JPS6329254B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for forming a heat-developable color diffusion transfer image, and more specifically, a method for forming a heat-developable color diffusion transfer image, in which a clear color image can be obtained by subjecting an image formed in a heat-developable photosensitive material to sublimation transfer. Regarding. Color image forming methods using a photosensitive substance (silver halide) include, for example, a method using a dye formed by an oxidized color developing agent and a coupler, and a method to obtain an image by bleaching the dye with silver (silver dye). Bleaching method) or color diffusion transfer method, which uses an alkaline processing solution to diffusely transfer pigments used in so-called instant photography, are known, but both require a water-soluble processing solution and are difficult to form images. This has the disadvantage that the processing required to do so is complicated. Therefore, there is a need for a new photosensitive and thermal development color image forming method that forms color images using a dry process and simple processing. As a heat development color image forming method, for example, Japanese Patent Publication No. 7782/1978, U.S. Pat. No. 3,761,200, U.S. Pat.
No. 3764328, JP-A-56-27132, and JP-A No. 56-
As described in No. 27133, there is a color image forming method using an oxidized color developing agent and a coupler, but in these methods, a silver image is also formed where a dye image is formed. This may cause color turbidity, and staining of the white background may occur due to printouts after development. To eliminate these problems, desilvering and fixing steps are required, which impairs the simple and dry processing method that is an advantage of thermal development photography. Other thermal development color image forming methods include, for example, JP-A Nos. 52-105821, 52-105822, and 56-
There are silver dye bleaching methods described in No. 50328 and US Pat. No. 4,235,957. However, these methods require the use of an activation sheet containing a strong acid or a silver halide complexing agent for dye image bleaching, and have drawbacks such as complicated processing and the use of strong acids. There is. Still another heat-developable color image forming method is, for example, the dye silver salt method described in Research Disclosure No. 16966 published in May 1978. This method is attracting attention as a method to compensate for the drawbacks of the two methods mentioned above, but it is difficult to completely convert the dye into silver salt when synthesizing the dye silver salt, and the dye remains as a silver salt. Therefore, this causes fog in the image. Furthermore, since the dye is transferred to a solvent when it is transferred, it has the disadvantage that not only the dye but also other undesirable additives are transferred, resulting in color turbidity. Accordingly, a first object of the present invention is to provide a method for forming a heat-developable color diffusion transfer image using a thermally non-diffusible color-providing substance capable of releasing a sublimable dye having chelating ability upon thermal development. It is in. A second object of the present invention is to provide a method for forming a heat-developable color diffusion transfer image in which the formed dye image is stable against environmental conditions such as heat, light, and humidity. The object of the present invention is to provide a thermally non-diffusible color-providing substance represented by the general formula (1) or (2) below and capable of releasing a chelatable sublimable dye as a function of development, and an organic silver salt. The photothermographic material is imagewise exposed and then thermally developed to form an imagewise distribution of a chelatable sublimable dye from the color-providing substance, and at least a part of the imagewise distribution is This is achieved by thermally transferring to an image-receiving layer containing polyvalent metal ions in a stacked relationship with the photothermographic material, and forming an imagewise distribution of sublimable dyes chelated with polyvalent metal ions in the image-receiving layer. Ta. “Sublimability” generally refers to “the property of changing from a solid to a gas without passing through a liquid state,” and many dyes that exhibit this sublimability are known in the industry (specific examples include “ Dye Handbook” (Maruzen)). Sublimable dyes are immobile solids at low temperatures and non-diffusible in the absence of a solvent. When it is heated and exceeds a certain temperature, it sublimates and becomes a gas, exhibiting diffusivity and being able to move through space. For example, a sublimable dye coated on a support vaporizes when heated, leaves the support, and diffuses. If there is an image-receiving layer nearby, the pigment will be adsorbed and deposited on the surface or inside the image-receiving layer, forming a dye image even if it is not in close contact with the support. Sublimable dyes also have the ability to diffuse between layers in a gaseous state. That is, even if there is an intermediate layer between the layer in which the sublimable dye is released and the image-receiving layer, the dye can be diffused and transferred without requiring a solvent. Therefore, by utilizing this property, it is easy to design a multilayer color heat-developable photosensitive material. Since the formed dye image is chelated, it becomes a non-sublimable dye and does not have re-sublimation property, which is a drawback when using a sublimable dye. According to the method of the present invention, an image is generated and fixed only by thermal processing, and a color image can be obtained with very simple processing. Of course, since the present invention uses a diffusion transfer method, there is no need for desilvering, and since the image formed is a chelated dye image, it is stable against environmental conditions such as heat, light, and moisture, and is particularly light-resistant. This is a pigmented image with excellent quality. In the present invention, the sublimable dye that can be chelated has a sublimation temperature of 50 to 250°C, more preferably 50 to 170°C.
℃, and is capable of forming at least a bidentate or higher coordination chelate complex with a polyvalent metal ion, and more preferably has a sublimation temperature of 50 to 170℃.
It is an azo dye that can form a tridentate chelate complex. Compared to the conventional so-called instant photography method, in which an image is formed by dyes diffusing in a concentrated alkaline solution that is harmful to the human body, the heat-developable color diffusion transfer method of the present invention allows the transferred image to be created by simply heating at a constant temperature for a certain period of time. It is excellent in terms of safety and other aspects. Furthermore, in the conventional method of transferring dyes formed or released in a heat-developable photosensitive material using a thermal solvent, it is difficult to achieve a multilayer system, but with the method of the present invention, This is easily possible. In the present invention, the color-providing substance is thermally non-diffusive and does not substantially cause intralayer or interlayer diffusion even when heated. In the present invention, the color-providing substance is one that can release a sublimable dye or a sublimable dye precursor as a function of development, that is, as a result of thermal development, and is capable of releasing a sublimable dye or a sublimable dye precursor as a function of development, that is, as a result of thermal development, and can directly or directly react with the redox reaction that occurs during development, or as a cross-oxidizing agent, etc. The release reaction occurs by acting indirectly through the mediation of The sublimable dye or sublimable dye precursor released in the heat development reaction has a low molecular weight,
Due to its small dipole moment and high hydrophobicity,
The interaction with the hydrophilic binder is small, that is, the solubility in the hydrophilic binder is low, and it easily diffuses in the hydrophilic binder without requiring a solvent. Therefore, in the present invention, the combination of a sublimable dye or a sublimable dye precursor with a hydrophilic binder is advantageous for diffusion and transfer, i.e. the color from which the sublimable dye or sublimable dye precursor can be released. Preferably, the donor material is added into a hydrophilic binder. When a hydrophilic binder is used in this manner, the color-providing substance is non-diffusible (for example, has a ballast group and/or a hydrophilic group) in order to be non-sublimable in the binder. In addition,
It is also possible to add a hydrophobic binder to the hydrophilic binder insofar as it does not interfere with the non-diffusibility of the color-providing substance and does not interfere with the diffusibility of the dye or dye precursor. Reactions in which a color donor releases a sublimable dye or a sublimable dye precursor include decomposition, elimination, and ligand exchange reactions, but in the present invention, a diazo coupling method using an active site substitution coupler is used. Alternatively, an oxidation coupling method is effective. For example, a dye formed by diazo coupling or oxidative coupling between an oxidized aromatic primary amine color developing agent and a coupler having a ballast group via a bond at its active site has sublimation properties. For example, in diazo coupling or oxidative coupling between an oxidized product of an aromatic primary amine color developing agent and a coupler having a sublimable dye or a sublimable dye precursor as a leaving group via a bond to the active site, the sublimable dye or This is a reaction in which a sublimable dye precursor is released. The method of the present invention is the latter, and the non-diffusible color-providing substances (hereinafter simply referred to as "color-providing substances") capable of releasing the chelatable sublimable dye of the present invention are as follows. There is a compound represented by formula (1). General formula (1) In the formula, X ¹ represents an atomic group necessary to form an aromatic ring or a heterocycle in which at least one ring is composed of 5 to 7 atoms, and the adjacent carbon atoms bonded to the azo bond at least one of the
(a) It is a nitrogen atom, or (b) It is a carbon atom substituted with a nitrogen atom, an oxygen atom, or a sulfur atom, and the ring may be substituted with an appropriate substituent, and a preferable substituent is an alkyl group. , an alkoxy group, a cyano group, a hydroxyl group, a thiol group, a thioalkoxy group, or a halogen atom. X ² represents an atomic group necessary to complete an aromatic ring or a heterocycle in which at least one ring is composed of 5 to 7 atoms, even if the ring is substituted with an appropriate substituent. Preferred rings are benzene, naphthalene, pyridine, or quinoline, and preferred substituents are alkyl, alkoxy, cyano, hydroxyl, amino, or halogen. G represents a chelating group, preferably a hydroxyl group, an amino group, a methoxy group, a thiol group or a thioalkoxy group. A represents a group capable of releasing sublimable dye moieties as a function of thermal development. Another preferred color-providing substance is the following general formula (2):
There is a compound represented by General formula (2) In the formula, X ¹ and A are each the same as defined in general formula (1). Z ¹ is an electron-withdrawing group, preferably an acetyl group, benzoyl group, cyano group or acetamido group, and Z ² is an alkyl group (preferably a methyl group) or an aryl group (preferably a phenyl group). In the general formulas (1) and (2), the group represented by A that can release a sublimable dye moiety as a function of thermal development includes a group represented by the following general formula (3) or (4). General formula (3) General formula (4) In the formula, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and
R ₈ is a hydrogen atom, a halogen atom (preferably a chlorine atom, a bromine atom, an iodine atom), an alkyl group (preferably an alkyl group having 1 to 24 carbon atoms), such as a methyl group, an ethyl group, or a t-butyl group. group, s-octyl group, pentadecyl group, cyclohexyl group, trifluoromethyl group, benzyl group, phenethyl group, etc.), aryl group (e.g. phenyl group, naphthyl group, tolyl group, mesityl group, etc.),
Acyl groups (e.g. acetyl group, titradecanoyl group, pivaloyl group, benzoyl group, etc.), alkyloxycarbonyl groups (e.g. methoxycarbonyl group, benzyloxycarbonyl group, etc.), aryloxycarbonyl groups (e.g. phenoxycarbonyl group, p-tolyl group, etc.) Oxycarbonyl group, α-
naphthoxycarbonyl group, etc.), alkylsulfonyl group (e.g., methylsulfonyl group, etc.), arylsulfonyl group (e.g., phenylsulfonyl group, etc.), carbamoyl group (e.g., methylcarbamoyl group, butylcarbamoyl group, tetradecylcarbamoyl group, N-methyl -N-dodecylcarbamoyl group, phenylcarbamoyl group, etc.), acylamino group (e.g. n-butylamide group, β-phenoxyethylamide group, phenoxyamide group,
β-Methanesulfonamidoethylamide group, β-
methoxyethylamide group, etc.), alkoxy group (preferably an alkoxy group having 1 to 18 carbon atoms, such as methoxy group, ethoxy group, octadecyloxy group, etc.), sulfamoyl group (such as methylsulfamoyl group, phenylsulfamoyl group), amoyl group, etc.), a sulfamino group (eg, methylsulfamino, tolylsulfamino), or a hydroxy group. However, preferably at least one of R ₁ , R ₂ , R ₃ and R ₄ and at least one of R ₅ , R ₆ , R ₇ and R ₈ are ballast groups that reduce thermal diffusivity, for example, It has a group containing a hydrophilic group such as a sulfo group, a carboxy group, or a hydroxy group, or a group containing an alkyl group and having 8 or more carbon atoms. In addition, at least one set of R ₁ and R ₂ , R ₃ and R ₄ , and at least one set of R ₅ and R ₆ , R ₆ and R ₇ are bonded to each other, and saturated or unsaturated 5- 6
It may form a membered ring. J represents a divalent bonding group, preferably

[Example sublimable dye]

Dye-(1) 2-(4-methoxy-2-pyridylazo)phenol Dye-(2) 1-(4-methoxy-2-pyridylazo)-2-naphthol Dye-(3) 2-(2-hydroxyphenyl azo)−
4-methoxy-1-naphthol Dye-(4) 2-(2-hydroxyphenylazo)-
4-Methoxy-phenol Dye-(5) 8-(2-hydroxyphenylazo)-
Quinoline Dye-(6) 2-(2-hydroxyphenylazo)-
1,4-dimethoxy-phenol Dye-(7) 1-(2-pyridylazo)-2-naphthol Dye-(8) 2-(2-pyridylazo)-1-naphthol Dye-(9) 2-(3-methoxy -2-pyridylazo)-4-methoxy-5-nitrophenol Dye-(10) 2-(3-chloro-2-pyridylazo)
-4-Chlorphenol Dye-(11) 2-(4-hydroxy-2-pyridylazo)-4-methoxyphenol Dye-(12) 2-(4-hydroxy-2-pyridylazo)-4-methoxy-1-naphthol In addition, in the chemical structural formulas of CPM-(1) to (6) above,

【ceremony

[Developer]

The dried sample was exposed to 30,000 CMS through a step wedge. On the other hand, an aqueous solution containing 15% water-soluble polyvinyl butyral and 10% nickel chloride was deposited on ivory paper at a concentration of 1.40 polyvinyl butyral per square meter.
An image-receiving paper containing nickel chloride was prepared by applying the following coating to give an amount of nickel chloride. The coated surface of the exposed sample and the coated surface of the image-receiving paper were brought into close contact, and after heating and pressing with an iron having a surface temperature of 150° C. for 30 seconds, the sample and the image-receiving paper were peeled off. A negative image of a yellow step wedge with a maximum reflection density of 0.78 and a minimum reflection density of 0.19 was obtained on the surface of the receiver paper. Example 2 4.5 g of silver behenate, 20 c.c. of alcohol, 5 c.c. of water, and 15 c.c. of a 25% aqueous solution of water-soluble polyvinyl butyral.
Add and use an ultrasonic homogenizer to make the dispersion - [1]
was prepared. Meanwhile, 0.20 g of phthalic acid, 0.13 g of phthalazine, 0.89 g of the above-mentioned exemplary color donor CPM-(2), and 2.55 g of the following developer were mixed with 40 c.c. of a water-soluble polyvinyl butyral 8% water-alcohol (1:1) solution. A solution-[1] was obtained by dispersing in a ball mill for 24 hours. [Developer] Further, silver trifluoroacetate and lithium bromide were reacted in a 10% by weight polyvinyl butyral acetone solution to obtain emulsion-[1]. The above dispersion - [1] 0.05 of the following sensitizing dye in 10 c.c.
0.3 cc of wt% methanol solution and 20 mg of mercuric acetate were added. [Sensitizing dye] Finally, Solution-[1] was added and coated onto a transparent polyester film using a wire bar to a wet film thickness of 74 μm to form a photosensitive layer. A white reflective layer and an image-receiving layer having the following compositions were provided thereon, and another transparent polyester film was adhered onto the image-receiving layer. <White reflective layer> (Unit: g/m ² ) Titanium dioxide (average particle size: 1.5 μ) 15 Cellulose diacetate 1.2 Sodium dodecyl sulfate 0.08 Ethanol 25 Water 30 <Image-receiving layer> (Unit: g/m ² ) Cellulose diacetate 1.6 Chloride Nickel 1.0 Ethanol 21 Water 42 The photosensitive layer side of this sample was exposed to 30,000 CMS through a step wedge, and an iron with a surface temperature of 100° C. was pressed onto the photosensitive layer side for 30 seconds. A negative silver image and a positive image of the unreacted color donor were formed in the photosensitive layer, and a magenta negative image with a maximum reflection density of 1.06 and a minimum reflection density of 0.17 was obtained in the image-receiving layer. Example 3 4-hydroxybenzotriazole silver 8.71 g CPM-(1) 12.8 g Ossein gelatin 10% by weight aqueous solution 84 c.c. Water 120 c.c. Methanol 96 c.c. The above composition was dispersed in an alumina ball mill,
Dispersion liquid [3] was obtained. Similarly, a solution [2] having the following composition was prepared. Ossein gelatin 10% by weight aqueous solution 42c.c. Developer

[Formula] 1.80g 4-aryl-3-amino-5-mercapto-
1,2,4-triazole 28 mg Methanol 10.5 cc Emulgen 950 (KAO-ATLAS) 245 mg Dimethylurea 3.5 g After mixing the above dispersion - [3] 25 c.c. and solution - [2] 15 c.c. A silver bromide emulsion having an average grain size of 0.04 μm was added in an amount of 0.11 g in terms of silver, and was coated on photographic baryta paper to obtain a first photosensitive layer. Then, instead of 8.71 g of 4-hydroxybenzotriazole silver in dispersion [3], 7.80 g of 5-nitrobenzotriazole and the color-providing substance were added.
A dispersion [4] was similarly obtained by using 11.5 g of CPM-(2) instead of 12.8 g of CPM-(1). Take 25cc of the dispersion liquid [4], add 3.2cc of a 0.02% methanol solution of the following sensitizing dye to it,
Furthermore, 15 c.c. of solution-[2] was added and coated on the first photosensitive layer to form a second photosensitive layer. [Sensitizing dye] The obtained sample was exposed to white light of 100,000 CMS through a step wedge, and the sample (A) was
Sample (B) was obtained by using Kodatsu Kura Ten Filter No. 74 in addition to the conditions of sample (A), and sample (B) was obtained by using Kodatsu Kura Ten Filter No. 94 in addition to the conditions of sample (A). (C). Separately, a nickel chloride-containing polyvinyl butyral layer was coated on photographic baryta paper in the same manner as described in Example 1 to prepare an image-receiving paper. The coated surfaces of the image-receiving paper on the photosensitive layer side of each sample were aligned and heated for 30 seconds using an iron with a surface temperature of 160°C. The maximum and minimum reflection densities of the image-receiving paper of each sample obtained by peeling are shown in the table below for each measurement light.
Shown in 1. Example 4 (Fixing properties and light resistance) 50 mg each of Dye-(2), Dye-(4), and Dye-(7) were added to 10 c.c. of an 8% methanol solution of polyvinyl butyral.
is dissolved in the polyester film and forms a wet film thickness on the polyester film.
It was applied with a wire bar to a thickness of 55μ and dried. Next, the above dyes [Dye-(2),
Dye-(4), Dye-(7)] was transferred for 1 minute using an iron having a surface temperature of 150°C. The dyed image-receiving paper obtained in this way was retransferred for 10 minutes with an iron at a surface temperature of 110°C, and the optical density by λmax immediately after transfer dyeing and after retransfer (D ₀ before retransfer, D after retransfer) was measured, and the value of D/D ₀ ×100 was defined as the residual rate (%), which is shown in Table 2 below. The higher the residual rate, the better the fixing performance. The dyed image-receiving paper obtained in the same way was irradiated with a 6000W xenon lamp for 48 hours (the illuminance on the image-receiving paper surface was 60,000
lux) and measure the optical density according to λmax (D ₀ before exposure, D after exposure) before and after exposure,
The value of D/D ₀ ×100 was defined as the residual rate (%) and is shown in Table-2. As is clear from these results, according to the present invention, stable color images can be obtained through simple processing, and multicolor images are also possible.

【table】

【table】

[Table] Comparative Example 1 A sample was prepared in the same manner except that the following dyes (A) and (B) were used in place of the dye of the present invention in Example 4 of the present invention,
The same treatment as in Example 4 was carried out. In addition, dyes (A) and (B)
Both are dyes used in color diffusion transfer photographic materials using alkaline processing solutions. As is clear from the results shown in Table 3 below,
Although dyes (A) and (B) have no difference in fixing performance regardless of the presence or absence of metal ions on the receiving paper, they are found to be unsuitable for heat-developable color diffusion transfer image forming methods due to extremely poor transferability. .

【table】

[Table] 〓 Amount of dye before transfer 〓
In addition, dyes (2), (4), and (7) have a transfer rate of 66% and 64%, respectively.
%, 61% (value for Ni-containing receiver paper). As can be understood from the above results, when dyes are used for color diffusion transfer photographic materials using known alkaline processing liquids, in the image forming method of the present invention, there is no significant difference in fixability regardless of the presence or absence of chelate. However, it is difficult to obtain images due to extremely low transferability.

Claims (1)

[Scope of Claims] 1 Contains a thermally non-diffusible color-providing substance represented by the following general formula (1) or (2) and capable of releasing a chelatable sublimable dye as a function of development, and an organic silver salt The photothermographic material is imagewise exposed and then thermally developed to form an imagewise distribution of a chelatable sublimable dye from the color-providing substance, and at least a part of the imagewise distribution is thermally transferred to an image-receiving layer containing polyvalent metal ions in a stacked relationship with the photothermographic material;
A method for forming a heat-developable color diffusion transfer image, the method comprising forming an imagewise distribution of a sublimable dye chelated with a polyvalent metal ion in the image-receiving layer. General formula (1) [In the formula, X ¹ represents an atomic group necessary to form an aromatic ring or a heterocycle in which at least one ring is composed of 5 to 7 atoms, and At least one of the adjacent positions
(a) is a nitrogen atom, or (b) is a carbon atom substituted with a nitrogen atom, an oxygen atom, or a sulfur atom, and X ² is an aromatic ring in which at least one ring is composed of 5 to 7 atoms; or represents the atomic group necessary to complete the heterocycle, G represents a chelating group, and A
represents a group capable of releasing sublimable dye moieties as a function of thermal development. ] General formula (2) [In the formula, X ¹ and A each have the same meaning as defined in general formula (1), Z ¹ represents an electron-withdrawing group, and Z ² represents an alkyl group or an aryl group. 2. The heat-developable color diffusion transfer image forming method according to claim 1, wherein A is represented by the following general formula (3) or (4). General formula (3) General formula (4) [In the formula, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and
R ₈ is a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an acyl group, an alkyloxycarbonyl group, an aryloxycarbonyl group, an alkylsulfonyl group, an arylsulfonyl group, a carbamoyl group, an acylamino group, an alkoxy group,
Represents a sulfamoyl group, a sulfamino group or a hydroxy group. However, at least one of R ₁ , R ₂ , R ₃ and R ₄ and at least one of R ₅ , R ₆ , R ₇ and R ₈ are ballast groups that reduce thermal diffusivity. Furthermore, at least one pair of R ₁ and R ₂ , R ₃ and R ₄ , and at least one pair of R ₅ and R ₆ , R ₆ and R ₇ , and R ₇ and R ₈ are bonded to each other and are saturated. Alternatively, an unsaturated 5- to 6-membered ring may be formed. J represents a divalent bonding group, and m represents 0 or 1. ] 3 Polyvalent metal ions include copper (), nickel (), zinc (), platinum (), palladium ()
2. The heat-developable color diffusion transfer image forming method according to claim 1, wherein cobalt () is used.