JP3038419B2 - Photothermographic materials and dye receiving materials - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photothermographic material and a dye image-receiving material. The present invention relates to a photothermographic material and a dye material having improved transportability of the photothermographic material and the dye image receiving material at the time.

[0002]

BACKGROUND OF THE INVENTION Thermal development processing in which the development step is carried out by heating is known, and those for obtaining a black-and-white image and a color image are known. Also, a so-called transfer type photothermographic material which transfers an image obtained by thermal development from a photosensitive material to an image receiving layer is well known.

A photothermographic material usually has a binder, a photosensitive silver halide emulsion, a reducing agent, and, if necessary, a dye-providing substance, an organic silver salt and various other photographic additives on a support. doing. In the transfer type photothermographic material, the case where the photosensitive material has an image receiving layer capable of receiving silver or a dye and the case where the image receiving layer has an image receiving layer capable of receiving silver or a dye separately from the photosensitive material are combined. May be used for

In particular, when a heat-developable light-sensitive material is used as a heat-developable color light-sensitive material, a method in which a dye image-receiving material is used, and an image dye is diffused and transferred to the dye-image receiving material after forming a diffusible dye image. It is preferable from the viewpoint of obtaining a dye image with high purity.

[0005] Regarding this method, many methods and improved techniques have been disclosed in the past.

Thermal development is generally carried out at a temperature of 60 ° C. or higher, preferably 80 ° C.
It is carried out in the absence of water or in the presence of a very small amount of water at a temperature of not less than ℃, but the problem at that time is the occurrence of unevenness due to various causes. In particular, in the method of diffusing and transferring the diffusible dye to the image receiving layer during thermal development, transfer unevenness of the image dye becomes a problem.

The transfer unevenness may be caused by unevenness of the thermal development itself or uneven transferability of the dye. In any case, this problem is a serious problem in image quality.

[0008] Transfer unevenness is caused by the presence of foreign matter such as dust, and unevenness caused by heat shrinkage of the support when heated when the photosensitive material and the dye receiving material are superimposed. There are several causes such as unevenness due to uneven presence of water and a thermal solvent, unevenness due to poor adhesion between the photothermographic material and the dye receiving material, and unevenness due to uneven temperature of the sample.

Above all, unevenness due to poor adhesion between the photothermographic material and the dye image-receiving material is a large defect in the form of dots and white spots, which is a serious defect in image quality.

The adhesiveness between the photothermographic material and the dye image-receiving material is determined by applying pressure in the presence of a small amount of water or a hot solvent which is solid at room temperature but melts under heating when superimposed. However, the adhesion is easily affected by the shrinkage of the support, the dispersion of the water or thermal solvent, or the dispersion of the heating temperature. It is hard to say that it is.

Another problem during thermal development is the releasability when the photosensitive material is peeled off from the dye image-receiving material after thermal development and dye transfer. This is because if the photosensitive material is not peeled clean,
The problem is that a part of the photosensitive layer remains in the image receiving layer, or a part of the support of the photosensitive material or the dye receiving material peels off. This problem also causes a serious problem in image quality.

Japanese Patent Application Laid-Open No. 61-25144 discloses a photothermographic material containing a cationic compound in a protective layer in order to improve the above-mentioned transfer unevenness and releasability. Also, JP-A-61-20944 discloses that a fluorine-based surfactant is added to at least one of the uppermost layers on the contact surface side between the photothermographic material and the dye image-receiving material, to improve releasability, and during storage. It is disclosed that sticking of a photothermographic material or a dye image-receiving material is prevented.

The use of a fluorine compound in a photothermographic material is known in addition to the above.
Japanese Patent No. 44945 discloses a photothermographic material containing a fluorine-containing surfactant and having no coating unevenness.

JP-A-62-50753 discloses that a release layer containing a fluorine-based surfactant is provided between a photothermographic material and a dye image-receiving material.

Japanese Patent Application Laid-Open No. 62-135826 discloses that a fluorine-based surfactant and a nonionic water-soluble polymer are used in combination to give a sufficient transfer image and to improve the releasability.

Japanese Patent Application Laid-Open No. 62-136648 discloses that a polymer latex and a fluorine compound are used in combination to give a sufficient transfer image and to improve the releasability.

Further, JP-A-61-25144 exemplifies cationic surfactants as fluorine compounds and specific compounds as cationic compounds.

However, even with the techniques described in each of the above publications, it is still not sufficient to achieve more complete peelability and reduce transfer unevenness, and more stable peeling is possible and transfer unevenness is further reduced. There is a need for technology that makes it harder to wake up.

In particular, when the photothermographic material or the dye image-receiving material is stored under high humidity, such peeling property tends to decrease, and the probability of occurrence of transfer unevenness tends to increase. It is necessary that the dye image-receiving material be easily peeled off from the photothermographic material stably without causing the occurrence of the dye.

Another problem of the heat development processing is that, due to the peculiarity of high-temperature processing, the material is charged, the transportability is reduced, and a jam failure easily occurs inside the heat development apparatus. In order to solve this problem, it is disclosed that a fluorine-based surfactant is added to the back surface of the dye image-receiving material to improve the charging characteristics and improve the transportability of the material. However, although the charging characteristics of the material are certainly improved by this technique, it is not always sufficient from the viewpoint of transportability.

[0021]

The object of the present invention is to solve the above-mentioned problems by the first aspect of the present invention.
It is an object of the present invention to provide a photothermographic material and a dye image-receiving material in which transfer unevenness is further reduced when a heat-developable photosensitive material and a dye image-receiving material are superimposed and thermally developed and / or dye-transferred. Further, a second object of the present invention is to provide a photothermographic material and a dye image-receiving material which give good releasability when the photothermographic material is separated from the dye image-receiving material after heat development and dye transfer. . A third object of the present invention is to provide a photothermographic material and a dye image-receiving material having improved transportability inside a thermal developing device.

[0022]

The object of the present invention is to provide at least one photosensitive layer containing a hydrophilic binder, a photosensitive silver halide and a dye-donating substance which releases or forms a diffusible dye upon thermal development on a support. A heat-developable photosensitive material comprising a fluorine-containing cationic surfactant and an anionic surfactant in at least one layer on the side of or opposite to the photosensitive layer with respect to the support. A developing photosensitive material, and a dye image-receiving material having a dye-receiving substance having a dye-receiving ability on a support, wherein at least one layer on the side containing or opposite to the dye-receiving substance with respect to the support has a fluorine-containing cationic surfactant. This is achieved by a dye image-receiving material characterized by containing an agent and an anionic surfactant.

The heat-developable photosensitive material contains a nonionic surfactant in at least one layer on the photosensitive layer side of the support, and the dye image-receiving material contains a nonionic surfactant on the support. On the other hand, it is a preferred embodiment of the present invention that at least one layer on the dye receiving substance containing side contains the dye.

Hereinafter, the present invention will be described specifically.

The fluorine-containing cationic surfactant used in the present invention is a compound represented by the following general formula [F].

The general formula _{[F] R f -T-X} + Y - However, R _f is a 1-20 hydrocarbon group having a carbon number of at least one of the hydrogen atoms are replaced with fluorine atoms. T represents a chemical bond or a divalent group. X represents a cationic group, and Y represents a counter anion.

[0027]

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[0028]

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Specific examples of the fluorine-containing cationic surfactant preferably used in the present invention are described below.

[0030]

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[0031]

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[0032]

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In the present invention, it is more preferable to use a sparingly soluble sulfonamide type fluorinated surfactant in the same layer as the anionic surfactant. Here, the poor solubility means that 2 g of the surfactant is added to 100 cc of H ₂ O at 23 ° C.
After stirring for 1 hour and leaving at 23 ° C. for 24 hours, a precipitate is formed, or when a suspended matter is observed, the substance is made hardly soluble. For example, FK-1, FK-8, FK-15, FK-16, and the like correspond to, but are not limited to, and can be separated by the above test.

The photothermographic material of the present invention preferably contains an anionic surfactant in the above-mentioned fluorine-containing cationic surfactant-containing layer from the viewpoint of preventing cissing failure and generation of fine particles during coating.

The anionic surfactant preferably used in the present invention is selected from those represented by the following general formula [A].

Wherein R is an alkyl group or alkenyl group having 4 to 24 carbon atoms,
An aralkyl group and a fluorinated hydrocarbon group in which a hydrogen atom of these groups is substituted with a fluorine atom. K represents a divalent linking group, and n represents 0 or 1. L is a sulfonic acid group,
Sulfonic acid ester group, carboxylic acid group, phosphonic acid group,
Represents a phosphonate group, a phosphite group and their salts. Specific examples of the divalent group of K are shown below.

[0037]

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Next, specific examples of the anionic surfactant used in the present invention will be shown, but it should not be construed that the invention is limited thereto.

[0039]

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[0040]

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[0041]

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[0042]

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[0043]

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[0044]

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[0045]

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[0046]

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[0047]

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[0048]

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Among them, a fluorine-containing anionic surfactant is preferable, and it is more preferable to use a sulfonamide type fluorine-containing anionic surfactant.

The fluorinated anionic surfactant according to the present invention or the fluorinated cationic surfactant according to the present invention includes, for example, US Pat. Nos. 2,559,751 and 2,567,011,
No. 2,732,398, No. 2,764,602, No. 2,806,866, No. 2,8
09,998, 2,915,376, 2,915,528, 2,934,450
Nos. 2,937,098, 2,957,031, 3,472,8
No. 94, 3,555,089, 2,918,501, British Patent 1,
143,927, 1,130,822, JP-B-45-37304, JP
47-9613, 50-121243, 50-117705, 49-1346
No. 14, No. 50-117727, No. 52-41182, No. 51-12392, Journal of British Chemical Society (J. Chem. Soc.) 1950 No. 2789
1957, pp. 2574 and 2640, Journal of the American Chemical Society (J.
Amer. Chem. Soc.) 79, 2549 (1957), Oil Chemistry (J. Jap
an.Oil ChemistsSoc.) Volume 12, page 653, Journal of the Society of Organic Chemistry (J.
Org. Chem.), Vol. 30, p. 3524 (1965) and the like. Of these fluorinated surfactants according to the present invention, certain are under the trade name Megafac F from Dainippon Ink and Chemicals, Inc., and Fluorad from Minnesota Mining and Manufacturing Company.
Under the trade name of FC, under the trade name of Monflor from Imperial Chemical Industries, under the trade name of Zonyls from EIDupont Nemeras and Company, or under the trade name of Licovet from Farbeberke Hoechst )
It is commercially available under the trade name VPF.

The place where the fluorine-containing anion activator and the fluorine-containing cationic activator of the present invention are added is not particularly limited, and may be any of a silver halide emulsion layer, an intermediate layer, an undercoat layer, a protective layer and the like. , A protective layer is preferred.

The fluorine-containing cationic surfactant and the anionic surfactant of the present invention are preferably added to the protective layer, but may be added to layers other than the protective layer. Also,
The layers containing no combination of the fluorine-containing cationic surfactant and the anionic surfactant of the present invention can be used alone. Of course, a surfactant other than the present invention (for example, a fluorine-free cationic surfactant, a nonionic surfactant, or the like) can be used in any layer.

When the fluorine-containing cationic surfactant and anionic surfactant of the present invention are added to a layer on the dye receiving material containing layer (hereinafter referred to as image receiving layer) side of the dye receiving material, the added layers are an image receiving layer, Although it can be added to any layer such as an undercoat layer and a protective layer, the effect of the present invention is great when the layer is farthest from the support. When the layer farthest from the support is the image receiving layer, it is preferably added to the image receiving layer.

The fluorinated cationic surfactant and anionic surfactant of the present invention are added to the back surface of a photothermographic material and a dye image-receiving material (that is, in the case of a photothermographic material, opposite to the photosensitive layer with respect to the support). On the other hand, in the case of an image-receiving material, when it is added as a back layer to the support on the side opposite to the image-receiving layer, it can be added to any layer of the back layer.
In particular, it is preferable to add to the layer farthest from the support in the back layer.

The amount of the fluorinated cationic surfactant used in the present invention is as follows when used on the photosensitive side of the photothermographic material.
0.0001 to 1 g, preferably 0.01 g per m ^{2 of the} photothermographic material
It is 005 to 0.3 g, particularly preferably 0.001 to 0.2 g.

The amount of the fluorinated surfactant relative to the hydrophilic binder constituting the layer containing the fluorinated surfactant is 0.1 to 10% by weight, preferably 0.2 to 5% by weight.

When the fluorine-containing cationic surfactant of the present invention is used on the image receiving layer side of the dye image receiving material, it is used in an amount of 0.0001 to 1 g, preferably 0.0005 to 0.2 g / m ^{2 of} the image receiving material.
g, particularly preferably 0.001 to 0.1 g.

The ratio of the amount of the anionic surfactant to the amount of the fluorine-containing surfactant used is from 1:10 to 10: 1, preferably from 3: 7 to 7: 3.

When the fluorinated cationic surfactant and anionic surfactant of the present invention are used in an image receiving material, the binder constituting the layer to which the fluorinated cationic surfactant and the anionic surfactant are added is hydrophilic. It may be either hydrophilic or hydrophobic, but is preferably a hydrophilic binder.

The photothermographic material of the present invention preferably contains a nonionic surfactant on the photosensitive layer side.

When a nonionic surfactant is contained, the increase in fog over a long period of storage at a relatively low temperature due to the combined use of a transition metal compound and a fluorine-containing cationic surfactant is further improved. Not only that, there is an advantage that the transfer speed and the releasability are improved.

The nonionic surfactant preferably used in the present invention is a polyethylene glycol nonionic surfactant represented by the following general formula [N].

Formula [N] R ₃₀ -J- (CH ₂ CH ₂ O) pH In the formula, R ₃₀ represents an alkyl group, an alkenyl group, an aryl group or an R ₃₁ CO- group, and J represents an oxygen atom or -N (R ₃₂₎ - represents a group. R ₃₁ represents an alkyl group, and R ₃₂ represents a hydrogen atom, an alkyl group, an aryl group, or — (CH ₂ CH ₂ O) qH. p and q are each represented by an integer of 3 to 100.

In the general formula [N], the alkyl group represented by R ₃₀ , the alkenyl group, the aryl group, the alkyl group represented by R ₃₁ , and the alkyl group or aryl group represented by R ₃₂ each have a substituent. May have.

Next, specific examples of the polyethylene glycol-based nonionic surfactant represented by the general formula [N] are shown below.

[0066]

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In addition to the above, Japanese Patent Publication No. 1-59572, 42
The compounds described from page, column 84, line 27 to page 43, column 86, line 31 can also be preferably used in the present invention.

The nonionic surfactant is added in an amount of 0.01 to ² g, preferably 0.05 to ² g per m ^{2 of the} photothermographic material.
It is in the range of 1 g.

Hereinafter, the photothermographic material of the present invention will be described.

The photothermographic material of the present invention has on a support at least one photosensitive layer containing a photosensitive silver halide and a dye-donating substance which releases or forms a diffusible dye during thermal development. But preferably forms or emits diffusible dyes of yellow, magenta and cyan.
For a photosensitive layer comprising two or more photosensitive layers and forming or releasing dyes of different hues, an intermediate layer is preferred from the viewpoint of preventing color mixing. As the photosensitive silver halide used in the photothermographic material of the present invention, conventionally known photosensitive silver halides can be used, and examples thereof include silver chloride, silver bromide, silver iodobromide, silver chlorobromide, and chloroiodide. Silver bromide can be used.

The silver halide may have a uniform composition from the inside to the surface of the grain, or may have a composition that changes continuously or stepwise between the inside and the surface.

The shape of the silver halide may be one having a distinct crystal habit such as tabular, cubic, spherical, octahedral, dodecahedral, or tetrahedral, or one having no such crystal habit.

Further, for example, US Pat. Nos. 2,592,250 and 3,2,250
20,613, 3,271,257, 3,317,322, 3,511,62
No. 2, 3,531,291, 3,447,927, 3,761,266,
Internal latent image type silver halide emulsions described in 3,703,584, 3,736,140, 3,761,276, JP-A-52-15661, and 55-127549 can also be used.

In the photosensitive silver halide, metal ion species such as iridium, gold, rhodium, iron and lead can be added in the form of a suitable salt at the stage of grain formation.

The light-sensitive silver halide emulsion has a particle size of about 0.5.
02 to 2 μm, preferably about 0.05 to 0.5 μm.

In the present invention, as a method for preparing a photosensitive silver halide, a photosensitive silver salt-forming component such as a water-soluble halide is allowed to coexist with an organic silver salt described later, and a part of the organic silver salt is subjected to the photosensitive halide. It can also be formed by converting to a part of silver.

The photosensitive silver halide emulsion is prepared by chemically sensitizing the surface of silver halide grains with a known sensitizer (eg, active gelatin, inorganic sulfur, sodium thiosulfate, thiourea dioxide, sodium chloroaurate, etc.). And chemical sensitization can also be carried out in the presence of a nitrogen-containing heterocyclic compound or a mercapto group-containing heterocyclic compound.

Further, the photosensitive silver halide can be subjected to spectral sensitization to blue, green, red, and near-infrared light by a known spectral sensitizing dye such as cyanine and merocyanine which is usually used in photography.

These sensitizing dyes are used in an amount of 1 μmol to 1 mol, preferably 10 μmol to 0.1 mol, per 1 mol of silver halide.
Can be added at the time of formation of silver halide grains, at the time of removal of soluble salts, before chemical sensitization, at the time of chemical sensitization, or after the end of chemical sensitization.

The dye-providing substance used in the photothermographic material of the present invention includes, for example, JP-A Nos. 61-61157 and 61-611.
No. 58, No. 62-44738, No. 62-129850, No. 62-129851,
Nos. 62-129852, 62-169158 and couplers forming diffusible dyes described in Japanese Patent Application No. 1-200859, such as leuco dyes described in JP-A-61-88254, U.S. Pat. 95
No. 7, azo dyes described in U.S. Pat.No. 4,463,079, U.S. Pat.
439,513, JP-A-59-60434, JP-A-59-65839, JP-A-59-71
046, 59-87450, 59-123837, 59-124329
Nos. 59-165054 and 59-165055. In particular, a compound which forms a diffusible dye by a coupling reaction is preferable. For example, JP-A-2-863, page 9, lower left column 2
This is represented by the general formula (A) on the line.

Among them, a polymer coupler having a polymer chain having a repeating unit derived from a monomer represented by the general formula (II) described in the right column of the lower right column on page 9 of the same publication is preferable.

Examples of the positive dye-providing substance include, for example,
JP-A-59-55430, JP-A-59-165054, JP-A-59-154445,
59-116655, 59-124327, 59-152440, 64-13
There are compounds described in various publications such as No. 546.

The above dye-providing substances may be used alone or in combination of two or more. Further, in the present invention, the polymer UV agent of the present invention may be contained in the same layer together with the above-mentioned dye-providing substance. At this time, the dye-providing substance and the polymer UV agent of the present invention can be simultaneously dispersed.

Further, the photothermographic material of the present invention includes, for example,
JP-A-2-293753 and JP-A-2-308162, together with a polymerizable compound, a dye-providing substance is contained in a microcapsule, and this is thermally developed, so that the polymerization reaction of the polymerizable compound is image-formed. Alternatively, the present invention can be applied to a photothermographic material of a system in which an image is formed by causing microcapsules to be hardened and changing the diffusibility of a dye-providing substance into an image-receiving layer by inverting the microcapsules.

In the photothermographic material of the present invention, known organic silver salts can be used for the purpose of increasing sensitivity and improving developability.

The organic silver salt which can be used in the present invention is
For example, JP-B-43-4921, JP-A-49-52626, 52-14
No. 1222, No. 53-36224, No. 53-37626, No. 53-36224,
Nos. 53-37610 and other publications and U.S. Pat.
Nos. 3,794,496 and 4,105,451, etc., silver salts of long-chain aliphatic carboxylic acids and silver salts of carboxylic acids having a heterocyclic ring (for example, silver behenate, α- (1-phenyltetrazolethio) Silver acetate etc.), JP-B-44-26582, 45-
No. 12700, No. 45-18416, No. 45-22815, JP-A-52-1373
No. 21, No. 58-118638, No. 58-118639, U.S. Pat.
Silver salts of compounds having an imino group described in JP-A No. 274 and the like and acetylene silver described in JP-A-61-249044 can be exemplified.

A silver salt of a compound having an imino group is particularly preferred. For example, silver salts of benzotriazole and its derivatives (for example, silver benzotriazole, silver 5-methylbenzotriazole, etc.) are particularly preferred.

The photothermographic material of the present invention preferably uses a reducing agent. The reducing agent preferably used is selected from those conventionally known for photothermographic materials according to the developing mechanism and the dye formation / release mechanism.
The reducing agent referred to herein includes a reducing agent precursor that releases the reducing agent during thermal development.

The reducing agents usable in the present invention include, for example, US Pat. Nos. 3,351,286 and 3,761,270,
3,764,328, 3,342,599, 3,719,492, Research Disclosure 12,146, 15,108
No. 15,127, and JP-A-56-27132, 53-135628
No. 57-79035, p-phenylenediamine and p-aminophenol developing agents, phosphoramidophenol developing agents, sulfonamidoaniline developing agents, and hydrazone developing agents, phenols, sulfone Amidophenols, polyhydroxybenzenes,
There are naphthols, hydroxybisnaphthyls, methylenebisphenols, ascorbic acids, 1-aryl-3-pyrazolidones, hydrazones, and precursors of the above various reducing agents.

The dye-providing substance can also serve as a reducing agent.

A particularly preferred reducing agent is described in JP-A-56-146133.
No. 62-227141 and N- (p-N ′, N′-dialkylamino) phenylsulfamate and derivatives thereof,
Specific examples include compounds described in JP-A No. 2-863, page 7, lower left column, line 6 to page 8, lower right column.

In the photothermographic material of the present invention, a thermal solvent can be used for the purpose of accelerating the transfer of a dye and other purposes. The thermal solvent is a compound which is liquefied during thermal development and has an action of promoting thermal development and thermal transfer of a dye, and is preferably in a solid state at normal temperature.

The thermal solvents usable in the present invention include, for example, US Pat. Nos. 3,347,675, 3,667,959,
438,776, 3,666,477, Research Disclosure No. 17,643, JP-A-51-19525, 53-24829, 5
3-60223, 58-118640, 58-198038, 59-2295
No. 56, No. 59-68730, No. 59-84236, No. 60-1912
No. 51, No. 60-232547, No. 60-14241, No. 61
-52643, 62-78554, 62-42153, 62-44737
No. 63-53548, No. 63-161446, JP-A 1-224751
And compounds described in JP-A Nos. 2-863, 2-20739 and 2-123354. Specifically, urea derivatives (urea, dimethylurea, phenylurea, etc.), amide derivatives (eg, acetamido, stearylamide, p-
Toluamide, p-propanoyloxyethoxybenzamide, etc.), sulfonamide derivatives (eg, p-toluenesulfonamide, etc.), and polyhydric alcohols (eg, 1,6 hexanediol, pentaerythritol, polyethylene glycol, etc.) are preferably used.

The above thermal solvent can be added to any layer such as a light-sensitive silver halide emulsion layer, an intermediate layer, a protective layer, or an image receiving layer of an image receiving material. Wt% to 500 wt%, more preferably 20 wt% to 2 wt%
00% by weight.

Examples of the hydrophilic binder used in the photothermographic material of the present invention include, for example, JP-A-2-863.
The binders described in the upper right column, line 14 to the lower left column, line 10 of the page can be used including preferred combinations.
Particularly preferred binders are gelatin, polyvinylpyrrolidone and combinations thereof.

Various additives can be added to the photothermographic material of the present invention, if necessary, in addition to the above.

As the development accelerator, for example, JP-A-59-177
No. 550, No. 59-111636, No. 59-124333, No. 61-72233
No. 61-236548, JP-A-1-152454, JP-A-61-1596
No. 42, JP-A-1-104645, and development accelerator releasing compounds described in Japanese Patent Application No. 1-110767, or metal ions having an electronegativity of 4 or more described in JP-A-1-104645 can also be used. .

As the antifoggant, for example, US Pat.
No. 645,739, higher fatty acids, second mercury salts described in JP-B-47-11113, N-halides described in JP-A-51-47419, U.S. Pat. 50
No. 725, Japanese Patent Application Nos. 1-69994 and 1-104271, mercapto compound-releasing compounds described, arylsulfonic acids described in JP-A-49-125016, lithium carboxylate described in JP-A-51-47419, Oxidizing agents described in British Patent 1,455,271 and JP-A-50-101019, sulfinic acids and thiosulfonic acids described in JP-A-53-19825, thiouracils described in JP-A-51-3223, sulfur described in JP-A-51-26019, 51-42529, 51-811
No. 24, and disulfides and polysulfides described in Nos. 55-93149, rosin or diterpenes described in No. 51-57435, polymer acids having a carboxyl group or a sulfonic acid group described in No. 51-104338, U.S. Pat. Thiazolythion described in 4,138,265, JP-A-54-51821, 55-142,331
No. 4,137,079, thiosulfinic acid esters described in JP-A-55-140883, JP-A-59-46641, JP-A-59-57233 and JP-A-59-57234.
-Or tri-halides, thiol compounds described in JP-A-59-111636, hydroquinone derivatives described in JP-A-60-198540 and JP-A-60-227255, and having a hydrophilic group described in JP-A-62-78554. Antifoggants, polymer antifoggants described in JP-A-62-121452, antifoggants having a ballast group described in JP-A-62-123456, non-colored couplers described in JP-A-1-61239, and the like. Can be

Examples of the base precursor include, for example, JP-A-56-130745, JP-A-59-157637, JP-A-59-166943, and JP-A-59-166943.
180537, 59-174830, 59-195237, 62-10824
No. 9, No. 62-174745, No. 62-187847, No. 63-97942,
Compounds and base releasing techniques described in JP-A-63-96159 and JP-A-1-68746.

Various known photographic additives other than those described above can be used in the photothermographic material of the present invention. Examples thereof include antihalation dyes, antiirradiation dyes, colloidal silver, fluorescent brighteners, Hardeners, antistatic agents, surfactants, inorganic and organic matting agents, anti-fading agents, ultraviolet absorbers, anti-mold agents, white-tone color adjusting agents, activated carbon and other contaminant-adsorbing solid fine particles may be contained. it can.

These various additives can be appropriately added not only to the photosensitive layer but also to any constituent layer such as an intermediate layer, an undercoat layer, a protective layer or a back layer.

As the support used in the photothermographic material of the present invention, for example, those described in JP-A-2-863, page 12, line 15 from the upper left column to line 1 in the upper right column can be used. . Preferably, a polyethylene terephthalate support or a paper support such as cast coated paper or baryta paper is used.

In the back layer of the photothermographic material of the present invention, either a hydrophilic binder such as gelatin or a hydrophobic binder such as polyester can be used, but a hydrophilic binder is preferable. The back layer may be composed of one layer or two or more layers. The fluorine-containing cationic surfactant and / or anionic surfactant of the present invention can be added to the uppermost layer of the back layer.

The dye receiving material of the present invention comprises a support and an image receiving layer having dye receiving ability provided thereon.

The image receiving layer can be broadly classified into a case where the binder constituting the image receiving layer itself has a dye receiving ability, and a case where a mordant capable of receiving a dye is contained in the binder. When the binder has a dye-accepting ability, a substance preferably used has a glass transition temperature of about 40 ° C. or more and about 250 ° C.
It is preferably formed of a polymer having a temperature of not more than ℃, specifically, “Polymer Handbook Second Edition” (Joy Brand Wrap, EH.
Inmargat), John Willie and Sons Publishing, Polymer Handbook 2nd. Ed. (J. Brandrup, E.
H. Immergut) Synthetic polymers having a glass transition temperature of about 40 ° C. or more described in John Wily & Sons II are useful. Generally, the molecular weight of the polymer is 2,000 to 20.
A value of about 0,000 is useful. These polymers may be used alone or in combination of two or more, or may be copolymerizable polymers having two or more types of repeating units.

Specifically, JP-A-2-863, page 14, upper left column 1
The polymers described from the fourth line to the upper right column, line 14 can be used, including preferred polymers.

In the image receiving material in which the image receiving layer contains a mordant in a binder, a polymer containing a tertiary amine or a quaternary ammonium salt is preferably used as the mordant. For example, US Pat. No. 3,709,690 and US Pat. 1964-
Compounds described in JP 13546 gazette and the like can be mentioned. As a binder used for holding these mordants, a hydrophilic binder such as gelatin or polyvinyl alcohol is preferably used.

A dye receiving layer obtained by dispersing a hydrophobic polymer latex having dye receiving ability in a hydrophilic binder in a similar manner to the image receiving layer having the mordant in the binder can also be used in the present invention.

The layer containing a fluorinated cationic surfactant and an anionic surfactant of the present invention is preferably a hydrophilic binder, and the hydrophilic binder is a hydrophilic binder which can be used in a photothermographic material. Although a binder can be used, a particularly preferred hydrophilic binder is gelatin.

The image-receiving material of the present invention may have a single image-receiving layer provided on a support, or may have a plurality of constituent layers coated thereon. It may be an image receiving layer, or only a part of the constituent layers may be an image receiving layer.

Various known additives can be added to the image receiving material of the present invention. Such additives include, for example, antifouling agents, ultraviolet absorbers, fluorescent whitening agents, image stabilizers, development accelerators, antifoggants, pH regulators (acid and acid precursors, base precursors, etc.), heat Solvent, oil drops,
Examples include surfactants, hardeners, matting agents, and various metal ions.

When the image receiving material of the present invention has a back layer, the transportability during thermal development can be improved by adding the fluorinated cationic surfactant and the anionic surfactant of the present invention to the back layer. it can. The back layer may be a single layer or may be composed of two or more layers. When the back layer is composed of two or more layers, the fluorine-containing cationic surfactant and the anionic surfactant of the present invention are added to the uppermost layer. Is preferred. As the binder for the back layer of the image receiving material, either a hydrophilic binder or a hydrophobic binder can be used.

The photothermographic material of the present invention can be exposed by a known exposure means suitable for the color sensitivity of the photosensitive material.

As the exposure light source that can be used, those described in JP-A-2-863, page 12, lower left column, lines 13 to 16 can be used.
T light source and LED are used. The semiconductor laser, the SHG element (second harmonic generation element) and the photothermographic material of the present invention may be used after or at the same time as the imagewise exposure.
0 ° C, more preferably 90-170 ° C, preferably 1-180
For 2 seconds, more preferably for 2 to 120 seconds to form a dye image. The transfer of the diffusible dye to the image receiving material may be performed simultaneously with the thermal development by causing the image receiving layer surface of the image receiving material to adhere to the photosensitive layer side of the photosensitive material during thermal development.
Further, the dye may be transferred by bringing the image receiving material into close contact with the photosensitive material after the thermal development, and further, after supplying water, the photosensitive material and the image receiving material may be brought into close contact with each other. Also, before exposure 70-160
Preheating the photosensitive material in the temperature range of
As described in No. 8 and No. 61-162041, immediately before development, at least one of the photosensitive material and the image receiving material is heated to 80 to 120 ° C.
Preheating can also be performed in the temperature range described above.

When the photothermographic material of the present invention is thermally developed, known heating means can be applied. For example, JP-A-2-863, page 13, upper left column, lines 12 to 19 The method described, a method using far-infrared heating, and the like can be used.

[0116]

EXAMPLES Examples of the present invention will be shown below, but the embodiments of the present invention are not limited thereto.

Example 1 [Preparation of photothermographic material] A photothermographic material 1 having the following layer constitution was prepared on a polyethylene terephthalate support having a thickness of 100 µm.

Here, the added amount of each material is shown per 1 m ^{2 of the} photothermographic material.

The light-sensitive silver halide emulsion and the organic silver salt were each expressed in terms of silver.

(The same amount of the following additives is used.) (Layer composition of photothermographic material 1) Sublayer Polyphenylene ether 2.0g Polystyrene 2.0g Antifoggant-2 1.0g First layer (red light sensitive) Layer) Benzotriazole silver 0.2 g Dye-donating substance (3) 0.9 g Red-sensitive silver halide emulsion 0.23 g (Ag) Gelatin 1.0 g DAP 0.04 g Thermal solvent-A 2.1 g Anti-irradiation dye-2 0.01 g Potassium bromide 0.005 g Second layer (first intermediate layer) Gelatin 0.05 g Activated carbon 0.02 g Reducing agent 1.26 g Third layer (green photosensitive layer) Silver benzotriazole 0.26 g Dye donating substance (2) 0.49 g Green-sensitive silver halide emulsion 0.21 g ( Ag) Reducing agent 0.66 g Gelatin 1.0 g Hot solvent-A 0.4 g Anti-irradiation dye 0.02 g Sodium chloride 0.002 g 4th layer (2nd intermediate layer) Gelatin 0.82 g UV absorber-1 0.3 g Yellow filter dye 0.26 g 5 layers (blue photosensitive layer) Benzoto Azole silver 0.41 g Dye-donating substance (1) 1.0 g Blue-sensitive silver halide emulsion 0.21 g (Ag) Gelatin 1.1 g Thermal solvent-A 0.8 g Sixth layer (protective layer) Gelatin 0.4 g Polyvinylpyrrolidone (K-30) 0.1 g DAP 0.1 g Surfactant Amount shown in Table 1 UV absorber-1 0.10 g Each addition amount represents the amount applied per 1 m ² . Each layer,
0.03 g of bisvinylsulfonylmethyl ether per 1 g of gelatin is contained as a hardener, and a surfactant (F-30) required for coating is contained in the first to fifth layers in the following amounts. The reducing agent is 7: 3 of reducing agent-1 and reducing agent-2.
(Weight ratio).

The structural formula of the additive used in the photosensitive layer of the photothermographic material is shown below.

Addition amount of surfactant (A-30) First layer 0.018 g Second layer 0.0072 g Third layer 0.011 g Fourth layer 0.0091 g Fifth layer 0.014 g

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[0124]

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[0126]

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[Silver Benzotriazole Emulsion] An aqueous solution of ammoniacal silver nitrate and benzotriazole (containing 0.2 mol of ammonia water with respect to benzotriazole) were simultaneously mixed in a 10% aqueous solution of phenylcarbamoyl gelatin at 50 ° C., and the addition was completed. Reduce the pH of the post solution, aggregate and desalinate to form needle-like crystals (0.1-0.2 μm wide, 0.5-2 μm long)
m).

To this was added 20 mg of ST-2 as a stabilizer per mole of silver benzotriazole. The photosensitive silver halide emulsion (AgBrCl) used is shown below.

Item Blue photosensitive green photosensitive (GEM-1) Red photosensitive halogen composition (Br mol%) 70 60 70 Particle shape Hexagonal cubic cubic Average particle diameter * 1 0.30 μm 0.19 μm 0.20 μm Particle diameter Distribution coefficient * 2 0.15 0.17 0.13 Surface chemical sensitization method * 3 S + Au S S + Au Stabilizer ST-1 ST-1 ST-2 Sensitizing dye BSD-1 GSD-1 RSD-1 * 1 Spherical diameter * 2 grains Diameter distribution coefficient = (Standard diameter of particle size distribution) / (Average particle size) * 3 S + Au: Gold-sulfur sensitization with sodium thiosulfate and potassium chloroaurate S: Sulfur sensitization with sodium thiosulfate Each silver emulsion was added with 10 ^-6 moles of sodium iridium (IV) chloride per mole of silver halide during grain formation.

ST-1: 6 -methyl- 4-hydroxy- 1,3,3a, 7-tetrazaindene Each chemical sensitization was performed in the presence of a sensitizing dye.

[0131]

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On the other hand, in the photothermographic material-1, except that the kind and amount of the surfactant to be added to the sixth layer were changed as shown in Table 1, the photothermographic material-1 was treated in the same manner as in the photothermographic material-1. Developed photosensitive materials 2 to 16 were prepared.

The resulting photothermographic materials 1 to 10 were stored at 40 ° C. and a relative humidity of 65% for 30 hours to harden to a desired degree of hardening. (The amount of water absorption on the photosensitive layer side at 30 ° C. is 1.7 to 1.9 with respect to the total amount of gelatin on the photosensitive layer side.) [Preparation of dye receiving material] On a baryta paper support having a thickness of 160 μm, An image receiving layer was applied to prepare Dye-image receiving material-1. The addition amount indicates the amount per 1 m ² of the image receiving material. Gelatin 2.2g Polyvinyl chloride latex 12g Thermal solvent-B 3.0g Hardener-1 0.012g Hardener-2 0.024g Surfactant (A-1) 0.022g

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[Evaluation of Photothermographic Materials] The obtained photothermographic materials 1 to 18 were uniformly exposed to white light.
A heat development process was performed for seconds. Next, the image receiving layer side of the dye receiving material-1 is overlapped with the photothermographic material on the side of the photosensitive layer of the image receiving material, and heated and pressurized (20 kg / cm ² ) at 120 ° C. for 20 seconds to form a dye image on the image receiving layer. After the transfer, the photothermographic material was peeled off from the image receiving material.

An almost neutral gray image was obtained on the image receiving layer.

This was repeated for each photothermographic material.
Each sheet was processed.

The number of dot-like irregularities of each white plate per 20 cm × 20 cm of the image receiving layer surface was determined, and the above-mentioned 40 sheets were processed, and the photosensitive layer was adhered to the image receiving layer surface or the image receiving layer was destroyed. Are counted. Table 1 shows the obtained results.
Shown in

[0139]

[Table 1]

From the results shown in Table 1, the photothermographic materials 16, 7, 10 to 18 of the present invention in which the protective layer contains both the fluorinated cationic surfactant of the present invention and an anionic surfactant are shown below. It can be seen that it has excellent peelability and less uneven transfer as compared with the photothermographic material contained alone.

Example 2 A cycle of storing the photothermographic materials 1 to 18 prepared in Example 1 at 40 ° C. and a relative humidity of 80% for 1 day, and then storing at 5 ° C. for 1 day was repeated 5 times. Thereafter, transfer unevenness and releasability were evaluated in the same manner as in Example-1.

Table 2 shows the results.

[0143]

[Table 2]

From the results shown in Table 2, it can be seen that all of the photothermographic materials 6, 7, and 10 to 18 of the present invention show little deterioration in transfer unevenness and peelability even after storage.

In particular, when a fluorine-containing anionic surfactant is used as the anionic surfactant, the effect of the present invention is remarkable.

Example 3 The photothermographic materials 11 to 26 were prepared by changing the activators of the fourth and sixth layers as shown in Table 3 in the photothermographic material-11 prepared in Example-1. It was prepared in the same manner as in Example-1.

By the method described in Example 1, transfer unevenness and releasability were evaluated, and the results shown in Table 3 were obtained.

[0148]

[Table 3]

From the results shown in Table 3, it can be seen that when the fluorine-containing cationic surfactant and the fluorine-containing anionic surfactant of the present invention were added to the fourth layer, the transfer unevenness was reduced and the peelability was improved. It turns out that it becomes a little smaller.

Example-4 In the dye image-receiving material-1 prepared in Example-1, the dye image-receiving materials 2 to 18 were prepared by changing the surfactant as shown in Table 4.
Was prepared in the same manner as in Example-1.

However, the image receiving material-17 further contains 0.030 g of the nonionic surfactant NS-1, and the image receiving material-18 also has NS-
0.030 g of No.3.

Photothermographic material-1 prepared in Example-1
Was evaluated for transfer unevenness and releasability in the same manner as in Example-1.

Table 4 shows the results.

[0154]

[Table 4]

From the results shown in Table 4, it can be seen that the dye image-receiving material containing the fluorine-containing cationic surfactant and the fluorine-containing anion surfactant of the present invention in the same layer has improved transfer unevenness and peelability. I have.

Example-5 A photothermographic material-21 was prepared by providing the back layer composed of the following layers on the back of the support with a subbing layer on the back of the support from the photothermographic material prepared in Example-1. .

First back layer: gelatin 4.0 g carbon black 0.4 g black colloidal silver 0.4 g surfactant (shown in Table 5) Hardener-1 0.2 g Second back layer: gelatin 1.0 g colloidal silica 0.2 g surfactant Agent (shown in Table 5) Hardener-1 0.05 g On the other hand, photothermographic materials 22 to 26 in which the surfactants of the first back layer and the second back layer were changed as shown in Table 5 were also prepared.

[0158]

[Table 5]

On the other hand, in the dye image material-1 prepared in Example-1, the support was changed from baryta paper to a white polyethylene terephthalate support having a thickness of 125 μm and subjected to double-sided latex subbing. Was coated with the following back layer on the back surface of. Dye receiving material-21 was prepared.

Back layer: gelatin 3.0 g Surfactant (shown in Table 6) Hardener-1 0.12 g

[0161]

[Table 6]

Further, Dye-receiving materials -22 to 25 were prepared in the same manner as in Dye-receiving material 21, except that the surfactant in the back layer was changed as shown in Table 6 in Dye-receiving material-21.

The photothermographic materials 21 to 26 obtained as described above
Using the dye receiving materials 21 to 25, the respective combinations were evaluated through a heat developing apparatus shown in FIG. 1 of JP-A-1-93739. However, at this time, heat development and dye transfer were performed at 150 ° C and 60 ° C.
The same process was performed every second.

For each combination of samples, 100 sheets were continuously processed and the number of occurrences of transport trouble was examined. Table 7 shows the results.

[0165]

[Table 7]

From the results shown in Table 7, it can be seen that the samples containing the fluorinated cationic surfactant of the present invention in the back layer have few transportation troubles.

It can be seen that it is particularly preferable to use the surfactant of the present invention in combination with the back layer of both the photothermographic material and the dye image-receiving sample.

Example-6 Dye-receiving materials 1 to 1 prepared in Example-1 and Example-4
Using No. 18 and thermal transfer dye-providing material described in Example 1 of JP-A-3-81193, thermal transfer recording was performed under the conditions described in Example 1 of the publication.

At that time, 100 sheets were continuously recorded in B-6 size, and the fusion of the dye-providing material and the dye-receiving material and the number of sheets produced were examined. Table 8 shows the results.

[0170]

[Table 8]

From the results shown in Table 8, it can be seen that the dye image-receiving material of the present invention has excellent heat fusion resistance.

[0172]

According to the present invention, transfer unevenness is reduced when the photothermographic material and the dye image-receiving material are superposed on each other to perform heat development and dye transfer, and the photothermographic material is separated from the dye image-receiving material after the dye transfer. Thus, a photothermographic material and a dye image-receiving material having good peelability at the time and improved transportability in the heat developing apparatus could be provided.

Claims (6)

(57) [Claims] 1. A photothermographic material having at least one photosensitive layer containing a hydrophilic binder, a photosensitive silver halide and a dye-donating substance which releases or forms a diffusible dye during thermal development, is provided on a support. A photothermographic material characterized in that at least one layer on the photosensitive layer side with respect to the support contains a fluorine-containing cationic surfactant and an anionic surfactant. 2. The photothermographic material according to claim 1, wherein a nonionic surfactant is contained in at least one layer on the photosensitive layer side with respect to the support. 3. A dye image-receiving material having a dye-receiving substance having dye-receiving ability on a support, and a fluorine-containing cationic surfactant and an anion in at least one layer on the dye-receiving substance-containing side of the support. A dye image-receiving material comprising a surfactant. 4. The dye image-receiving material according to claim 3, wherein a nonionic surfactant is contained in at least one layer on the side having the dye receiving substance with respect to the support. 5. A support comprising at least one photosensitive layer containing a hydrophilic binder, a photosensitive silver halide and a dye-donating substance which releases or forms a diffusible dye upon thermal development.
The photothermographic material having a layer, wherein at least one layer provided on the side opposite to the photosensitive layer side with respect to the support contains a fluorine-containing cationic surfactant and an anionic surfactant. Characteristic photothermographic material. 6. A dye image-receiving material having a dye-receiving substance having a dye-receiving ability on a support, wherein at least one layer provided on the side opposite to the dye-receiving substance-containing layer side with respect to the support has a fluorine-containing material. A dye image-receiving material comprising a cationic surfactant and an anionic surfactant.