patent No. 3473925, U.S. Patent No.
3415646 and 3415645.
As shown in the above, it is provided between the image-receiving layer and the image-receiving layer support.
Also, U.S. Patent No. 3,573,043 and
As described in each specification etc. of No. 3573042, the photosensitive element and
It may be provided between the photosensitive element support, or
As stated in the specifications of license No. 3594164 and 3594165, etc.
In the processing sheet or between the image-receiving layer and the image-receiving layer support, as shown in
It may be provided between the holding bodies, and furthermore, as described in US Patent No.
In the case of the layer structure described in the specification of No. 3615421, the exposure requirement is
element, photosensitive element support and/or image-receiving layer, and image-receiving element
It may also be provided between the layer and the support. In addition, the peeling means
The layer structure described in Japanese Patent Application Laid-Open No. 47-3480 has
In this case, it may be provided between the image-receiving layer and the image-receiving layer support.
stomach. Also, together with the above neutralizing layer, it controls the decrease in PH.
timing layer (neutralization speed adjustment layer) for
can be provided. This timing layer is
Delays pH drop until after development and transfer of
It works to That is, silver halide development and
A neutralizing layer before the formation of the diffusion transfer dye image takes place.
As a result, the transferred color is caused by the rapid drop in the PH within the system.
To prevent an undesirable decrease in the density of a raw image. Various timing layers can be used for this timing layer.
For example, gelatin, as described in U.S. Patent No.
Polyvinyl alcohol as described in specification No. 3362819
Partial acetalization of alcohol, polyvinyl alcohol
Partially Hydrolyzed Polyvinyl Acetate, U.S. Patent No.
cyanoethylated polyester as described in No. 3419389.
Vinyl alcohol, US Pat. No. 3,433,633
Hydroxypropyl methyl cellulose as described
Isopropylcellulose, Special Publication No. 1267-1973
Polyvinylamides, as described in the official publication, 1977-
Polyvinylamide graph as described in Publication No. 41214
Copolymer, JP-A No. 49-22935 and No. 49-
Penetration with latex liquid as described in Publication No. 91642 etc.
Combinations with agents are useful. Furthermore, depending on the layer structure of the photographic material, the processing sheet is
Can be used. The treatment sheet is intended to block light.
and/or alkaline treatment composition.
The aim is to achieve uniform distribution and good diffusion.
You can use any of the following:
Ru. For the former, use a sheet that can block light.
In the latter case, any transparent or opaque
Uniformly distribute and diffuse the lukewarm treatment composition
Any sheet that can be used will suffice. The processing sheet has its support
Apply a layer containing a mordant as a scavenger on the body.
neutralizing layer and/or timing layer.
A layer may also be provided. As a support for processing sheets
is intended for the same purpose as the support for the image-receiving layer described above.
It can be used as desired. Aimed at blocking light
The processed sheet used as
pigments such as titanium oxide in the support.
You can also tighten the binder as needed on the support.
It may also be applied using a der. After treatment with an alkaline processing solution, the photosensitive element and receiver are
When removing the image layer to obtain a dye image, use a release agent.
Can be used. Release agent is silver halide emulsion
on the surface of the layer or on the image receiving layer containing a mordant; or
It can be included in the processing agent. Appropriate peeling
As a release agent, it is used in photosensitive elements and image-receiving layers.
A binder with a composition different from that used is used.
It can be done. For example, alkali-permeable polysaccharides,
Carboxymethyl cellulose, hydroxyethyl
cellulose, hydroxypropyl cellulose,
4,4'-dihydroxyphenol glucose,
Sucrose, sorbitol, resorcinol, phytin
acid sodium salt, zinc oxide, fine particle polyethylene
Microparticle polytetrafluoroethylene, US patent no.
Polyvinyl pylori as described in specification No. 3325283
Don/Polyvinylhydrodiene phthalate, US
Ethylene as described in National Patent No. 3376137
- Maleic anhydride copolymers are useful. The above alkaline processing solution is used for silver halide emulsion.
Processing components necessary for development and formation of diffusion transfer dye images
Any liquid composition containing
Can be used. This alkaline treatment solution
As a medium, water, methanol, methyl cellosolve, etc.
Hydrophilic solvents such as can optionally be used.
The alkaline processing solution is necessary for the development of the emulsion layer.
Maintains the required pH during development and dye image formation processes.
a sufficient amount of alkaline agent to neutralize the acid formed in
It is desirable that it contains. As an alkaline agent
Sodium hydroxide, potassium hydroxide, hydroxide
calcium chloride, tetramethylammonium hydroxide
sodium carbonate, sodium phosphate, diethyl
Ruamine etc. can be used, alkaline treatment
It is desirable that the liquid has a pH of approximately 12 or higher at room temperature.
stomach. Alkaline processing solutions may contain thickeners, such as hydroxyl.
ethylcellulose, sodium carboxymethylate
cellulose, hydroxypropylcellulose
Polymer thickener that is inert to alkaline solutions
can be included. The concentration of thickener is alkaline
It is desirable that the amount is about 1 to 10% by weight of the cleaning solution.
This results in approximately 100 to 200,000 centipoise.
Processing that can impart viscosity to alkaline processing liquids
Facilitates uniform spread of alkaline processing solution during
as well as to the photosensitive element and image-receiving layer during processing.
The aqueous solvent moves and the alkaline processing solution is concentrated.
When processed, a non-flowing film is formed to protect the processed image.
Assists in the integration of true materials. This polymer
– The membrane is substantially finished forming the diffusion transfer dye image.
After that, further dye image-forming components are image-receiving.
Prevents changes in dye images by suppressing migration to layers
It can also be useful for In addition, the alkaline processing solution is used as a main silver halide developer.
Preferably, it contains a drug. The silver halide developing agent depends on the type of CPM used.
More different. The CPM used is [B] and [C] type CPM,
In other words, it cannot couple with the oxidized developing agent.
It is a reactive CPM with a coupling reaction.
as a result of or a cup with oxidized developer.
Adjacent positions of reaction points following ring reaction
Due to the intramolecular ring-closing reaction with the substituents of
Releases soluble and diffusible dyes into the processing solution
For example, if the CPM is capable of
minophenol, N-methylaminophenol,
N,N-diethyl-p-phenylenediamine, 3
-Methyl-N,N-diethyl-p-phenylenedi
Amine, 3-methoxy-N-ethyl-N-ethoxy
C-p-phenylenediamine, 4-amino-N-
Ethyl-N-(β-methanesulfonamidoethyl)
)-Meta-toluidine sulfate, N-ethyl
-N-(β-hydroxyethyl)-p-phenylene
N-diamine sulfate, 3-methyl-N-ethyl
Ru-N-(β-hydroxyethyl)-p-pheni
Diamine sulfate, 3-methyl-N-ethyl
Chil-N-(β-ethoxyethyl)-p-pheni
Color developing agents such as diamine sulfate
Can be used alone or in combination of two or more
can. Also, the CPM used is [D] [E] and
[F] type CPM, that is, development in which CPM is oxidized
It is oxidized by the main chemical and is oxidized by the alkaline processing solution.
CPM that decomposes to release a diffusible dye or
CPM is oxidized by the oxidized developing agent,
The ensuing intramolecular ring closure reaction results in expansion.
CPM that releases a dispersive dye, or CPM that releases an alkali
It is cleaved in a oxidizing treatment solution to release a diffusible dye, but acid
In the presence of a modified developing agent, cleavage does not substantially occur.
If you have a CPM that does not
In addition to image agents, for example, hydroquinone, 2-chloro
Rohydroquinone, catechol, resorcinol, N
-Methyl-p-aminohydroquinone, 1-phene
Nyl-3-pyrazolidone, 1-phenyl-4,4
-Dimethyl-3-pyrazolidone, 1-phenyl-
4-methyl-4-hydroxymethyl-3-pyrazo
Silver halide dye for black and white such as lydone and ascorbic acid
Image agents may be used alone or in combination of two or more.
can be done. However, contamination occurs in the dye image area that is formed.
In order to reduce the
Preferred drugs, especially 1-phenyl-3-pyrazolide
A developing agent based on pigments is preferred. The above silver halide developing agent is alkaline processed.
Although it is common to include it in the liquid,
Silver halide emulsion layer, CPM-containing layer, intermediate layer,
Contained in at least one layer such as a protective layer or an image receiving layer
It is also possible to keep it in place. Furthermore, alkali
It is included both in the treatment solution and in the layer mentioned above.
You can also When pre-containing in the above layer,
It may also be contained in the form of a surfactant. Furthermore, the alkaline processing solution is specific to the CPM used.
It may also contain processing components. For example, dye developer
In the case of para-aminophenol, 4-methyl
Phenylhydroquinone, 1-phenyl-3-pi
Auxiliary developers such as lazolidone, N-benzyl-
Onium compounds such as α-picolinium bromide
Antifoggants such as benizotriazole
It is desirable to include it. The alkaline processing solution must be stored in a breakable container.
It is preferable that the e.g. liquid and air
Fold the sheet of material that is impervious to the
Processing agent is placed in a sealed hollow container.
When the photographic element passes through the pressure tool, it is
location determined by internal pressure applied to the chemical
When destroyed, alkaline processing solution will be released.
It is desirable to be familiar. form the above container
The material is polyethylene terephthalate/polyethylene.
Rivinyl alcohol/polyethylene laminate
lead foil/vinyl chloride-vinyl acetate copolymer laminated
Materials such as laminates and the like are advantageously used. Also
These containers are secured along the leading edge of the photographic element.
The storage liquid is directed essentially in one direction towards the surface of the photosensitive element.
It is desirable that it spreads out over a surface.
Preferred examples of containers include U.S. Pat. No. 2,543,181;
No. 2643886, No. 2653732, No. 2723051,
Same No. 3056491, Same No. 3056492, Same No. 3152515
and the specifications of the same No. 3173580.
There is. A highly white light reflection is used as a background for the formed pigment image.
Providing the propellant layer on the side opposite to the viewing direction with respect to the image-receiving layer
It is better. The position of the light reflector layer is particularly limited.
After processing, the photosensitive element and image receiving layer are pulled apart.
If not removed, the gap between the photosensitive element and the image-receiving layer
It is preferable to provide a light reflecting agent layer on the surface. The light reflector layer is
It may be provided as a coating layer, or it may be treated with an alkaline treatment.
A light reflecting agent is included in the liquid during treatment.
A light reflecting agent layer may be formed on the surface. light reflector and
Titanium dioxide, zinc oxide, barium sulfate,
Flake silver, alumina, barium stearate
aluminum, zirconium oxide, etc. alone or in combination
Can be used in combination. Set up as a layer in advance
Hydrophilic solution permeable to alkaline solution
Binders, e.g. gelatin, polyvinylalcohol
In any hydrophilic binder such as
Just let it happen. Further, as a method of forming a light reflecting agent layer, for example,
Described in JP-A-46-486 and JP-A-47-477
Methods such as those described may also be used. The above light reflector layer also contains still steel as a brightening agent.
Ben, coumarin, etc. may be added. halo after exposure
When developing a silver germide emulsion in a bright place,
Opaque to protect silver halide emulsion from light
It is preferable to provide a layer of agent. The opacifying agent layer is
It can be provided as a layer or it can be formed during processing.
You can force it. Carbon block is used as an opacifying agent.
Ratsukuya, JP-A-47-26, JP-A-47-27
Indicator dyes as described in Publication No. 47-28
can also be added. Also, U.S. Patent No.
Desensitizing agents as described in specification no. 3579333
It is also advantageous to use The light reflecting agent layer and the opacifying agent layer are the same layer.
or as separate adjacent layers.
may exist. CPM fraction obtained according to the dispersion method of the present invention
Film units and layer configurations to which scattering can be applied
There are various methods, such as U.S. Patent No. 3415644.
Specification No. 3415645, No. 3415646
Specification, Specification No. 3473925, Specification No. 3573042
Specification, Specification No. 3573043, Specification No. 3594164
Specification No. 3594165, Specification No. 3615421
Specification No. 3576626, Specification No. 3658524
Specification No. 3635707, Specification No. 3672890
, Specification No. 3730718, Specification No. 3701656
Specification No. 3689262, Japanese Patent Application Laid-Open No. 1983-6337
Belky Patent No. 757959 or Belky Patent No. 757959
Film unit and layer structure described in specification No. 757960
One example is growth. For the various film units and layer configurations mentioned above.
The light entering the silver halide emulsion during exposure is
Photographic characteristics as required at any position on the emission side
Add filter dyes, etc. suitable for improving
You can also do that. Normal PH for filter dye
However, it is stable when treated with an alkaline treatment solution.
Uses dyes that decompose and become colorless if they come in contact with
It can also be used. In addition, after the dye image is diffusely transferred to the image-receiving layer, the photograph
The element contains a silver image and a corresponding diffusion transfer dye image.
images from dyes or dye breakers remain.
I'm staying. Remove this residual silver and silver halide
Treated with bleach and fixing baths or bleach-fixing baths
Remove the dye precursor and add color if necessary.
If you apply a process to change it into a bare element, it will form on the image-receiving layer.
Obtain an inverted dye image for the dye image created.
You can also The present invention will be explained below with reference to Examples. Example 1 Preparation of comparative sample (1) [A] type CPM, 1 g of exemplified compound (7) was added to methyl
25ml mixed solvent of alcohol acetone (1:2)
dissolve in Keep the resulting solution at 35℃ for 100ml.
Add CPM gradually to the water with stirring.
disperse inside. Disperse CPM in water
During this period, keep the water temperature at 15℃±0.3℃.
CPM dispersion is flocculated into water.
It precipitates. The resulting precipitate was treated with dodecylbenze.
Mix with 0.15g of sodium sulfonic acid salt and add water.
forming a slurry. The resulting aqueous slurry
- mixed with 60ml of 3.3% by weight gelatin aqueous solution
Ultrasonic homogenizer (USH-150N25 type:
(manufactured by Ultrasound Kogyo Co., Ltd.)
Evenly distribute the particles in the gelatin matrix.
Closed. Divide the resultant into two and divide it into two parts.
1% by weight aqueous solution of saponin as a coating aid.
1.5ml of mucochloric acid as gelatin hardening agent
Prepare the coating solution by adding 0.5 ml of 2% by weight aqueous solution.
Made of transparent polyethylene teleph with a thickness of 100μm
Dry film thickness on tallate film support is 1.6μ
A comparative sample (A) was prepared by applying the material so that the amount of
Ta. The other one was stored in a cool dark place for 6 months.
After that, prepare comparative sample (a) using the same method as comparative sample (A).
did. (2) Same CPM1g and polyvinyl as comparative sample (A)
Pyrrolidone (K-30, number average molecular weight 40000) 0.3
g of acetone-methyl alcohol (2:1)
Dissolve in 25ml of mixed solvent. The resulting solution was heated to 35°C.
Add gradually to 100ml of water while stirring.
The CPM was then dispersed in water. CPM underwater
During the dispersion, the water temperature was kept at 15℃±0.3℃.
Keep it. 40 from the aqueous dispersion of CPM obtained.
°C, organic solvent and under reduced pressure of 150-200 mmHg.
19.8% by weight of gelatin after some water is removed by evaporation
Add 10 ml of Chin aqueous solution and use an ultrasonic homogenizer.
Transfer the CPM dispersion to a gelatin matrix using
It was evenly distributed throughout the tree. (gelatin 3
weight% aqueous solution) The thus obtained product was divided into two parts.
On the other hand, a comparative sample (B) was prepared according to the comparative sample (A).
The others were stored in a cool and dark place for 6 months according to comparative sample (a).
After storage, a comparison sample (b) was prepared. (3) Add 1 g of CPM, the same as comparative sample (A), to acetone-methoxy
Dissolved in 25ml of mixed solvent of alcohol (2:1)
did. The resulting solution was kept at 35 °C and the polyvinyl
0.3g of pyrrolidone and dodecylbenzenesulfate
100ml aqueous solution containing 0.3g of sodium salt of fonic acid
Add CPM gradually to the water while stirring.
It was dispersed into Disperse CPM into water
During this period, the temperature of the aqueous solution was kept at 15℃±0.3℃.
Ku. From the obtained CPM aqueous dispersion at 40℃, 150~
organic solvent and some water under reduced pressure of 200 mmHg.
After evaporation removal, 19.8% by weight gelatin in water
Add 10ml of liquid and use an ultrasonic homogenizer
The dispersion of CPM was evenly distributed in the gelatin matrix.
uniformly distributed. (Gelatin 3% by weight water soluble)
liquid) Divide the thus obtained into two parts, one of which
Comparative sample (C) was prepared according to comparative sample (A), and the others were
Stored in a cool and dark place for 6 months according to comparative sample (a)
After that, a comparative sample (c) was prepared. (4) 1g of CPM, the same as comparative sample (A), was added to N,N-diethyl
Dissolved in 2 ml of laurylamide and 2.5 ml of ethyl acetate.
I understand. The resulting solution was added to 1 g of gelatin and
Dissolve 0.3g of Na salt of decylbenzenesulfonic acid
Add Menton Gaulin to 90 ml of aqueous solution.
Create an oil-protected dispersion of CPM using
After that, add 10ml of 19.8wt% gelatin aqueous solution.
Then, remove the CPM oil using an ultrasonic homogenizer.
LeProtect dispersion in gelatin matrix
It was evenly distributed. thus obtained
Divide the sample into two, and use one as a comparative sample according to the comparative sample (A).
Sample (D) was prepared, and other samples were prepared for 6 months according to comparative sample (a).
After storing it in a cool and dark place, a comparative sample (d) was prepared. Preparation of the sample of the present invention (5) 1 g of CPM, which is the same as the comparative sample (A), was mixed with acetone-methyl
Dissolved in 25ml of mixed solvent of alcohol (2:1)
did. The resulting solution was kept at 35 °C and
100 in which 0.3g of Na salt of Zenzenesulfonic acid was dissolved.
ml of aqueous solution while stirring.
CPM was dispersed in water. CPM in water
During the dispersion, the temperature of the aqueous solution was kept at 15℃±0.3℃.
Keep it. 40 from the aqueous dispersion of CPM obtained.
Organic solvent and liquid under reduced pressure of 150-200mmHg
After evaporation of water, 19.8% by weight of gelatin
Add 10 ml of Chin aqueous solution and use an ultrasonic homogenizer.
Transfer the CPM dispersion to a gelatin matrix using
evenly distributed throughout the bath. (gelatin 3 weight
% aqueous solution) The thus obtained product was divided into two parts,
One is the sample of the present invention (Z) according to the comparative sample (A).
The other samples were kept cool and dark for 6 months according to comparative sample (a).
After storing it at a place, a sample (z) of the present invention was prepared.
Ta. (6) The surfactant used in the sample (Z) of the present invention.
The sodium salt of dodecylbenzenesulfonic acid is
-2-ethylhexylsulfosuccinic acid sodium salt
The samples of the present invention (Z) and
Samples (Y) and (Y) of the present invention are exactly the same as (z).
(y) was prepared. (7) Add 1 g of CPM, the same as comparative sample (A), to acetone-methoxy
Dissolved in a mixed solvent of alcohol (2:1)
Ta. In addition, dodecylbenzenesulfonic acid
Prepare 100ml of an aqueous solution containing 0.3g of Na salt.
Ta. Mix both solutions with CPM and water using the apparatus shown in Figure 3.
It was dispersed inside. While mixing both solutions, the aqueous solution
5℃±0.3℃, and CPM solution at 35℃±0.3℃
I kept it there. The resulting CPM aqueous dispersion
Just like samples (Z) and (z) of the present invention
to prepare samples (X) and (x) of the present invention.
did. The CPM of each sample above is the [A] type.
CPM, exemplified compound (21) and [F] type CPM,
Replace the exemplified compound (40) and replace the organic solvent with tetrahydrogen.
Dorofuran-acetone-methyl alcohol (1:
2:1) Comparison as shown in the table below except for changing to a mixed solvent
A sample and a sample of the present invention were prepared.

【table】

[Table] The optical absorption spectra of each of the samples (42 types) prepared above and the optical absorption spectra of each CPM in methyl alcohol were observed using a Hitachi EPS-3T self-recording spectrophotometer. The measured values are shown in Table 1. In the table, λmax represents the maximum absorption wavelength, and Γ1/2 represents the width (half width) of the optical density spectrum at 1/2 of the optical density at the maximum absorption wavelength. In addition, in order to investigate the degree of light scattering due to differences in each dispersion method, the ratio of the optical density near the absorption maximum to the optical density at the base of absorption was determined. Measurement points are blue region (B) at 436nm, green region
(G) was determined to be 546 nm, and the red region (R) was determined to be 644 nm. Figure 4 shows [A] type, which is magenta CPM.
The spectral absorption curve of a typical coated sample of CPM/Exemplary Compound (7) is shown. It can be seen from the figure that the spectral absorption characteristics of the coated sample according to the present invention are extremely close to those of the methyl alcohol solution and are ideal.

[Table] As is clear from Table 1, the samples obtained according to the dispersion method of the present invention have smaller Γ1/2, and B, G As can be seen from the ratio of ,R, each CPM
The absorption base is getting smaller. From these facts, the CPM dispersion obtained according to the dispersion method of the present invention has a silver halide emulsion layer combined with another CPM on the side opposite to the exposure. It is expected that the sensitivity will not be affected. Furthermore, after being left for 6 months, the samples obtained using the dispersion method of the present invention showed smaller fluctuations in each measured value and were extremely stable compared to samples obtained using the dispersion method of the prior art. It can be seen that it is. This is a great advantage in actual manufacturing. Example 2 A red-sensitive silver iodobromide emulsion was coated on a polyethylene terephthalate film and divided into 15 parts.
Comparative samples (A), (B), (C), (D) prepared in Example 1,
(a), (b), (c), (d) and the sample (Z) of the present invention,
A total of 14 types of coating solutions prepared for (Y), (X), (z), (y), and (x) were coated on the above emulsion layer to the same thickness, and the samples shown in the table below were coated. was created.

【table】

[Table] Using a light source with a color temperature of 4850〓, 1
A prescribed exposure was applied through a total of 30 stages of light wedges consisting of silver wedges with a difference in density between stages of 0.15, followed by development, and the sensitivity of the emulsion of each sample was examined. As a blank, a CPM methyl alcohol solution filter adjusted to the same optical density as the CPM layer of Sample No. 103 of the present invention was used instead of the CPM layer, and the sensitivity of the blank emulsion was normalized to 100. The results are shown in Table 2.

[Table] As is clear from Table 2, a dispersion of CPM obtained according to the dispersion method of the present invention (where the CPM is magenta) is combined with a green-sensitive silver halide emulsion and is not exposed to light with respect to the emulsion layer. The emulsion layer located on the opposite side is a red-sensitive silver halide emulsion layer) was found not to inhibit the sensitivity of the red-sensitive silver halide emulsion. It can also be seen that results stored for 6 months are similar to those obtained on the same day. Note that CPM is [A] type CPM, and instead of exemplified compound (7), [D] type CPM, exemplified compound (27),
Instead of (39) and (56), those obtained by the various dispersion methods of Example 1 were also [A] type CPMs, which were obtained according to the dispersion method of the present invention, similar to exemplified compound (7).
It was found that the CPM dispersion is excellent and does not impede the sensitivity of the red-sensitive emulsion. Example 3 [A] type CPM, which is the CPM used to prepare each sample in Example 1, and Exemplified Compound (7) were replaced with [D] Type CPM, Exemplified Compound (15) and [D] Type CPM, and Exemplified Compound ( Coated samples were prepared in the same manner as in Example 1, except that 56) was used, and a blue-sensitive internal latent image type silver bromide emulsion (17.5 mg/100
cm ² ) was applied to a dry film thickness of 2.5 μm to prepare a sample as follows. The emulsion was prepared according to the description in US Pat. No. 3,761,276, and 1-acetyl-
2-[p-{5-amino-2-(2,4-di-t
-Pentylphenoxy)benzamido}phenyl]hydrazine was added in an amount of 3 g per mole of silver.

[Table] After each of these samples was exposed to a light source with a color temperature of 4850㎓, the image-receiving layer and emulsion surface of the image-receiving element shown below were superimposed, and then treated at 25°C with the processing liquid composition shown below. Image receiving element: The following layers were sequentially coated on a 100 μm thick transparent polyethylene terephthalate film support. (1) Neutralizing layer of ethyl acrylate and acrylic acid (25/75% by weight) (220 mg/100 cm ² ) with a dry film thickness of 22.0 μm. (2) Neutralization rate control layer with a dry film thickness of 5.1 μm containing cellulose diacetate (5.0 mg/100 cm ² ). (3) 1:1 copolymer of styrene and N-benzyl-N,N-dimethyl-N-(3-maleimidopropyl) ammonium chloride (22.0 mg/
100cm ² ) and gelatin (22.0mg/100cm ² ) with a dry film thickness of approximately 2.0 μm. Treatment liquid composition Potassium hydroxide 56.1g Sodium sulfite 2.0g 4-methyl-4-hydroxymethyl-1-phenyl-3-pyrazolidone 8.0g 5-methylbenzotriazole 2.8g Anhydrous sodium sulfite 2.0g Carboxymethylcellulose sodium salt
50.0g Titanium dioxide 500.0g Add distilled water to make 1000ml. The reflection density of the dye transferred to the receiver element immediately after processing as a function of time for red (λmax =
644nm) filter and blue (λmax=436nm)
Densitometer (Sakura photoelectric densitometer) through a filter
Observations were made with a PDA-60 model (manufactured by Konishiroku Photo Industry Co., Ltd.). The results are shown in Table 3.

[Table] As is clear from Table 3, the samples prepared according to the dispersion method of the present invention have a high maximum reflection density and a short diffusion transfer time. Example 4 An integrally laminated multicolor photosensitive element was prepared by coating the following layers in the order listed on a 100 μm thick transparent polyethylene terephthalate film support. (Unless otherwise specified, apply amount is
It is expressed in mg/ ^100cm2 . ) (1) Copoly [styrene-co-N-vinylbenzyl-N-benzyl-NN-dimethylammonium sulfate-co-divinylbenzene] latex (22) and gelatin (22) image-receiving layer. (2) Titanium dioxide (220) and gelatin (22)
reflective layer. (3) Opaque layers of carbon black (28) and gelatin (18). (4) Cyan CPM {[D] type CPM, exemplified compound (15)} (5.4) and gelatin (11). (5) Red-sensitive internal latent gelatin - silver bromide emulsion (14 silver, 15 gelatin), potassium 2-octadecylhydroquinone-5-sulfonate (16 g per mole of silver), and nucleating agent: 1-acetyl. -2-{4-[5-amino-2-(2,4-
di-t-pentylphenoxy)benzamide]
phenyl}hydrazine and 1-p-formylhydrazinophenyl-3-phenyl-2-thiourea (150 mg and 6 mg per mole of silver, respectively). (6) Interlayer of gelatin (13) and 2,5-di-sec-dodecylhydroquinone (13). (7)* Magenta CPM {[D] type CPM, exemplified compound (57)} (5.4) and gelatin (12). (8) Green-sensitive internal latent gelatin-silver bromide emulsion (15.5 silver, 17 gelatin), potassium 2-octadecylhydroquinone-5-sulfonate (16 g per mole of silver), and nucleating agent: 1-acetyl. -2-{4-[5-amino-2-(2,4
-di-t-pentylphenoxy)benzamido]phenyl)hydrazine and 1-formylhydrazinophenyl-3-phenyl-2-thiourea (120 mg and 1 mole of silver, respectively)
2.5mg). (9) Interlayer of gelatin (14) and 2,5-di-sec-dodecylhydroquinone (13). (10)* Yellow CPM {[D] type CPM, exemplified compound (56)} (6.5) and gelatin (13.2). (11) Blue-sensitive internal latent gelatin-silver bromide emulsion (15.0 silver, 16 gelatin), potassium 2-octadecylhydroquinone-2-sulfonate (16 g per mole of silver), and nucleating agent: 1-p ―
Formylhydrazinophenyl-3-phenyl-
2-thiourea (5.8 mg per mole of silver). (12) Gelatin (9.0) and 2,5-didodecylhydroquinone overcoat (protective film layer). In preparing each CPM layer of layer (4), layer (7), and layer (10), various dispersion methods of Example 1 were used to prepare comparative samples and samples of the present invention. (For the same sample, the preparation method and dispersion method for the coating solution for each CPM layer above are the same.)

[Table] Next, the two types of photosensitive element samples prepared as described above were subjected to prescribed exposure using a light source with a color temperature of 4850〓 through a light wedge of 30 steps with a density difference of 0.15 per step. Gave. Thereafter, a film unit was made in which a pot containing a processing agent having a content of about 0.8 ml and having the composition shown below was integrated with a processing cover sheet shown below. The obtained film unit was passed between a pair of juxtaposed pressure rollers to destroy the pot and spread the contents of the pot between the photosensitive element and the cover sheet for processing. Treatment agent composition: Potassium hydroxide 56.1g 4-hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone 8.4g 5-methylbenzotriazole 2.8g t-butylhydroquinone 0.3g Sodium sulfite 2.0g Carpoxymethyl cellulose sodium salt
60g carbon black 160g (R-450 manufactured by Columbian Carbon) Add distilled water to make 1000.0ml cover sheet; A treated cover sheet was created by sequentially applying the following layers on a 100 μm thick polyethylene terephthalate film support. . (1) Dry film thickness of ethyl acrylate and acrylic acid copolymer (25/75% by weight) (220mg/100cm ² ) approx.
22 μm neutralization layer. (2) Cellulose diacetate (degree of acetylation 40 mol%) (50
mg/100cm ² ) timing layer with a dry film thickness of approximately 5.0 μm. The resulting dye image was observed through the transparent support of the photosensitive element. The reflection density of the obtained dye image is defined as red (λmax;
644nm) green (λmax; 546nm) and blue (λ
Observation was made using a Sakura Photodensitometer PDA-60 model (manufactured by Konishiroku Photo Industry Co., Ltd.) through each filter (max; 436 nm). The results are shown in Table 4. Here, Dmax and t0.5 have already been presented in Example 3. Dmin indicates the minimum concentration under the conditions under which Dmax was obtained. The sensitivity is B of the comparative sample,
G and R were each set to 100 and expressed as relative values. As is clear from the table, the photosensitive element according to the present invention has excellent transfer speed, maximum density, and sensitivity.
It can be seen that all of them have features that are significantly superior to those of conventional photosensitive elements.

[Table] Example 5 [A] type CPM, 1 g of exemplified compound (7) was added to 2.5 ml of a mixed solvent of methyl alcohol and acetone (1:2).
dissolve in The resulting solution was kept at 35°C and used as a surfactant. The CPM was dispersed in water by slowly adding 0.5 g of CPM to 100 ml of an aqueous solution containing the polymers listed in Table 6 below. While dispersing CPM in water, maintain the temperature of the aqueous solution at 15°C ± 0.3°C. After evaporating the organic solvent and some water from the obtained CPM aqueous dispersion at 40°C and under reduced pressure of 150 to 200 mmHg, 10 ml of a 19.8 wt% gelatin aqueous solution was added, and the CPM was dissolved using an ultrasonic homogenizer. The dispersion was uniformly distributed in the gelatin matrix. A coating solution was prepared by adding 3 ml of a 1% by weight aqueous solution of saponin as a coating aid and 1 ml of a 2% by weight aqueous solution of mucochloric acid as a gelatin hardening agent to the obtained CPM dispersion. (The coating liquid contains 3 gelatin.
Contains % by weight. ) Each coating solution was coated to the same thickness on a red-sensitive silver iodobromide emulsion layer coated on a polyethylene terephthalate film to prepare each sample. Each sample was subjected to the same exposure and development treatment as in Example 2, and the sensitivity was examined. As a blank, instead of the CPM layer, [sample]
The sensitivity of the blank emulsion was normalized to 100 using a CPM methyl alcohol solution filter adjusted to the same optical density as the CPM layer. The results are shown in Table 5. However, the number average molecular weight is _W.

【table】

[Table] As is clear from Table 5, it is recognized that the sensitivity of the samples was inhibited.

[Brief explanation of the drawing]

FIG. 1 is an explanatory diagram of a dispersion device used in the dispersion method of the present invention, FIG. 2 is an explanatory diagram of another dispersion device, and FIG.
The figure is an explanatory diagram of another dispersion device, and Figure 4 is a light absorption spectrum. The vertical axis represents the relative value of optical density, the horizontal axis represents the wavelength, and each spectrum represents the maximum of the light absorption spectrum in methanol solution. The solid line represents the light absorption spectrum in methanol solution, the dashed line represents the comparative sample (A), and the dotted line represents the light absorption spectrum of the sample (X) of the present invention. 1, 7...Liquid storage tank, 2...Water containing surfactant, 3,9...Conduit, 4,10...Water feed pump,
5, 11, 12, 14...nozzle, 6...container, 8...
CPM solution, 13...suction mixer, 15, 16
...Valve, 17...Static mixer.

Claims (1)

[Claims] 1. A method for dispersing a water-insoluble dye image-providing substance for color diffusion transfer, which comprises the steps (a) and (b). Number average molecular weight 2000
A method for dispersing a water-insoluble dye image-providing substance for a color diffusion transfer method, the method being carried out in the substantial absence of the above polymer. (a) Dissolving a water-insoluble dye image-providing material for color diffusion transfer in a water-miscible organic solvent. (b) mixing the solution formed in step (a) with water containing a surfactant and dispersing the dye image-providing material in the water containing the surfactant; 2. The solution formed in step (a) is the first stream, the water containing the interfacial spreader is the second stream,
The first flow and the second flow are in a separated state at least at the starting point, and the second flow continues at least while the first flow is present, and the first flow and the second flow are separated. A method of dispersing a water-insoluble dye image-providing material for color diffusion transfer as claimed in claim 1, characterized in that said second stream is mixed. 3. A patent claim characterized in that step (b) is carried out while the solution formed in step (a) is at a temperature of 30°C or higher and the water containing the surfactant is at a temperature of 10°C or lower. A method for dispersing a water-insoluble dye image-providing substance for a color diffusion transfer method according to item 1 or 2.