JP2001117201A - Image forming material, heat developable photographic sensitive material, silver halide photographic sensitive material, image forming method, optical filter and substrate for image forming material such as silver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an image forming material, a heat developable photographic sensitive material and a silver halide photographic sensitive material each using a dye excellent in solubility in an organic solvent and excellent also in suitability to solid dispersion and oil dispersion, having good sharpness, little residual color stain, a favorable cold black tone as the color tone of image silver and good shelf stability and excellent in dry processability, to provide an image forming method for each of the materials, to provide an optical filter having favorable spectral characteristics and to provide a substrate for an image forming material such as a silver halide photographic sensitive material. SOLUTION: The image forming material contains a dye having a transmission density of <0.03 at 420 nm wavelength when the transmission density at the maximum absorption wavelength in methyl ethyl ketone is 1.0.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an image forming material containing a specific dye, a heat-developable photographic light-sensitive material, a silver halide photographic light-sensitive material, an image forming method thereof, an optical filter, and a silver halide photographic light-sensitive material. The present invention relates to a support for an image forming material.

[0002]

2. Description of the Related Art Upon exposure of a photographic light-sensitive material, incident light is reflected and refracted by silver halide, other additives or a layer interface, thereby blurring an image and degrading sharpness. So-called anti-halation to prevent this
(AH) dyes and anti-irradiation (AI) dyes have been widely used.

Conventionally, the performance required for AH and AI dyes is to absorb light of a desired wavelength, not to have an undesired effect on silver halide emulsions, and to completely decolor or flow out during processing. No coloring was left on the photosensitive material.

[0004] In recent years, there has been a remarkable tendency for rapid processing and dry processing, and the problem of so-called residual color stain, in which coloring derived from dyes remains after processing, has increased, and improvement thereof has been strongly demanded. In particular, in the case of the dry treatment using no water for the treatment, no outflow of the dye can be expected at all, and the residual color stain tends to be large, and improvement thereof has been awaited.

[0005] Typical examples of AI and AH dyes are organic dyes, and many compounds have been proposed. Of these, cyanine dyes and oxonol dyes are particularly often used, but all have a large absorption in the visible region and are insufficient in terms of residual color stain because the decomposition product has yellow absorption.
The compounds are relatively unstable and easily decomposed, and have the disadvantage of high cost.

[0006] Squarylium dyes and croconium dyes generally have low solubility in organic solvents, and have drawbacks in that they are difficult to add to silver halide photographic materials and that the spectral absorption characteristics change when dispersed. , The improvement was required.

[0007] Japanese Patent Publication No. 9-509503, Japanese Patent Laid-Open No. 8-2
No. 62986, No. 10-236695, No. 10-10
Nos. 4779, 10-158253 and 10-20
JP-A-4310 proposes a heat-developable photographic material using a squarylium dye having a naphthalene ring, but these dyes are yellowish and have a problem that the residual color stain is large. Further, the disadvantage that the thermal stability of the dye was low and the storage stability of the photosensitive material was low was also apparent. The image forming method described in JP-A-10-24654 is an image forming method called “thermosensitive coloring” in which an image is substantially formed only by exposure to infrared rays, and a latent image is formed by exposure, 2. The method according to claim 1, wherein an image is substantially formed by heat development.
Does not mention at all. As a result of intensive studies, the present inventors have surprisingly found that the color tone of the formed image silver is "cool black tone" which is preferable for appreciation or image diagnosis. In addition, Japanese Patent Application Laid-Open
Since S-1 and S-4 described in JP-A-24654 have four hydroxyl groups in the molecule, they have relatively low solubility in organic solvents, and it is relatively difficult to obtain sufficient antihalation and antiirradiation effects. Met. JP 1
The dyes described in JP-A Nos. 0-36695 and 10-158253 were difficult to produce industrially. The dyes described in JP-A-10-104779 have disadvantages of low solubility in organic solvents and high production cost. "

[0008] A squarylium dye having a thiopyrylium nucleus (herein referred to as a thiopyrylium squarylium dye. Similarly, a squarylium dye having a pyrylium nucleus is herein referred to as a pyrylium squarylium dye) is disclosed in US Patent No. 4,508,811. 5,667,943 and 4,
No. 508,811, there is no suggestion to apply those dyes to silver halide photographic materials, and there is no description suggesting that.

[0009]

An object of the present invention is to use a dye having excellent solubility in an organic solvent, excellent solid dispersion and oil dispersibility, excellent sharpness, low residual color stain,
The color tone of the image silver is preferably "cool black tone", and the image forming material has excellent storage stability and excellent dry processability, a heat-developable photographic light-sensitive material, a silver halide photographic light-sensitive material, and an image forming method thereof. An object of the present invention is to provide an optical filter having preferable spectral characteristics and a support for an image forming material such as a silver halide photographic light-sensitive material.

[0010]

The above objects of the present invention are as follows. An image forming material comprising a dye having a transmission density at 420 nm of less than 0.03 when the transmission density at the maximum absorption wavelength is 1.0 in methyl ethyl ketone;

2. Maximum absorption wavelength is 600 nm or more and 900
The image forming material as described in 1 above, wherein

3. Maximum absorption wavelength is 750nm or more 900
The image forming material as described in 1 above, wherein

4. An image forming material, wherein the transmission density at 420 nm is 0.15 or less when the transmission density at the maximum absorption wavelength after development processing is 1.0;

5. 5. The image forming material as described in any one of the above items 1 to 4, wherein the image forming material contains a silver halide. The image forming material according to any one of the above items 1 to 5, wherein the image forming material contains an organic silver salt.

[0015] 7. An image forming method for forming an image by developing an image forming material after imagewise exposing the image forming material,
An image forming method using the image forming material according to any one of the above 1 to 6,

8. A method for forming an image of a photothermographic material in which a latent image is formed by exposure and subsequently an image is substantially formed by subsequent thermal development, wherein the photothermographic material is the image forming material according to claim 6. 8. a method for forming an image on a heat-developable photographic light-sensitive material, The image-forming material according to any one of the above 1 to 6, wherein the dye is a compound represented by the following general formula 1, 2, 3 or 4.

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"In the formula, A ₁ and B ₁ each represent a substituent excluding a naphthalene group."

[0018]

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"Wherein A ₂ and B ₂ represent a substituent."

[0020]

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In the formula, R _{1 to} R ₄ represent a hydrogen atom or an alkyl group. A ₃ , B ₃ , A ₄ and B ₄ represent a bond between the carbon atom represented by C in the general formula and the carbon Represents a group that can completely overlap the original group when rotated 180 ° about the line connecting the atoms, provided that the sum of the hydroxyl groups of A ₃ and B ₃ is 0 or more and 1 or less; , A ₄ and B ₄ also have a total of 0 or more and 1 or less. ”

10. A heat development method comprising a support having a layer containing at least one of the dyes described in any one of the above 1 to 3 and a water-soluble binder, and being spectrally sensitized to 600 nm or more and 700 nm or less. Image forming materials such as photographic light-sensitive materials,

11. An image-forming material such as a silver halide photographic light-sensitive material, having a layer containing at least one of the dyes according to any one of the above 1 to 3 and a water-soluble binder on a support.

12. Thiopyrylium squarylium dye, thiopyrylium crokonium dye, pyrylium squarylium dye, pyrylium croconium dye, selenapyrylium squarylium dye, selenapyrylium croconium dye, tellropyrilium squarylium dye, and An image forming material such as a silver halide photographic light-sensitive material, comprising a layer containing at least one selected from a ium croconium dye and a water-soluble binder;

13. The image forming material according to any one of 1 to 6, 9 to 12, wherein the image forming material contains a hydrazine compound.

14. An optical filter comprising at least one of the dyes according to any one of the above 1 to 3,

15. A support for an image forming material such as a silver halide photographic light-sensitive material, which comprises at least one of the dyes according to any one of the above 1 to 3,

16. At least one of the dyes represented by the following general formula 1 characterized in that a latent image is formed by exposure and subsequently an image is substantially formed by thermal development.
Image forming method of heat-developable photographic light-sensitive material containing seeds,

[0029]

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"In the formula, A ₁ and B ₁ each represent a substituent excluding a naphthalene group."

17. A photothermographic material comprising a dye represented by the following general formula 2:

[0032]

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"Wherein A ₂ and B ₂ represent a substituent."

18. A silver halide photographic light-sensitive material comprising a dye represented by the following formula (3) or (4).

[0035]

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In the formula, R _{1 to} R ₄ represent a hydrogen atom or an alkyl group. A ₃ , B ₃ , A ₄ and B ₄ represent a bond between the carbon atom represented by C in the general formula and the carbon atom. Represents a group that can completely overlap the original group when rotated 180 ° about the line connecting the atoms, provided that the sum of the hydroxyl groups of A ₃ and B ₃ is 0 or more and 1 or less; , A ₄ and B ₄ also have a total of 0 or more and 1 or less. ”

19. The image forming material such as the silver halide photographic light-sensitive material according to the above 9 or 18, wherein the dye represented by the general formula 3 or 4 is represented by the following general formula 5 or 6:

[0038]

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In the formula, R _{1 to} R ₄ represent a hydrogen atom or an alkyl group. ZA3, ZB3, ZA4, and ZB4 each represent an atomic group necessary for constructing a 6-membered heterocyclic ring together with a carbon atom. "

20. Thiopyrylium squarylium dye, thiopyrylium croconium dye, pyrylium squarylium dye, pyrylium croconium dye, selenapyrylium squarylium dye, selenapyrylium croconium dye, telluropyrylium squarylium dye,
And an image forming material such as a silver halide photographic light-sensitive material, characterized by containing at least one member selected from the group consisting of:

21. Thiopyrylium squarylium dye, thiopyrylium croconium dye, pyrylium squarylium dye, pyrylium croconium dye, selenapyrylium squarylium dye, selenapyrylium croconium dye, telluropyrylium squarylium dye,
And a telluropyrylium croconium dye represented by the following general formula 7
21. An image forming material such as a silver halide photographic light-sensitive material as described in 20 above, which is a compound having a nucleus represented by

[0042]

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Wherein X ₁ and X ₂ are each an oxygen atom,
It represents a sulfur atom, a selenium atom, or a tellurium atom, and R ₅ and R ₆ represent a hydrogen atom or an alkyl group. "

22. Thiopyrylium squarylium dye, thiopyrylium croconium dye, pyrylium squarylium dye, pyrylium croconium dye, selenapyrylium squarylium dye, selenapyrylium croconium dye, telluropyrylium squarylium dye,
And a telluropyrylium croconium dye represented by the following general formula 8
An image forming material such as the silver halide photographic light-sensitive material according to the above 20, which is represented by:

[0045]

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Wherein X ₁ and X ₂ are each an oxygen atom,
It represents a sulfur atom, a selenium atom, or a tellurium atom, and R ₅ and R ₆ represent a hydrogen atom or an alkyl group. R ₇ and R ₈
Represents a monovalent group, and a plurality of R ₇ and R ₈ may combine with each other to form a ring. m and n represent an integer of 0 to 4 "

23. A silver halide photographic light-sensitive material containing at least one solid dispersion or oil dispersion of the dye represented by the general formula 1, general formula 2, general formula 3, general formula 4, general formula 5, or general formula 6. And other image forming materials.

24. Thiopyrylium squarylium dye, thiopyrylium croconium dye, pyrylium squarylium dye, pyrylium croconium dye, selenapyrylium squarylium dye, selenapyrylium croconium dye, telluropyrylium squarylium dye,
And an image forming material such as a silver halide photographic light-sensitive material containing at least one kind of solid dispersion or oil dispersion selected from tellurium pyrroleium croconium dyes.

25. A photothermographic material comprising: a support; and a layer containing at least one dye represented by Formula 1 and a water-soluble binder, and spectrally sensitized to 600 nm or more and 700 nm or less. material,

26. Halogenation characterized by having a layer containing at least one of the dyes represented by the above general formula 2, general formula 3, general formula 4, general formula 5 or general formula 6 and a water-soluble binder on a support. Silver photographic materials,

27. Thiopyrylium squarylium dye, thiopyrylium crokonium dye, pyrylium squarylium dye, pyrylium croconium dye, selenapyrylium squarylium dye, selenapyrylium croconium dye, tellropyrilium squarylium dye, and A silver halide photographic material, comprising a layer containing at least one selected from ium croconium dyes and a water-soluble binder;

28. The photothermographic material according to the above 16, 17, or 25, further comprising a hydrazine compound.

29. The above 18, 19, 20, 21, 22, 23, comprising a hydrazine compound.
24. The silver halide photographic material according to 24, 26 or 27,

(30) The above (1) to (4), (18) or (18), which is spectrally sensitized to a wavelength of not less than 600 nm and not more than 900 nm.
19, 20, 21, 22, 23, 24, 26, 27 or 29, an image forming material such as a silver halide photographic light-sensitive material,

31. Forming an image by heat development after being exposed by a laser beam;
6. The image forming method of the photothermographic material according to 6,

32. 18, 19, 20, 21, 2
The silver halide photographic light-sensitive material according to 2, 23, 24, 26, 27, 29, or 30, wherein an image is formed by exposing the silver halide photographic light-sensitive material to a laser beam, followed by developing. Image forming method,

33. 33. The method for forming an image of a silver halide photographic light-sensitive material according to the above item 32, wherein the development processing is a heat development processing.

34. An image forming material such as a silver halide photographic light-sensitive material, wherein the dye according to any one of the above 1 to 3 and 16 to 30, is a compound represented by the following general formula 11;

[0059]

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In the formula, R ₁ , R ₂ , R ₃ and R ₄ represent an alkyl group which does not substitute an acidic substituent, and R ₅ and R ₆ represent a monovalent substituent. Represents an integer of 0 to 4 "

35. In the general formula 11, R ₁ , R ₂ , R ₃ ,
35. An image-forming material such as a silver halide photographic material as described in 34 above, wherein at least one of R ₄ is an alkoxy-substituted alkyl group or an alkyl group having 5 or more carbon atoms.

36. An optical filter comprising at least one compound represented by the general formula 1, general formula 2, general formula 3, general formula 4, general formula 5, or general formula 6,

37. Thiopyrylium squarylium dye, thiopyrylium croconium dye, pyrylium squarylium dye, pyrylium croconium dye, selenapyrylium squarylium dye, selenapyrylium croconium dye, telluropyrylium squarylium dye,
And an optical filter comprising at least one member selected from telluropyrylium croconium dyes,

38. An image of a silver halide photographic material or the like comprising at least one of the compounds represented by the general formula 1, general formula 2, general formula 3, general formula 4, general formula 5, or general formula 6. Support for forming material,

39. Thiopyrylium squarylium dye, thiopyrylium croconium dye, pyrylium squarylium dye, pyrylium croconium dye, selenapyrylium squarylium dye, selenapyrylium croconium dye, telluropyrylium squarylium dye,
And a support for an image-forming material such as a silver halide photographic light-sensitive material, which comprises at least one member selected from the group consisting of:

[0066]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. The dye used in the present invention has a transmission density of 1.0 at the maximum absorption wavelength in methyl ethyl ketone when the transmission density is 420.
A compound having a transmission density of less than 0.03 in nm. In particular, the maximum absorption wavelength is 600 nm or more and 900 nm or less, particularly, the maximum absorption wavelength is 750 nm or more and 90 nm or less.
0 nm or less. The image forming material of the present invention (all materials capable of forming an image such as a silver halide photographic light-sensitive material and a heat-developable photographic light-sensitive material) has a transmission density of 1.0 at the maximum absorption wavelength after the development processing. At one time, the transmission density at 420 nm is 0.15 or less.
One specific example satisfying such conditions is to incorporate the dye used in the present invention into a support and / or a constituent layer.

The dye used in the present invention is dissolved in methyl ethyl ketone as a solvent, and when the transmission density at the maximum absorption wavelength in this methyl ethyl ketone is 1.0, the transmission density at 420 nm is less than 0.03; Preferably 0.025 or less, more preferably 0.025
2 or less.

The image-forming material of the present invention has a maximum absorption wavelength at the maximum absorption wavelength after being subjected to development processing (all development processing such as black-and-white development, color development, heat development, diffusion transfer development, and reversal development). 420 when the transmission density is 1.0
The transmission density in nm is 0.15 or less, preferably 0.13 or less, more preferably 0.10 or less.
Specific examples of the dye used in the present invention (hereinafter, also referred to as the dye of the present invention) will be described below.

First, the dyes represented by the general formulas 1 and 2 will be described. In the dye represented by the general formula 1 of the present invention, A ₁ and B ₁ each represent a substituent excluding a naphthalene group,
Specific examples of A ₁ and B ₂ represent an alkyl group, an alkenyl group, a cycloalkyl group, a phenyl group, and a heterocyclic group, and are preferably an alkenyl group, a phenyl group, and a heterocyclic group. Particularly preferred is an alkenyl group.

Next, the dye represented by Formula 2 will be described. In the dye represented by the general formula 2 of the present invention, A ₂ ,
B ₂ represents a substituent, and specific examples of A ₂ and B ₂ represent an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, and a heterocyclic group, and preferably an alkenyl group, an aryl group, and a heterocyclic group. Group. Particularly preferred is an alkenyl group.

Next, the dyes represented by the general formulas 3 and 4 will be described. In the dyes represented by the general formulas 3 and 4 of the present invention, A ₃ , B ₃ , A ₄ and B ₄ each represent a line connecting the bonding point with the carbon atom represented by C in the general formula and the carbon atom. Represents a group that can completely overlap the original group when rotated about the axis by 180 °, and a monocyclic 6-membered ring group that satisfies the requirements is preferable. The sum of the hydroxyl groups of A ₃ and B ₃ is 0 or more and 1 or less, and the sum of the hydroxyl groups of A ₄ and B ₄ is also 0 or more and 1 or less. Preferably, the sum of all the hydroxyl groups is 0.

Next, the dyes represented by the general formulas 5 and 6 will be described. In the general formula, ZA3, ZB3, ZA4,
ZB4 represents a group of atoms necessary for constructing a 6-membered hetero ring together with carbon atoms, and the constructed hetero ring may be a monocyclic hetero 6-membered ring containing one hetero atom in the ring. preferable. As the hetero atom, a nitrogen atom and a sulfur atom are preferable.

In the present invention, thiopyrylium squarylium dye, thiopyrylium crokonium dye, pyrylium squarylium dye or pyrylium croconium dye, selenapyrylium squarylium dye, selenapyrylium croconium dye, telluropyrylium squarylium dye, And the telluropyrylium croconium dye is a compound having a thiopyrylium nucleus, a pyrylium nucleus and a squarylium nucleus, a croconium nucleus, a selenapyrylium nucleus, and a telluropyrylium nucleus.

The compound having a squarylium nucleus refers to 1-cyclobutene-2-hydroxy-4- in the molecular structure.
A compound having an chromonium nucleus is a compound having 1-cyclopentene-2-hydroxy-4,5-dione in its molecular structure. here,
The hydroxy group may be dissociated. General formula 7 of the present invention
Represents only the mother nucleus of the dye, and may have an optional substituent.

In the general formula 8 of the present invention, R ₇ and R ₈ each represent a monovalent substituent. There is no particular limitation on the monovalent substituent, but an alkyl group (for example, a methyl group, an ethyl group, an isopropyl group, a tertiary butyl group, a methoxyethyl group,
Methoxyethoxyethyl group, 2-ethylhexyl group, 2
-Hexyldecyl group, benzyl group, etc.), aryl group (e.g., phenyl group, 4-chlorophenyl group, 2,6-dimethylphenyl group, etc.), more preferably alkyl group, and tertiary butyl group. Is particularly preferred. R ₇ and R ₈ may form a ring together. m and n each represent an integer of 0 to 4, and preferably 2 or less.

The dyes used in the present invention are illustrated below, but the present invention is not limited to these dyes.

[0077]

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[0078]

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[0079]

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[0080]

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[0081]

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[0082]

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[0083]

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[0084]

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Illustrative compounds thiopyrylium squarylium dye, thiopyrylium crokonium dye, pyrylium squarylium dye, pyrylium crokonium dye, selenapyrylium squarylium dye, selenapyrylium croconium dye, telluropyrylium squarylium dye, and tellurium Pyrylium croconium dye

[0086]

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[0087]

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[0088]

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[0089]

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Hereinafter, general formula 11 of the present invention will be described. In the general formula 11, R ₁ , R ₂ , R ₃ , and R ₄ represent an alkyl group having no acidic substituent, and R ₅ and R ₆ represent 1
Represents a valent substituent.

Examples of the alkyl group represented by R ₁ , R ₂ , R ₃ and R ₄ include, for example, methyl group, ethyl group, isopropyl group, tert-butyl group, methoxyethyl group, methoxyethoxyethyl group, Examples thereof include an ethylhexyl group, a 2-hexyldecyl group, and a benzyl group. In the present invention, the acidic substituent means a sulfonic acid group, a carboxylic acid group, a phosphonic acid group, SO ₂ NHSO ₂ R or CON.
HSO ₂ R (R represents a lower alkyl group having 1 to 5 carbon atoms or a phenyl group), a sulfonic acid group is a sulfo group or a salt thereof, a carboxylic acid group is a carboxyl group or a salt thereof, and phosphonic acid is The group means a phosphono group or a salt thereof, respectively.

R ₁ , R ₂ , R ₃ , and R ₄ are preferably an alkyl group substituted with an alkoxy group or an alkyl group having 5 or more carbon atoms because solubility in an organic solvent is improved.
The monovalent substituent represented by R ₅ or R ₆ is not particularly limited, but may be an alkyl group (eg, an alkyl group represented by R ₁ ), an aryl group (eg, a phenyl group, a 4-chlorophenyl group, a 2,6 -Dimethylphenyl group, etc.), a hydroxyl group, an amino group, an acyl group (eg, an acetyl group, etc.), more preferably an alkyl group, an aryl group, a hydroxyl group, and the synthesis is easy and preferable. Most preferably, it is a hydroxyl group in that a spectral absorption spectrum can be obtained.

R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ may form a ring together, for example, R ₁ , R ₂ and R ₅ may form a julolidyl group together. May be. 1 and m each represent an integer of 0 to 4, and are preferably 0 or 1 in view of the ease of dye synthesis, and particularly preferably 1 in view of spectral absorption characteristics. Hereinafter, dyes represented by the general formula 11 will be exemplified, but the present invention is not limited to these dyes.

[0094]

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[0095]

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[0096]

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The following is a synthesis example, but the present invention is not limited to this synthesis example. Synthesis of Exemplified Compound 1

[0098]

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Intermediate 1, 2.39 g, Croconic acid 0.7
5 g was heated to reflux with 20 ml of 1-propanol for 1 hour,
After the reaction product is extracted and washed with ethyl acetate, the solvent is removed, and recrystallization from methanol gives dark green crystals. Yield 7
The structure was confirmed by MS and NMR at 2%. Λmax in ethyl acetate was 813 nm. Other exemplified compounds can be synthesized according to the above synthesis method.

A synthesis example is shown below, but the present invention is not limited to this synthesis example. Synthesis of Exemplified Compound 1

[0101]

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Intermediate 1, 2.39 g, Croconic acid 0.7
5 g was heated to reflux with 20 ml of 1-propanol for 1 hour,
After the reaction product is extracted and washed with ethyl acetate, the solvent is removed, and recrystallization from methanol gives dark green crystals. Yield 7
The structure was confirmed by MS and NMR at 2%. Λmax in ethyl acetate was 813 nm. Other exemplified compounds can be synthesized according to the above synthesis method.

The "image forming method of a heat-developable photographic light-sensitive material in which a latent image is formed by exposure and subsequently an image is substantially formed by thermal development" according to claims 8 and 16 of the present invention. Specifically, the exposure method is not particularly limited, and any known exposure method may be used. The light source is preferably a laser light source, and the laser light according to the present invention may be a gas laser, a YAG laser, a dye, or the like. Lasers and semiconductor lasers are preferred. Further, a semiconductor laser and a second harmonic generation element can be used. It is preferable as the energy of the exposure is 40mmJ / mm ² less than 1mmJ / mm ² or more in one millisecond. A latent image is an image that cannot be recognized by human eyes as an image, but is an image that can form a visible image by development processing, and is a term that is self-evident in the art. The heating temperature in the heat development of the present invention is 80 ° C.
The temperature is preferably 200 ° C. or less, more preferably 10 ° C. or less.
0 ° C or more and 150 ° C or less. If the heating temperature is lower than 80 ° C., a sufficient image density cannot be obtained in a short time, and if the heating temperature is higher than 200 ° C., the binder is melted and adversely affects not only the image itself but also transportability such as transfer to a roller and a developing machine. Effect. The development time is preferably from 1 to 180 seconds, preferably from 10 to 180 seconds.
~ 90 seconds is more preferred. Although any known method may be used as the thermal development method, it is preferably performed by heating on a heat roller or a heat block heated to a desired temperature. The photothermographic material of the present invention is for forming a photographic image by using a heat development process, and contains a photosensitive silver halide, a reducing agent, and, if necessary, an organic silver salt as a reducible silver source. It is preferable that the photothermographic material contains a color tone adjusting agent for adjusting the color tone of silver dispersed or dissolved in a binder matrix. The photothermographic material of the present invention is stable at room temperature, but is exposed to high temperature (for example, 80 ° C.).
Above) to develop. Image formation is performed only by this heat treatment, and proceeds without the supply of water or the like from the outside.

The silver halide photographic light-sensitive materials according to claims 5, 11 and 18 of the present invention are not particularly limited, and conventionally known color negative films, color reversal films, color papers, printing plate making films, medical radiography. Film and the like. Preferably, a printing plate making film and a medical X-ray film are used. Particularly preferred are the film for printing plate making and the film for radiography in which an image is formed by the above-mentioned thermal development.

The solid dispersions of the dyes according to the twenty-third and twenty-fourth aspects of the present invention have an average particle size of 0.05 to 3.0 μm when the average volume of the dispersion particles is converted into the same volume of spheres. It is preferable that 70 wt% or more of the whole particles is 0.1%.
μm or more and 1.5 μm or less, more preferably 0.1 μm or more.
It is preferably 0 μm or less. The particle size can be measured by a particle size measuring device utilizing light scattering by light or coherent light such as laser light. The shape of the particles is almost spherical. The solid dispersion of the dye of the present invention is preferably a solid fine particle dispersion using a dispersant in order to obtain fine particles without aggregation. The method of dispersing the dye of the present invention into solid fine particles is carried out by using a known fine-graining means (for example, a ball mill, a vibration ball mill, a planetary ball mill, a sand mill, a colloid mill, a jet mill, a roller mill) in the presence of a dispersing agent, Can be dispersed mechanically. In addition, a dye is dissolved in a water-insoluble organic solvent having a boiling point lower than that of water (eg, ethyl acetate), and fine oil droplets are formed by ultrasonic dispersion or the like, and then the solvent is evaporated by heating to form a fine solid dispersion. Can also be preferably used.

When the solid fine particles are dispersed using a dispersant, for example, polyacrylic acid, a copolymer of acrylic acid, a maleic acid copolymer, a maleic acid monoester copolymer, and acryloylmethylpropanesulfone copolymer may be used. Polymer,
Synthetic anionic polymers such as carboxymethyl starch and carboxymethyl cellulose; anionic polymers such as alginic acid and pectic acid; JP-A-52-92716; WO 88/04794.
Surfactants described in Japanese Patent Application No. Hei 7-35
No. 0753, or known anionic, nonionic, cationic surfactants and other known polymers such as polyvinyl alcohol, polyvinylpyrrolidone, carboxymethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, or gelatin. A polymer compound existing in nature can be appropriately selected and used.

It is a general method that the dispersant is mixed with the dye powder or the dye in a wet cake state before the dispersion, and then sent as a slurry to a dispersing machine. To give a powder of dye or a wet cake. The pH may be controlled by an appropriate pH adjuster before, during or after dispersion.

Instead of mechanically dispersing, fine particles may be formed by coarsely dispersing in a solvent by controlling the pH and then changing the pH in the presence of a dispersing aid. At this time, an organic solvent may be used as a solvent used for the coarse dispersion, and the organic solvent is usually removed after the completion of the fine particle formation.

The prepared solid fine particle dispersion may be stored with stirring for the purpose of suppressing sedimentation of the fine particles during storage.
It can also be stored in a highly viscous state (for example, in a jelly state using gelatin) by a hydrophilic colloid. Further, a preservative can be added for the purpose of preventing the propagation of various bacteria during storage.

The oil dispersions of the dyes according to the twenty-third and twenty-fourth aspects of the present invention are obtained by dissolving the dyes in a water-insoluble high-boiling organic solvent (for example, tricresyl phosphate, dibutyl phthalate, dinonylphenol, etc.). Preferably, it can be obtained as a fine oil dispersion by a method such as ultrasonic dispersion. The boiling point of the water-insoluble high-boiling organic solvent is preferably 100 ° C. or higher, particularly preferably 140 ° C.
A solvent having a temperature of at least 300 ° C. and at most 300 ° C. is preferable. The dispersion medium at the time of dispersion is not particularly limited. For example, polyacrylic acid,
Synthetic anionic polymers such as acrylic acid copolymer, maleic acid copolymer, maleic acid monoester copolymer, acryloylmethylpropanesulfone copolymer, semi-synthetic polymers such as carboxymethyl starch and carboxymethyl cellulose, alginic acid, pectin Anionic polymers such as acids, JP-A-52-92716, WO8
8/04794 and the like.
Compounds described in Japanese Patent Application No. 7-350753, or known anionic, nonionic, cationic surfactants, and other known polymers such as polyvinyl alcohol, polyvinylpyrrolidone, carboxymethylcellulose, hydroxypropylcellulose, and hydroxypropylmethylcellulose Alternatively, a naturally occurring polymer compound such as gelatin can be appropriately selected and used.

Claims 10, 11, 12, 25, 26, 2
7, water-soluble binders such as gelatin and / or gelatin derivatives (for example, phthalated gelatin), water-soluble polymers such as polyvinyl alcohol, methylcellulose, carboxymethylcellulose, and hydroxypropylcellulose; arabic gum; polyvinylpyrrolidone;
Examples include various emulsions such as casein, styrene-butadiene latex, acrylonitrile-butadiene latex, polyvinyl acetate, polyacrylate, and ethylene-vinyl acetate copolymer.

The amount of the binder used is preferably 0.5 to 5 g / m ² in terms of solid content. As the water-soluble binder used in the present invention, particularly, styrene-
Latexes of butadiene copolymer are preferred. Styrene-
The weight ratio of the monomer unit of styrene to the monomer unit of butadiene in the butadiene copolymer is from 50:50 to 9
The ratio is preferably 5: 5. The proportion of the styrene monomer unit and the butadiene monomer unit in the copolymer is preferably 50 to 99% by weight. The preferred molecular weight range is the same as described above.

Styrene which is preferably used in the present invention
As the butadiene copolymer latex, commercially available LACSTAR 3307B, 7132C, DS20
6, Nipol Lx416, Lx433, and the like.

The heat-developable photographic material spectrally sensitized to a wavelength of 600 nm or more and 700 nm or less according to the tenth and twenty-fifth aspects is developed after being exposed by an exposure light source having a wavelength of 600 nm or more and 700 nm or less. It is preferable that the photothermographic material is capable of substantially forming an image. The exposure light source is preferably a laser light source, and the laser light according to the present invention is preferably a gas laser, a YAG laser, a dye laser, a semiconductor laser, or the like. Further, a semiconductor laser and a second harmonic generation element can be used. 40mmJ to 1 millisecond as exposure energy / mm ² less than 1mmJ
/ Mm ² or more. The photothermographic material of the present invention has the same meaning as the photothermographic materials of claims 6, 8 and 16.

Preferred hydrazine compounds among the hydrazine compounds described in claims 13, 28 and 29 are compounds represented by the following general formula [H].

[0116]

Embedded image

[In the formula, A ₀ represents an aliphatic group, an aromatic group, a -G ₀ -D ₀ group or a heterocyclic group which may have a substituent, B ₀ represents a blocking group, and A ₁ , a ₂ are both hydrogen atoms, or one is a hydrogen atom and the other represents an acyl group, a sulfonyl group or an oxalyl group. G ₀ is a -CO- group,-
A COCO— group, a —CS— group, a —C (＝ NG ₁ D ₁ ) — group,
—SO— group, —SO ₂ — group or —P (O) (G ₁ D ₁ ) —
G ₁ represents a simple bond, —O— group, —S— group or —N (D ₁ ) — group, D ₁ represents an aliphatic group, an aromatic group,
Represents a heterocyclic group or a hydrogen atom, and D ₀ represents a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an amino group, an alkoxy group, an aryloxy group, an alkylthio group, or an arylthio group. ]

In the general formula [H], the aliphatic group represented by A ₀ preferably has 1 to 30 carbon atoms, and particularly a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms. Preferably, for example, a methyl group, an ethyl group, a t-butyl group,
Octyl group, cyclohexyl group, benzyl group, which are further substituted with suitable substituents (for example, aryl group, alkoxy group, aryloxy group, alkylthio group, arylthio group, sulfoxy group, sulfonamide group, sulfamoyl group, acylamino group, Ureido group).

In the general formula [H], the aromatic group represented by A ₀ is preferably a monocyclic or condensed ring aryl group, for example, a benzene ring or a naphthalene ring, and a heterocyclic group represented by A _0. The group is preferably a heterocyclic ring containing at least one heteroatom selected from nitrogen, sulfur, and oxygen atom in a single ring or a condensed ring, for example, a pyrrolidine ring, an imidazole ring, a tetrahydrofuran ring, a morpholine ring, a pyridine ring, a pyrimidine ring, A quinoline ring, a thiazole ring, a benzothiazole ring, a thiophene ring, and a furan ring; particularly preferred as A ₀ are an aryl group and a heterocyclic group; and the aromatic and heterocyclic groups of A ₀ have a substituent. And particularly preferred groups include pKa7 to
Examples of the substituent having an acidic group of 11 include a sulfonamide group, a hydroxyl group, and a mercapto group.

In the general formula [H], represented by A ₀
The G ₀ -D ₀ group will be described. G ₀ is a -CO- group,-
A COCO— group, a —CS— group, a —C (＝ NG ₁ D ₁ ) — group,
—SO— group, —SO ₂ — group or —P (O) (G ₁ D ₁ ) —
And preferred G ₀ is -CO- group, -COC
Among the O- groups, particularly preferred is a -COCO- group. G ₁ is a mere bond, -O- group, -S- group or -N
Represents a (D ₁ ) — group, wherein D ₁ represents an aliphatic group, an aromatic group, a heterocyclic group or a hydrogen atom, and when a plurality of D ₁ are present in a molecule, they may be the same or different. Is also good.

D ₀ is a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an amino group, an alkoxy group, an aryloxy group,
Represents an alkylthio group or an arylthio group, and is preferably D ₀
Examples thereof include a hydrogen atom, an alkyl group, an alkoxy group, an amino group, an aryl group and the like.

In the general formula [H], A ₀ preferably contains at least one diffusion-resistant group or silver halide-adsorbing group. As the diffusion-resistant group, a ballast group commonly used in immobile photographic additives such as couplers is preferable. As the ballast group, a photographically inactive alkyl group having 8 or more carbon atoms, alkenyl group, alkynyl group, alkoxy group Group, phenyl group, phenoxy group, alkylphenoxy group and the like.

In the general formula [H], examples of the silver halide adsorption promoting group include thiourea, thiourethane group, mercapto group, thioether group, thione group, heterocyclic group, thioamide heterocyclic group, mercapto heterocyclic group, 64-9
No. 0439.

[0124] In formula (H), B ₀ represents a blocking group, preferably a -G ₀ -D _0, is synonymous with -G ₀ -D ₀ group in A _0, A ₀ and B ₀ are It may be the same or different.

A ₁ and A ₂ are both hydrogen atoms, or one is a hydrogen atom and the other is an acyl group (eg, acetyl, trifluoroacetyl, benzoyl, etc.), a sulfonyl group (eg, methanesulfonyl, toluenesulfonyl, etc.) ),
Or an oxalyl group (such as an ethoxalyl group).

Next, specific examples of the compound represented by the formula [H] are shown below, but the present invention is not limited thereto.

[0127]

Embedded image

[0128]

Embedded image

[0129]

Embedded image

[0130]

Embedded image

[0131]

Embedded image

[0132]

Embedded image

As the hydrazine compound used in the present invention, the following compounds can be used in addition to the above.

RESEARCHDISCLOSURE Item 23516 (11/1983
, P. 346) and the references cited therein, as well as U.S. Pat. Nos. 4,080,207 and 4,269,929,
4,276,364, 4,278,748, 4,385,108, 4,459,347, 4,478,928, 4,560,638, and 4 No. 4,686,167, 4,912,016, 4,988,604, 4,994,365, 5,041,355, 5,104,769, British Patent No. 2 , 011,391B, EP 217,3
No. 10, No. 301,799, No. 356,898, JP-A-60-179834, JP-A-61-170733,
Nos. 61-270744, 62-178246, 62-270948, 63-29751, 63
No. 32538, No. 63-104047, No. 63-1
Nos. 21838, 63-129337, 63-22
No. 3744, No. 63-234244, No. 63-234
No. 245, No. 63-234246, No. 63-2945
No. 52, No. 63-306438, No. 64-10233
No., JP-A-1-90439, JP-A-1-100530,
No. 1-1055941, No. 1-105943, No. 1-
No. 276128, No. 1-280747, No. 1-283
No. 548, No. 1-283549, No. 1-285940
No. 2-2541, No. 2-77057, No. 2-1
39538, 2-196234, 2-1962
No. 35, No. 2-198440, No. 2-198441
No. 2-198442, No. 2-220042, No. 2-221953, No. 2-221954, No. 2-2
No. 85342, No. 2-285343, No. 2-2898
No. 43, No. 2-302750, No. 2-304550
No. 3-37642, 3-54549, 3-
No. 125134, No. 3-184039, No. 3-240
No. 036, No. 3-240037, No. 3-259240
No. 3-2820038, No. 3-282536, No. 4-51143, No. 4-56842, No. 4-841
No. 34, No. 2-230233, No. 4-96053,
4-216544, 5-45761, 5-4
No. 5762, No. 5-45763, No. 5-45764
No. 5-45765, No. 6-289524, No. 9
-160164 and the like.

Other than these, compounds represented by (Chemical Formula 1) described in JP-B-6-77138, specifically, compounds described on pages 3 and 4 of the same publication. Compounds represented by formula (I) described in JP-B-6-93082, specifically, compounds 1 to 38 described on pages 8 to 18 of the publication. JP 6
General formulas (4) and (5) described in JP-A-230497
And compounds represented by formula (6), specifically, compounds 4-1 to 4-
Compounds 5-1 to 5-4 described on page 10, pages 28 to 36
2, and compounds 6-1 to 6-7 described on pages 39 and 40. Compounds represented by formulas (I) and (2) described in JP-A-6-289520, specifically, compounds 1-1) to 1-1 described on pages 5 to 7 of the same.
7) and 2-1). Compounds represented by (Chemical Formula 2) and (Chemical Formula 3) described in JP-A-6-313936, specifically, compounds described on pages 6 to 19 of the same. JP-A-6-3
Compounds represented by Chemical Formula 1 described in No. 13951, specifically, compounds described on pages 3 to 5 of the same publication. JP-A-7-
A compound represented by the general formula (I) described in No. 5610,
Specifically, Compounds I-1 to I-5 described on pages 5 to 10 of the publication are described.
I-38. The general formula (I) described in JP-A-7-77783.
Compounds represented by I), specifically, pages 10 to 2 of the publication
Compounds II-1 to II-102 described on page 7. JP 7
Compounds represented by general formula (H) and general formula (Ha) described in JP-A-104426, specifically, from page 8 to
Compounds described in Compounds H-1 to H-44 on page 15 can be used.

The hydrazine derivative-added layer is a photosensitive layer and / or a constituent layer adjacent to the photosensitive layer. The optimum amount is not uniform depending on the particle size of the silver halide grains, the halogen composition, the degree of chemical sensitization, the type of reducing agent, the type of inhibitor, etc., but it is 10 ^-6 per mol of silver halide. Mol ~
The range is preferably about 10 ^-1 mol, particularly preferably 10 ^-5 mol to 10 ^-2 mol.

[0137] Claims 30 etc.
A silver halide photographic light-sensitive material spectrally sensitized to 0 nm or less is a heat developing method which can substantially form an image when developed after being exposed by an exposure light source having a wavelength of 600 nm to 900 nm. It is preferably a photographic light-sensitive material. The exposure light source is preferably a laser light source, and the laser light according to the present invention is preferably a gas laser, a YAG laser, a dye laser, a semiconductor laser, or the like. Further, a semiconductor laser and a second harmonic generation element can be used. Less than 40mmJ / mm ² to 1 millisecond as exposure energy 1MmJ /
mm ² or more. The silver halide photographic light-sensitive material in this claim has the same meaning as the heat-developable photographic light-sensitive material in claims 6, 16 and the like.

The content of the dye of the present invention in a support for an image forming material such as an image forming material, a heat-developable photographic light-sensitive material, a silver halide photographic light-sensitive material, an optical filter, and a silver halide photographic light-sensitive material is particularly limited. However, the transmission density at the spectral absorption maximum of the dye is preferably 0.01 or more and 3 or less, particularly preferably 0.1 or more and 1.5 or less.

In the heat-developable photographic light-sensitive material and the silver halide photographic light-sensitive material, the dye may be contained in any layer coated on the support, but preferably the photosensitive layer and the back layer of the support are used. It is. Particularly preferred is a photosensitive layer. The dye is preferably dissolved in an organic solvent (methyl ethyl ketone, ethyl acetate, toluene, etc.) and added directly to the photographic material. In addition, the above-described method of adding as a solid dispersion or an oil dispersion is also preferably used.

The light-sensitive material of the present invention can have a dye on any side of the support, but preferably has a dye on a side different from the emulsion. In the present invention, when the dye of the present invention is added to the support itself, the effect of improving sharpness is large, which is preferable. When the present invention is applied to a silver halide photographic light-sensitive material containing a dye represented by the general formula 1 on both sides of a support, the effect of the present invention of high sharpness is easily obtained, which is preferable.

The processing method of the silver halide photographic light-sensitive material of the present invention is not particularly limited, and may be processing using a solution such as C-41 manufactured by Kodak Corporation or thermal development. Preparation of processing solution,
It is more preferable to apply heat development in that processing can be performed in a short time without the need for management.

When the present invention is applied to a heat-developable silver halide photographic light-sensitive material containing an organic silver salt and a binder on a support, the effect of the present invention that the residual color stain is small is particularly remarkably obtained, which is preferable.

When the treatment with a solution is applied, in addition to the C-41 treatment, a Konica CPK-2-22 treatment or the like can be preferably applied. The development is not particularly limited, but may be immersed in a processing solution in a tank, or may be sprayed or applied to the photosensitive material.

Halogenation wherein the silver halide photographic material containing the dye according to any one of claims 1 to 3, especially the dye represented by the general formula 1 or 2, is subjected to reversal development with secondary exposure. When applied to a processing method of a silver photographic light-sensitive material, an image having good sharpness is obtained, and stable photographic characteristics are obtained, which is preferable.

When the dye of the present invention, such as the dye of the general formula 1 or 2, is added to the light-sensitive material, it is advantageous to apply the coating by mixing the dye dispersion with a binder such as gelatin or a polymer. Is preferred.

When the solid dispersion dye of the general formula 1 is used,
The sharpness improving effect is particularly large, and the residual color stain is particularly small, which is preferable. In particular, when a developing process using a liquid developing solution is performed, the residual color stain is small, which is preferable. When the present invention is applied to an ornamental light-sensitive material, the residual color stain is small, which is preferable.

The filter of the present invention is not particularly limited, and can be used for all uses for absorbing light.
The filter of the present invention can be particularly preferably used when it is required to absorb infrared light but not to sense the dye with the naked eye. The support constituting the filter is not limited, and it is preferable to use glass, resin, or the like.

The dye may be contained in the support constituting the filter, or may be coated on one side or both sides of the support. Coating means fixing a dye on a support by a method such as coating, spraying, or vapor deposition. As a method for incorporating the dye into the support, a known method can be used, but a method in which the dye is dissolved in a resin and molded, or a method in which the dye is added to a resin monomer and polymerized, is preferable. When applying the dye to the support, it is preferable to use a binder, and gelatin, polyvinyl alcohol, polybutyl acrylate and the like are preferably used as the binder.

Although the amount of light absorption by the dye can be adjusted as required, the optical density is preferably from 0.01 to 3, particularly preferably from 0.1 to 2.

In particular, the dye of the present invention has a transmission density of less than 0.03 at 420 nm when the transmission density at the maximum absorption wavelength is 1.0 in methyl ethyl ketone, and the dye has a maximum absorption wavelength of 600 nm to 900 n.
m, and more preferably, the maximum absorption wavelength is 750 nm or more and 900 nm or less. The image forming material containing the dye of the present invention has a transmission density at 420 nm of 0.15 or less when the transmission density at the maximum absorption wavelength after development processing is 1.0.

A heat-developable photosensitive material for forming a photographic image by using a heat-development processing method is described, for example, in US Pat. No. 3,152,904.
No. 3457075 and D.C. Morgan and B.A. "Thermally Processed Silver Systems" by Shely
(Imaging Processes and Materials Neblette 8
Edition, Sturge, V. Walworth
th), A. Edited by Shepp, page 2, 1969
Year).

The present invention can be preferably applied to a photosensitive material containing an organic silver salt. Organic silver salts are reducible silver sources, and silver salts of organic acids and heteroorganic acids containing a reducible silver ion source, especially long-chain (10-30, preferably 15-25) aliphatic aliphatic acids. Carboxylates and nitrogen-containing heterocyclic salts are preferred.

Organic or inorganic silver salt complexes in which the ligand has a total stability constant for silver ions of 4.0 to 10.0 are also useful. An example of a suitable silver salt is Research Di.
Nos. 17029 and 29996, and includes the following: salts of organic acids (eg, salts of gallic acid, oxalic acid, behenic acid, stearic acid, palmitic acid, lauric acid, etc.); silver carboxyalkylthios Urea salts (eg, 1- (3-carboxypropyl) thiourea, 1- (3-carboxypropyl) -3,3-dimethylthiourea, etc.); silver of a polymer reaction product of an aldehyde and a hydroxy-substituted aromatic carboxylic acid Complexes (for example,
Aldehydes (formaldehyde, acetaldehyde,
Butyraldehyde), hydroxy-substituted acids (for example,
Salicylic acid, benzoic acid, 3,5-dihydroxybenzoic acid, 5,5-thiodisalicylic acid), silver salts or complexes of thioenes (for example, 3- (2-carboxyethyl) -4-
Hydroxymethyl-4- (thiazoline-2-thioene,
And 3-carboxymethyl-4-thiazoline-2-thioene), imidazole, pyrazole, urazole, 1,
Complexes or salts of nitrogen acids with silver selected from 2,4-thiazole and 1H-tetrazole, 3-amino-5-benzylthio-1,2,4-triazole and benzotriazole; saccharin, 5-chlorosalicylaldoxime And silver salts of mercaptides. The preferred silver source is silver behenate. The organic silver salt preferably has a silver content of 3
g / m ² or less. More preferably, 2 g / m ²
It is as follows.

The organic silver salt compound can be obtained by mixing a water-soluble silver compound and a compound which forms a complex with silver.
A controlled double jet method or the like described in No. 7643 is preferably used.

The silver halide grains used in the present invention are not particularly limited, but the average grain size is preferably small in order to suppress white turbidity after image formation and to obtain good image quality. 0.20 μm or less, more preferably 0.03 μm to 0.15 μm, particularly 0.03 μm
m to 0.11 μm is preferred. The term "grain size" as used herein refers to the length of a ridge of a silver halide grain when the silver halide grain is a cubic or octahedral so-called normal crystal. In the case of non-normal crystals, for example, in the case of spherical, rod-shaped or tabular grains, it refers to the diameter of a sphere equivalent to the volume of silver halide grains.

The shape of the silver halide grains used in the present invention is not particularly limited, but the ratio occupied by the Miller index [100] plane is preferably high, and this ratio is 50% or more, more preferably 70% or more, especially It is preferably at least 80%. The ratio of the Miller index [100] plane is determined by the T.M. Tani, J .; Imaging Sc
i. , 29, 165 (1985).

The halogen composition of the silver halide grains used in the present invention is not particularly limited, and may be any of silver chloride, silver chlorobromide, silver chloroiodobromide, silver bromide, silver iodobromide and silver iodide. There may be. The photographic emulsion used in the present invention is P.I. Glaf
Chimieet Physique P.
photographique (Paul Montel)
G., 1967); F. Duffin's Pho
graphicalEmulsion Chemist
ry (The Focal Press, 1966)
Year), V. L. Mak by Zelikman et al
ing and Coating Photograph
hic Emulsion (TheFocal Pre
ss, 1964) and the like. That is, any of an acidic method, a neutral method, an ammonia method and the like may be used, and a method of reacting a soluble silver salt with a soluble halide may be any one of a one-sided mixing method, a double-sided mixing method, a combination thereof and the like. Good. The silver halide may be added to the image forming layer by any method, in which case the silver halide is arranged close to the reducible silver source. Further, the silver halide may be prepared by converting a part or all of the silver in the organic acid silver by the reaction of the organic acid silver and the halogen ion into silver halide, or may be prepared by preparing silver halide in advance. In advance, this may be added to a solution for preparing an organic silver salt, or a combination of these methods is possible, but the latter is preferred.
Generally, silver halide is 0.75 to 30 with respect to the organic silver salt.
It is preferably contained in an amount of% by weight.

The silver halide used in the present invention preferably contains ions or complex ions of metals belonging to groups IB, IIB, IIIA, VA, VA, VIA, VIIA and VIII of the Periodic Table of the Elements. The above metals include W (VIA group), Fe, Co,
Ni (at least VIII), Cu (at IB), Ru, Rh, Pd (at least VIII), Re (at VIIA), Os, Ir, Pt (at least VIII)
Group) and Au (group IB).

One of these metal ions or complex ions may be used, or two or more of the same or different metals may be used in combination. The content of these metal ions or complex ions is generally from 1 × 10 ⁻⁹ to 1 × 10 ⁻² mol, preferably from 1 × 10 ⁻⁸ to 1 × 10 ⁻² mol per mol of silver halide. × 10 ^-4 mol.

The compounds providing these metal ions or complex ions are preferably added during silver halide grain formation and incorporated into silver halide grains. Preparation of silver halide grains, ie, nucleation and growth , Physical aging,
It may be added at any stage before and after chemical sensitization, but it is particularly preferable to add at the stage of nucleation, growth, and physical ripening.
Further, it is preferably added at the stage of nucleation and growth, most preferably at the stage of nucleation. In the addition, it may be added in several divided portions, and may be uniformly contained in the silver halide grains.
3-29603, JP-A-2-306236 and 3-
Nos. 167545, 4-76534, 6-1101
As described in JP-A Nos. 46 and 5-273683, they can be contained in the particles with a distribution. Preferably, a distribution can be provided inside the particles. These metal compounds can be added by dissolving them in water or a suitable organic solvent (eg, alcohols, ethers, glycols, ketones, esters, amides). A method in which an aqueous solution or an aqueous solution in which a metal compound and NaCl and KCl are dissolved together is added to a water-soluble silver salt solution or a water-soluble halide solution during grain formation, or a silver salt solution and a halide solution are mixed at the same time. To prepare silver halide grains by a method of simultaneous mixing of three liquids, a method of charging a required amount of an aqueous solution of a metal compound into a reaction vessel during grain formation, or a method of preparing silver halide. There is a method in which another silver halide grain doped with a metal ion or a complex ion in advance is sometimes added and dissolved. In particular, an aqueous solution of a metal compound powder or a metal compound and NaCl, KC
A preferred method is to add an aqueous solution in which 1 is dissolved together with a water-soluble halide solution. When adding to the particle surface, a required amount of an aqueous solution of a metal compound can be charged into the reaction vessel immediately after the formation of the particles, during or at the end of physical ripening, or at the time of chemical ripening.

When the present invention is applied to a photothermographic material, it is preferable to incorporate a reducing agent. Examples of suitable reducing agents are described in U.S. Patent Nos. 3,770,448 and 3,773.
No. 3,512, No. 3,593,863, and Res
Ear Disclosure No. 17029 and 2
9963, for example, the following can be mentioned. Aminohydroxycycloalkenonone compounds (eg, 2-hydroxypiperidino-2-cyclohexenone); aminoreductones esters (eg, piperidinohexose reductone monoacetate) as precursors of reducing agents; N- Hydroxyurea derivatives (for example, Np-methylphenyl-N
Hydrazones of aldehydes or ketones (e.g. anthracene aldehyde phenylhydrazone); phosphoramidophenols; phosphoramidoanilines; polyhydroxybenzenes (e.g.
Hydroquinone, t-butyl-hydroquinone, isopropylhydroquinone and (2,5-dihydroxy-phenyl) methylsulfone); sulfhydroxamic acids (eg, benzenesulfhydroxamic acid); sulfonamidoanilines (eg, 4- (N- Methanesulfonamido) aniline); 2-tetrazolylthiohydroquinones (eg, 2-methyl-5- (1-phenyl-5-tetrazolylthio) hydroquinone); tetrahydroquinoxalines (eg, 1,2,3,4-tetrahydro) Aminooxins; Azines (eg, a combination of an aliphatic carboxylic acid arylhydrazide and ascorbic acid); a combination of polyhydroxybenzene and hydroxylamine, reductone and / or hydrazine; Hydroxanoic acids Combinations of azines and sulfonamidophenols; α-cyanophenylacetic acid derivatives; combinations of bis-β-naphthol and 1,3-dihydroxybenzene derivatives; 5-pyrazolones; sulfonamidophenol reducing agents; 2-phenylindane-1 ,
3-dione or the like; chroman; 1,4-dihydropyridine (eg, 2,6-dimethoxy-3,5-dicarbethoxy-1,4-dihydropyridine); bisphenols (eg, bis (2-hydroxy-3-t) -Butyl-5
-Methylphenyl) methane, bis (6-hydroxy-m
-Tri) mesitol, 2,2-bis (4-hydroxy-3-methylphenyl) propane,
4,5-ethylidene-bis (2-t-butyl-6-methyl) phenol), ultraviolet-sensitive ascorbic acid derivatives and 3-pyrazolidones. Among them, particularly preferred reducing agents are hindered phenols.

Examples of the hindered phenols include compounds represented by the following general formula (A).

[0163]

Embedded image In the formula, R represents a hydrogen atom, or an alkyl group having 1 to 10 carbon atoms (e.g., -C ₄ H _9, 2,4,4-trimethyl pentyl), R 'and R "1 carbon atoms 5 represents an alkyl group (for example, methyl, ethyl, t-butyl).

Specific examples of the compound represented by formula (A) are shown below. However, the present invention is not limited to the following compounds.

[0165]

Embedded image

The amount of the reducing agent including the compound represented by formula (A) is preferably 1 × 1 per mol of silver.
It is from 0 ^-2 to 10 mol, especially from 1 x 10 ^{-2 to} 1.5 mol.

The binders suitable for the light-sensitive material of the present invention are transparent or translucent, generally colorless, and include natural polymer synthetic resins, polymers and copolymers, and other film-forming media such as gelatin, gum arabic and poly (vinyl). Alcohol), hydroxyethyl cellulose, cellulose acetate, cellulose acetate butyrate,
Poly (vinylpyrrolidone), casein, starch, poly (acrylic acid), poly (methyl methacrylic acid), poly (vinyl chloride), poly (methacrylic acid), copoly (styrene-maleic anhydride), copoly (styrene-acrylonitrile) , Copoly (styrene-butadiene), poly (vinyl acetal) s (eg, poly (vinyl formal) and poly (vinyl butyral)), poly (esters), poly (urethane) s, phenoxy resins, poly (vinylidene chloride) , Poly (epoxides), poly (carbonates), poly (vinyl acetate), cellulose esters, and poly (amide) s. It may be hydrophilic or non-hydrophilic.

In the present invention, the binder amount of the photosensitive layer is preferably 1.5 to 6 g / m ² . More preferably, it is 1.7 to 5 g / m ² .

In the present invention, a matting agent is preferably contained on the photosensitive layer side, and a polymer matting agent or an inorganic matting agent is contained in a weight ratio of 0.5 to 10% with respect to all binders on the emulsion layer side. Is preferred.

The material of the matting agent used in the present invention may be either an organic substance or an inorganic substance. For example, inorganic substances include silica described in Swiss Patent No. 330,158, glass powder described in French Patent No. 1,296,995, etc., and alkali described in British Patent No. 1,173,181 and the like. An earth metal or a carbonate such as cadmium or zinc can be used as a matting agent. As organic matter,
Starch described in U.S. Pat. No. 2,322,037, Belgian Patent 625,451 and British Patent 981,19
No. 8 and the like, and starch derivatives described in JP-B-44-3643.
No. 33, Swiss Patent No. 33
No. 0,158, polystyrene or polymethacrylate; U.S. Pat. No. 3,079,257; polyacrylonitrile; U.S. Pat. No. 3,022,16.
An organic matting agent such as polycarbonate described in No. 9 or the like can be used.

The shape of the matting agent may be either regular or irregular, but it is preferably regular and spherical. The size of the matting agent is represented by a diameter when the volume of the matting agent is converted into a sphere. In the present invention, the particle diameter of the matting agent indicates the diameter converted into a sphere.

The matting agent used in the present invention preferably has an average particle size of 0.5 μm to 10 μm, more preferably 1.0 μm to 8.0 μm. The matting agent has a coefficient of variation of the particle size distribution of preferably 50% or less, more preferably 40% or less, and particularly preferably 30% or less.

Here, the variation coefficient of the particle size distribution is a value represented by the following equation. (Standard deviation of particle size) / (average value of particle size) × 100 The matting agent according to the present invention can be contained in any constituent layer, but is preferably photosensitive in order to achieve the object of the present invention. It is a constituent layer other than the layer, more preferably the outermost layer as viewed from the support.

The method of adding a matting agent according to the present invention may be a method of dispersing in a coating solution in advance and applying the solution.
A method of spraying a matting agent after the application liquid is applied and before the drying is completed may be used. When a plurality of types of matting agents are added, both methods may be used in combination.

The hydrazine compound of the present invention can be prepared by using a suitable organic solvent such as alcohols (methanol, ethanol,
Propanol, fluorinated alcohol), ketones (acetone, methyl ethyl ketone), dimethylformamide,
It can be used by dissolving it in dimethyl sulfoxide, methyl cellosolve or the like. In addition, by an already well-known emulsification dispersion method, dissolution is performed using an oil such as dibutyl phthalate, tricresyl phosphate, glyceryl triacetate or diethyl phthalate, and an auxiliary solvent such as ethyl acetate or cyclohexanone, and mechanically emulsified and dispersed. An object can be prepared and used. Alternatively, a hydrazine compound powder can be dispersed in water by a ball mill, a colloid mill, or ultrasonic waves by a method known as a solid dispersion method and used. In the present invention, it is preferable to use indazoles (for example, nitroindazole) as an antifoggant in combination with a hydrazine compound.

In the light-sensitive material of the present invention, a nucleation accelerator such as an amine derivative, an onium salt compound, a disulfide derivative and a hydroxyamine derivative can be added in combination with the hydrazine compound.

When the present invention is applied to a photothermographic material, the photosensitive material is stable at room temperature, but is developed by heating to a high temperature (for example, 80 ° C. to 140 ° C.) after exposure.
Heating generates silver through an oxidation-reduction reaction between an organic silver salt (functioning as an oxidizing agent) and a reducing agent. This oxidation-reduction reaction is accelerated by the catalytic action of the latent image generated on the silver halide upon exposure. The silver formed by the reaction of the organic silver salt in the exposed areas provides a black image, which contrasts with the unexposed areas, resulting in the formation of an image. This reaction process proceeds without supplying a processing liquid such as water from the outside.

The light-sensitive material of the present invention has at least one light-sensitive layer on a support. Although only a photosensitive layer may be formed on the support, it is preferable to form at least one non-photosensitive layer on the photosensitive layer. The photosensitive layer may be composed of a plurality of layers, and the sensitivity may be changed to a high-sensitive layer / low-sensitive layer or a low-sensitive layer / high-sensitive layer for adjusting the gradation. Various additives may be added to any of the photosensitive layer, the non-photosensitive layer, and other forming layers. The light-sensitive material of the present invention may contain, for example, a surfactant, an antioxidant, a stabilizer, a plasticizer, an ultraviolet absorber, and a coating aid.

When the present invention is applied to a photothermographic material, a toning agent is preferably added. Examples of suitable toning agents are Research Disclosure No. 170
No. 29. Preferred toning agents are phthalazone or phthalazine.

The light-sensitive material of the present invention includes, for example,
No. 159841, No. 60-140335, No. 63-2
No. 31437, No. 63-259651, No. 63-30
Nos. 4242 and 63-15245, U.S. Pat.
Nos. 414, 474,455 and 474,966,
Sensitizing dyes described in JP-A Nos. 4751175 and 4835096 can be used. Useful sensitizing dyes for use in the present invention are, for example, RESEARCH DISCLOSURE Item 17643
Item IV-A (p.23, December 1978), Item 18
It is described in the literature described or cited in section 31X (August 1978, p. 437). JP-A-59-191
No. 032, JP-A-60-80841, and tricarbocyanines described in JP-A-59-192242 and JP-A-3-67242, represented by general formulas (IIIa) and (IIIb). Dicarbocyanines containing a quinoline nucleus are advantageously selected. Further, when the wavelength of the infrared laser light source is 750 nm or more, more preferably 800 nm or more, in order to support a laser in such a wavelength range, Japanese Patent Application Laid-Open Nos. 4-18239 and 5-34143.
2. Tokuho 6-52387, 3-10931, US
Sensitizing dyes described in US Pat. No. 5,441,866 and JP-A-7-13295 are preferably used. These sensitizing dyes may be used alone or in combination, and a combination of sensitizing dyes is often used particularly for supersensitization. Along with the sensitizing dye, the emulsion may contain a dye which does not itself have a spectral sensitizing effect or a substance which does not substantially absorb visible light and exhibits supersensitization.

The dye used in the present invention is disclosed in US Pat. No. 4,508,811.
It can be synthesized by the method described in the specification. Further, it can be synthesized by the method described below, and a person skilled in the art can easily synthesize a similar compound according to the method.

Hereinafter, examples of compounds that can be synthesized by the production method of the present invention are shown, but the present invention is not limited only to the synthesis of these compounds.

[0183]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the present invention is limited thereto. Except where otherwise indicated, the structures of the compounds including the synthetic intermediates were confirmed by NMR spectra and mass spectra. Example 1

[0184]

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Under a nitrogen atmosphere, 6.1 g of metallic magnesium powder was cooled in an ice-water bath while stirring in diethyl ether, and 25.2 g of ethyl bromide was added dropwise. Further, 20 g of tert-butylacetylene was added dropwise, and after completion of the addition, the mixture was stirred at room temperature for 3 hours. This was cooled again in an ice water bath, and 9.0 g of ethyl formate was added dropwise. After the addition, 50 ml of diethyl ether was added, and 6N hydrochloric acid was added to 8 ml.
0 ml was added dropwise. The organic matter was extracted from the mixture after the reaction, and the separated organic layer was washed with water, concentrated and then purified by column chromatography to obtain 2,6-di-tert-butyl-1,4, -pentadiyn-3-ol 1a. 32.
8 g were obtained. (70% yield)

The Journal of Organic Chemistry of Ireland et al.
of Organic Chemistry, Vol. 58, page 2899 (1
993) in a solution prepared by dissolving 66 g of Dess-Martin periodinane in 400 ml of methylene chloride prepared according to the method described in the article published in 2,993), 2,6-di-tert-butyl-1,4-pentadiin-3-. A solution prepared by dissolving 30 g of all in 300 ml of methylene chloride was added.
Stirred for hours. To the reaction mixture was added diethyl ether 1000
Add 1N sodium hydroxide aqueous solution 1500ml
The organic matter was extracted by pouring into the mixture, and the separated organic layer was washed with water. The concentrated organic layer was purified by silica gel column chromatography to obtain 2,6-di-tert-butyl-
23.7 g of 1,4-pentadiin-3-one 1b was obtained. (80% yield)

In 240 ml of a 0.5 M solution of sodium ethoxide in ethanol, 2,6-di-tert-butyl- was added.
15 g of 1,4-pentadiin-3-one was added, and 18 g of sodium sulfide nonahydrate was further added, followed by stirring at room temperature for 3 hours. The reaction mixture was poured into 400 ml of water, methylene chloride was added to extract an organic substance, and the separated organic layer was washed with water. The concentrated organic layer was purified by silica gel column chromatography to obtain 11.3 g of 2,6-di-tert-butyl-4H-thiopyran-4-one 1c.
(Yield 64%)

10 g of 2,6-di-tert-butyl-4H-thiopyran-4-one was added to 150 ml of diethyl ether.
The mixture was cooled in an ice water bath, 20 ml of a 1M solution of methylmagnesium iodide in diethyl ether was added dropwise under a nitrogen atmosphere, and the mixture was stirred and reacted at room temperature for 3 hours.
The reaction mixture was poured into 700 ml of a saturated aqueous solution of ammonium chloride to extract an organic substance, and 100 ml of a 60% aqueous solution of perchloric acid was added to the separated organic layer. The precipitated crystals are collected by filtration, and 2,6-di-t-perchloric acid is added.
tert-butyl-4-methyl-4H-thiopyrylium 1
9.3 g of d were obtained. (55% yield)

2,6-di-tert-butyl perchlorate
8.0 g of 4-methyl-4H-thiopyrylium and 1.4 g of squaric acid were added to 50 ml of 1-butanol and 50 g of toluene.
dispersed in a mixed solvent of 1.0 ml and mixed with 1.0 g of quinoline to give 2
Heated to reflux for hours. The reaction mixture is concentrated and toluene 2
After adding 00 ml and filtering off the insoluble matter, the concentrate of the filtrate was recrystallized from acetonitrile to obtain 3.9 g of Exemplified Compound P-1. (Yield 60%, total yield of all 5 steps 9.
6%)

Embodiment 2

[0191]

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In a nitrogen atmosphere, a solution of 20 g of 1-octyne dissolved in 50 ml of tetrahydrofuran was added dropwise while cooling 170 ml of a 1M solution of ethyl magnesium bromide in tetrahydrofuran with ice water. After completion of the dropwise addition, the reaction vessel was removed from the ice-water bath, stirred at room temperature for 3 hours, and 6.7 g of ethyl formate was added dropwise while cooling again in the ice-water bath. After the addition, 50 ml of tetrahydrofuran was added, and 60 ml of 6N hydrochloric acid was added dropwise. The organic matter was extracted from the mixture after the reaction, the separated organic layer was washed with water, concentrated, and then purified by column chromatography to obtain heptadec-7,10-diyn-9-ol 2a at 16.6.
g was obtained. The structure of the compound was confirmed by NMR spectrum, mass spectrum, infrared spectrum, and gas chromatography. (Yield 85%)

The Journal of Organic Chemistry of Ireland et al.
of Organic Chemistry, Vol. 58, page 2899 (1
993), 20.5 g of Dess-Martin periodinane prepared by the method described in the article published in 150 ml
Was dissolved in methylene chloride at room temperature. To this solution was added a solution of 12.0 g of heptadec-7,10-diyn-9-ol dissolved in 50 ml of methylene chloride, and the mixture was stirred at room temperature for 3 hours. 300 ml of diethyl ether was added to the reaction mixture, and the mixture was poured into 500 ml of a 1N aqueous solution of sodium hydroxide to extract organic substances. The organic layer was separated and washed with water. The separated organic layer was concentrated and purified by silica gel column chromatography to obtain 9.5 g of heptadec-7,10-diyn-9-one 2b.
Obtained. (Yield 85%)

Heptadeca was added to 35 ml of acetonitrile.
7.0 g of 7,10-diyn-9-one was added, and an aqueous solution prepared with 14.0 g of sodium sulfide nonahydrate and 35 ml of water was added, followed by stirring at room temperature for 30 minutes. After the reaction mixture was allowed to stand and the separated aqueous layer was removed, a saturated ammonium chloride aqueous solution (80 ml) and ethyl acetate (30 ml) were added to extract an organic substance.The separated organic layer was washed with water, concentrated, and then purified by silica gel column chromatography.
5.5 g of 2,6-di-n-hexyl @ 4H-thiopyran-4-one 2c was obtained. (Yield 69%)

4.0 g of 2,6-di-n-hexyl-4H-thiopyran-4-one was added to 100 ml of diethyl ether.
And a 1M solution of methylmagnesium iodide in diethyl ether 1 under a nitrogen atmosphere while cooling in an ice water bath.
6 ml was added dropwise, and the mixture was stirred and reacted at room temperature for 3 hours. After adding 500 ml of a saturated aqueous solution of ammonium chloride to the reaction mixture, the organic matter was extracted. The separated organic layer was washed with water, dried over anhydrous sodium sulfate, and concentrated. The concentrated organic matter was used for the next reaction without purification.

The reaction product obtained in the previous step and 0.75 g of squaric acid were dispersed in 60 ml of 1-propanol and heated to reflux for 4 hours while stirring. The reaction mixture was allowed to cool, concentrated, concentrated and recrystallized by adding 20 ml of methanol, and the obtained crude crystal was recrystallized from 6 ml of ethyl acetate to obtain 1.8 g of Exemplified Compound P-24. (40% yield in two steps,
(A total yield of all 5 steps 19.9%)

Embodiment 3

[0198]

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Under a nitrogen atmosphere, a solution of 20 g of phenylacetylene in 50 ml of tetrahydrofuran was added dropwise while cooling 185 ml of a 1M solution of ethyl magnesium bromide in tetrahydrofuran with ice water. After completion of the dropwise addition, the reaction vessel was removed from the ice-water bath, stirred at room temperature for 3 hours, and 7.3 g of ethyl formate was added dropwise while cooling again in the ice-water bath. After the addition, 50 ml of tetrahydrofuran was added, and 60 ml of 6N hydrochloric acid was added dropwise. The organic matter was extracted from the mixture after the reaction, and the separated organic layer was washed with water, concentrated and precipitated with hexane to give 1,5-diphenyl-
16.4 g of 1,4-pentadiin-3-ol 3a was obtained. The structure of the compound is an NMR spectrum, a mass spectrum,
It was confirmed by infrared spectrum and gas chromatography. (Yield 72%)

A solution obtained by dissolving 11.2 g of 1,5-diphenyl-1,4-pentadiyn-3-ol in 50 ml of acetone and mixing 9.0 g of sodium dichromate and 12.0 g of sulfuric acid in 40 ml of water. Was added dropwise under ice cooling. After the completion of the dropwise addition, the reaction mixture was poured into 300 g of ice to extract an organic substance, and the separated organic layer was washed with water, concentrated and purified by silica gel column chromatography to obtain 1,5-diphenyl-1,4-pentadiyne- 3-
7.4 g of ON3b was obtained. (Yield 67%)

To 50 ml of a 0.5 M sodium ethoxide solution in ethanol was added 7.0 g of 1,5-diphenyl-1,4-pentadiin-3-one, and 14 g of sodium sulfide nonahydrate was added. Stirred. The mixture was poured into 300 ml of water, methylene chloride was added to extract an organic substance, the separated organic layer was washed with water, concentrated, and then purified by silica gel column chromatography.
2,6-diphenyl-4H-thiopyran-4-one 3c
Was obtained in an amount of 5.1 g. (Yield 64%)

2,6-diphenyl-4H-thiopyran-
4.0 g of 4-one was dissolved in 100 ml of diethyl ether, and while cooling in an ice water bath, 21 m of a 1M solution of methylmagnesium iodide in diethyl ether under a nitrogen atmosphere.
1 was added dropwise, and the mixture was stirred and reacted at room temperature for 3 hours. The reaction mixture was poured into a saturated aqueous ammonium chloride solution (500 ml) to extract an organic substance. To the separated organic layer, 100 ml of a 60% aqueous solution of perchloric acid was added, and the mixture was allowed to stand overnight for precipitation. The precipitated crystals were collected by filtration to obtain 3.7 g of 2,6-phenyl-4-methyl-4H-thiopyrylium perchlorate 3d. (54% yield)

3.0 g of 2,6-diphenyl-4-methyl-4H-thiopyrylium perchlorate and 0.93 of squaric acid
g was dispersed in a mixed solvent of 50 ml of 1-butanol and 50 ml of toluene, and 1.2 g of quinoline was added, followed by heating under reflux for 2 hours. The reaction mixture was allowed to cool and then concentrated, and toluene 200
Then, the filtrate was recrystallized from acetonitrile to give 3.2 g of Exemplified Compound P-25.
Obtained. (Yield 65%, total yield of all 5 steps 10.8%)

Embodiment 4

[0205]

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In a nitrogen atmosphere, a solution of 10 g of 1-octyne dissolved in 25 ml of tetrahydrofuran was added dropwise while cooling 85 ml of a 1M solution of ethyl magnesium bromide in tetrahydrofuran with ice water. After completion of the dropwise addition, the reaction vessel was removed from the ice water bath, stirred at room temperature for 3 hours, and 3.4 g of ethyl formate was added dropwise while cooling again in the ice water bath. After the addition was completed, 25 ml of tetrahydrofuran was added, and 30 ml of 6N hydrochloric acid was added dropwise. The organic matter was extracted from the mixture after the reaction, and the separated organic layer was washed with water, concentrated, and then purified by column chromatography to obtain 8.2 g of heptadeca-7,10-diyn-9-ol 4a.
Obtained. The structure of the compound was confirmed by NKR spectrum, mass spectrum, infrared spectrum, and gas chromatography. (Yield 73%)

The Journal of Organic Chemistry of Ireland et al. (The Journal
of Organic Chemistry, Vol. 58, page 2899 (1
993) in a solution prepared by dissolving 12.8 g of Dess-Martin periodinane in 80 ml of methylene chloride.
A solution prepared by dissolving 7.5 g of diin-9-ol in 50 ml of methylene chloride was added, and the mixture was stirred at room temperature for 3 hours. 200 ml of diethyl ether was added to the reaction mixture, and the mixture was poured into 300 ml of a 1N aqueous solution of sodium hydroxide to extract organic substances. The separated organic layer was washed with water. The concentrated organic layer was purified by silica gel column chromatography to obtain 6.1 g of heptadec-7,10-diyn-9-one 4b. (Yield 82%)

Heptadeca was added to 30 ml of acetonitrile.
6.0 g of 7,10-diyn-9-one was added, and an aqueous solution prepared with 12 g of sodium sulfide nonahydrate and 30 ml of water was added, followed by stirring at room temperature for 30 minutes. After the reaction mixture was allowed to stand and the separated aqueous layer was removed, 50 ml of a saturated aqueous solution of ammonium chloride and 30 ml of ethyl acetate were added to extract organic substances.The separated organic layer was washed with water, concentrated, and then purified by silica gel column chromatography. 2,6
-Di-n-hexyl-4H-thiopyran-4-one 4c
Was obtained 4.5 g. (Yield 66%)

2.0 g of 2,6-di-n-hexyl-4H-thiopyran-4-one was added to 100 ml of diethyl ether.
And a 1M solution of methylmagnesium iodide in diethyl ether 1 under a nitrogen atmosphere while cooling in an ice water bath.
6 ml was added dropwise, and the mixture was stirred and reacted at room temperature for 3 hours. After adding 500 ml of a saturated aqueous solution of ammonium chloride to the reaction mixture, the organic matter was extracted. The separated organic layer was washed with water, dried over anhydrous sodium sulfate, and concentrated. The concentrated organic matter was used for the next reaction without purification.

The reaction product obtained in the previous step and 0.92 g of croconic acid were mixed with 30 ml of 1-butanol and 30 ml of toluene.
The mixture was dispersed in ml of a mixed solvent, quinoline (0.1 g) was added, and the mixture was heated and refluxed for 4 hours while stirring. After allowing the reaction mixture to cool, it was purified by column chromatography and further recrystallized to obtain 1.6 g of crystals of Exemplified Compound P-26.
(34% yield in 2 steps, 13.4 total yield in 5 steps)
%)

Example 5 (Preparation of silver halide grains) In 900 ml of pure water, 7.5 g of gelatin and 10 mg of potassium bromide were dissolved, and the temperature was adjusted to 35.
After adjusting the pH and the pH to 3.0, 370 ml of an aqueous solution containing 74 g of silver nitrate and an aqueous solution containing potassium bromide and potassium iodide in a molar ratio of (96/4) maintained at pAg 7.7 by a controlled double jet method. For 10 minutes. Thereafter, 4-hydroxy-6-methyl-1,3,3
a, 7-tetrazaindene was added to 0.3 g, and the pH was adjusted to 5 with NaOH to obtain a cubic iodobromide having an average grain size of 0.06 μm, a variation coefficient of projected diameter area of 8%, and a {100} plane ratio of 86% Silver particles were obtained. This emulsion was subjected to coagulation sedimentation using a gelatin coagulant, and after desalting, 0.1 g of phenoxyethanol was added to adjust the pH to 5.9 and the pAg to 7.5. Thereafter, sensitizing dye SD-1 was added in an amount of 5 × 10 ⁻⁵ mol per mol of silver halide, and 0.4% of 2- (4-chlorobenzoyl) benzoic acid was added thereto.
It was added so as to be 4 g / m ² . Thereafter, the temperature was raised to 60 ° C., 2 mg of sodium thiosulfate was added, the mixture was aged for 100 minutes, and then cooled to 38 ° C. to complete the chemical sensitization to obtain silver halide grains.

[0212]

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(Composition of Photosensitive Layer) Organic Fatty Acid Silver Emulsion 1.75 g (in silver) / m ² Bisacetamidohydrogenbromide perbromide 0.07 g / m ² Calcium bromide 0.05 g / m ^{2 2} -mercapto-5 - methylbenzimidazole 0.04 g / m ² 2-tribromomethylsulfonylpyridine 0.36 g / m ² hexamethylene diisocyanate 0.16 g / m ² phthalazine 0.30 g / m ² 4-methylphthalic 0.14 g / m ² tetra the chlorophthalic acid 0.10 g / m ² exemplified compound P-1 0.088g / m ² solvents were used methyl ethyl ketone, acetone, methanol appropriately.

(Surface Protective Layer Composition) A surface protective layer coating solution was prepared as follows. Cellulose acetate 2.3 g / m ² polymethyl methacrylate (particle size 10 μm) 0.02 g / m ² 1,1 bis (2-hydroxy-3,5-dimethylphenyl) -3,5,5-trimethylhexane 4 the .8 × 10 ^-3 mol / m ² benzotriazole 0.021 g / m ² of silicon dioxide (particle size 2μm) 0.22g / m ² solvents were used methyl ethyl ketone, acetone, methanol appropriately.

(Composition of Backing Layer) A coating solution for the backing layer was prepared as follows. Cellulose acetate 4g / m ² Exemplified compound P-1 0.019g / m ² Polymethyl methacrylate (particle size 10μm) 0.02g / m ²

The coating liquid having the above composition was biaxially stretched to a thickness of 1
Sample No. 101 was prepared by coating and drying on a 75 μm polyethylene terephthalate film. Samples Nos. 102 to 108 and 10A to 10L were prepared in the same manner as in Sample No. 101 except that the dye of Sample No. 101 was changed to the dye shown in Table 1. The amount of dye added was equimolar to that of Exemplified Compound 1 of Sample No. 101. Prepared photothermographic materials No. 101-108, 10A-10
L was processed to a half-cut size, and a 810 nm laser diode was exposed to a beam inclined by 13 ° from the vertical plane. Thereafter, heat development was performed at 120 ° C. for 15 seconds using a heat drum to obtain Sample Nos. 111 to 118 and 11A to 11L, respectively (see Table 1).

[0219]

[Table 1]

The following comparative dyes were used in the table.

[0219]

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Each of the above samples was evaluated according to the following evaluation method. "Evaluation of sharpness" Sample Nos. 111 to 118, 11A to 11L
The MTF at 0 lines / mm was measured, and the MTF value of sample No. 111 was 100
The relative values are shown below.

"Evaluation of residual color stain" The residual color stain was compared visually. The evaluation was based on a subjective evaluation using 10 monitors.The total score was 3 points where there was no practical problem and there were practical problems. Was compared.

[Evaluation of Transmission Density A] The transmission density of the dye used was measured at 420 nm when the transmission density at the maximum absorption wavelength was 1.0 in methyl ethyl ketone. [Evaluation of Transmission Density B] The transmission density at 420 nm of a photosensitive material containing a dye was measured when the transmission density at the maximum absorption wavelength after development processing was 1.0. Table 2 shows the evaluation results.

[0223]

[Table 2]

Table 2 shows that the sample of the present invention had good sharpness and little residual color stain. On the other hand, in the sample using the comparative organic dye, absorption in the visible region was large, and residual color stain was not acceptable.

Example 5-2 To a dye was added 10 times by weight of ethyl acetate and 10 times by weight of tricresyl phosphate (TCP). The mixture was ultrasonically dispersed while removing ethyl acetate under reduced pressure to obtain an average particle size. A 90 nm dye oil dispersion was prepared. Photosensitive material No. 101 of Example 5
Samples were prepared in the same manner as in Example 5 except that this dispersion was used instead of the dye solution when preparing the 10A to 10 L samples, and heat-developed in the same manner as in Example 5 to obtain samples No. 1
21 to 128 and 12A to 12L. The transmission density B and the sharpness and the residual color stain were evaluated in the same manner as in Example 5, and the results are shown in Table 3.

[0226]

[Table 3]

From Table 3, it can be seen that the sharpness of the comparative sample was deteriorated due to the oil dispersion, whereas the sample of the present invention surprisingly showed no deterioration in the sharpness and residual color stain even when the oil was dispersed. It turns out that it is preferable. Therefore, Example 5-
2, it can be seen that the present invention can obtain a more remarkable effect when dispersed in oil.

Example 5-3 A dye, an aqueous solution of gelatin and an aqueous solution of sodium dodecylbenzenesulfonate were mixed and ground together with zirconia beads for 24 hours using a ball mill, and the beads were removed.
An 80 nm dye solid particulate dispersion was prepared. Example 5 Example 5 was repeated except that this dispersion was used in place of the dye solution when preparing the light-sensitive material Nos. 101 to 108 and 10A to 10 L samples of Example 5.
Samples were prepared in the same manner as described above, and subjected to heat development in the same manner as in Example 5 to obtain Sample Nos. 131 to 138 and 13A to 13L, respectively. The transmission density B, sharpness, and residual color stain were evaluated in the same manner as in Example 5, and the results are shown in Table 4.

[0229]

[Table 4]

Example 5-4 The dye was added by mixing and kneading when the polyester was melted for biaxial stretching of the polyester.
In the same manner as described above, a support was prepared by biaxial stretching. Except for using this support, the same procedures as in Example 5 were carried out, and photosensitive materials Nos. 401 to 40 were used.
8, 40A to 40L were prepared. These samples were exposed and heat-developed in the same manner as in Example 5 to obtain samples Nos. 411 to 418 and 41A.
４１41 L. The transmission density B, residual color stain, and sharpness were evaluated in the same manner as in Example 5, and compared with the sample of Example 5, and the results are shown in Table 5.

[0231]

[Table 5]

Example 6 (Preparation of silver halide particles B) 24 g of phthalated gelatin and 30 mg of potassium bromide were dissolved in 700 ml of water, and the pH was adjusted to 5.0 at a temperature of 40 ° C.
159 ml of an aqueous solution containing 7 g and an aqueous solution containing potassium bromide and potassium iodide at a molar ratio of 92: 8 were added over 10 minutes by a controlled double jet method while maintaining a pAg of 7.8.

Subsequently, an aqueous solution 47 containing 55.4 g of silver nitrate
6 ml and 7 μmole of dipotassium hexachloride dipotassium /
An aqueous solution containing 1 liter and potassium bromide at 1 mol / liter was added over 30 minutes by a controlled double jet method while maintaining the pAg at 7.6. Thereafter, the pH was lowered to perform coagulation sedimentation and desalting treatment, and 0.2 g of phenoxyethanol was added to adjust the pH to 5.9 and the pAg to 8.0. Silver iodide content core 8 mol%, average 2 mol%, grain size 0.07 μm, variation coefficient of projected area diameter 10%,
Cubic particles having a (100) face ratio of 85%.

With respect to the obtained silver halide grains B, the temperature was raised to 60 ° C. to give 85 μmole of sodium thiosulfate per mole of silver and 2,3,4,5,6-pentafluorophenyldiphenylphosphine per mole of silver. 6 μmole selenide, 3.9 μmole chloroauric acid, 220 μm thiocyanate
Mole was added and aged for 120 minutes. After that the temperature is raised to 50
The temperature was changed to ° C., and 5 × 10 ^-4 mol of sensitizing dye C and 3 × 10 ^-4 mol of sensitizing dye D were added to 1 mol of silver halide with stirring. Further, potassium iodide was added to silver at a ratio of 3.7.
The resulting mixture was stirred for 30 minutes and rapidly cooled to 30 ° C. to complete the preparation of silver halide grains B.

[0235]

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(Preparation of Organic Acid Silver Crystalline Dispersion B) 40 g of behenic acid, 7.3 g of stearic acid and 500 ml of water were stirred at 90 ° C. for 20 minutes, and 187 ml of 1N NaOH was added over 15 minutes, and 1N NaOH was added. A nitric acid aqueous solution (61 ml) was added, and the temperature was lowered to 50 ° C.

Next, 124 ml of a 1N silver nitrate aqueous solution was added over 2 minutes, and the mixture was stirred for 40 minutes. Thereafter, the solid content was separated by centrifugal filtration, and the conductivity of the filtrate was 30 μS / cm.
The solid content was washed with water until it became. The solid content thus obtained was handled as a wet cake without drying, and 12 g of polyvinyl alcohol and 150 ml of water were added to a wet cake equivalent to 33.4 g of dry solid content and mixed well to form a slurry. This slurry was charged into a dispersing machine (trade name: Microfluidizer M-110-E / H, manufactured by Microfluidics Corporation, wall collision type chamber) to perform a dispersion operation. The pressure at the time of the collision at this time was 500 kg / cm ² . Thus, the preparation of the microcrystal dispersion B of the organic acid silver, which is needle-like particles having an average minor axis of 0.04 μm, an average major axis of 0.8 μm, and a projected area variation coefficient of 35% by electron microscopy was completed.

(Preparation of Dispersion of Reducing Agent Solid Fine Particles) 1,1-
Bis (2-hydroxy-3,5-dimethylphenyl)-
1.5 g of hydroxypropylmethylcellulose and 88.5 m of water per 10 g of 3,5,5-trimethylhexane
The mixture was stirred well and left as a slurry for 3 hours. Then, 0.5g zirconia beads 360g
Prepare and put it in the vessel together with the slurry.
/ 4G sand grinder mill: manufactured by Imex Co., Ltd.) for 3 hours to prepare a dispersion of solid fine particles of a reducing agent.
The particle size is such that 80 wt% of the particles are 0.3 μm or more and 1.0 μm.
m or less.

(Preparation of antifoggant solid fine particle dispersion) 1.5 g of hydroxypropylmethylcellulose and 88.5 g of water per 10 g of tribromomethylphenylsulfone.
The mixture was added, stirred well, and left as a slurry for 3 hours.
Thereafter, a solid fine particle dispersion of the antifoggant was prepared in the same manner as in the preparation of the reducing agent solid dispersion. Particle size is 70wt%
(% By weight, the same in the present specification) was 0.3 μm or more and 1.0 μm or less.

(Preparation of Solid Fine Particle Dispersion of Color Tone) 1.5 g of hydroxypropylmethylcellulose and 88.5 g of water were added to 10 g of phthalazine, and the mixture was stirred well and allowed to stand for 5 hours. Thereafter, a solid fine particle dispersion of a color tone agent was obtained in the same manner as in the preparation of the reducing agent fine particle dispersion. The average particle diameter was 0.3 μm or more and 1.0 μm or less for all of 60 wt% or more.

(Preparation of Development Accelerator Fine Particle Dispersion)
0.7 g of hydroxypropylmethylcellulose and 94.3 ml of water were added to 5 g of -dihydro-4-oxo-1,2,3-benzotriazine, stirred well, and left for 2 hours. Thereafter, a fine particle dispersion of a development accelerator was prepared in the same manner as in the preparation of the reducing agent fine particle dispersion. The average particle diameter of 70 wt% was 0.4 μm or more and 1.0 μm or less.

(Preparation of Emulsion Layer Coating Solution) The silver halide grains B were added to the previously prepared organic acid silver microcrystal dispersion B (corresponding to 1 mol of silver) at 10 mol% of silver halide / 1 mol of organic acid silver. The following polymer latex and materials were added to obtain an emulsion coating solution.

LACSTAR3307B (manufactured by Dainippon Ink and Chemicals, SBR latex) 431 g 1,1-bis (2-hydroxy-3,5-dimethylphenyl) -3,5,5-trimethylhexane (solid fine particle dispersion) 98 g tribromomethylphenylsulfone (solid fine particle dispersion) 21.8 g 3,4-dihydro-4-oxo-1,2,3-benzotriazine (solid fine particle dispersion) 4.3 g

(Preparation of Coating Solution for Emulsion Surface Protective Layer) For 10 g of inert gelatin, 0.26 g of surfactant A, 0.10 g of surfactant B, and silica fine particles (average particle size: 2.5 μm) 0 g, 0.4 g of 1,2- (bisvinylsulfonylacetamide) ethane, 65 mg of 4-methylphthalic acid, and 66 g of water were added to form a surface protective layer.

[0245]

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(Preparation of Dye Dispersion) To 35 g of ethyl acetate, 2.5 g and 7.5 g of the following compounds 1 and 2, respectively.
Add and stir to dissolve. 50 g of a 10% by weight solution of polyvinyl alcohol dissolved in advance was added to the solution, and the mixture was stirred with a homogenizer for 5 minutes. Thereafter, the ethyl acetate was volatilized by removing the solvent, and finally diluted with water to prepare a color former dispersion.

[0247]

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(Preparation of Back Surface Coating Solution) The color former dispersion 51 previously prepared was added to 30 g of polyvinyl alcohol.
g, the following compound 320 g, water 250 g, and Sildex H121 (spherical silica manufactured by Dokai Chemical Co., Ltd., average size 12 μm)
m) 2.0 g was added to obtain a back surface coating solution.

[0249]

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(Preparation of coating sample) The coating solution of the emulsion layer prepared as described above was 175 μm colored with a blue dye.
The coating amount of silver was adjusted to 1.8 g / m ² on the polyethylene terephthalate support, and the coating amount of gelatin was adjusted to 1.8 g / m ² on the emulsion coating layer.
At the same time. After drying, the coating solution for the back surface was coated on the surface opposite to the emulsion layer with an optical density of 650 nm of 0.7.
And the preparation of the coated sample 601 was completed.
In "Preparation of Dye Dispersion", coating samples prepared as shown in Table 6 were prepared in the same manner as coating sample 601, except that Compounds 1 and 2 were removed, and the dyes shown in Table 6 were added in the same molar amount as Compound 1.

(Evaluation of photographic performance) A Kr laser sensitometer of 647 nm (maximum output: 500 mW) was 30
After exposing the photographic material at an angle of degrees, the coated sample is
The image was developed for 20 seconds, and the obtained image was evaluated in Example 1.
The same was done. The results are shown in Table 6.

[0252]

[Table 6]

As is clear from Table 6, the samples of the present invention had good sharpness and little residual color stain.

Example 7 In the preparation of silver halide grains B prepared in Example 6, sensitizing dyes E and F were used in place of sensitizing dyes C and D, and otherwise the same as in the preparation of silver halide grains B. Thus, silver halide grains C were prepared and used in place of silver halide grains B. The photographic performance was evaluated using a laser sensitometer equipped with an 810 nm diode instead of the sensitometer used in the evaluation of the photographic performance in Example 6. The dyes shown in Table 7 were changed. The preparation and evaluation of the sample were conducted in the same manner as in Example 6 except for the above, and the results shown in Table 7 were obtained.

[0255]

[Table 7]

[0256]

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Example 8 (Preparation of silver halide particles α) 7.5 g of inert gelatin and 10 mg of potassium bromide were dissolved in 900 ml of water, and the pH was adjusted to 3.0 at a temperature of 35 ° C.
An aqueous solution containing 370 ml of an aqueous solution containing 4 g of potassium bromide and potassium iodide in a molar ratio of 94: 6 and containing K3 [IrCl6] was added over 10 minutes by a control double jet method while keeping the pAg at 7.7. [IrCl
l6 3- is 3 × 10 per mol of silver ^- was added to a ⁷ molar. Then, 4-hydroxy-6-methyl-1,3,
0.3 g of 3a, 7-tetrazaindene was added and NaO was added.
The pH was adjusted to 5 with H to obtain cubic silver iodobromide grains having an average size of 0.06 μm, a variation coefficient of projected area of 8%, and a {100} face ratio of 87%. This emulsion was subjected to coagulation sedimentation using a gelatin coagulant and desalting, and then 0.1 g of phenoxyethanol.
Was adjusted to pH 5.9 and pAg 7.5.

(Preparation of Organic Acid Silver Emulsion α) Behenic acid
6 g and 300 ml of distilled water were mixed at 90 ° C. for 15 minutes, and 31.1 ml of a 1N aqueous solution of NaOH was added over 15 minutes with vigorous stirring.
The temperature was lowered to ° C. Next, 7 ml of a 1N-phosphoric acid aqueous solution is added, and 0.13 g of N-bromosuccinimide is added while stirring more vigorously. Then, the silver halide particles A prepared in advance have a silver halide amount of 2.5 mmol. Was added as follows. Further, 25 ml of a 1N silver nitrate aqueous solution was added to 2 ml.
The mixture was continuously added over a period of minutes, and stirring was continued for 90 minutes.
37 g of a 1.2% by weight butyl acetate solution of polyvinyl acetate was added to the aqueous mixture to form flocs of the dispersion, and then water was removed, followed by two additional water washes and water removal. Thereafter, a 2.5 wt% butyl acetate / isopropyl alcohol 1: 2 mixed solution 20 of polyvinyl butyral (Denka Butyral # 3000-K manufactured by Denki Kagaku Kogyo Co., Ltd.) was used.
g was added with stirring.

Then, polyvinyl butyral (Denka Butyral # 4000-2, manufactured by Denki Kagaku Kogyo Co., Ltd.) was added to the thus obtained mixture of the gelled organic acid and silver halide.
8 g and 2-butanone (57 g) were added and dispersed with a homogenizer to obtain a silver behenate emulsion (acicular particles having an average minor axis of 0.04 μm, an average major axis of 1 μm, and a variation coefficient of 30%).

[0260]

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(Preparation of Emulsion Layer Coating Solution α) The following chemicals were added to the above-obtained organic acid silver emulsion in the following amounts per mole of silver. At 25 ° C., 10 mg of sodium phenylthiosulfonate, 25 mg of sensitizing dye AA, 20 mg of sensitizing dye BB, 18 mg of sensitizing dye CC, and 2-mercapto-5
2-methylbenzimidazole (2 g), 4-chlorobenzophenone-2-carboxylic acid (21.5 g) and 2-butanone (580)
g and dimethylformamide (220 g) were added with stirring and left for 3 hours. Then, 4,6-ditrichloromethyl
4 g of 2-phenyltriazine, 2 g of disulfide compound A, 170 g of 1,1-bis (2-hydroxy-3,5-dimethylphenyl) -3,5,5-trimethylhexane, 5 g of tetrachlorophthalic acid, 15 g of phthalazine, 10 g of hydrazine compound A, 1.1 g of Megafax F-176P (fluorinated surfactant manufactured by Dainippon Ink and Chemicals, Inc.), 1.1 g of 2-butanone, and 10 g of methyl isobutyl ketone were added with stirring.

(Preparation of Emulsion Surface Protective Layer Coating Solution α) CAB1
75 g of 71-15S (cellulose acetate butyrate manufactured by Eastman Chemical Company), 5.7 of 4-methylphthalic acid (C-8)
g, tetrachlorophthalic anhydride 1.5 g, tribromomethylsulfonylbenzene 8 g, 2-tribromomethylsulfonylbenzothiazole 6 g, phthalazone 3
g, 0.3 g of Megafax F-176P, Sildex H31 (average size of spherical silica 3 μm manufactured by Dokai Chemical Co., Ltd.)
m) 2 g, 6 g of sumidur N3500 (polyisocyanate manufactured by Sumitomo Bayer Urethane Co., Ltd.) in 2-butanone 3
A solution dissolved in 070 g and 30 g of ethyl acetate was prepared.

(Preparation of Support Having Back Surface) Polyvinyl butyral (Denka Butyral # manufactured by Denki Kagaku Kogyo KK)
4000-2) 6 g, 0.2 g of Sildex H121 (average size of true spherical silica 12 μm, manufactured by Dokai Chemical Co.), 0.2 g, 0.1 g of Sildex H51 (average size 5 μm of true spherical silica, manufactured by Dokai Chemical). Megafax F-17
6P was added to 64 g of 2-propanol with stirring, dissolved and mixed. Further, a mixed solution of 410 mg of Dye A in 10 g of methanol and 20 g of acetone and a solution of 0.8 g of 3-isocyanatomethyl-3,5,5-trimethylhexyl isocyanate in 6 g of ethyl acetate were added, and the coating solution was added. Prepared.

A coating solution for the back side was applied to a polyethylene terephthalate film having a moisture-proof undercoat containing vinylidene chloride on both sides so as to have an optical density of 780 nm of 0.7.

After coating the emulsion layer coating solution on the support prepared as described above so that the silver content was 2 g / m ² , the emulsion surface protective layer coating solution was dried on the emulsion surface to a dry thickness of 5 μm. To prepare a sample 801 of the heat-developable recording material. A sample was prepared in the same manner as in 801 except that Dye A was replaced with the dye shown in Table 8 and an equivalent amount of Dye A, as shown in Table 8.

[0266]

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[0267]

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(Exposure, Development) Exposure to xenon flash light with a light emission time of 10-4 sec through a step wedge through an interference filter having a peak at 780 nm,
After processing (developing) at 115 ° C. for 25 seconds, photographic performance was evaluated.

(Evaluation of Sharpness) Evaluation was performed in the same manner as in Example 1. (Evaluation of Remaining Color) Evaluation was made in the same manner as in Example 1. The results are shown in Table 8.

[0270]

[Table 8]

Example 9 (Preparation of silver halide grains β) After dissolving 22 g of phthalated gelatin and 30 mg of potassium bromide in 700 ml of water and adjusting the pH to 5.0 at a temperature of 40 ° C., silver nitrate 1
159 ml of an aqueous solution containing 8.6 g and an aqueous solution containing potassium bromide were added over 10 minutes by a control double jet method while maintaining the pAg at 7.7. K3 [IrCl
6] An aqueous solution containing 8 × 10 ^-6 mol / l of 3- and potassium bromide at 1 mol / l was added over 30 minutes by the control double jet method while maintaining the pAg at 7.7. Thereafter, pH was adjusted to 5.9 and pAg to 8.0.

The obtained particles had an average particle size of 0.07
Cubic particles having a μm, a variation coefficient of projected area diameter of 8%, and a (100) area ratio of 86%.

The above silver halide grains β were heated to a temperature of 60 ° C., and 8.5 × 10 ⁻⁵ mol of sodium thiosulfate and 1.1 × 10 ⁻⁵ mol of 2,3, 4,5,6-
Pentafluorophenyldiphenylsulfine selenide,
3.3 × 10 ^-6 mol of chloroauric acid and 2.3 × 10 ^-4 mol of thiocyanic acid were added and the mixture was aged for 120 minutes. Thereafter, the temperature was raised to 50 ° C., 8 × 10 ⁻⁴ mol of sensitizing dye C was added with stirring, and 3.5 × 10 ⁻² mol of potassium iodide was further added, followed by stirring for 30 minutes. The mixture was rapidly cooled to ℃ to complete the preparation of silver halide grains.

(Preparation of Dispersion of Organic Crystalline Silver Crystals) 40 g of behenic acid, 7.3 g of stearic acid and 500 ml of distilled water were added to 9
Mix at 0 ° C. for 15 minutes and, with vigorous stirring,
187 ml of an OH aqueous solution was added over 15 minutes, and 61 ml of a 1N-nitric acid aqueous solution was added, and the temperature was lowered to 50 ° C. next,
124 ml of a 1N silver nitrate aqueous solution is added and
Stirred for minutes. Thereafter, the solid content was filtered by suction filtration, and the solid content was washed with water until the conductivity of the filtrate reached 30 μS / cm. The solid content thus obtained was handled as a wet cake without drying, and 12 g of polyvinyl alcohol was added to a wet cake equivalent to 34.8 g of dry solid content.
And 150 ml of water were added and mixed well to form a slurry. 840 g of zirconia beads having an average diameter of 0.5 mm
Was prepared and put into a vessel together with the slurry, and dispersed for 5 hours with a dispersing machine (1 / 4G-sand grinder mill: manufactured by Imex Co., Ltd.) to obtain a silver microparticle dispersion of organic acid silver having a volume weighted average of 1.5 μm. Was. Particle size measurement is available from Malver
n Instruments Ltd. Performed by MasterSaizerX.

(Preparation of Material Solid Fine Particle Dispersion) Tetrachlorophthalic acid, 4-methylphthalic acid, 1,1-bis (2-hydroxy-3,5-dimethylphenyl) -3,5,5-trimethylhexane, phthalazine And a solid fine particle dispersion of tribromomethylsulfonylbenzene.

To tetrachlorophthalic acid, 0.81 g of hydroxypropylcellulose and 94.2 ml of water were added, stirred well, and left as a slurry for 10 hours. Thereafter, 100 ml of zirconia beads having an average diameter of 0.5 mm and a slurry were put together in a vessel, and dispersed in a dispersing machine of the same type as that used for preparing the silver salt of organic acid microcrystals for 5 hours. A solid microcrystalline dispersion of the acid was obtained. As for the particle size of the solid fine particles, 70 wt% was 1.0 μm or less.

With respect to the other materials, the amount of the dispersant used and the dispersion time were appropriately changed in order to obtain a desired average particle size, and a solid fine particle dispersion was obtained.

(Preparation of Emulsion Layer Coating Solution) The following compositions were added to the previously prepared organic acid silver microcrystal dispersion to prepare emulsion coating solutions. Organic acid silver microcrystal dispersion 1 mol Silver halide particles β 0.05 mol Binder: SBR latex (LACSTAR3307B manufactured by Dainippon Ink and Chemicals, Inc.) 430 g Material for development: Tetrachlorophthalic acid 5 g 1,1-bis (2-bis) (Hydroxy-3,5-dimethylphenyl) -3,5,5-trimethylhexane 98 g phthalazine 9.2 g tribromomethylphenylsulfone 12 g 4-methylphthalic acid 7 g hydrazine compound A 7 g LACSTAR3307B is a latex of a styrene-butadiene copolymer. Yes, the average particle size of the dispersed particles is 0.1 to 0.15 μm,
The equilibrium water content in H was 0.6 wt%.

[0279]

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(Preparation of Emulsion Protective Layer Coating Solution) The following compositions were added to inert gelatin to prepare an emulsion protective layer coating solution. Inert gelatin 10 g Surfactant A 0.26 g Surfactant B 0.09 g Silica fine particles (average particle size 2.5 μm) 0.9 g 1,2- (bisvinylsulfone acetamide) ethane 0.3 g Water 64 g

[0281]

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[0282]

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(Preparation of Back Surface Coating Solution) The following components were added to polyvinyl alcohol to prepare a back surface coating solution. Polyvinyl alcohol 30 g Dye A 5 g Water 250 g Sildex H121 (Dorokai Chemical Co., Ltd., spherical silica average size 12 μm) 1.8 g

The emulsion layer coating solution prepared as described above was coated with 1.6 g / m ^{2 of} silver on a polyethylene terephthalate support.
It was applied so that The emulsion layer protective layer coating solution was coated thereon so that the coating amount of gelatin became 1.8 g / m ² . After drying, apply the back side coating solution on the side opposite to the emulsion layer for 7 minutes.
The sample was applied so that the optical density at 80 nm was 0.7, and a sample 901 was formed. A sample was prepared in the same manner as in 901 except that Dye A was replaced with the dye shown in Table 9 and an equivalent amount of Dye A, as shown in Table 9. The photosensitive material thus produced was evaluated in the same manner as in Example 9. Table 9 shows the results.

[0285]

[Table 9]

The following is a description of embodiments of claims 34 and 35. Example 10 (Preparation of silver halide grains) In 900 ml of pure water, 7.5 g of gelatin and 10 mg of potassium bromide were dissolved and the temperature was adjusted to 3
After adjusting the pH to 5 ° C. and the pH to 3.0, 370 ml of an aqueous solution containing 74 g of silver nitrate and a controlled double jet while maintaining an aqueous solution containing potassium bromide and potassium iodide in a molar ratio of (96/4) at pAg 7.7. The method was added over 10 minutes. Thereafter, 4-hydroxy-6-methyl-1,
0.3 g of 3,3a, 7-tetrazaindene was added and Na was added.
Adjust the pH to 5 with OH and average particle size 0.06μ
m, coefficient of variation of projected diameter area 8%, {100} surface ratio 8
6% of cubic silver iodobromide grains were obtained. This emulsion was subjected to coagulation sedimentation using a gelatin coagulant, and after desalting, 0.1 g of phenoxyethanol was added to adjust the pH to 5.9 and the pAg to 7.5. Thereafter, sensitizing dye SD-1 was added at 5 × 10 ⁻⁵ mol per mol of silver halide, and 2- (4-chlorobenzoyl) benzoic acid was added at 0.44 g / m ² . Thereafter, the temperature was raised to 60 ° C. to remove sodium thiosulfate for 2 m.
After ripening for 100 minutes and cooling to 38 ° C., chemical sensitization was completed to obtain silver halide grains.

(Preparation of Organic Fatty Acid Silver Emulsion) 300 ml of water
10.6 g of behenic acid was put therein, dissolved by heating at 90 ° C., and 31.1 ml of 1N sodium hydroxide was sufficiently stirred.
Was added and left as it was for 1 hour. Then 3
After cooling to 0 ° C., 7.0 ml of 1N phosphoric acid was added, and 0.01 g of N-bromosuccinimide was added with sufficient stirring. Thereafter, the silver halide grains prepared at 40 ° C. were adjusted to 10 mol% as silver based on the behenic acid.
While stirring while heating. Further, 25 ml of a 1N aqueous solution of silver nitrate was continuously added over 2 minutes, and the mixture was allowed to stand for 1 hour with stirring.

To this emulsion, polyvinyl butyral dissolved in ethyl acetate was added, stirred sufficiently, and allowed to stand to separate into an ethyl acetate phase containing silver behenate grains and silver halide grains and an aqueous phase. After removing the aqueous phase, silver behenate grains and silver halide grains were collected by centrifugation. Thereafter, 20 g of synthetic zeolite A-3 (sphere) manufactured by Tosoh Corporation and 22 ml of isopropyl alcohol were added, and the mixture was allowed to stand for 1 hour and filtered. Further, 3.4 g of polyvinyl butyral and 23 ml of isopropyl alcohol were added, and the mixture was sufficiently stirred and dispersed at 35 ° C. at a high speed to complete the preparation of the organic fatty acid silver emulsion.

(Photosensitive Layer Composition) Organic Fatty Acid Silver Emulsion 1.75 g (in silver) / m ² Pyridinium Hydrobromide Perbromide 0.07 g / m ² Calcium Bromide 0.05 g / m ^{2 2} -mercapto-5-methylimidazole 0.04 g / m ² tribromomethylsulfonylquinoline 0.36 g / m ² hexamethylene diisocyanate 0.16 g / m ² phthalazine 0.30 g / m ² 4-methylphthalic acid 0.14 g / m ² tetrachlorophthalic acid 0.10 g As the / m ² solvent, methyl ethyl ketone, acetone, and methanol were appropriately used.

(Composition of Surface Protective Layer) A coating solution for a surface protective layer was prepared as follows. ^3. Cellulose acetate 2.3 g / m ² polymethyl methacrylate (particle size 10 μm) 0.02 g / m ² 1,1-bis (2-hydroxy-3,5-dimethylphenyl) -3,5,5-trimethylhexane 8 × the 10 ^-3 mol / m ² exemplified compound 1 0.024 g / m ² benzotriazole 0.021 g / m ² of silicon dioxide (particle size 2μm) 0.22g / m ² solvent, suitably ethyl ketone, acetone, methanol Using.

(Composition of Backing Layer) A coating solution for the backing layer was prepared as follows. Cellulose acetate 4g / m ² Exemplified Compound 1 0.019 g / m ² Polymethyl methacrylate (particle size 10μm) 0.02g / m ² was applied to a polyethylene terephthalate film having a thickness of 175μm, which is biaxially stretched with a composition as described above And dried to prepare a sample 101. Sample 102 was prepared in the same manner as Sample 101 except that Dye 1 of Sample 101 was changed to the dye shown in Table 1.
~ 111 were created. When the comparative dyes G and H were used, the solubility of the dyes was low and required twice as much solvent as other samples.
The amount of dye added was equimolar to that of Exemplified Compound 1 of Sample 101.

The prepared photothermographic materials 101 to 111 were processed into half-cut sizes, and a 810 nm laser diode was exposed to a beam inclined by 13 ° from the vertical plane. Thereafter, heat development was performed at 120 ° C. for 15 seconds using a heat drum to obtain samples 111 to 1111, respectively.

[0293]

[Table 10]

[0294]

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[0295]

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"Evaluation of Sharpness" Samples 1101-1111
The MTF at 10 lines / mm was measured.
Are shown as relative values with the MTF value of 100 as 100.

"Evaluation of residual color stain" The residual color stain was compared visually. The evaluation was made by subjective evaluation using 10 monitors. The total score was 3 points where there was no practical problem and there were practical problems. Was compared. Table 11 shows the results.

[0298]

[Table 11]

Table 11 shows that the sample of the present invention had good sharpness and little residual color stain. In the sample using the comparative organic dye, the absorption in the visible region was large, and the residual color stain was unacceptable.

Example 11 Each dye used in Example 10 was added to a 10-fold weight of tricresyl phosphate (T
CP) was added thereto, and the mixture was ultrasonically dispersed while removing ethyl acetate under reduced pressure to prepare an oil-dispersed dye having an average particle diameter of 90 nm. A sample was prepared in the same manner as in Example 1 except that this oil-dispersed dye was used in place of the dye solution when preparing the samples of the photosensitive materials 101 to 111 of Example 1, and subjected to heat development in the same manner as in Example 10. To obtain samples 1201 to 1211, respectively. The sharpness and the residual color stain were evaluated in the same manner as in Example 10. Table 12 shows the results.

[0301]

[Table 12]

While the comparative sample was deteriorated in sharpness by using an oil-dispersed dye, the sample of the present invention surprisingly deteriorated both sharpness and residual color stain even in an oil-dispersed dye. Not preferred. Sample 1204,
In No. 1205, precipitation of the dye occurred, and the transparency of the sample was impaired.

From Example 11, it can be seen that the present invention can obtain more remarkable effects when dispersed in oil.

Example 12 A dye and an aqueous solution of gelatin and an aqueous solution of sodium dodecylbenzenesulfonate were mixed and ground together with zirconia beads for 24 hours using a ball mill, and the beads were removed to prepare a solid dispersion dye of a dye having an average particle diameter of 80 nm. did. Example 1 Example 1 was repeated except that this solid dispersion dye was used instead of the dye solution when preparing the samples of the light-sensitive materials 101 to 109 of Example 10.
Samples were prepared in the same manner as in Sample No. 0 and subjected to heat development in the same manner as in Example 10 to obtain Samples 131 to 139, respectively. The sharpness and the residual color stain were evaluated in the same manner as in Example 10. Table 13 shows the results.

[0305]

[Table 13]

While the sharpness of the comparative sample was deteriorated by using the solid dispersion dye, the sample of the present invention surprisingly showed that both the sharpness and residual color stain deteriorated even with the solid dispersion dye. Not preferred.

Example 13 In Example 10, the addition of Exemplified Compound 1 which had been added to the backing layer was stopped, and instead, it was added to a polyester support so that the amount per unit area became equal. The dye was added by mixing and kneading when the polyester was melted for biaxial stretching of the polyester, and then biaxially stretched in the same manner as in Example 10 to prepare a support.

Light-sensitive materials 401 to 409 were prepared in the same manner as in Example 10 except that this support was used. These samples were exposed and thermally developed in the same manner as in Example 10,
419. The residual color stain and sharpness were evaluated in the same manner as in Example 10, and compared with the sample of Example 10. Table 1 shows the results
It is shown in FIG.

[0309]

[Table 14]

Sample 41 in which the dye of the present invention was added to a support
Samples Nos. 1, 412, and 413 were samples 1 added to the backing layer.
Sharpness is more preferable than 12, and the residual color stain is not deteriorated. On the other hand, although some of the comparative samples have slightly improved sharpness, the residual color stain is deteriorated in all samples, which is not preferable.

Example 13 shows that the technique of the present invention shows a remarkable effect when applied to a support.

[0312]

According to the present invention, a dye having excellent solubility in an organic solvent and excellent in solid dispersion and oil dispersion suitability is used.
Image forming materials, heat-developable photographic photosensitive materials, halogens with good sharpness, little residual color stain, good image silver tone "cool black tone", good storage stability and excellent dry processability A silver halide photographic material, an image forming method thereof, an optical filter having preferable spectral characteristics, and a support for an image forming material such as a silver halide photographic material can be provided.

 ──────────────────────────────────────────────────の Continued on the front page (72) Inventor Kaori Ohno 1 Sakura-cho, Hino-shi, Tokyo Inside Konica Corporation (72) Inventor Ikemi Dai-ichi 1 Sakura-machi, Hino-shi, Tokyo Inside Konica Corporation (72) Inventor Norio Miura 1 Sakuracho, Hino-shi, Tokyo Konica Corporation F-term (Reference) 2H023 AA00 BA00 CD15 FA00 FD01 2H048 AA16 BA29 CA04 CA14 2H123 AB00 AB03 AB23 BB00 BB11 BB31 CA16 CA22 CB00 CB03 4H056 CA02 CA05 CB01 CC02 CC02

Claims (39)

[Claims] 1. An image-forming material comprising a dye having a transmission density of less than 0.03 at 420 nm when the transmission density at a maximum absorption wavelength is 1.0 in methyl ethyl ketone. (2) a maximum absorption wavelength of not less than 600 nm and not more than 900 nm;
2. The image forming material according to claim 1, wherein: 3. The absorption maximum wavelength is 750 nm or more and 900 nm.
2. The image forming material according to claim 1, wherein: 4. An image forming material, wherein the transmission density at 420 nm is 0.15 or less when the transmission density at the maximum absorption wavelength after development processing is 1.0. 5. The image forming material according to claim 1, wherein said image forming material contains silver halide. 6. The image forming material according to claim 1, further comprising an organic silver salt. 7. An image forming method for forming an image by imagewise exposing and developing the image forming material, wherein the image forming material according to claim 1 is used. Forming method. 8. A method for forming an image of a photothermographic material, wherein a latent image is formed by exposure and subsequently an image is substantially formed by thermal development. An image forming method for a heat-developable photographic light-sensitive material, comprising: 9. The image forming material according to claim 1, wherein the dye is a compound represented by the following general formula 1, 2, 3 or 4. Embedded image "In the formula, A ₁ and B ₁ each represent a substituent excluding a naphthalene group." "Wherein A ₂ and B ₂ represent a substituent." "In the formula, R _{1 to} R ₄ represent a hydrogen atom or an alkyl group.
A ₃ , B ₃ , A _4, and B ₄ represent the bond between the carbon atom represented by C in the general formula and the original group when the line connecting the carbon atom is rotated 180 ° about the axis. Represents a group that can completely overlap. However, the sum of the hydroxyl groups of A ₃ and B ₃ is 0 or more and 1 or less, and the sum of the hydroxyl groups of A ₄ and B ₄ is also 0 or more and 1 or less. " 10. A support having a layer containing at least one of the dyes according to claim 1 and a water-soluble binder, and having been spectrally sensitized to 600 nm or more and 700 nm or less. An image forming material such as a heat-developable photographic light-sensitive material characterized by the following. 11. An image formation of a silver halide photographic material or the like, comprising a layer containing at least one of the dyes according to claim 1 and a water-soluble binder on a support. material. 12. A thiopyrylium squarylium dye, a thiopyrylium croconium dye, a pyrylium squarylium dye, a pyrylium crokonium dye, a selenapyrylium squarylium dye, a selenapyrylium croconium dye, a telluropyrylium squarylium An image forming material such as a silver halide photographic light-sensitive material, having a layer containing at least one selected from a dye and a telluropyrylium croconium dye and a water-soluble binder. 13. The image forming material according to claim 1, further comprising a hydrazine compound. 14. An optical filter comprising at least one of the dyes according to claim 1. Description: 15. A support for an image forming material such as a silver halide photographic light-sensitive material, comprising at least one of the dyes according to claim 1. 16. A thermal image containing at least one dye represented by the following general formula 1, characterized in that a latent image is formed by exposure and subsequently an image is substantially formed by thermal development. An image forming method for a developed photographic photosensitive material. Embedded image "In the formula, A ₁ and B ₁ represent a substituent excluding a naphthalene group." 17. A photothermographic material comprising a dye represented by the following general formula 2. Embedded image "In the formula, A ₂ and B ₂ represent a substituent." 18. A silver halide photographic light-sensitive material containing a dye represented by the following formula 3 or 4. Embedded image "In the formula, R _{1 to} R ₄ represent a hydrogen atom or an alkyl group.
A ₃ , B ₃ , A _4, and B ₄ represent the bond between the carbon atom represented by C in the general formula and the original group when the line connecting the carbon atom is rotated 180 ° about the axis. Represents a group that can completely overlap. However, the sum of the hydroxyl groups of A ₃ and B ₃ is 0 or more and 1 or less, and the sum of the hydroxyl groups of A ₄ and B ₄ is also 0 or more and 1 or less. " 19. The silver halide photographic light-sensitive material according to claim 9, wherein the dye represented by the general formula 3 or 4 is represented by the following general formula 5 or 6. And other image forming materials. Embedded image "In the formula, R _{1 to} R ₄ represent a hydrogen atom or an alkyl group.
ZA3, ZB3, ZA4, ZB4 have 6 carbon atoms.
Represents the atoms necessary to construct a membered heterocycle. " 20. A thiopyrylium squarylium dye, a thiopyrylium croconium dye, a pyrylium squarylium dye, a pyrylium crokonium dye, a selenapyrylium squarylium dye, a selenapyrylium croconium dye, a telluropyrylium squarylium dye, and a tellurium dye An image-forming material such as a silver halide photographic light-sensitive material, comprising at least one selected from pyrylium croconium dyes. 21. A thiopyrylium squarylium dye, a thiopyrylium crokonium dye, a pyrylium squarylium dye, a pyrylium croconium dye, a selenapyrylium squarylium dye, a selenapyrylium croconium dye, a telluropyrylium squarylium dye, and a tellurium dye The pyrylium croconium dye is a compound having a nucleus represented by the following general formula 7:
0. An image-forming material such as a silver halide photographic light-sensitive material described in 0. Embedded image “In the formula, X ₁ and X ₂ each represent an oxygen atom, a sulfur atom, a selenium atom, or a tellurium atom, and R ₅ and R ₆ represent a hydrogen atom or an alkyl group.” 22. A thiopyrylium squarylium dye, a thiopyrylium crokonium dye, a pyrylium squarylium dye, a pyrylium croconium dye, a selenapyrylium squarylium dye, a selenapyrylium croconium dye, a telluropyrylium squarylium dye, and a tellurium 21. The image forming material according to claim 20, wherein the pyrylium croconium dye is represented by the following general formula 8. Embedded image In the formula, X ₁ and X ₂ each represent an oxygen atom, a sulfur atom, a selenium atom, or a tellurium atom, R ₅ and R ₆ represent a hydrogen atom or an alkyl group, and R ₇ and R ₈ are monovalent And a plurality of R ₇ and R ₈ may combine with each other to form a ring, and m and n each represent an integer of 0 to 4. ” 23. A halogen containing at least one solid dispersion or oil dispersion of the dye represented by the general formula 1, general formula 2, general formula 3, general formula 4, general formula 5 or general formula 6. Image forming materials such as silver halide photographic materials. 24. A thiopyrylium squarylium dye, a thiopyrylium croconium dye, a pyrylium squarylium dye, a pyrylium croconium dye, a selenapyrylium squarylium dye, a selenapyrylium croconium dye, a telluropyrylium squarylium dye, and a tellurium An image forming material such as a silver halide photographic light-sensitive material containing at least one solid dispersion or oil dispersion selected from pyrylium croconium dyes. 25. A support comprising a layer containing at least one dye represented by formula 1 and a water-soluble binder, and being spectrally sensitized to 600 nm or more and 700 nm or less. Heat-developable photographic photosensitive material. 26. A support comprising a layer containing at least one of the dyes represented by the general formulas 2, 3, 4, 5 or 6 and a water-soluble binder. Characteristic silver halide photographic material. 27. A thiopyrylium squarylium dye, a thiopyrylium croconium dye, a pyrylium squarylium dye, a pyrylium crokonium dye, a selenapyrylium squarylium dye, a selenapyrylium croconium dye, a telluropyrylium squarylium on a support A silver halide photographic material having a layer containing a water-soluble binder and at least one selected from a dye and a telluropyrylium croconium dye. 28. The photothermographic material according to claim 16, further comprising a hydrazine compound. 29. The method according to claim 18, wherein the hydrazine compound is contained.
28. The silver halide photographic material described in 4, 26 or 27. 30. The method according to claim 1, wherein the light is spectrally sensitized to 600 nm or more and 900 nm or less.
9, 20, 21, 22, 23, 24, 26, 27 or 2
10. An image forming material such as the silver halide photographic light-sensitive material described in 9 above. 31. An image is formed by heat development after being exposed by a laser beam.
3. The method for forming an image on a photothermographic material according to item 1. 32. The method according to claim 18, 19, 20, 21, 22,
After exposing the silver halide photographic material described in 23, 24, 26, 27, 29 or 30 by a laser beam,
An image forming method for a silver halide photographic material, wherein an image is formed by a developing process. 33. The image forming method for a silver halide photographic light-sensitive material according to claim 32, wherein the development processing is a heat development processing. 34. An image-forming material such as a silver halide photographic light-sensitive material, wherein the dye according to any one of claims 1 to 3 and 16 to 30 is a compound represented by the following general formula 11. . Embedded image In the formula, R ₁ , R ₂ , R ₃ , and R ₄ each represent an alkyl group which does not substitute an acidic substituent, and R ₅ and R ₆ each represent a monovalent substituent. Represents an integer. " 35. The method according to claim 34, wherein at least one of R ₁ , R ₂ , R ₃ and R _{4 in} the general formula 11 is an alkoxy-substituted alkyl group or an alkyl group having 5 or more carbon atoms. Image forming materials such as silver halide photographic materials. 36. An optical filter comprising at least one of the compounds represented by the general formula 1, general formula 2, general formula 3, general formula 4, general formula 5, or general formula 6. 37. A thiopyrylium squarylium dye, a thiopyrylium crokonium dye, a pyrylium squarylium dye, a pyrylium croconium dye, a selenapyrylium squarylium dye, a selenapyrylium croconium dye, a telluropyrylium squarylium dye, and a tellurium dye An optical filter comprising at least one selected from pyrylium croconium dyes. 38. A silver halide photograph containing at least one of the compounds represented by the general formula 1, general formula 2, general formula 3, general formula 4, general formula 5 or general formula 6. Supports for image forming materials such as photosensitive materials. 39. Thiopyrilium squarylium dye, thiopyrylium croconium dye, pyrylium squarylium dye, pyrylium croconium dye, selenapyrylium squarylium dye, selenapyrylium croconium dye, telluropyrylium squarylium dye, and tellurium A support for an image forming material such as a silver halide photographic light-sensitive material, which comprises at least one selected from pyrylium croconium dyes.