JP2881052B2 - Thermal development color photosensitive material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

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BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a multi-layer heat-developable color light-sensitive material capable of obtaining an image excellent in color separation from near-infrared light to infrared light, especially to a semiconductor laser. The present invention relates to a heat-developable color light-sensitive material having excellent sensitivity and raw storage stability.

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2. Description of the Related Art Photothermographic materials are known in the art. For details of the photothermographic materials and processes thereof, see, for example, "Basics of Photographic Engineering", Non-silver salt photography (ed. 1982, Corona Co., Ltd., p. 242). ２５255, U.S. Pat.
No. 0626 and the like.

In addition, for example, US Pat. Nos. 3,761,270 and 4,221,240 disclose a method of forming a dye image by a coupling reaction between an oxidized form of a developing agent and a coupler. A method of forming a positive color image by a photosensitive silver dye bleaching method is described in U.S. Pat. No. 4,235,957.

Recently, there has been proposed a method in which a diffusible dye is released or formed in an image form by thermal development, and the diffusible dye is transferred to a dye fixing element. In this method, a negative dye image and a positive dye image can be obtained by changing the type of the dye-donating compound to be used or the type of silver halide to be used. More specifically, U.S. Pat. Nos. 4,500,626 and 4,483,914, and U.S. Pat.
Nos. 503137 and 4559290, JP-A-58-1
No. 49046, JP-A-60-133449 and JP-A-59-133449.
Nos. 218443 and 61-238056, EP-A-220746A2, JP-A-87-6199, and EP-A-210660A2.

Many methods have been proposed for obtaining a positive color image by thermal development. For example, U.S. Pat. No. 4,559,290 discloses that a compound obtained by converting a so-called DRR compound into an oxidized form having no ability to emit a color image in the presence of a reducing agent or a precursor thereof is used. A method has been proposed in which a diffusible dye is released by being oxidized and reduced by a reducing agent remaining without being oxidized. In addition, European Patent Publication No. 220746 and Published Technical Report 87-6199 (Vol. 12, No. 22) describe NX bonds (X is an oxygen atom, a nitrogen atom or A heat-developable color light-sensitive material using a compound which releases a diffusible dye by reductive cleavage of a sulfur atom) is described.

Conventional color light-sensitive materials are usually blue, green,
It has red spectral sensitization, and it is common to use a color CRT (cathode ray tube) as an exposure light source to obtain an image on such a color photosensitive material by using image information once converted into an electric signal. However, CRTs are not suitable for obtaining large size prints.

Further, a light emitting diode (LED) is used as a write head capable of obtaining a large-sized print.
And semiconductor lasers (LDs) have been developed. However, those optical writing heads that efficiently emit blue light have not been developed.

Accordingly, for example, a light emitting diode (LED)
When using near infrared (800 nm), red (670 n
m) and a light source combining three light emitting diodes of yellow (570 nm), it is necessary to expose a color photosensitive material having three layers spectrally sensitized to near infrared, red and yellow. Is a system to record images at "Nikkei New Materials", September 14, 1987 issue No. 4
It is described on pages 7 to 57, and is partially used.

A system for recording on a color photosensitive material having three photosensitive layers having a spectral sensitivity at each wavelength with a light source combining three semiconductor lasers emitting at 880 nm, 820 nm, and 760 nm is disclosed in Japanese Patent Application Laid-Open No. 61-1986. No. 137149.

In general, in the case where yellow, magenta, and cyan colors are exposed to three different spectral regions in a multi-layered color photosensitive material to form colors, it is necessary to reproduce the colors without mixing. Has become an important technology. In particular, when a light emitting diode (LED) or a semiconductor laser (LD) is used as an exposure light source, three spectral sensitivities must be designed in a narrow spectral range (red to infrared).
How to reduce the overlap between the spectral sensitivities was the key to improving the color separation.

Conventionally used sensitizing dyes in the near-infrared to infrared region have very broad spectral sensitivities, so that spectral sensitivities tend to overlap and poor color separation occurs.

In order to ensure color separation, US Pat.
As described in Japanese Patent No. 198992, a technique for sequentially increasing the sensitivity on the short wavelength side and providing a filter layer is known. However, increasing the sensitivity at short wavelengths sequentially has the disadvantage of causing an increase in fog and deteriorating the raw storage stability. Moreover, it is known that the raw storage stability of infrared sensitization is originally low. Further, it has been difficult to achieve high sensitivity in infrared sensitization.

As described above, it has been particularly desired to develop a photosensitive material having high sensitivity, excellent raw storage stability, and good color separation.

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SUMMARY OF THE INVENTION The object of the present invention is to
An object of the present invention is to provide a heat-developable color light-sensitive material which is excellent in color separation property, high sensitivity and excellent in raw storage stability when exposed to a semiconductor laser having a long wavelength of 0 nm or more.

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This and other objects are attained by the present invention which is defined below as (1) and (2).

(1) There are at least three silver halide emulsion layers having different spectral sensitivities on a support, and when silver ions are reduced to silver under a high temperature condition, the reaction corresponds to or reverses this reaction. In a heat-developable color light-sensitive material having at least three layers containing a dye-donating compound which emits or produces a dye having a mutually different hue, at least one of the silver halide emulsion layers is The silver halide emulsion layer contains at least one thiadicarbocyanine dye represented by Formula (4), and the wavelength of the maximum spectral sensitivity of the silver halide emulsion layer is from 700 nm to 900 nm;
In addition, at least one silver halide emulsion spectrally sensitized so that the spectral sensitivity to light having a wavelength longer by 20 nm than the wavelength of the maximum spectral sensitivity is 1/3 or less of the maximum spectral sensitivity.
A heat-developable color light-sensitive material comprising a seed.

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In formula 3, Q ₁ and Q ₂ each represent a methylene group, and R ₁ and R ₂ each represent an alkyl group. R ₃ and R ₄ each represent a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, and R ₃ and R ₄ are not simultaneously hydrogen atoms. L ₁ , L ₂ and L ₃ each represent a methine group. A ₁ and A ₂ each represent an atomic group necessary for forming a benzene ring or a naphthalene ring. R ₁ and L ₁ , and R ₂ and L ₃ may be bonded to each other to form a ring. M ₁ represents a charge balancing counter ion, and m ₁ represents a value required to neutralize the charge. Chemical 4
, R ₁ , R ₂ , A ₁ , A ₂ , M ₁ and m ₁
Has the same meaning as in Chemical formula 3, respectively. R ₁ and R ₂ may each be bonded to a methine group to form a ring. R
₅ represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group. ]

(2) A silver halide emulsion sensitized so that the spectral sensitivity to light having a wavelength longer than 20 nm from the wavelength of the maximum spectral sensitivity of the silver halide emulsion layer is not more than 1/3 of the maximum spectral sensitivity. Is a thermal sensitizer according to the above (1) obtained by performing chemical sensitization in the presence of at least one of the thiazicarbocyanine dyes represented by the above formulas 3 and 4 and a tetraazaindene compound. Developed color photosensitive material.

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[Specific Configuration] Hereinafter, a specific configuration of the present invention will be described in detail.

The heat-developable color light-sensitive material of the present invention has at least three silver halide emulsion layers having different spectral sensitivities on a support.

At least one of the silver halide emulsion layers contains at least one thiadicarbocyanine dye and has a wavelength (λmax) of a maximum spectral sensitivity of 700.
９００900 nm, and 2 nm from the wavelength of the maximum spectral sensitivity.
The silver halide emulsion contains at least one silver halide emulsion spectrally sensitized so that the spectral sensitivity (S ₁ ) to light having a long wavelength of 0 nm is 1/3 or less of the maximum spectral sensitivity (S ₀ ).

This makes it possible to improve the color separation of a semiconductor laser or the like with respect to exposure in the near-infrared to infrared region, and it may be unnecessary to provide a filter layer.

It is generally known that a raw material which has been subjected to infrared sensitization has poor raw storage stability. However, in order to improve color separation, a method of sequentially increasing the sensitivity on the short wavelength side is proposed. (US Pat. No. 4,619,892) causes a problem that fog is increased and raw storage stability is further deteriorated. However, in the present invention, the color separation can be improved without such a problem. Further, there has been a problem that high sensitivity cannot be obtained with a photosensitive material that has been subjected to infrared sensitization. However, this problem can be solved by the present invention.

And, as described above, using a thiazylcarbocyanine dye, λmax is 700-900 nm,
In addition, the effects of the present invention can be obtained only when all the conditions that the S ₁ / S ₀ ratio is 1/3 or less are satisfied. If even one of these conditions is missing, the effects of the present invention can be obtained. Absent. For example, even when the λmax and the S ₁ / S ₀ ratio are satisfied, the use of a dye other than the thiazicarbocyanine dye has the drawback that the color separation property is sufficient but the raw storage stability is not sufficient. Further, even when the thiazicarbocyanine dye has an S ₁ / S ₀ ratio exceeding 1/3, not only the color separation property is not sufficient, but also the raw storage stability and sensitivity are not sufficient. Often occurs.

In the present invention, the lower limit of the ratio S ₁ / S ₀ is not limited, and the smaller the value, the better the color separation.

In the present invention, in at least three silver halide emulsion layers having different spectral sensitivities, a dye-donating compound which emits or produces a dye having a different hue is used in combination, and such a dye-donating compound is used. Has at least three layers. In this case, the dye-donating compound may be contained in the silver halide emulsion layer or in a non-photosensitive layer adjacent to the silver halide emulsion layer. Alternatively, it may be contained in both the silver halide emulsion layer and the non-photosensitive layer adjacent thereto. The dye donating compound will be described later.

Next, the silver halide emulsion used in the present invention will be described.

(1) Kinds of Sensitizing Dyes A thiazicarbocyanine dye is used in the silver halide emulsion of the present invention, and is represented by the following chemical formula (3) or (4).

In formula 3, Q ₁ and Q ₂ each represent a methylene group, and R ₁ and R ₂ each represent an alkyl group. R ₃ and R ₄ each represent a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, and R ₃ and R ₄ are not simultaneously hydrogen atoms. L ₁ , L ₂ and L ₃ each represent a methine group. A ₁ and A ₂ each represent an atom group necessary for forming a benzene ring or a naphthalene ring.
R ₁ and L ₁ , and R ₂ and L ₃ may be bonded to each other to form a ring. M ₁ represents a charge balancing counter ion, and m ₁ represents a value required to neutralize the charge.

The alkyl group represented by R ₁ and R ₂ may be unsubstituted or substituted, and preferably has 1 to 18 carbon atoms, such as methyl and ethyl. Propyl, butyl, pentyl, octyl, decyl, dodecyl and octadecyl groups. Further, as a substituent when having a substituent,
There are a sulfonic acid group, a carboxy group, a cyano group and the like.

The alkyl groups represented by R ₃ and R ₄ may be unsubstituted or substituted, and preferably have 1 to 10 carbon atoms, for example, methyl group, Ethyl groups are mentioned.

R ₁ and L ₁ and R ₂ and L ₃ may form a ring with each other. It preferably has a carbon atom forming an unsubstituted 5-, 6- or 7-membered ring, and particularly preferably 6
Carbon atoms forming a member ring.

R ₁ and R ₂ are preferably an unsubstituted alkyl group (for example, methyl group, ethyl group, n-propyl group, n-butyl group), a sulfoalkyl group (for example, 2-
Sulfoethyl group, 3-sulfopropyl group, 4-sulfobutyl group, 3-sulfobutyl group), R ₁ and L ₁ , R ₂
And L ₃ are also preferably bonded to each other to form a 5- or 6-membered ring.

The aryl groups represented by R ₃ and R ₄ may be unsubstituted or substituted, and include, for example, a phenyl group.

The heterocyclic groups represented by R ₃ and R ₄ include, for example, 2-pyridyl group, 2-thiazoyl group,
Examples thereof include a furyl group and a 2-quinolyl group.

R ₃ and R ₄ are preferably a hydrogen atom, a methyl group, an ethyl group, a phenyl group or the like.

The benzene ring or naphthalene ring completed by A ₁ and A ₂ may be unsubstituted or have a substituent, and the substituent may be a halogen atom such as a chlorine atom. A hydroxyl group; an alkyl group such as a methyl group;
An alkoxy group such as a methoxy group and an ethoxy group; an aryl group such as a phenyl group; a carboxy group; a cyano group;
And sulfonic acid groups.

Examples of M ₁ include halide ions (bromide ions, iodide ions, etc.), anions such as perchlorate ion and paratoluenesulfonate ion, and cations such as triethylammonium ion and sodium ion.

When the dye molecule itself forms an inner salt to maintain the charge balance, m ₁ is 0.

In Chemical Formula 4, R ₁ and R ₂ each represent an alkyl group, and specific examples and preferred examples thereof are the same as those in Chemical Formula 3.

R ₅ represents an alkyl group, an aryl group or a heterocyclic group, and specific examples thereof are the same as those described for R ₃ and R ₄ in Chemical formula ₃ .

Of these, preferred are a methyl group,
Examples include an ethyl group and a benzyl group.

The benzene ring or naphthalene ring completed by A ₁ and A ₂ and the ring formed by R ₁ and a methine group, and the ring formed by R ₂ and a methine group are the same as those in Chemical formula 3. Further, M ₁ and m ₁ are the same as those in Chemical formula 3.

Specific examples of the thiazicarbocyanine dye preferably used in the present invention are shown in Chemical formulas (5) to (18), but are not limited thereto. It should be noted that R ₁ , R
The combination of _{2 and the} like is shown in Chemical formula 6, 7 and 8, and the combination of R ₁ and R ₂ in Chemical formula 15 is the chemical formula 16
It is shown in FIG.

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Among them, anionic sensitizing dyes are
Perhaps because the absorption is good, the spectral sensitivity tends to sharpen, and the oil solubility is low, so that it is stable over the dissolution time of the emulsion coating solution to which the gelatin dispersion containing the dye-providing substance is added. Can be Further, although the reason is not clear, anionic dyes are preferable because they have better raw storage stability than cationic dyes.

The sensitizing dyes described above may be used alone or in combination, or may be used in combination with other known sensitizing dyes (for example, US Pat. No. 4,617,257, JP-A-59-180550). No. 60-140335, R
D17029 (1978), pp. 12-13). In particular, those combinations are frequently used for supersensitization. A dye which has no spectral sensitizing effect or a compound which does not substantially absorb visible light together with the sensitizing dye and which exhibits supersensitization may be contained in the emulsion (for example, US Pat. No. 3615641 and JP-A-63-23145).

The sensitizing dye of the present invention can be synthesized with reference to the following literature.

A) Heterocyclic Compounds by Hemerocycli, FM Hamer (Chemine Cyclic Dye and Related Compounds)
c Compounds-Cyanine dyes and related compounds)
(John Wiley and Sons John Wiley
& Sons, New York, London, 1964)

B) DMSturme
r)-Heterocyclic Compounds-Special topics in Heterocyclic Compounds-Special topics
in heterocyclic chemistry-) "(John Wiley & Sons, New York, London, 1977)

The silver halide emulsion of the present invention is spectrally sensitized by the above-described sensitizing dye. In the present invention, in combination with such a silver halide emulsion, spectral sensitization by another sensitizing dye is carried out. The felt silver halide emulsion can be used. Other spectral sensitizing dyes include known cyanine dyes,
Merocyanine dyes and composite merocyanine dyes are used. In addition, complex cyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes, and hemioxonol dyes are used.

Specifically, see US Pat. No. 4,617,257.
JP-A-59-180550 and JP-A-60-14033
No. 5, RD17029 (1978), pp. 12-13, and the like.

These sensitizing dyes, including those of the present invention, are used in an amount of from 5 × 10 ^-7 mol to 8 × 10 ⁷ mol / mol of silver halide.
^-3 mol, preferably 1 × 10 ⁻⁷ mol to 5 × 10 ⁻³ mol, particularly preferably 2 × 10 ⁻⁷ mol to 2 × 10 ⁻³ mol, in the silver halide emulsion.

In the present invention, the sensitizing dye used in the light-sensitive material can be directly dispersed in the emulsion. Also,
These are first suitable solvents, for example methyl alcohol,
It may be added by dissolving in a water-compatible organic solvent such as ethyl alcohol, methyl cellosolve, acetone, fluorinated alcohol, dimethylformamide, or propyl alcohol, or water (which may be alkaline or acidic), or as described above. May be used in combination of two or more. It may also be added in the form of a dispersion in a water / gelatin dispersion or in the form of a lyophilized powder. Further, it may be added in the form of a powder or a solution dispersed using a surfactant.

(2) Method of Adding Sensitizing Dye The sensitizing dye in the present invention may be added at any time, and the emulsion may be added at 50 ° C. to 85 ° C. in a state where the sensitizing dye is present in the silver halide emulsion. For 15 minutes or more (preferably 30 minutes or more).

That is, the timing of addition may be at the beginning of the formation of silver halide emulsion grains (may be added before nucleation), during or after the formation, or at the beginning, during or after the desalting step, at the time of gelatin addition. At the time of redispersion, before, during or after chemical sensitization, or during preparation of a coating solution. Preferably, it is added during or after the formation of silver halide grains, or before, during or after chemical sensitization. Addition after chemical sensitization means adding a sensitizing dye after all chemicals necessary for chemical sensitization have been added.

The addition method may be added at once, or may be added in several steps over the same step or different steps. The addition may take place gradually over time.

The amount of addition should be 30% or more of the amount of adsorption saturated coating.
It is preferable to add at 50% or less. More preferably, the addition amount is 50% or more and 100% or less. here,
The adsorption saturated coating amount is the amount of the sensitizing dye necessary for the sensitizing dye to cover the entire surface of the silver halide emulsion grain, and can be determined from the area occupied by the sensitizing dye on the surface of the silver halide emulsion grain. it can. For example, the area occupied on the silver halide emulsion grain surface Ji azide carbocyanine dyes of the present invention, as about 100A ^2, can be calculated from the total surface area of the added molar amount and the silver halide emulsion grains of a sensitizing dye.

When a sensitizing dye is added before, during or after the formation of silver halide grains, the formation of the grains at a low temperature of 50 ° C. or lower is required even if the grains are formed in a subsequent step (for example, chemical sensitization). The emulsion may be stirred for 15 minutes or more at a temperature of not less than 50 ° C and not more than 850 ° C.
It is preferable to raise the temperature to 5 ° C. or lower and stir the emulsion for 15 minutes or more. At a temperature of 50 ° C. or more and 85 ° C. or less, a sensitizing dye may be added to stir the emulsion. When sensitizing dyes are added at the same time when silver halide grains are formed, if the sensitizing dyes are added at once, the amount of sensitizing dyes added is close to the saturation coverage. Since this may cause a problem, the sensitizing dye may be added continuously or in several portions.

In the desalting step, a gelatin flocculant (for example, one described in JP-A-58-140322) is used. Chemical 1
In order to prevent sensitizing dye adsorption inhibition, P-2 of No. 9 is particularly preferably added before and after silver halide grain formation before the desalting step. When the sensitizing dye is added after the desalting step (including at the time of chemical sensitization), P-1 of Chemical Formula 19, which causes less inhibition of sensitizing dye adsorption, is preferably used. Alternatively, a desalting step using an ultrafiltration apparatus described in U.S. Pat. No. 4,758,505 is also preferable in terms of adsorption of a sensitizing dye.

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In the present invention, a nitrogen-containing heterocyclic compound, particularly a tetraazaindene compound (preferably 4-hydroxy-6-methyl-) is used for stabilizing raw storage, controlling chemical sensitization and suppressing fog. (1,3,3
It is preferable to stir at 50 ° C. or more and 85 ° C. or less for 15 minutes or more (preferably 30 minutes or more) in the state where (a, 7) -tetraazaindene) and the sensitizing dye are present in the emulsion. By doing so, the adsorption of the sensitizing dye can be enhanced.

In particular, in the chemical sensitization method in the presence of a nitrogen-containing heterocyclic compound, particularly a tetraazaindene compound (Japanese Patent Application Laid-Open No. 62-255159), the timing of addition of the sensitizing dye depends on the formation of silver halide grains. At the beginning, during and after, or at the beginning of the desalting step, during, after, or during gelatin redispersion, or during or before or after chemical sensitization. is there.

In particular, in the emulsion of the present invention which is subjected to spectral sensitization with a thiazicarbocyanine dye, it is preferable to perform chemical sensitization in the presence of the thiazicarbocyanine dye and a tetraazaindene compound.

In this case, the timing of addition of the thiazicarbocyanine dye and the tetraazaindene compound is not particularly limited as long as both compounds are present at one time during chemical sensitization.
It is preferred to add both compounds together.

When the sensitizing dye is added in a step other than the chemical sensitization, it is preferable to add the tetraazindene compound together, but basically, the sensitizing dye and the tetraazaindene compound are added. Emulsion in the presence of 50 ° C or higher 8
If stirring can be performed at 5 ° C. or less for 15 minutes or more (preferably 30 minutes or more), the tetraazaindene compound may be added in a subsequent step or a step before that.

In the above, when the sensitizing dye and the tetraazaindene compound are added together, the timing of addition of both compounds may be off by about 10 seconds to 10 minutes, and the order of addition may be any. There may be. Further, a mixture of a sensitizing dye and a tetrazaindene compound may be added.

During and before and after the addition of the sensitizing dye,
Soluble calcium compounds, soluble iodides, soluble bromides, soluble chlorides, and soluble thiocyanates may be added together. Preferably, KI, CaCl ₂ ,
It is preferable to use KCl, KBr, KSCN, or the like.

(3) Basic Structure and Preparation Method of Silver Halide Grains Silver halides usable in the present invention include silver chloride, silver bromide,
Any of silver iodobromide, silver chlorobromide, silver iodochloride and silver chloroiodobromide may be used, but silver iodobromide containing 10 mol% or less of silver iodide, silver chloride, silver bromide and It is silver chlorobromide.

The silver halide emulsion used in the present invention may be a surface latent image type or an internal latent image type. The internal latent image type emulsion is used as a direct reversal emulsion in combination with a nucleating agent or a shiny fogging. Further, so-called multi-structure grains having different halogen compositions between the inside and the grain surface may be used. Of the multiple structure grains, those having a double structure may be particularly referred to as a core-shell emulsion.

The silver halide emulsion used in the present invention is preferably a monodisperse emulsion.
The coefficient of variation described in the above item is preferably 20% or less.
More preferably 16% or less, still more preferably 10%
It is as follows. However, the present invention is not limited to this monodispersed emulsion.

The average grain size of the silver halide grains used in the present invention is from 0.1 μm to 2.2 μm, preferably from 0.1 μm to 1.2 μm. More preferably,
It is between 0.1 μm and 0.8 μm.

The crystal habit of the silver halide grains may be any one of cubic, octahedral, tabular with a high aspect ratio, potato and the like.

Specifically, US Pat. No. 4,500,626, column 50, US Pat. No. 4,628,021 and Research Disclosure Magazine (hereinafter abbreviated as RD) 17029 (197).
8) and any of the silver halide emulsions described in JP-A-62-25159 and the like can be used.

In the process of preparing the silver halide emulsion of the present invention, when a so-called desalting step for removing excess salt is carried out, as a means for this purpose, gelling of gelatin, which has been known for a long time, is carried out by gelling with Nudel water. Or an inorganic salt comprising a polyvalent anion, such as sodium sulfate, an anionic surfactant, an anionic polymer (eg, polystyrenesulfonic acid), or a gelatin derivative (eg, aliphatic acylated gelatin, aromatic acyl A sedimentation method (flocculation) using hydrated gelatin, aromatic carbamoylated gelatin, etc.) may be used. Preferably, a precipitation method using a compound represented by Chemical Formula 19 or the like is used, but the present invention is not limited thereto. The removal of the excess salt may be omitted. Alternatively, U.S. Pat. No. 4,758,505,
No. 3137, JP-B-59-43727, U.S. Pat.
The removal of excess salt may be carried out by using an ultrafiltration apparatus shown in 334012.

The silver halide emulsion used in the present invention may contain heavy metals such as iridium, rhodium, platinum, cadmium, zinc, thallium, lead, iron, chromium, ruthenium and rhenium for various purposes. These compounds are
They may be used alone or in combination of two or more. The addition amount depends on the purpose of use, but is generally about 10 ^-9 to 10 ^-3 mol per mol of silver halide. When the particles are contained, they may be uniformly introduced into the particles, or may be localized on the surface or inside of the particles.

In the present invention, at the stage of forming silver halide grains, a rhodan salt, NH ₃ ,
And compounds represented by Chemical formula 20
An organic thioether derivative described in 1386 or a sulfur-containing compound described in JP-A-53-144319 can be used.

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At the stage of forming silver halide grains, a nitrogen-containing compound as described in JP-B-46-7781, JP-A-60-222842, JP-A-60-122935, etc. can be added. .

Gelatin is advantageously used as a protective colloid used in the preparation of the emulsion of the present invention and as a binder for other hydrophilic colloids, but other hydrophilic colloids can also be used.

For example, gelatin derivatives, graft polymers of gelatin and other high polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethylcellulose and cellulose sulfates; sodium alginate and starch derivatives; polyvinyl alcohol and polyvinyl alcohol moieties Various kinds of synthetic hydrophilic polymer substances such as a single or copolymer such as acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole and the like can be used.

Examples of gelatin include lime-processed gelatin, acid-processed gelatin, britain, and soyatyob.
The Scientific, Photography of Japan (Bull. Soc. Sci. Phot., Japan), Number (No.) 1
6, p (p) 30 (1966), enzyme-treated gelatin may be used, and a hydrolyzate or enzyme-decomposed product of gelatin may also be used.

For other conditions, refer to Graph Graph
(P.Glafkides), Chemieet Physique Photographique (Paul Montel, 1967), GFDuffin, GFDuffin, Photographic Emulsion
on Chemistry) [The Focal P
ress), 1966], VLZelikman et al., Making and Coating Photographic Emulsion (Making)
and Coating Photographic Emulsion) (The Focal Press, published in 1964). That is, any of an acidic method, a neutral method, and an ammonia method may be used, and a method of reacting a soluble silver salt and a soluble halide may be any of a one-side mixing method, a double-mixing method, and a combination thereof.

A method of forming grains in the presence of excess silver ions (so-called reverse mixing method) can also be used. As one type of the double jet method, a method of maintaining a constant pAg in a liquid phase in which silver halide is formed, that is, a so-called controlled double jet method can be used.

Further, in order to accelerate the grain growth, the concentration, amount or rate of silver salt and halogen salt to be added may be increased (JP-A-55-142329 and JP-A-55-158124; U.S. Pat. No. 3650575).

During or after grain formation, the surface of the silver halide grains may be replaced with a halogen which forms sparingly soluble silver halide grains.

Further, the stirring method of the reaction solution may be any known stirring method. The temperature and pH of the reaction solution during the formation of silver halide grains may be set in any manner.

(4) Chemical Sensitization The silver halide emulsion used in the present invention may be used after unripe ripening (unchemical sensitization). Is preferred.

The chemical sensitization may be any of sulfur sensitization, gold sensitization, reduction sensitization, and the like, or a combination thereof.

In addition, chemical sensitization with a compound containing a chalcogen element other than sulfur such as selenium or tellurium, or chemical sensitization with a noble metal such as palladium or iridium may be combined with the above-described chemical sensitization.

Further, 4-hydroxy-6-methyl-
A method of adding an inhibitor such as (1,3,3a, 7) -tetrazaindene at the beginning, during, or after chemical sensitization is also preferably used.

In particular, in the emulsion of the present invention, as described above,
It is preferable to perform chemical sensitization in the presence of a thiazicarbocyanine dye and a tetraazaindene compound.

The sulfur sensitizer is a compound containing sulfur which can react with active gelatin or silver. Examples thereof include thiosulfate, allylthiocarbamide, thiourea, allylisothiocyanate, cystine, p-toluenethiosulfone. Acid salts, rhodan, mercapto compounds and the like are used.

In addition, US Pat. Nos. 1,574,944, 2,410,689, 2,278,947, and 27286.
Nos. 68 and 3656955 can also be used.

[0111] The coating amount of the photosensitive silver halide used in the present invention, to terms of silver 1 g / m ² not in the range of 10 g / m ^2.

In the present invention, an organic metal salt can be used as an oxidizing agent together with the photosensitive silver halide. Among such organic metal salts, an organic silver salt is particularly preferably used.

Organic compounds which can be used to form the above-mentioned organic silver salt oxidizing agents include US Pat. No. 4,500,626.
No. 52-53, benzotriazoles, fatty acids and other compounds. Japanese Patent Application Laid-Open No. 60-1132
A silver salt of a carboxylic acid having an alkynyl group such as silver phenylpropiolate described in JP-A No. 35;
The acetylene silver described in No. 044 is also useful. Two or more organic silver salts may be used in combination.

The above-mentioned organic silver salt is a photosensitive silver halide 1
0.01 to 10 mol, preferably 0.1 to 10 mol, per mol.
01 to 1 mol can be used in combination. The total coating amount of the photosensitive silver halide and the organic silver salt is 50 mg / m ^{2 in} terms of silver.
To 10 g / m ² is appropriate.

In the present invention, various antifoggants or photographic stabilizers can be used. Examples thereof include azoles and azaindenes described in RD17643 (1978), pp. 24-25, and JP-A-59-1684.
No. 42 nitrogen-containing carboxylic acids and phosphoric acids,
Alternatively, a mercapto compound and a metal salt thereof described in JP-A-59-111636, an acetylene compound described in JP-A-62-87957, and the like are used.

As the binder for the constituent layers of the light-sensitive material and the dye-fixing element, hydrophilic binders are preferably used. Examples thereof include pages (26) to (2) of JP-A-62-253159.
8) Those described on page 8 are mentioned. Specifically, transparent or translucent hydrophilic binders are preferred, for example, gelatin, proteins or cellulose derivatives such as gelatin derivatives, starch, gum arabic, dextran, natural compounds such as polysaccharides such as pullulan, polyvinyl alcohol, Examples include polyvinylpyrrolidone, acrylamide polymers, and other synthetic polymer compounds. Further, a superabsorbent polymer described in JP-A-62-245260, that is, a homopolymer of a vinyl monomer having —COOM or —SO ₃ M (M is a hydrogen atom or an alkali metal), or those vinyl monomers or other vinyl monomers. (For example, sodium methacrylate, ammonium methacrylate, Sumikagel L-5H manufactured by Sumitomo Chemical Co., Ltd.) may also be used. These binders can be used in combination of two or more kinds.

When a system for performing thermal development by supplying a small amount of water is employed, the use of the above superabsorbent polymer makes it possible to rapidly absorb water.
Further, when the superabsorbent polymer is used for the dye fixing layer and its protective layer, it is possible to prevent the dye from being re-transferred from the dye fixing element to another after transfer.

In the present invention, the coating amount of the binder is 1
It is preferably 20 g or less per m ² , particularly preferably 10 g or less, more preferably 7 g or less.

The constituent layers (including the back layer) of the light-sensitive material or the dye-fixing element are used for the purpose of improving film physical properties such as dimensional stability, curl prevention, adhesion prevention, film crack prevention and pressure increase / decrease sensation. Various polymer latexes can be included. Specifically, any of the polymer latexes described in JP-A Nos. 62-245258, 62-136648, and 62-110066 can be used. In particular,
When a polymer latex having a low glass transition point (40 ° C. or less) is used for the mordant layer, cracking of the mordant layer can be prevented, and when a polymer latex having a high glass transition point is used for the back layer, a curl preventing effect can be obtained. .

As the reducing agent used in the present invention, those known in the field of photothermographic materials can be used. Further, a dye-providing compound having a reducing property described later is also included (in this case, another reducing agent may be used in combination). Further, a reducing agent precursor which does not itself have a reducing property but expresses a reducing property by the action of a nucleophilic reagent or heat during the development process can be used.

Examples of the reducing agent used in the present invention include:
U.S. Pat. No. 4,500,626, columns 49-50, 44.
No. 83914, columns 30-31, No. 4330617,
Nos. 4590152 and pp. 17-17 of JP-A-60-140335, pp. 57-40245 and pp. 56
138736, 59-178458, 59-
Nos. 53831, 59-182449 and 59-18
No. 2450, No. 60-119555, No. 60-128
From No. 436 to No. 60-128439, No. 60-1
No. 98540, No. 60-181742, No. 61-25
No. 9253, No. 62-244444, No. 62-131
From 253 to 62-131256, there are reducing agents and reducing agent precursors described in EP 220746A2, pages 78 to 96 and the like.

Various combinations of reducing agents such as those disclosed in US Pat. No. 3,039,869 can also be used.

When a diffusion-resistant reducing agent is used, an electron transfer agent and / or an electron transfer agent may be used, if necessary, to promote electron transfer between the diffusion-resistant reducing agent and the developable silver halide.
Alternatively, an electron transfer agent precursor can be used in combination.

The electron transfer agent or its precursor can be selected from the above-mentioned reducing agents or its precursors. It is desirable that the mobility of the electron transfer agent or its precursor is higher than that of the diffusion-resistant reducing agent (electron donor). A particularly useful electron transfer agent is 1-phenyl-3-
Pyrazolidones or aminophenols.

The non-diffusible reducing agent (electron donor) used in combination with the electron transfer agent may be any one which does not substantially move in the layer of the photosensitive material among the above-mentioned reducing agents.
Preferred are hydroquinones, sulfonamidophenols, sulfonamidonaphthols, and JP-A-53-11.
Compounds described as electron donors in No. 0827 and dye-donating compounds having a diffusion-resistant and reducing property described later are exemplified.

In the present invention, the amount of the reducing agent added is preferably 0.001 to 20 mol, particularly preferably 0.1 to 1 mol, per mol of silver.
01 to 10 mol.

When the dye-donating compound (also referred to as a dye-donating substance) used in the present invention is reduced to silver ions under a high-temperature condition, its diffusivity (corresponding to this reaction or inversely) is increased. (Mobile) A compound that forms or releases a dye.

Examples of the dye-donating compounds usable in the present invention include compounds (couplers) which form a dye by an oxidative coupling reaction. The coupler may be a 4-equivalent coupler or a 2-equivalent coupler. Further, a 2-equivalent coupler which has a diffusion-resistant group as a leaving group and forms a diffusible dye by an oxidative coupling reaction is also preferable. The diffusion resistant group may form a polymer chain. Examples of color developers and couplers are THJames
"The Theory of the Photographic Process" 4th edition 2
Pages 91 to 334, and pages 354 to 361,
-123533, 58-149046, 58-
No. 149047, No. 59-111148, No. 59-1
No. 24399, No. 59-174835, No. 59-23
No. 1539, No. 59-231540, No. 60-295
Nos. 0, 60-2951, 60-14242, 60-23474, and 60-66249.

Examples of other dye-donating compounds include:
Compounds having a function of releasing or diffusing a diffusible dye in an image form can be mentioned. This type of compound can be represented by the following general formula [LI].

(Dye-Y) n-Z [LI]

Dye represents a dye group, a temporarily shortened dye group or a dye precursor group, Y represents a simple bond or linking group, and Z corresponds to a photosensitive silver salt having an image-like latent image. Alternatively, the diffusivity of the compound represented by (Dye-Y) nZ may be changed in the opposite manner, or Dye may be released and the released Dye and (Dye-Y) nZ may be separated. Represents a group having such a property as to cause a difference in diffusibility therebetween, and n represents 1 or 2, and when n is 2, two Dye-Ys may be the same or different.

Specific examples of the dye-donating compound represented by the general formula [LI] include the following compounds. The following (1) to (4) are to form a diffusible dye image (positive dye image) in reverse correspondence to the development of silver halide, and "(1)" is to form a diffusible dye image (positive dye image) in (A negative dye image).

US Pat. Nos. 3,134,764 and 336, US Pat.
No. 2819, No. 3597200, No. 3544545
No. 3,482,972. A dye developer in which a hydroquinone-based developer and a dye component are linked. This dye developer is diffusible in an alkaline environment, but becomes non-diffusible when reacted with silver halide.

As described in US Pat. No. 4,503,137, a non-diffusible compound which releases a diffusible dye in an alkaline environment but loses its ability when reacted with silver halide can be used. For example, US Pat.
Compounds capable of releasing a diffusible dye by an intramolecular nucleophilic substitution reaction described in US Pat.
Compounds which release a diffusible dye by an intramolecular reversal reaction of an isoxazolone ring described in JP-A No. 54, etc.

US Pat. No. 4,559,290, European Patent No. 220746A2, US Pat. No. 4,783,396,
As described in JP-A-87-6199, a non-diffusible compound that reacts with a reducing agent remaining without being oxidized by development to release a diffusible dye can also be used.

As an example, US Pat.
Nos. 9 and 4139379, JP-A-59-185333.
And compounds which release a diffusible dye by a nucleophilic substitution reaction in the molecule after reduction described in U.S. Pat. No. 4,232,107, and JP-A-59-84453.
-101649, 61-88257, RD240
No. 25 (1984) and the like, compounds which release a diffusible dye by an intramolecular electron transfer reaction after reduction, West German Patent No. 308588A, JP-A-56-14.
No. 2530, U.S. Pat. Nos. 4,434,893 and 4,619.
No. 8450, etc., compounds which release a diffusible dye by cleavage of a single bond after reduction, US Pat.
Examples include a nitro compound which releases a diffusible dye after electron acceptance described in JP-A-223 No. 223 and the like, and a compound which releases a diffusible dye after electron acceptance described in US Pat. No. 4,609,610 and the like.

Further, as more preferable examples, European Patent No. 220746A2, Japanese Patent Publication No. 87-6199, US Pat. No. 4,783,396, and JP-A-63-201653 are preferred.
In one molecule described in JP-A-63-201654 and the like.
Compounds having an -X bond (X represents an oxygen, sulfur or nitrogen atom) and an electron-withdrawing group, Japanese Patent Application No. 62-106885.
SO ₂ -X (X is as defined above) in one molecule described in
And compounds having an electron-withdrawing group, JP-A-63-2713
No. 44, a compound having a PO-X bond (X is as defined above) and an electron-withdrawing group in one molecule.
Compounds having a C—X ′ bond (X ′ has the same meaning as X or —SO ₂ —) and an electron-withdrawing group in one molecule described in No. 271341 can be mentioned. In addition, Japanese Patent Application No. 62
No. 3,319,891 and JP-A-62-320977, compounds capable of releasing a diffusible dye by cleavage of a single bond after reduction by a π bond conjugated to an electron accepting group can also be used.

Of these, compounds having an NX bond and an electron-withdrawing group in one molecule are particularly preferred. Examples thereof are EP 220746A2 or U.S. Pat.
No. 96, compounds (1) to (3), (7) to
(10), (12), (13), (15), (23)-
(26), (31), (32), (35), (40),
(41), (44), (53)-(59), (64),
(70), Compounds (11) to of Published Technical Report 87-6199
(23).

Compounds having a diffusible dye as a leaving group and releasing a diffusible dye upon reaction with an oxidized reducing agent (DDR coupler). Specifically, British Patent No. 1,330,524, JP-B-48-39165, U.S. Patent Nos. 3,443,940, 4,474,867, and 448
No. 3914 and the like.

Compounds (DRR compounds) which are reducible to silver halides or organic silver salts and release diffusible dyes when the partner is reduced. Since this compound does not need to use another reducing agent, it is preferable because there is no problem of image contamination due to oxidized decomposition products of the reducing agent. Representative examples are U.S. Pat. Nos. 3,923,312, 4,053,312 and 405.
Nos. 5428 and 4336322, JP-A-59-658.
No. 39, No. 59-69839, No. 53-3819,
Nos. 51-104343, RD17465, U.S. Pat. Nos. 3,725,062, 3,728,113 and 3,443.
No. 939, JP-A-58-11637 and JP-A-57-17.
No. 9840, U.S. Pat. No. 4,500,626, and the like. Specific examples of the DRR compound include the compounds described in the above-mentioned U.S. Pat. No. 4,500,626, columns 22 to 44. Among them, compounds (1) to (3) described in the aforementioned U.S. Pat. (10) to (13), (1
6) to (19), (28) to (30), (33) to (3)
5), (38) to (40), and (42) to (64) are preferable. The compounds described in U.S. Pat. No. 4,639,408 at columns 37 to 39 are also useful.

Other examples of the above-mentioned couplers and dye-donating compounds other than the general formula [LI] include dye silver compounds in which an organic silver salt is combined with a dye (Research Disclosure Magazine, May 1978, pp. 54-58). Azo dyes used in the heat-developed silver dye bleaching method (U.S. Pat.
957, Research Disclosure Magazine, 1976
April, pp. 30-32), leuco dyes (U.S. Pat. Nos. 3,985,565 and 4,022,617) can also be used.

A hydrophobic additive such as a dye-donating compound or a nondiffusible reducing agent can be introduced into a layer of a light-sensitive material by a known method such as the method described in US Pat. No. 2,322,027. In this case, JP-A-59-83154,
59-178451, 59-178452, 59-178453, 59-178454, 5
A high boiling organic solvent as described in JP-A Nos. 9-178455 and 59-178457 may be used, if necessary, with a boiling point of 50 ° C.
It can be used in combination with a low-boiling organic solvent of up to 160 ° C.

The amount of the high-boiling organic solvent is 10 g or less, preferably 5 g or less, per 1 g of the dye-providing compound used. Also, 1 cc or less, more preferably 0.5 cc or less, especially 0.3 cc or less is suitable for 1 g of the binder.

JP-B-51-39853 and JP-A-51-39853
A dispersion method using a polymer described in No. 59943 can also be used.

In the case of a compound which is substantially insoluble in water, it can be dispersed and contained as fine particles in a binder in addition to the above method.

In dispersing the hydrophobic compound in the hydrophilic colloid, various surfactants can be used. For example, JP-A-59-157636, (37) to (38)
The surfactants listed on the page can be used.

In the present invention, a compound capable of activating development and simultaneously stabilizing an image can be used in the light-sensitive material. Specific compounds preferably used are described in U.S. Pat. No. 4,500,626, columns 51 to 52.

In a system for forming an image by diffusion transfer of a dye, a dye fixing element is used together with a photosensitive material. The dye-fixing element may be in the form of being separately coated on a support separate from the light-sensitive material, or in the form of being coated on the same support as the light-sensitive material. As for the relationship between the photosensitive material and the dye fixing element, the relationship with the support, and the relationship with the white reflective layer, the relationship described in column 57 of US Pat.

The dye fixing element preferably used in the present invention has at least one layer containing a mordant and a binder. As the mordant, those known in the field of photography can be used, and specific examples thereof are described in U.S. Pat. No. 4,500,626, columns 58 to 59 and JP-A-61-88256, No. (32) to U.S. Pat.
(41) Mordant described on page 41, JP-A-62-244043
And Nos. 62-244036. Further, a dye-receiving polymer compound as described in U.S. Pat. No. 4,463,079 may be used. A protective layer, a release layer,
An auxiliary layer such as an anti-curl layer can be provided. It is particularly useful to provide a protective layer.

In the constituent layers of the light-sensitive material and the dye-fixing element, a plasticizer, a slipping agent, or a high-boiling organic solvent can be used as an agent for improving the releasability of the light-sensitive material and the dye-fixing element. Specific examples include (2) of JP-A-62-253159.
5), pages 62-245253 and the like.

Further, various silicone oils (all silicone oils from dimethyl silicone oil to modified silicone oil obtained by introducing various organic groups into dimethyl siloxane) can be used for the above purpose. As examples thereof, various modified silicone oils described in "Modified Silicone Oil" Technical Document P6-18B issued by Shin-Etsu Silicone Co., Ltd., particularly carboxy-modified silicone (trade name: X-22-3710) are effective.

Also, JP-A-62-215953 and 63-159
No. 46449 is also effective.

An anti-fading agent may be used in a light-sensitive material or a dye-fixing element. Anti-fading agents include, for example, antioxidants, ultraviolet absorbers, or certain metal complexes.

Examples of the antioxidant include chroman compounds, coumaran compounds, phenol compounds (eg, hindered phenols), hydroquinone derivatives, hindered amine derivatives, and spiroindane compounds. The compounds described in JP-A-61-159644 are also effective.

Examples of the ultraviolet absorber include benzotriazole compounds (US Pat. No. 3,533,794),
Thiazolidone-based compounds (US Pat. No. 3,352,681, etc.) and benzophenone-based compounds (JP-A-46-2784)
No. JP-A-54-48535 and JP-A-64-28535.
There are compounds described in JP-A-1366641, JP-A-61-88256 and the like. Further, ultraviolet absorbing polymers described in JP-A-62-260152 are also effective.

As the metal complex, US Pat.
No. 55, No. 4245018, Columns 3-36, No. 4254
195, columns 3-8, JP-A-62-174741, JP-A-61-88256, pp. 27-29, 63-1
No. 99248, JP-A-1-75568 and 1-742
No. 72 and the like.

Examples of useful discoloration inhibitors are described in JP-A-62-21.
No. 5272, pages (125) to (137). An anti-fading agent for preventing fading of the dye transferred to the dye-fixing element may be contained in the dye-fixing element in advance, or may be supplied to the dye-fixing element from the outside such as a photosensitive material. .

The above antioxidants, ultraviolet absorbers and metal complexes may be used in combination.

A fluorescent whitening agent may be used for the light-sensitive material and the dye fixing element. In particular, it is preferable to incorporate a fluorescent whitening agent into the dye-fixing element or to supply it from outside such as a photosensitive material. For example, K. Veenkataraman ed., "The Chemis
try of Synthetic Dyes ", Volume V, Chapter 8, JP-A-61-
No. 143752 and the like. More specifically, a stilbene compound, a coumarin compound, a biphenyl compound, a benzoxazolyl compound, a naphthalimide compound, a pyrazoline compound, a carbostyril compound, and the like can be given. The fluorescent whitening agent can be used in combination with an anti-fading agent.

Examples of the hardening agent used in the constituent layers of the light-sensitive material and the dye-fixing element include US Pat. No. 4,678,739 No. 41.
Column, JP-A-59-116655 and JP-A-62-24526.
No. 1, No. 61-18942 and the like. More specifically, aldehyde hardeners (such as formaldehyde), aziridine hardeners, epoxy hardeners, and vinyl sulfone hardeners (N, N'-ethylene-bis (vinylsulfonylacetamide)) Ethane), N-
Methylol-based hardeners (such as dimethylol urea) and polymer hardeners (compounds described in JP-A-62-234157) can be mentioned.

In the constituent layers of the light-sensitive material and the dye-fixing element, various surfactants can be used for the purpose of coating aid, improving releasability, improving slipperiness, preventing static charge, and promoting development. Specific examples of the surfactant are described in JP-A-62-173463.
And No. 62-183457.

The constituent layers of the light-sensitive material and the dye-fixing element may contain an organic fluoro compound for the purpose of improving sliding property, preventing static charge, improving releasability, and the like. Representative examples of organic fluoro compounds include JP-B-57-9053, columns 8 to 17,
JP-A-61-20944, JP-A-62-135826, etc., such as fluorine-based surfactants, or oil-like fluorine-based compounds such as fluorine oil or solid fluorine compound resins such as tetrafluoroethylene resin, etc. And hydrophobic fluorine compounds.

A matting agent can be used for the light-sensitive material and the dye fixing element. Examples of the matting agent include silicon dioxide, polyolefin and polymethacrylate.
JP-A-63-274944 such as benzoguanamine resin beads, polycarbonate resin beads, and AS resin beads in addition to the compounds described on page 1-88256 (29).
And No. 63-274952.

In addition, the constituent layers of the light-sensitive material and the dye-fixing element may contain a heat solvent, an antifoaming agent, an antibacterial and antibacterial agent, colloidal silica, and the like. Specific examples of these additives are described in JP-A-61-88256, pages (26) to (32).

In the present invention, an image formation accelerator can be used in the light-sensitive material and / or the dye-fixing element.
Examples of the image formation accelerator include the promotion of a redox reaction between a silver salt oxidizing agent and a reducing agent, the promotion of a reaction such as the formation of a dye from a dye-providing substance or the decomposition or release of a diffusible dye, and the photosensitive material layer. From the physicochemical function to bases or base precursors, nucleophilic compounds, high-boiling organic solvents (oils), thermal solvents, surfactants, silver Or, it is classified into a compound having an interaction with silver ions. However, these substance groups generally have a composite function and usually have some of the above-mentioned promoting effects. Details of these are described in U.S. Pat. No. 4,678,739, columns 38-40.

Examples of the base precursor include salts of an organic acid and a base which are decarboxylated by heat, compounds which release amines by an intramolecular nucleophilic substitution reaction, Lossen rearrangement or Beckmann rearrangement, and the like. An example is described in US Pat.
93 and JP-A-62-65038.

In a system in which thermal development and transfer of a dye are carried out simultaneously in the presence of a small amount of water, it is preferable to include a base and / or a base precursor in the dye-fixing element from the viewpoint of improving the storability of the light-sensitive material.

In addition to the above, European Patent Publication No. 210660
No. 4,740,445, a combination of a compound which is capable of forming a complex with a metal ion constituting the hardly soluble metal compound (referred to as a complex-forming compound), and JP-A-61-232451. Compounds that generate a base by electrolysis described in the above item can also be used as the base precursor. In particular, the former method is effective. The sparingly soluble metal compound and the complex forming compound are advantageously added separately to the light-sensitive material and the dye-fixing element.

In the present invention, various development stopping agents can be used in the light-sensitive material and / or the dye-fixing element for the purpose of always obtaining a constant image with respect to fluctuations in processing temperature and processing time during development.

The term "development terminator" used herein means that after proper development,
It is a compound that quickly neutralizes a base or reacts with a base to reduce the base concentration in the film and stop development, or a compound that interacts with silver and a silver salt to suppress development. In particular,
Examples include an acid precursor that releases an acid when heated, an electrophilic compound that causes a substitution reaction with a coexisting base when heated, or a nitrogen-containing heterocyclic compound, a mercapto compound, and a precursor thereof. For further details, see JP-A-62-2531.
No. 59, pages (31) to (32).

In the present invention, as the support for the light-sensitive material and the dye-fixing element, those which can withstand the processing temperature are used. Generally, paper, synthetic polymer (film)
Is mentioned. Specifically, it is made of polyethylene terephthalate, polycarbonate, polyvinyl chloride, polystyrene, polypropylene, polyimide, celluloses (for example, triacetylcellulose), or films containing pigments such as titanium oxide, and polypropylene. For example, mixed paper made from synthetic resin pulp such as polyethylene and natural pulp, Yankee paper, baryta paper, coated paper (especially cast-coated paper), metal, cloth, glass and the like are used.

These can be used alone,
It can also be used as a support laminated on one or both sides with a synthetic polymer such as polyethylene.

In addition, the supports described in JP-A-62-253159, pages (29) to (31) can be used.

On the surface of these supports, a hydrophilic binder and a semiconductive metal oxide such as alumina sol or tin oxide,
Carbon black or another antistatic agent may be applied.

As a method of exposing and recording an image on a photosensitive material, for example, a method of directly photographing a landscape or a person using a camera or the like, a method of exposing through a reversal film or a negative film using a printer or a enlarger, A method of scanning and exposing an original image through a slit or the like using an exposure device of a copying machine, a method of exposing image information by emitting light from a light emitting diode or various lasers via an electric signal, a method of exposing image information to a CRT, a liquid crystal display, There is a method of outputting an image to an image display device such as an electroluminescence display or a plasma display and exposing the image directly or via an optical system.

As a light source for recording an image on a photosensitive material,
As noted above, U.S. Pat. No. 4 for natural light, tungsten lamps, light emitting diodes, laser light sources, CRT light sources, etc.
The light source described in 50626, column 56 can be used.

Further, image exposure can be performed using a wavelength conversion element in which a non-linear optical material and a coherent light source such as laser light are combined. Here, the non-linear optical material is a material that can exhibit nonlinearity between polarization and electric field that appears when a strong optical electric field such as laser light is applied, such as lithium niobate and potassium dihydrogen phosphate (KD).
P), inorganic compounds such as lithium iodate, BaB ₂ O ₄ , and urea derivatives, nitroaniline derivatives, for example, nitropyridine-N such as 3-methyl-4-nitropyridine-N-oxide (POM) -Oxide derivatives, JP-A-61-53462 and JP-A-62-121032.
The compounds described in (1) are preferably used. As a form of the wavelength conversion element, a single crystal optical waveguide type, a fiber type, and the like are known, and any of them is useful.

In addition, the image information is a video camera,
Image signals obtained from electronic still cameras, television signals represented by the Nippon Television Signal Standards (NTSC),
An image signal obtained by dividing an original image into a large number of pixels such as a scanner, and an image signal created using a computer represented by CG and CAD can be used.

The light-sensitive material and / or the dye-fixing element
A form having a conductive heating element layer as a heating means for heat development or diffusion transfer of a dye may be used. The transparent or opaque heating element in this case is disclosed in
What is described in -145544 specification etc. can be utilized.
Note that these conductive layers also function as antistatic layers.

The heating temperature in the heat development step is about 50 ° C. to about 2 ° C.
Developable at 50 ° C, especially about 80 ° C to about 180 ° C
Is useful. The dye diffusion transfer step may be performed simultaneously with the heat development, or may be performed after the heat development step.
In the latter case, the heating temperature in the transfer step can be transferred in the range from the temperature in the heat development step to room temperature.
As described above, the temperature is more preferably about 10 ° C. lower than the temperature in the heat development step.

Although the transfer of the dye is caused only by heat,
Solvents may be used to promote dye transfer. Also,
As described in detail in JP-A-59-218443 and JP-A-61-238056, it is also useful to carry out development and transfer simultaneously or continuously by heating in the presence of a small amount of a solvent (particularly water). is there. In this method, the heating temperature is 50 ° C.
The boiling point of the solvent is preferably equal to or lower than the above. For example, when the solvent is water, the temperature is preferably from 50 ° C to 100 ° C.

Examples of the solvent used for accelerating the development and / or transferring the diffusible dye to the dye fixing layer include water or a basic aqueous solution containing an inorganic alkali metal salt or an organic base (these bases). Examples thereof include those described in the section of the image formation accelerator). In addition, a low-boiling solvent or a mixed solution of a low-boiling solvent and water or a basic aqueous solution can also be used. Further, a surfactant, an antifoggant, a sparingly soluble metal salt and a complex-forming compound may be contained in the solvent.

These solvents can be used by a method for imparting them to the dye fixing element, the light-sensitive material, or both.
The amount used may be as small as not more than the weight of the solvent corresponding to the maximum swelling volume of the entire coating film (especially not more than the weight of the solvent corresponding to the maximum swelling volume of the entire coating film minus the weight of the entire coating film).

As a method for imparting a solvent to the photosensitive layer or the dye fixing layer, there is, for example, a method described in JP-A-61-147244, page 26. Further, the solvent can be used by being incorporated in the light-sensitive material or the dye-fixing element or both in advance, for example, by enclosing the solvent in microcapsules.

In order to promote dye transfer, a system in which a hydrophilic heat solvent which is solid at normal temperature and dissolves at high temperature is incorporated in the light-sensitive material or dye-fixing element can be adopted. The hydrophilic thermal solvent may be incorporated in either the photosensitive material or the dye fixing element, or may be incorporated in both. The layer to be incorporated may be any of an emulsion layer, an intermediate layer, a protective layer and a dye-fixing layer, but is preferably incorporated in the dye-fixing layer and / or an adjacent layer. Examples of hydrophilic thermal solvents include ureas, pyridines, amides, sulfonamides, imides, alcohols, oximes, and other heterocycles.

In order to promote dye transfer, a high-boiling organic solvent may be contained in the light-sensitive material and / or the dye-fixing element.

As a heating method in the developing and / or transferring step, a heating block or a plate is contacted, or a hot plate, a hot presser, a heat roller, a halogen lamp heater, an infrared or far infrared lamp heater, or the like is contacted. Or passing through a high temperature atmosphere.

A photosensitive element and a dye-fixing element are overlapped,
Japanese Patent Application Laid-Open No. Sho 6
The method described on page 1-127244 (27) can be applied.

For processing the photographic element of the present invention, any of various heat developing apparatuses can be used. For example, JP-A-59-7
No. 5247, No. 59-177547, No. 59-181
No. 353, No. 60-18951, Shokai 62-259
An apparatus described in No. 44 or the like is preferably used.

[0190]

The present invention will be specifically described below with reference to examples.

Example 1 A method for preparing the emulsion (1) will be described. Solution I and Solution II shown in Table 2 were simultaneously added to a well-stirred aqueous gelatin solution (composition is shown in Table 1) over 18 minutes. Five minutes after the addition of the solution I, the solutions III and IV shown in Table 2 were simultaneously added over 42 minutes. After washing with water (pH = 4.1) using the precipitant (P-1) shown in Chemical formula 19, 22 g of gelatin was added, and an aqueous solution of NaCl and NaOH was added to obtain pH = 6.
1. Adjusted to pAg = 7.6 (measured at 40 ° C.) and redispersed. Thereafter, triethylthiourea and 4-hydroxy-
Optimal chemical sensitization at 6O <0> C with 6-methyl- (1,3,3a, 7) -tetrazaindene. The optimum is a condition under which the sensitivity is maximized in a range where no fog occurs.
The resulting emulsion was a cubic emulsion having an average grain size of 0.26 µm, and the yield was 635 g. This emulsion was a monodisperse emulsion having a coefficient of variation of 8.5%.

[0192]

[Table 1]

[0193]

[Table 2]

Compound A in Table 1 is shown in Chemical Formula 21.

[0195]

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Next, a method for preparing a gelatin dispersion of a dye-providing substance will be described.

14.64 g of the magenta dye-donating substance (A) shown in Chemical formula 22, and 0.81 of the reducing agent shown in Chemical formula 26
g, 0.20 g of the mercapto compound (1) shown in Chemical formula 27
0.38 g of the surfactant (3) and 5.1 g of the high boiling organic solvent (2) shown in Chemical formula 28 were weighed, and 70 ml of ethyl acetate was weighed.
Was added and dissolved by heating at about 60 ° C. to obtain a uniform solution.
This solution, 100 g of a 10% solution of lime-processed gelatin and 60 ml of water were stirred and mixed, and then dispersed with a homogenizer at 10,000 rpm for 10 minutes. This dispersion is referred to as a magenta dye-donating substance dispersion.

A cyan dye-donating substance (B
₁ ), 7.3 g of the cyan dye-donor substance (B ₂ ) shown in Chemical formula 24, and 1.0 g of the reducing agent shown in Chemical formula 26.
0.3 g of the mercapto compound (1) shown in Chemical formula 27;
0.38 g of the surfactant (3) and 9.8 g of the high-boiling organic solvent (1) shown in Chemical formula 28 were weighed, and 50 ml of ethyl acetate was added, and the mixture was heated and dissolved at about 60 ° C. to obtain a uniform solution. This solution, 100 g of a 10% solution of lime-processed gelatin and 60 parts of water
After stirring and mixing with a homogenizer for 10 minutes,
Dispersed at 0000 rpm. This dispersion is referred to as a cyan dye-donating substance dispersion.

18.75 g of the yellow dye-providing substance (C) shown in Chemical formula 25 and 1.0 g of the reducing agent shown in Chemical formula 26
0.12 g of the mercapto compound (1) shown in Chemical formula 27
1.5 g of the surfactant (3), 7.5 g of the high-boiling organic solvent (1), 2.1 g of the dye (F) shown in Chemical formula 29, and 45 ml of ethyl acetate were added. About 60 ° C
To make a homogeneous solution. This solution, 100 g of a 10% solution of lime-processed gelatin and 60 ml of water were stirred and mixed, and then homogenized for 10 minutes at 10,000 rpm.
Was dispersed. This dispersion is referred to as a yellow dye-providing substance dispersion.

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[0201]

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[0202]

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[0203]

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[0204]

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[0205]

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[0206]

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[0207]

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The high-boiling organic solvents (1) and (2) in the above are as follows. High boiling organic solvent (1): triisononyl phosphate High boiling organic solvent (2): trihexyl phosphate

Thus, the heat-developable color light-sensitive materials 100 shown in Tables 3 and 4 can be formed. The sensitizing dye was added when preparing the coating solution. This sensitizing dye amount is
Optimized for highest sensitivity.

[0210]

[Table 3]

[0211]

[Table 4]

The surfactants (1), (2) and (4) in Tables 3 and 4 are those shown in Chemical formula 28.
The mercapto compound (2) is shown in Chemical formula 30. Further, the hardener is represented by Chemical Formula 31, the stabilizer (1) is represented by Chemical Formula 32, and the sensitizing dyes (1), (2), and (3) are represented by Chemical Formulas 33, 34, and 35, respectively. 1) is shown in Chemical formula 36, respectively. Antifoggant (1) is benzotriazole.

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[0216]

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[0219]

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[0218]

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[0219]

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Emulsion of the third layer of the light-sensitive material 100 (1)
In the above, triethylthiourea and 4-hydroxy-6
After the addition of methyl- (1,3,3a, 7) -tetrazaindene, the sensitizing dye (A) shown in Chemical formula 37 was added, and the mixture was stirred at 70 ° C. for 30 minutes. At the time of coating, the sensitizing dye (2) was removed to prepare a photosensitive material 101 of Comparative Example. The addition amount of the sensitizing dye (A) was 5.0 × 10 ⁻⁴ g / m ^{2 in} terms of coating amount.
Met.

[0221]

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Preparation of the light-sensitive material of the present invention Except that the sensitizing dye (A) was changed to the sensitizing dye D-38 shown in Chemical formula 10 in the emulsion of the third layer of the light-sensitive material 101, it was exactly the same as the light-sensitive material 101. And the photosensitive material 10
2 was created. The addition amount of the sensitizing dye is 7.
It was 0 × 10 ⁻⁴ g / m ² .

In the emulsion of the third layer of the photosensitive material 102,
Photosensitive material 1 except that sensitizing dye D-38 of Chemical Formula 10 was added, and the mixture was stirred for 30 minutes and then triethylthiourea was added.
Photosensitive material 103 was prepared in exactly the same manner as in No. 02.

In emulsion (1) of the third layer, solution III and solution IV
After the addition to the solution was completed, the temperature was raised to 75 ° C.
After addition of -methyl- (1,3,3a, 7) -tetraazaindene, 0.270 g of sensitizing dye D-
Emulsion (2) was prepared exactly in the same manner as Emulsion (1) except that No. 38 was added and the mixture was stirred for 30 minutes. A light-sensitive material 104 was prepared in exactly the same manner as the light-sensitive material 101 except that the emulsion (2) was used as the third layer emulsion.

In the emulsion of the third layer of the photosensitive material 102,
A photographic material 105 was prepared in exactly the same manner as the photographic material 102 except that the sensitizing dye D-38 in Chemical Formula 10 was changed to the sensitizing dye D-17 in Chemical Formula 7. The amount of the sensitizing dye added was 8.50 × 10 ⁻⁴ g / m ² in terms of coating amount.

A photosensitive material 106 was prepared in exactly the same manner as in the photosensitive material 105 except that the sensitizing dye D-17 in Chemical Formula 7 was changed to D-21 in Chemical Formula 7. The amount of the sensitizing dye added is
The application amount was 8.50 × 10 ⁻⁴ g / m ² .

In the emulsion of the third layer of the photosensitive material 102,
The sensitizing dye D-38 of Chemical Formula 10 is replaced with the sensitizing dye D-60 of Chemical Formula 17
A light-sensitive material 107 was prepared in exactly the same manner as the light-sensitive material 102, except that the light-sensitive material was changed to. The amount of the sensitizing dye added was 8.5 × 10 ⁻⁴ g / m ² as a coating amount.

In the light-sensitive material 102, a light-sensitive material 108 was prepared in exactly the same manner as in the light-sensitive material 100 except that the sensitizing dye D-38 of Chemical Formula 10 was added at the time of coating. The added amount of the sensitizing dye was 7 × 10 ⁻⁴ g in the amount of coating.
/ M ² .

In the emulsion of the third layer of the photosensitive material 101,
A photosensitive material 109 of Comparative Example was prepared in exactly the same manner as the photosensitive material 101 except that the sensitizing dye (A) was changed to the sensitizing dye (B) shown in Chemical formula 37. The amount of the sensitizing dye added was 8.50 × 10 ⁻⁴ g / m ² in terms of coating amount.

In the emulsion of the third layer of the photosensitive material 109,
A photographic material 110 was prepared in exactly the same manner as the photographic material 109 except that the sensitizing dye (B) was changed to the sensitizing dye D-5 in Chemical formula 6.

In the emulsion of the third layer of the photosensitive material 110,
The sensitizing dye D-5 in Chemical formula 6 was replaced with the sensitizing dye D-13 in Chemical formula 7, except that the sensitizing dye D-13 was changed to the sensitizing dye D-13.
11 was created.

In the photosensitive materials 101 to 111,
The amount of the sensitizing dye to be added is 50% to 100% of the amount of the adsorption saturated coating.
Range.

Next, a method for producing the dye fixing material will be described.

The composition was coated on a paper support laminated with polyethylene in the composition shown in Table 5 to prepare a dye fixing material.

[0235]

[Table 5]

The compounds used in Table 5 were those represented by Chemical Formula 38 as silicone oils and Chemical Formulas 3 as surfactants.
No. 9; those shown in Chemical Formula 40 as mordants; and those shown in Chemical Formula 41 as hardening agents.

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The polymers * 5 and * 7, the high-boiling organic solvent * 8, and the matting agent * 10 are shown below. Polymer * 5 Vinyl alcohol-sodium acrylate copolymer (75/25 molar ratio) Polymer * 7 Dextran (molecular weight 70,000) High boiling organic solvent * 8 Leophos 95 (Ajinomoto Co., Inc.)
Matting agent * 10 Benzoguanamine resin (18vol% of particles exceeding 10μ)

Next, evaluation was made by the following exposure and processing. Using the laser exposure device described in JP Hei 2-129625, exposure under the conditions shown in Table 6, the water of 12 cc / m ² was supplied with a wire bar on the emulsion surface of the exposed light-sensitive material,
Thereafter, the dye-fixing material and the film surface were overlaid so that they were in contact with each other. After heating for 20 seconds using a heat drum whose temperature was adjusted so that the temperature of the water-absorbing film became 90 ° C., the dye-fixing material was peeled off from the photosensitive material to obtain an image on the dye-fixing material. The spectral sensitivity was measured by exposing each photosensitive material to a series of monochrome light through a wedge for 5 seconds and performing the same processing as described above.

[0243]

[Table 6]

The transfer density was measured with a self-recording densitometer, and the fog and sensitivity (reciprocal of reversal of the exposure amount giving fog + 1.0) were determined.

The raw storage stability was evaluated by comparing the photographic performance of the one immediately after coating with the one stored at 60 ° C. and 60% RH for 3 days after coating.

The degree of color separation is the exposure amount that gives a density of (Dmax−0.1) for yellow by exposure at 810 nm.
log E1 and cyan (Dmin +
Difference from the exposure log E2, which gives a density of 0.1), log E
= Log E1-log E2. The smaller the value (negative value), the better the color separation.

By the above method, the light-sensitive materials 100 to 11
About 1, the spectral sensitivity, sensitivity, fog,
The color separation was measured and summarized in Table 7.

Table 7 shows the wavelength (λmax) at which the third layer provides the maximum spectral sensitivity, and the ratio (S1) of the spectral sensitivity (S ₁ ) to the light having a wavelength longer than this λmax by 20 nm to the maximum spectral sensitivity (S ₀ ). ₁ / S ₀ ). The sensitivity is shown as a relative sensitivity based on the sensitivity of the photosensitive material 100 immediately after coating as 100.

[0249]

[Table 7]

From the results shown in Table 7, it can be seen that the photosensitive material of the present invention has high sensitivity, excellent raw storage stability, and excellent color separation.

In the third layer of the photosensitive material 100,
The timing of adding the sensitizing dye (2) is determined by the photosensitive materials 101, 103,
Photosensitive materials which were changed in accordance with Example No. 104 were prepared, and the same processing and evaluation were performed. As a result, a result equivalent to that of the photosensitive material 100 was obtained.

In the third layer of the photosensitive material 101,
Photosensitive materials were prepared by changing the timing of adding the sensitizing dye (A) according to the photosensitive materials 103 and 104, and the same processing and evaluation were performed. As a result, the same result as that of the photosensitive material 101 was obtained.

[0253]

According to the present invention, color separation is excellent. Moreover, it has high sensitivity and excellent raw storage stability.

Continuation of the front page (56) References JP-A-62-262042 (JP, A) JP-A-63-159841 (JP, A) JP-A 64-13546 (JP, A) JP-A-3-296745 (JP) U.S. Pat. No. 4,476,220 (US, A) The Photographic Society of Japan, "Basics of Photographic Engineering-Silver halide photography-", Corona Co. (published January 30, 1979). 182−189 (58) Fields surveyed (Int. Cl. ⁶ , DB name) G03C 8/40 G03C 1/20

Claims (2)

(57) [Claims] 1. A support comprising at least three silver halide emulsion layers having different spectral sensitivities on a support, and when silver ions are reduced to silver at a high temperature, the reaction corresponds to or inversely corresponds to this reaction. A heat-developable color light-sensitive material having at least three layers containing a dye-donating compound that emits or produces dyes having different hues, wherein at least one of the silver halide emulsion layers is
Alternatively, the silver halide emulsion layer contains at least one kind of the thiazicarbocyanine dye represented by Chemical formula 2, and the wavelength of the maximum spectral sensitivity of the silver halide emulsion layer is 700 nm or more and 900 nm or less, and is 20 nm longer than the wavelength of the maximum spectral sensitivity. A heat-developable color light-sensitive material comprising at least one silver halide emulsion spectrally sensitized so that the spectral sensitivity to light having a wavelength is 1/3 or less of the maximum spectral sensitivity. Embedded image Embedded image [In formula 1, Q ₁ and Q ₂ each represent a methylene group, and R ₁ and R ₂ each represent an alkyl group. R ₃ and R ₄ each represent a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, and R ₃ and R ₄ are not simultaneously hydrogen atoms. L ₁ , L ₂ and L ₃ each represent a methine group. A ₁ and A ₂ each represent an atomic group necessary for forming a benzene ring or a naphthalene ring. R ₁ and L ₁ ,
And R ₂ and L ₃ may be bonded to each other to form a ring. M ₁ represents a charge balancing counter ion, and m ₁ represents a value required to neutralize the charge. In the chemical formula 2, R ₁ ,
R ₂ , A ₁ , A ₂ , M ₁ and m ₁ each have the same meaning as in Chemical formula 1. R ₁ and R ₂ may each be bonded to a methine group to form a ring. R ₅ represents an alkyl group, an aryl group or a heterocyclic group. ] 2. A silver halide emulsion which has been spectrally sensitized so that the spectral sensitivity to light having a wavelength longer than 20 nm from the wavelength of the maximum spectral sensitivity of the silver halide emulsion layer is 1/3 or less of the maximum spectral sensitivity. 2. The heat-developable color according to claim 1, which is obtained by performing chemical sensitization in the presence of at least one of the thiazicarbocyanine dyes represented by Chemical Formula 1 or Chemical Formula 2 and a tetraazaindene compound. Photosensitive material.