JP2001261664A - Silver halide photosensitive material, method for forming image, compound and method for synthesizing the same compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a new compound, a silver halide photosensitive material spectrally sensitized and improved in photographic characteristics by including the above compound, a method for forming image by using the above photosensitive material and a method for synthesizing a new pigment. SOLUTION: This silver halide photosensitive material comprises a heteroaromatic ring-substituted monomethylene pigment having a specific structure in a silver halide photosensitive material applied to an image-forming method comprising exposing digitalized information to light to provide an image and then developing the image.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel compound, a silver halide light-sensitive material which is spectrally sensitized by containing the compound and has improved photographic characteristics, an image forming method using the light-sensitive material, and a novel compound. The present invention relates to a dye synthesis method.

[0002]

2. Description of the Related Art In a silver halide photographic application, when a certain kind of dye is added to a photosensitive silver halide emulsion (hereinafter, also referred to as a silver halide emulsion or simply an emulsion), the photosensitive wavelength range of the silver halide emulsion is expanded. It is well known that optical sensitization is performed.

A large number of dyes used for this purpose have been known in the art. For example, the theory of the photographic process, 4th edition (1977, Macmillan, Inc.) , N .;
Y. ) P. 194-234, "The Cyanine Soy and Related Compounds" by Francis M. Harmer (1964, John Willy and
Sands, N. Y. ), Dem Stammer, "The Chemistry of Heterocyclic Compounds, Vol. 30," p. 441- (1977, John Willy and Sons, NY) and other various dyes such as styryl dyes, hemicyanine dyes, cyanine dyes, merocyanine dyes, and xanthene dyes are known. By selecting and combining the lengths of the heterocyclic nucleus or aromatic ring and the conjugated chain, and the substituents, a dye having an arbitrary absorption maximum wavelength in the near ultraviolet to near infrared region is derived.

[0004] These spectral sensitizing dyes must not only extend the photosensitive wavelength range of the silver halide emulsion but also satisfy the following conditions. 1) Spectral sensitization range is appropriate 2) Spectral sensitization efficiency is high 3) Poor interaction between other additives such as stabilizers, antifoggants, coating aids, high boiling solvents, etc. No effect 4) No adverse effect on the characteristic curve, such as fogging or gamma change 5) When a silver halide photographic material containing a sensitizing dye is aged (especially under high temperature and high humidity) 6) Do not change the photographic performance such as fog during storage. 6) The added photosensitive dye does not diffuse to layers of different photosensitive wavelength ranges to cause color turbidity. 7) After the development and fixing, the photosensitive dye is washed. Do not come off and cause color contamination. However, the spectral sensitizing dyes disclosed heretofore have not yet reached levels that sufficiently satisfy all of these conditions.

[0005] In sensitizing dyes, slight differences in structure greatly affect photographic performance such as sensitivity, fogging and storage stability. However, it is difficult to predict the effects in advance. Many researchers have attempted to synthesize a number of sensitizing dyes and examine their photographic performance. However, it is still impossible to predict the photographic performance.

For the above reasons, there is still a need for a technique for spectrally sensitizing silver halide grains with high sensitivity and without causing adverse effects such as fog. Also, in recent years, opportunities for handling images as digital data have been rapidly increasing in accordance with improvements in computer computing capabilities and advances in network technology. Image information digitized using a scanner or the like can be edited and processed on a computer, and data such as characters and illustrations can be added relatively easily. Hard copy materials for making hard copies based on such digitized image information include, for example, sublimation type thermal transfer print, melt type thermal transfer print, inkjet print, electrostatic transfer type print, thermo auto chrome print, halogenated A silver photographic light-sensitive material and the like can be mentioned, and among them, a silver halide photographic light-sensitive material (hereinafter, also simply referred to as a light-sensitive material) has high sensitivity, excellent gradation, and excellent image storability. Due to its excellent properties compared to other printing materials, it is widely used today especially for producing high-quality hard copies.

[0007] In recent years, there have been a wide variety of apparatuses for exposing digitized image information on photosensitive materials. Typical examples include those employing a scanning exposure method using a light emitting diode, a gas laser, a semiconductor laser, or a second harmonic obtained by combining the same with an SHG element as a light source. These digital exposure apparatuses are preferable because they can expose a photosensitive material with high resolution in a short time. However, since these digital exposure apparatuses use various types of light sources, their exposure wavelengths and exposure times also vary. Therefore, the quality of the obtained print also varies depending on the exposure apparatus used, and thus a photosensitive material capable of stably obtaining a high-quality print for various exposure apparatuses has been desired.

More specifically, a color print for direct viewing, which is widely used at present, is designed so that high quality can be obtained stably when exposed through a color negative film. Depending on the case, image bleeding or color mixing may occur. In particular, a blue-sensitive silver halide emulsion or a blue light-absorbing irradiation-preventing dye, etc.
Many photosensitive materials are designed with emphasis on blue light having a relatively long wavelength of about 470 nm, and therefore, depending on the blue exposure system of the digital exposure apparatus used, the sharpness of the yellow image component is degraded, or a black fine line image is formed. , And yellow color may occur in the peripheral portion of the image, and magenta and cyan may be mixed in the yellow image portion. In addition, with the digitization of used images, opportunities to output fine and complicated images such as thin lines and geometric patterns of characters and the like have been increasing, and faithful and stable reproduction of these images has been demanded.

In view of the above situation, as a method for preventing image bleeding, a method of including an antiirradiation dye or colloidal silver in a coating layer is widely known. However, as the amount of the dye is increased, the improvement effect is increased, but the photographic sensitivity of the light-sensitive material is reduced and the white background is deteriorated. Further, this cannot satisfy the requirement of stably obtaining high image quality in various exposure apparatuses intended by the present invention. On the other hand, Japanese Patent Application Laid-Open No. 8-36247 discloses a method of improving the tone reproducibility of the detail of a shadow by defining a point gamma in a high density portion. Also,
Japanese Patent Laid-Open No. 10-20461 discloses a method for improving the character quality by defining the latitude and the N value of the magenta coloring layer. However, these methods do not satisfy the intention of the present invention.

On the other hand, as a method for synthesizing a monomethine compound, a method described in US Pat. No. 2,310,640 (the above is referred to as synthesis method 1) and a method described in US Pat. No. 2,485,679 (the above is referred to as synthesis method 2). U.S. Pat.
No. 30257 (the above is referred to as synthesis method 3)
Etc. are known. Typical examples of these are shown below.

[0011]

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However, each of the above synthesis methods has the following problems. In the synthesis method 1, it is necessary to separately synthesize 2-alkylmercaptoazole used as a raw material in the synthesis method 1 from 2-mercaptoazole, and a process for isolating and purifying the 2-alkylmercaptoazole is required. Synthetic method 2 is based on 4-methylazole 4
A grade salinization step is required, and the operation becomes complicated.
When isolation and purification of the grade salt are difficult, it causes a reduction in the synthesis yield in the next step of dyeing. The synthesis method 3 requires isolation and purification steps of the raw materials as in the synthesis method 2, which complicates the operation and may cause a decrease in the synthesis yield of the dyeing in the next step.

[0013]

SUMMARY OF THE INVENTION An object of the present invention is to provide a novel compound, a silver halide emulsion which is spectrally sensitized by containing the compound and has improved photographic characteristics, a silver halide light-sensitive material and An object of the present invention is to provide an image forming method using the photosensitive material and a novel dye synthesizing method.

[0014]

The above objects of the present invention have been attained by the following constitutions. 1. A silver halide photographic material applied to an image forming method of developing digitized image information after imagewise exposure and then developing, wherein the halogen contains at least one compound represented by the following general formula (1). Silver halide photographic material.

[0015]

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(Wherein R ¹ and R ² each represent an aliphatic group or an aromatic group; R ³ , R ⁴ and R ⁵ each represent a hydrogen atom or a monovalent substituent; R ⁴ and R ⁵ And Z ¹ and Z ² each represent a group of non-metallic atoms necessary to form a 5- or 6-membered nitrogen-containing heterocyclic ring, and n ¹ ,
n ² each represents 0 or 1, X represents an ion necessary to neutralize the molecular charge, n ³ represents the number of ions necessary to neutralize the charge. )

2. A silver halide photographic light-sensitive material applied to an image forming method of developing digitized image information after imagewise exposure, wherein the silver halide photographic material contains at least one compound represented by the following general formula (2). Silver halide photographic material.

[0018]

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(Where A¹, A²Is O, S, Se, NR
²², CR²³, R²⁴And R ¹¹, R¹², R
²², R²³, R²⁴Represents an aliphatic group or an aromatic group, respectively.
Represents, R¹³~ R²¹Each represents a hydrogen atom or a monovalent substituent
And R¹⁴~ R²¹At least one of which is heteroaromatic
Represents a ring. X is an ion required to neutralize the charge in the molecule
And n³Indicates the number of ions required to neutralize the charge.
You. )

3. In a silver halide photographic material applied to an image forming method in which digitized image information is developed after imagewise exposure with an exposure time of 10 ^-3 seconds or less per pixel, the general formula (1) or (2) A silver halide photographic material comprising at least one of the compounds represented by the formula (I).

4. In a silver halide photographic material applied to an image forming method in which digitized image information is developed after imagewise exposure with an exposure time of ^10-3 seconds or less per pixel, at least one layer of an average silver chloride on a support Content 95
A silver halide emulsion having an image-forming silver halide emulsion layer containing at least mol% of a silver halide emulsion and being color sensitized with at least one of the compounds represented by formula (1) or (2) A silver halide photographic light-sensitive material comprising:

5. By using at least three types of light having different wavelengths, digitized image information can be converted into 10 pixels per pixel.
^In a silver halide photographic light-sensitive material applied to an image forming method for developing after imagewise exposure with an exposure time of ^-3 seconds or less, a silver halide having an average silver chloride content of at least 95 mol% in at least one layer on a support. An emulsion-containing silver halide emulsion layer, a magenta image-forming silver halide emulsion layer, and a cyan image-forming silver halide emulsion layer containing at least one of the compounds represented by formula (1) or (2). A silver halide photographic material comprising a silver halide emulsion which has been color-sensitized.

6. By using at least three types of light having different wavelengths, digitized image information can be converted into 10 pixels per pixel.
^In a silver halide photographic light-sensitive material applied to an image forming method for developing after imagewise exposure with an exposure time of ^-3 seconds or less, a silver halide having an average silver chloride content of at least 95 mol% in at least one layer on a support. A compound having a yellow image-forming silver halide emulsion layer, a magenta image-forming silver halide emulsion layer, and a cyan image-forming silver halide emulsion layer containing an emulsion, and represented by formula (1) or (2); And pA
g = 6.0 to 7.7, when added to a silver halide emulsion having an average silver chloride content of 95 mol% or more, from 380 nm to 4%.
A silver halide photographic material comprising a silver halide emulsion color-sensitized with at least one compound having a spectral absorption maximum in a wavelength range of up to 30 nm.

[7] 7. The silver halide photographic material according to any one of the above 1 to 6, wherein R ⁴ and R ⁵ of the general formula (1) are used.
In heteroaromatic ring or the formula represented ^{R 14} ~ (2)
The silver halide photographic light-sensitive material comprising a heteroaromatic ring represented by R ^{2 1} is a 5- or 6-membered heteroaromatic ring.

8. The silver halide photographic light-sensitive material according to any one of the above 1 to 7, wherein the heteroaromatic ring represented by R ⁴ or R ⁵ in the general formula (1) or R ^{14 to} R in the general formula (2).
^A silver halide photographic material, wherein the heteroaromatic ring represented by ²¹ is a thiophene ring, a furan ring, a pyrrole ring or a pyridine ring.

9. 9. The silver halide photographic light-sensitive material according to any one of 1 to 8, wherein an oscillation wavelength λ is used as a light source for blue light.
Semiconductor laser or semiconductor laser having a wavelength between 380 nm and 430 nm and a second harmonic generation element (SHG)
An image forming method comprising: performing imagewise exposure by a scanning exposure method using a combination of the above elements, and developing the resultant image.

10. 9. An image forming method, wherein the silver halide photographic light-sensitive material according to any one of 1 to 8 above is exposed imagewise with an exposure time of 10 ^-6 seconds or less per pixel, and then developed.

11. A compound represented by the following general formula (3).

[0029]

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Where R¹, R²Is an aliphatic group or
Represents an aromatic group;³, R³¹, R ³²Is a hydrogen atom
Or a monovalent substituent;³¹, R³²At least
One represents a nitrogen-containing heteroaromatic 6-membered ring. Z¹, Z²Is 5
Or a nonmetallic element necessary to form a 6-membered nitrogen-containing heterocycle
Represents a child group, n¹, N²Represents 0 or 1, respectively, and X represents minutes.
Represents the ions required to neutralize the charge in the³Is
Indicates the number of ions required to neutralize the load. )

12. A compound represented by the following general formula (4).

[0032]

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(Where A¹, A²Is O, S, Se, NR
⁵², CR⁵³R⁵⁴And R^{4 1}, R⁴²,
R⁵², R⁵³, R⁵⁴Is an aliphatic group or an aromatic group, respectively.
And R ⁴⁴~ R⁵¹Is a hydrogen atom or monovalent substitution
R represents a group⁴⁴~ R⁵¹At least one of which is nitrogen-containing
Represents a 6-membered aromatic ring. X is to neutralize the charge in the molecule
Represents the required ion, n³Is necessary to neutralize the charge.
Represents the number of on. )

13. R of the general formula (3) described in 11 above
^31. A compound, wherein at least one of R ³¹ and R ³² is a pyridine ring.

14. The general formula (4) R according to the above item 12,
^44. A compound, wherein at least one of R ⁵¹ is a pyridine ring.

15. A silver halide photographic material comprising a compound represented by the formula (3) or (4).

16. The silver halide photographic material containing the compound represented by the general formula (3) or (4) has an oscillation wavelength λ of 380 nm to 430 n as a blue light source.
An image forming method, wherein imagewise exposure is performed by a scanning exposure method using a semiconductor laser or a combination of a semiconductor laser and a second harmonic generation element (SHG element) between m and m, followed by development.

17. A compound represented by the following general formula (5).

[0039]

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(Wherein, R ⁶¹ represents a hydrogen atom, an aliphatic group, an aromatic group, or SR ⁶⁶ ; R ^{62 to} R ⁶⁶ represent a hydrogen atom or a monovalent substituent; at least one of R ^{62 to} R ⁶⁵ One represents a pyridine ring.) A compound represented by the following general formula (6).

[0041]

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(Wherein, R ⁷¹ represents a hydrogen atom, an aliphatic group, an aromatic group, SR ⁷⁴ , R ⁷² represents an aliphatic group, an aromatic group, R ⁷³ represents a pyridine ring, and n ⁴ represents Represents 0 or 1, Z ¹ represents a group of nonmetallic atoms necessary for forming a 5- or 6-membered nitrogen-containing heterocyclic ring, X represents an ion required for neutralizing an intramolecular charge, and n ³ represents the number of ions required to neutralize the charge.)

19. Monomethine represented by the general formula (9), wherein the compound represented by the following general formula (7) and the compound represented by the general formula (8) are reacted with an alkylating agent in the same system. A method for producing a cyanine compound.

[0044]

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[0045] In the formula, ^{Z 1} and ^{Z 2} represents an atomic group necessary for forming a nitrogen-containing heterocyclic 5- or ^{6-membered, R 81}
Represents a hydrogen atom or a monovalent substituent, and R ⁸² and R ⁸³
Represents an aliphatic group, n ¹ and n ² each represent 0 or 1, X represents a charge neutralizing ion, and n ³ represents a number necessary to maintain the charge balance of the whole molecule.

20. After reacting the compound represented by the general formula (7) and the compound represented by the general formula (8) with the alkylating agent in the same system as described in 19 above, the compound represented by the general formula (7) in the presence of an acid or a base. A method for producing a monomethinecyanine compound, which comprises obtaining the compound represented by (9).

[0047]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
First, the general formula will be described. General formula (1),
R in (3)¹, R²R in general formula (2)
¹¹, R ¹², R in the general formula (4)⁴¹, R⁴²,
R in the general formula (6)⁷²R in general formula (9)
⁸¹, R⁸²Examples of the aliphatic group represented by
A branched or straight-chain alkyl group having 1 to 10 elementary atoms (eg,
For example, methyl, ethyl, propyl, butyl, pen
Tyl group, iso-pentyl group, 2-ethyl-hexyl
Group, octyl group, decyl group, etc.), having 3 to 10 carbon atoms
Alkenyl group (for example, 2-propenyl group, 3-butenyl
Group, 1-methyl-3-propenyl group, 3-pentenyl
Group, 1-methyl-3-butenyl group, 4-hexenyl group
Aralkyl groups having 7 to 10 carbon atoms (for example,
And an aromatic group.
Are aryl groups (for example, phenyl group, naphthyl group
Etc.), a heteroaryl group (for example, a thienyl group, a furyl group)
Etc.).

R in the general formulas (1) and (3)¹,
R²R in general formula (2)¹¹, R ¹², General formula
R in (4)⁴¹, R⁴²In the general formula (6)
R⁷²R in general formula (9)⁸¹, R⁸²Indicated by
Groups further include a halogen atom (eg, a fluorine atom,
Atom, bromine atom, etc.), alkyl group (for example, methyl
Group, ethyl group, propyl group, butyl group, pentyl group, i
so-pentyl group, 2-ethyl-hexyl group, octyl
Group, decyl group, etc.), aryl group (for example, phenyl group,
Carboxyphenyl group), heterocyclic group (for example, imida
Zolyl, thiazolyl, benzoxazolyl, pyri
Jill, pyrrolyl, indolyl, pyrimidinyl
Alkenyl group (for example, 2-propenyl group, 3-
Butenyl group, 1-methyl-3-propenyl group, 3-pen
Thenyl group, 1-methyl-3-butenyl group, 4-hexenyl
Alkynyl group (eg, 1-propynyl group)
Etc.), alkoxy groups (for example, methoxy group, ethoxy
Group, propoxy group, etc.), aryloxy group (for example,
Phenoxy, p-tolyloxy, etc.), heteroaryl
Oxy group (for example, 2-pyridyloxy group), alkoxy
Cycarbonyl groups (eg methoxycarbonyl, ethoxy
Carbonyl, etc.), aryloxycarbonyl group (for example,
Phenyloxycarbonyl), alkoxycarbo
Nylamino group (for example, methoxycarbonylamino
An aryloxycarbonylamino group (eg,
Nyloxycarbonylamino), alkylsulfoni
(For example, methanesulfonyl, ethanesulfonyl, etc.)
An arylsulfonyl group (eg, benzenesulfonyl)
), Sulfinyl group (for example, methanesulfinyl
Benzenesulfinyl, etc.), ureido group (for example,
Ureide, methylureide, phenylureide, etc.),
Acyloxy groups (eg, acetoxy, benzoyloxy
Phosphoric acid amide group (for example, diethylphosphoric acid
Phenylphosphoramide, etc.), alkylthio group (eg
For example, a methylthio group, a trifluoromethylthio group, etc.),
Arylthio group (for example, phenylthio group, 2-naphthy
Ruthio group), heteroarylthio group (for example, 3-thienyl)
Ruthio), aralkyl group (for example, benzyl group,
Rolobenzyl group), carboxyl group, acylamino group
(For example, acetylamino group, benzoylamino group
Etc.), sulfonylamino group (for example, methanesulfonyl
Amino group, benzenesulfonylamino group, etc.), acyl group
(Eg, acetyl group, benzoyl group, etc.), carbamoy
(For example, carbamoyl group, N, N-dimethyl
Bamoyl group, N-morpholinocarbonyl group, etc.), sulf
Amoyl group (sulfamoyl group, N, N-dimethylsul
Famoyl group, morpholinosulfamoyl group, etc.)
Droxy, styryl, nitro, cyano, merka
Butoxy, oxo, thioxo, hydroxamic acid,
Drazino group, sulfonamide group (for example, methanesulfo
Amide group, butanesulfonamide group, etc.), amino group
(For example, amino group, N, N-dimethylamino group, N, N
-Diethylamino group), sulfo group, phosphono group,
Rufate group, sulfino group, sulfonylaminocarbo
Nyl group (for example, methanesulfonylaminocarbonyl,
Ethanesulfonylaminocarbonyl group), acylamido
Nosulfonyl groups (for example, acetamidosulfonyl,
Toxicacetamidosulfonyl group), acylaminoca
Rubonyl group (for example, acetamidocarbonyl, methoxy,
Siacetamide carbonyl group, etc.), sulfinylamino
Carbonyl group (for example, methanesulfinylaminocar
Bonyl, ethanesulfinylaminocarbonyl group, etc.)
May be substituted.

In the general formula (1), R³, R⁴,
R⁵R in general formula (2)¹³~ R ²⁴, General formula
R in (3)³¹, R³²In the general formula (4)
R⁴⁴~ R ⁵⁴R in the general formula (5)⁶²~
R⁶⁶R in the general formula (6)⁷⁴, To the general formula (9)
R in⁸¹As the monovalent substituent represented by, for example,
The R¹And the like, which may be substituted.
May be further substituted.

The general formulas (1), (3), (7), (8),
Z ¹ and Z ² in (9) and Z ³ in general formula (6)
Represents a group of non-metallic atoms necessary to form a 5- or 6-membered nitrogen-containing heterocyclic ring. The ring formed by Z ¹ , Z ² or Z ³ includes a saturated carbon ring, a benzene ring, a naphthalene ring,
A condensed ring may be formed together with the heterocyclic ring. Z ¹ , Z
^The nucleus formed by ² or Z ³ includes, for example,
Thiazole nucleus thiazole nucleus (for example, thiazole, 4-
Methylthiazole, 4-phenylthiazole, 4,5-
Dimethylthiazole, 4,5-diphenylthiazole), benzothiazole nucleus (e.g., benzothiazole, 4-chlorobenzothiazole, 5-chlorobenzothiazole, 6-chlorobenzothiazole, 5-nitrobenzothiazole, 4-methylbenzothiazole, 5-methylbenzothiazole, 6-methylbenzothiazole,
5-bromobenzothiazole, 6-bromobenzothiazole, 5-iodobenzothiazole, 5-phenylbenzothiazole, 5-methoxybenzothiazole, 6-methoxybenzothiazole, 5-ethoxybenzothiazole, 5-ethoxycarbonylbenzothiazole, 5 -Carboxybenzothiazole, 5-phenethylbenzothiazole, 5-fluorobenzothiazole, 5-chloro-
6-methylbenzothiazole, 5,6-dimethylbenzothiazole, 5,6-dimethoxybenzothiazole, 5
-Hydroxy-6-methylbenzothiazole, tetrahydrobenzothiazole, 4-phenylbenzothiazole), naphthothiazole nucleus (for example, naphtho [2,1-
d] thiazole, naphtho [1,2-d] thiazole, naphtho [2,3-d] thiazole, 5-methoxynaphtho [1,2-d] thiazole, 7-ethoxynaphtho [2,
1-d] thiazole, 8-methoxynaphtho [2,1-
d] thiazole, 5-methoxynaphtho [2,3-d] thiazole)}, a thiazoline nucleus (for example, thiazoline, 4
-Methylthiazoline, 4-nitrothiazoline), oxazole nucleus ｛oxazole nucleus (for example, oxazole,
-Methyloxazole, 4-nitrooxazole, 5-
Methyl oxazole, 4-phenyl oxazole, 4,
5-diphenyloxazole, 4-ethyloxazole), benzoxazole nucleus (for example, benzoxazole, 5-chlorobenzoxazole, 5-methylbenzoxazole, 5-bromobenzoxazole, 5-
Fluorobenzoxazole, 5-phenylbenzoxazole, 5-methoxybenzoxazole, 5-nitrobenzoxazole, 5-trifluoromethylbenzoxazole, 5-hydroxybenzoxazole, 5
-Carboxybenzoxazole, 6-methylbenzoxazole, 6-chlorobenzoxazole, 6-nitrobenzoxazole, 6-methoxybenzoxazole, 6-hydroxybenzoxazole, 5,6-dimethylbenzoxazole, 4,6-dimethylbenzoxazole , 5-ethoxybenzoxazole), naphthoxazole nucleus (for example, naphtho [2,1-d] oxazole, naphtho [1,2-d] oxazole, naphtho [2,3-d] oxazole, 5-nitronaphtho [2
1-d] oxazole)}, oxazoline nucleus (for example,
4,4-dimethyloxazoline), selenazole nucleus selenazole nucleus (for example, 4-methyl selenazole, 4-
Nitro selenazole, 4-phenyl selenazole), benzo selenazole nucleus (for example, benzo selenazole, 5
-Chlorobenzoselenazole, 5-nitrobenzoselenazole, 5-methoxybenzoselenazole, 5-hydroxybenzoselenazole, 6-nitrobenzoselenazole, 5-chloro-6-nitrobenzoselenazole, 5,
6-dimethylbenzoselenazole), naphtho selenazole nucleus (for example, naphtho [2,1-d] selenazole, naphtho [1,2-d] selenazole)}, selenazoline nucleus (for example, selenazoline, 4-methyl selenazoline) ,
Quinoline nucleus (eg, 2-quinoline, 3-methyl-2-
Quinoline, 5-ethyl-2-quinoline, 6-methyl-2
-Quinoline, 6-nitro-2-quinoline, 8-fluoro-2-quinoline, 6-methoxy-2-quinoline, 6-hydroxy-2-quinoline, 8-chloro-2-quinoline,
4-quinoline, 6-ethoxy-4-quinoline, 6-nitro-4-quinoline, 8-chloro-4-quinoline, 8-fluoro-4-quinoline, 8-methyl-4-quinoline, 8
-Methoxy-4-quinoline, 6-methyl-4-quinoline, 6-methoxy-4-quinoline, 6-chloro-4-quinoline), naphthoquinoline nucleus (for example, 2-naphthoquinoline, 3-methyl-2-naphthoquinoline, 5 -Ethyl-
2-naphthoquinoline, 6-phenyl-2-naphthoquinoline), pyridine nucleus (for example, 2-pyridine, 5-methyl-2-pyridine, 5-bromo-2-pyridine, 3-methyl-2-pyridine), indolenine nucleus (For example, 2-indolenine, 3,3′-dimethyl-2-indolenine), imidazole nucleus (2-imidazole, 4-methyl-2-imidazole, 2-phenyl-4-imidazole) and the like. . Z ¹ , Z ² or Z ³
Preferably, the nucleus formed by benzothiazole nucleus, naphthothiazole nucleus, benzoxazole nucleus,
It is a naphthoxazole nucleus. The ring formed by Z ¹ , Z ² or Z ³ may further be substituted with a substituent which may be substituted on R1.

X represents a cation or an acid anion;
As the cation, an organic ammonium ion (for example,
Triethylammonium, triethanolammonium, etc.), alkali metal ions, and alkaline earth metal ions. Specific examples of the acid anion include inorganic anions and organic anions. For example, halogen anions (eg, fluorine ions, chloride ions, bromine ions, iodine ions), substituted arylsulfonate ions (eg, p-toluenesulfonate ion, p-chlorobenzenesulfonate ion), aryldisulfonate ions (eg, For example, 1,3
-Benzenesulfonic acid ion, 1,5-naphthalenedisulfonic acid ion, 2,6-naphthalenedisulfonic acid ion), alkyl sulfate ion (for example, methyl sulfate ion), sulfate ion, thiocyanate ion, perchlorate ion, tetrafluoroborate Acid ion, picrate ion,
An acetate ion and a trifluoromethanesulfonic acid ion are mentioned. Preferably, they are perchlorate ion, iodine ion, and substituted aryl sulfonate ion (for example, p-toluene sulfonate ion). X, n ^3, when it is necessary to neutralize the ionic charge of the dye, it is included in the formula to indicate the presence or absence of a cation or anion. Whether a dye is a cation, an anion, or has a net ionic charge depends on its auxochrome and substituents. n ³ is 0 when an internal salt is formed and the charge is neutralized.

Specific examples of the compounds represented by formulas (1) to (6) used in the present invention are shown below, but the present invention is not limited thereto.

[0053]

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[0054]

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[0055]

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[0056]

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The general formulas (1), (2), (3), (4),
The compound represented by (9) has a structure having an azole nucleus as at least one basic nucleus, and can have an azolylidene structure and an azolium ion structure in the ultimate structure of the resonance system.

The compound represented by the general formula (8) is
The compound represented by the general formula (10) has a tautomeric relationship with the compound represented by the following general formula (10).
The compound represented by 0) has the same meaning.

[0059]

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The alkylating agent used in the synthesis of the compound represented by the general formula (9)
A compound capable of reacting with the nitrogen atom of the azole ring represented by the general formulas (7) and (8) to add an aliphatic group and form a quaternary ammonium salt. More specifically, alkylating agents include alkyl halides (eg, methyl iodide, ethyl bromide, 3-chloropropanesulfonic acid, benzyl chloride, etc.), esters (eg, p-toluenesulfonsanethyl, methylbenzenebenzenesulfonate, ethane). Ethyl sulfonate, etc.), trialkyloxonium salts (eg, trimethyloxonium tetrafluoroborate, triethyloxonium hexafluorophosphate, etc.), trialkylthioxonium salts (eg, triethylthioxonium tetrafluoroborate, etc.), alkyl Sultone (eg, propane sultone, butane sultone, etc.), dialkyl sulfate (eg, dimethyl sulfate, diethyl sulfate, etc.), olefin (eg, 1-butene, 1-hexene, etc.) and the like.

As is clear from the above description, the compounds represented by the general formulas (7) and (8) form a quaternary ammonium salt in the reaction system by the alkylating agent, and the compound represented by the general formula (7)
A quaternary ammonium salt starting from the compound represented by the formula (I) reacts with a quaternary ammonium salt starting from the general formula (8) to obtain a compound represented by the general formula (9). In the synthesis, the compound represented by the general formula (8) is generally about 1 mol in total, preferably 0.1 to 10 mol, per mol of the compound represented by the general formula (7) as a reaction raw material.
More preferably, 0.5 to 2 mol is used. The alkylating agent used to obtain a quaternary ammonium salt from the compound represented by the general formula (7) is usually 1 to 1 mole of the compound represented by the general formula (7).
It is used in an amount of about mol, preferably 0.1 to 10 mol, more preferably 0.5 to 2 mol. The alkylating agent used for obtaining the quaternary ammonium salt from the compound represented by the general formula (8) is usually 2 mol in total of the alkylating agent per 1 mol of the compound represented by the general formula (8). Degree, preferably 0.1 to 20 mol, more preferably 1 to 4 mol.

The reaction temperature is preferably from 0 to 200 ° C., more preferably from 20 to 180 ° C. If the temperature is lower than 0 ° C., the progress of the reaction is slow, and it is difficult to completely eliminate the raw materials. If it exceeds, the yield will be low due to decomposition of the product.

The reaction does not necessarily require a solvent.
However, depending on the reaction compound used, a solvent can be used if necessary. Examples of the solvent include aromatic hydrocarbons (eg, benzene, toluene, xylene, ethylbenzene, etc.), ethers (eg, anisole), aliphatic hydrocarbons (eg, hexane, ligroin,
Decalin), alcohol having 1 to 4 carbon atoms, 1 carbon atom
Amide of 8 to 8, sulfoxide of 2 to 8 carbon atoms, 2 of carbon atoms
A nitrile having 4 to 4 carbon atoms, a carboxylic acid having 1 to 4 carbon atoms, an ester having 3 to 10 carbon atoms, and an amine having 1 to 10 carbon atoms are used. Moreover, you may use these mixed solvents.

The reaction conditions may be neutral, acidic or alkaline. As the acid, for example, substituted benzenesulfonic acid, hydrochloric acid, sulfuric acid, acetic acid and the like can be used, and as the base, an organic base (eg, triethylamine, pyridine and the like) or an inorganic base (eg, sodium hydrogen carbonate, potassium acetate and the like) can be used.

The order of addition of the compound represented by the general formula (7), the compound represented by the general formula (8) or the alkylating agent can be changed as necessary. That is, after mixing the compound represented by the general formula (7) and the compound represented by the general formula (8), an alkylating agent may be added, or the compound represented by the general formula (7) may be added. After mixing or reacting with the alkylating agent, the compound represented by the general formula (8) may be added, or the compound represented by the general formula (8) and the alkylating agent may be mixed or reacted. Thereafter, the compound represented by the general formula (7) may be added, or the compound represented by the general formula (7), the compound represented by the general formula (8) and the alkylating agent may be added simultaneously. Is also good.

Specific examples of the compounds represented by formulas (7), (8) and (9) are shown below, but the present invention is not limited thereto.

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[0068]

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The general formula (1) used in the present invention,
The compounds represented by (2), (3), (4) and (9)
It can be added to a silver halide emulsion by a conventionally known method. For example, Japanese Patent Application Laid-Open Nos. 50-80826 and 50-8
No. 0827, Protonation dissolution addition method, U.S. Pat. No. 3,822,135, JP-A-50-114.
No. 19, a method of dispersing and adding together with a surfactant,
U.S. Pat. Nos. 3,676,147 and 3,469,98
No. 7,4,247,627, JP-A-51-5
Nos. 9942, 53-16624, 53-1027
No. 32, No. 53-102733, No. 53-13713
No. 1, JP-A No. 143,324, a method of adding as a solid solution, or a method of adding as a solid solution described in Japanese Patent No. 143,324, or Research Disclosure 21, 8
No. 02, Japanese Patent Publication No. 50-40659, Japanese Patent Application Laid-Open No. Sho 59-14
Water-soluble solvents dissolving dyes represented by 8053 (for example, water, low-boiling solvents such as methanol, ethanol, propyl alcohol, acetone, and fluorinated alcohol; dimethylformamide, methylcellosolve, phenylcellosolve, and the like) A solvent having a high boiling point) can be added to the emulsion by arbitrarily selecting or adding a method of dissolving in a single solvent or a mixed solvent thereof.

The general formulas (1), (2), (3),
The compound (4) or (9) used in the present invention may be added at any stage during the emulsion production process from physical ripening to completion of chemical ripening. It is preferred that it be added until the end.

Further, in order to obtain a high spectral sensitivity, the compound used in the present invention may be used during physical ripening, prior to the addition of the chemical sensitizer in the chemical ripening step, or immediately after the addition of the chemical sensitizer. Is preferably added. The amount of the compound used in the present invention varies greatly depending on the conditions used and the type of emulsion, but the coverage of the monomolecular layer on the surface of the photosensitive grains in the silver halide emulsion is 40% or more and 90% or less. It is preferable that the ratio is 50% to 80%.
Is preferable. The monolayer coverage is defined as the saturated adsorption amount when an adsorption isotherm is created at 50 ° C., and the coverage is 100%.
Is relatively determined as an amount corresponding to.

The silver halide emulsion of the present invention may be used in combination with a conventionally known methine dye, and the ratio of the used methine dyes can be arbitrarily selected in an amount that gives a desired sensitivity. Also,
A supersensitizer which does not itself have a spectral sensitizing effect or a compound which does not substantially absorb visible light and enhances the sensitizing effect of the sensitizing dye may be contained in the emulsion. Examples of the sensitizing dye include a cyanine dye, a merocyanine dye, a composite cyanine dye, a composite merocyanine dye, a holopolar cyanine dye, a hemicyanine dye, a styryl dye, a hemioxonol dye, and a polymethine dye including oxonol, merostyril, and streptocyanin. it can.

The silver halide emulsion of the present invention can be chemically sensitized by chalcogen sensitization such as sulfur sensitization, selenium sensitization, or tellurium sensitization, reduction sensitization, and noble metal sensitization alone or in combination as appropriate. The conditions of the chemical sensitization step, for example, p
There are no particular restrictions on H, pAg, temperature, time, etc.
It can be performed under conditions generally performed in the art.

In the present invention, fine grains of silver iodide may be added to the silver halide emulsion during the process from chemical ripening to coating. Here, the process from chemical ripening to coating includes during chemical ripening and means that fine grain silver iodide is added to the process from coating to coating.

The silver halide grains of the silver halide emulsion used in the present invention include silver halides such as silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide, silver chloroiodobromide and silver chloride. Silver particles can be used arbitrarily. In particular, silver iodochlorobromide, silver chlorobromide or silver chloride having a silver chloride content of 60 mol% or more improves the effect of the present invention.

As the silver halide grains used in the present invention, normal crystal grains and grains having any other shapes can be used. The normal crystal particles used in the present invention,
Particles grown isotropically without including anisotropic growth such as twin planes, that is, particles having a shape such as a cubic, tetrahedral, octahedral, or dodecahedral, and spherical, potato, etc. Particles having a shape like a letter can also be used. Further, grains having twins such as tabular silver halide grains may be used.

The grain size of the silver halide grains according to the present invention is not particularly limited, but is preferably 0.1 to 2.0 μm in consideration of other photographic properties such as rapid processing and sensitivity.
More preferably, it is in the range of 0.1 to 1.0 μm.

The silver halide grains used in the present invention are:
For example, it is preferable to grow the seed crystal by a method of precipitating silver halide on a seed crystal as described in Examples of JP-A-60-138538.

Further, the silver halide grains used in the present invention may be used in the course of forming and / or growing grains, in the form of cadmium salts, zinc salts, lead salts, thallium salts, iridium salts (including complex salts), rhodium salts. (Including complex salts) and iron salts (including complex salts) by adding at least one kind of metal ion, so that these metal elements can be contained inside the particles and / or in the particle surface layer. By placing in a reducing atmosphere, a reduction sensitizing nucleus can be provided inside the grain and / or on the grain surface.

The effect of the reducing agent added at a desired point in time of particle formation can be improved by adding an oxidizing agent such as hydrogen peroxide (water) and its adduct, peroxoacid salt, ozone, and I2 at a desired point in time. It is preferable to deactivate and suppress or stop the reducing agent.

The time of addition of the oxidizing agent can be arbitrarily selected from the time of silver halide grain formation to the time of chemical sensitization.

In the silver halide emulsion of the present invention, unnecessary soluble salts may be removed at the end of the growth of silver halide grains, or may be kept contained. To remove such salts, use Research Disclosure (hereinafter RD).
No.) It can be carried out based on the method described in 17643 No. II.

The silver halide emulsion layer containing the grains preferably used in the present invention may contain grains of various shapes as long as the effects of the present invention are not impaired.

The silver halide emulsion of the present invention contains various antifoggants and stabilizers for the purpose of preventing fog during the production process, storage or processing of the light-sensitive material and stabilizing photographic performance. Can be done. Specifically, tetrazaindenes, azoles, benzothiazolium salts, nitroindazoles, nitrobenzimidazoles, chlorobenzimidazoles, promobenzimidazoles, mercaptothiazoles, mercaptobenzimidazoles, aminotriazoles , Benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles, mercaptopyrimidines, mercaptotriazines, thioketo compounds, and also benzenethiosulfinic acid, benzenesulfinic acid, benzenesulfonamide, hydroquinone derivatives, aminophenol derivatives, gallic acid Derivatives and ascorbic acid derivatives.

Various photographic additives can be used in the silver halide light-sensitive material of the present invention. Known additives include, for example, Research Disclosure (RD) N
o. No. 17643 (December 1978); 187
16 (November 1979) and No. 16 308119
(December 1989). The types of compounds and the locations described in these three RDs are listed below.

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[Table 1]

The emulsion used in the silver halide photographic light-sensitive material of the present invention may contain a developing agent such as aminophenol, ascorbic acid, pyrocatechol, hydroquinone, phenylenediamine, hydrazine derivative or 3- A developing agent such as pyrazolidone may be included.

The silver halide emulsion used in the present invention may contain an antifoggant, a stabilizer and the like.

It is advantageous to use gelatin as a binder in the light-sensitive material according to the present invention. If necessary, other gelatin, gelatin derivatives, graft polymers of gelatin and other polymers, proteins other than gelatin, A hydrophilic colloid such as a sugar derivative, a cellulose derivative, or a synthetic hydrophilic polymer such as a homopolymer or a copolymer can also be used. As the hardener of these binders, it is preferable to use a vinyl sulfone hardener or a chlorotriazine hardener alone or in combination. JP-A-61-2
It is preferable to use the compounds described in JP-A-49054 and JP-A-61-245153. Further, it is preferable to add a preservative and an antifungal agent as described in JP-A-3-157646 to the colloid layer in order to prevent the growth of mold and bacteria which adversely affect photographic performance and image storability. Further, in order to improve the surface properties before and after processing of the light-sensitive material, a protective layer is disclosed in JP-A-6-118543 and JP-A-2-7325.
It is preferable to add a slipping agent or a matting agent described in the specification of Japanese Patent Publication No. 0-206.

The emulsion layer and other hydrophilic colloid layers can be hardened, and can contain a plasticizer and a dispersion (latex) of a water-insoluble or hardly soluble synthetic polymer.

A coupler is used in the emulsion layer of the color photographic light-sensitive material. As the coupler used in the light-sensitive material of the present invention, any compound capable of forming a coupling product having a spectral absorption maximum wavelength in a wavelength region longer than 340 nm by coupling reaction with an oxidized form of a color developing agent is used. Among them, particularly typical examples include a yellow dye-forming coupler having a spectral absorption maximum wavelength in a wavelength range of 350 to 500 nm, and a wavelength range of 500 to 600.
Typical examples are magenta dye-forming couplers having a spectral absorption maximum wavelength at nm and cyan dye-forming couplers having a spectral absorption maximum wavelength at a wavelength range of 600 to 750 nm.

Further, by coupling with a colored coupler having a color correcting effect, a competitive coupler and an oxidized form of a developing agent, a development accelerator, a bleaching accelerator, a developer, a silver halide solvent, a toning agent, Compounds that release photographically useful fragments such as hardeners, foggants, antifoggants, chemical sensitizers, spectral sensitizers and desensitizers can be used.

The light-sensitive material can be provided with an auxiliary layer such as a filter layer, an antihalation layer and an anti-irradiation layer. In these layers and / or the emulsion layers, dyes which flow out of the light-sensitive material or are bleached during the development processing may be contained.

The light-sensitive material can contain a matting agent, a lubricant, an image stabilizer, a surfactant, a color fogging inhibitor, a development accelerator, a development retarder and a bleaching accelerator.

As the support, paper laminated with polyethylene or the like, polyethylene terephthalate film, baryta paper, cellulose triacetate or the like can be used.
The surface of these supports may be provided with an undercoat layer for improving the adhesion of the coating layer, or may be subjected to corona discharge, ultraviolet irradiation, or the like.

In order to obtain a dye image using the silver halide photographic light-sensitive material of the present invention, a generally known color photographic processing can be performed after exposure.

Next, an image forming method for developing digitized image information after imagewise exposure and development and a silver halide photographic material applicable to the image forming method of the present invention will be described.

The light-sensitive material according to the present invention has a layer containing a silver halide emulsion spectrally sensitized to a specific region of a wavelength range of 380 to 900 nm in combination with a yellow coupler, a magenta coupler and a cyan coupler. The silver halide emulsion contains one kind or a combination of two or more kinds of sensitizing dyes.

As the spectral sensitizing dye used for spectral sensitization of the silver halide emulsion used for the light-sensitive material according to the present invention to light other than blue light, any known compounds can be used. As the sensitizing dye, the publication 2
GS-1 to GS-5 described on page 8 are preferably used.
As the red-sensitive sensitizing dye, R 29 described in
S-1 to S-8 are preferably used. In the case of performing image exposure with infrared light using a semiconductor laser or the like, it is necessary to use an infrared-sensitive sensitizing dye. The dyes of IRS-1 to 11 described in JP-A No. 6-8 are preferably used. These infrared, red and green photosensitive sensitizing dyes include supersensitizers SS-1 to SS-9 described on pages 8 to 9 of JP-A-4-285950 and JP-A-5-665.
Compounds S-1 to S described in JP-A No. 15 pages 15 to 17
It is preferable to use -17 in combination.

The present invention is characterized in that digitized image information is developed after imagewise exposure with an exposure time of 10 ⁻³ seconds or less per pixel using at least three types of light having different wavelengths. Generally, when image information is digitized and handled, it is common to use a method in which an original image is divided into small squares, and density information is digitized and handled for each square. In the present invention, the minimum unit is one pixel when the original image is divided into squares and handled. Therefore, the exposure time per pixel can be considered as the time during which the intensity or irradiation time of the light beam is controlled based on the digital data for one pixel. In the present invention, the exposure time per pixel is preferably 10 ⁻³ seconds or less from the viewpoint of shortening the exposure time, and more preferably 10 ⁻⁶ seconds or less.

Scanning exposure with a light beam is usually performed by linear exposure with a light beam (raster exposure: main scanning) and relative movement of a photosensitive material in a direction perpendicular to the linear exposure direction (sub-scanning). In general, the combination is performed in the following manner. For example, fixing the photosensitive material on the outer or inner circumference of a cylindrical drum, rotating the drum while irradiating a light beam, and performing main scanning, and simultaneously moving the light source perpendicular to the rotation direction of the drum A method of performing sub-scanning (drum method) or irradiating a rotated polygon mirror with a light beam to scan the reflected beam horizontally (main scanning) in the direction of rotation of the polygon mirror and rotate the photosensitive material to rotate the polygon A method of performing sub-scanning by transporting in a direction perpendicular to the direction (polygon method) or the like is often used. In addition, when using an exposure apparatus in which light sources are arranged in an array beyond the width of the photosensitive material to be exposed, a portion corresponding to main scanning can be regarded as being substituted by an array light source. It can be considered including.

In the present invention, the exposure intensity on the recording material surface represents the exposure intensity per unit area. By installing a beam monitor combining a beam slit and a power meter in the exposure light path, the beam diameter and the The beam intensity can be measured and can be derived from this measurement. The beam diameter referred to here is the diameter of the light beam when the light beam intensity is e-2.
Therefore, the exposure amount per pixel can be calculated as the product of the exposure intensity and the exposure time, and the exposure amount in the present invention is defined as the exposure amount per pixel.

The types of light sources that can be used in the present invention include a light emitting diode (LED), a gas laser, a semiconductor laser (LD), or a solid-state laser using the LD as an excitation light source and a nonlinear optical element (a so-called SHG).
Any known light source, such as a combination with an element, can be used.
It is preferable that the wavelength is between 0 nm and 490 nm. In particular, it is possible to relatively easily obtain a stable image density in which the second harmonic obtained by a semiconductor laser having a wavelength between 380 nm and 430 nm or a combination of a semiconductor laser and an SHG element is stable. preferable. A green light source has an oscillation wavelength between 510 nm and 570 nm, a red light source has an oscillation wavelength between 620 nm and 710 nm, and an infrared light source has an oscillation wavelength of 750.
It is preferable that the thickness is between nm and 900 nm.

In the photosensitive material and the image forming method according to the present invention, the minimum density after the development processing is (R, G, B) = (0.110, 0.110,
0.110) or less is preferable because fine and complicated images such as fine lines and geometric patterns of characters and the like are clearly visible. The minimum density as used herein refers to the density after development processing of the photosensitive material while being substantially unexposed, and eliminates the effects of flaws and the like due to scratches and pressure on the photosensitive material surface and improves the measurement accuracy. The measurement is performed a sufficient number of times to measure, and the average is calculated.

The composition of the silver halide emulsion used in the light-sensitive material according to the present invention includes silver chloride, silver chlorobromide, silver chloroiodobromide,
Although it may have any halogen composition such as silver chloroiodide, the effect of the present invention is particularly effective in the case of silver chlorobromide containing 95 mol% or more of silver chloride and substantially containing no silver iodide. Remarkable and preferable. Further, from the viewpoint of rapid processing property and processing stability, it is preferably 97 mol% or more, more preferably 98 mol% or more.
Silver halide emulsions containing 〜99.9 mol% of silver chloride are preferred.

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Embodiments (Embodiments for Digital Exposure) Next, the present invention will be described based on embodiments, but embodiments of the present invention are not limited thereto.

Example 1 (Preparation of Blue-Sensitive Silver Halide Emulsion (Em-B1))
In 1 liter of a 2% aqueous gelatin solution kept at 0 ° C., the following (solution A1) and (solution B1) were pAg = 7.3, pH =
The solution was added simultaneously while controlling to 3.0, and the following (solution C1) and (solution D1) were simultaneously added while controlling to pAg = 8.0 and pH = 5.5. At this time, the control of pAg is described in
The control of pH was performed using sulfuric acid or an aqueous sodium hydroxide solution.

(Solution A1) 3.42 g of sodium chloride 0.03 g of potassium bromide 200 ml with water added (Solution B1) 10 g of silver nitrate 200 ml with addition of water 200 ml (Solution C1) 102.7 g of sodium chloride Potassium hexachloroiridium (IV) ate 4 × 10 ⁻⁸ mol Potassium hexacyanoferrate (II) 2 × 10 ⁻⁵ mol Potassium bromide 1.0 g Add water 600 ml (D1 solution) Silver nitrate 300 g Add water 600 ml

After completion of the addition, Demol N manufactured by Kao Atlas Co., Ltd.
And a 20% aqueous solution of magnesium sulfate, and then mixed with an aqueous gelatin solution to give an average particle size of 0.70 μm, a variation coefficient of particle size distribution of 0.07, and a silver chloride content of 99. A 5 mol% monodispersed cubic emulsion EMP-1A was obtained.

Next, in the preparation of EMP-1A, (A
(Solution 1) and (solution B1) and (C1) and (D1
Liquid emulsion) EMP-1B having a mean particle size of 0.65 μm, a variation coefficient of the particle size distribution of 0.07, and a silver chloride content of 99.5 mol% was obtained in the same manner except that the addition time of the liquid was changed. Was.

EMP-1A and EMP-1B were optimally chemically sensitized at 60 ° C. using the following compounds. The sensitized EMP-1A and EMP-1B were mixed at a silver ratio of 1: 1 to obtain a blue-sensitive silver halide emulsion (Em-B1).

Sodium thiosulfate 0.8 mg / mol AgX Chloroauric acid 0.5 mg / mol AgX Stabilizer STAB-1 3 × 10 ⁻⁴ mol / mol AgX Stabilizer STAB-2 3 × 10 ⁻⁴ mol / mol AgX stability Agent STAB-3 3 × 10 ^-4 mol / mol AgX sensitizing dye (BS-1) 1 × 10 ^-4 mol / mol AgX sensitizing dye (BS-2) 4 × 10 ^-4 mol / mol AgX STAB-1 : 1- (3-acetamidophenyl) -5
-Mercaptotetrazole STAB-2: 1-phenyl-5-mercaptotetrazole STAB-3: 1- (4-ethoxyphenyl) -5-mercaptotetrazole

In addition to the sensitizing dyes (SB-1) and (SB-2) used at the time of chemical sensitization of EMP-1A and EMP-1B, the dyes shown in Table 2 (5 × 10 ⁻⁵ mol / mol AgX) were used. EMP-2A to EMP-10A, and EMP
-2B to EMP-10B were obtained. EMP-2A to EMP
-10A and EMP-2B to EMP-10B were mixed at a ratio of 1: 1 in combinations shown in Table 2 to obtain blue-sensitive emulsions (Em-B2) to (Em-B10).

[0114]

[Table 2]

(Green photosensitive silver halide emulsion (Em-G
1) Preparation) In the preparation of the silver halide emulsion EMP-1A described above, except that the addition time of (A1 solution) and (B1 solution) and the addition time of (C1 solution) and (D1 solution) were changed. The average particle size was 0.40 μm and the silver chloride content was 99.
A 5 mol% monodisperse cubic emulsion EMP-11A and a monodisperse cubic emulsion EMP-11B having an average particle size of 0.45 μm and a silver chloride content of 99.5 mol% were obtained.

The above-mentioned EMP-11A was optimally chemically sensitized at 60 ° C. using the following compounds. Also, EMP-
Similarly, after optimally sensitizing EMP-11B, the sensitized EMP-11A and EMP-11B were mixed at a silver ratio of 1: 1 to obtain a green-sensitive silver halide emulsion (Em-G
1) was obtained.

Sodium thiosulfate 1.5 mg / mol AgX Chloroauric acid 1.0 mg / mol AgX Sensitizing dye GS-1 4 × 10 ⁻⁴ mol / mol AgX Stabilizer STAB-1 3 × 10 ⁻⁴ mol / mol AgX Stabilizer STAB-2 3 × 10 ^-4 mol / mol AgX Stabilizer STAB-3 3 × 10 ^-4 mol / mol AgX

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(Red-sensitive silver halide emulsion (Em-R
1) Preparation) In the preparation of the silver halide emulsion EMP-1A described above, except that the addition time of (A1 solution) and (B1 solution) and the addition time of (C1 solution) and (D1 solution) were changed. The average particle size was 0.38 μm and the silver chloride content was 99.
A 5 mol% monodispersed cubic emulsion EMP-21A and a monodispersed cubic emulsion EMP-21B having an average particle size of 0.42 μm and a silver chloride content of 99.5 mol% were obtained.

The above-mentioned EMP-21A was optimally subjected to chemical sensitization at 60 ° C. using the following compounds. Also, EMP-
Similarly, after optimally chemical sensitizing 21B, the sensitized EMP-21A and EMP-21B were mixed at a silver amount of 1: 1 to obtain a red-sensitive silver halide emulsion (Em-R
1) was obtained.

Sodium thiosulfate 1.8 mg / mol AgX chloroauric acid 2.0 mg / mol AgX sensitizing dye RS-1 1 × 10 ⁻⁴ mol / mol AgX sensitizing dye RS-2 1 × 10 ⁻⁴ mol / mol AgX supersensitizer SS-1 2 × 10 ⁻³ mol / mol AgX stabilizer STAB-1 3 × 10 ⁻⁴ mol / mol AgX stabilizer STAB-2 3 × 10 ⁻⁴ mol / mol AgX stabilizer STAB- 33 × 10 ^-4 mol / mol AgX

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(Preparation of photosensitive materials 101 to 110) Basis weight 1
High-density polyethylene was laminated on both sides of 80 g / m ² paper pulp to prepare a paper support. However, on the side to which the emulsion layer was applied, a molten polyethylene containing anatase-type titanium oxide having a surface treatment dispersed therein at a content of 15% by weight was laminated. After subjecting this reflective support to a corona discharge treatment, a gelatin undercoat layer was provided, and further, each layer having the following constitution was provided thereon, whereby a multilayer photosensitive material 101 was produced.

In the preparation of the light-sensitive material, coating solutions for the respective layers were prepared so as to have the following coating amounts, and (H) was used as a hardening agent.
-1) and (H-2). Surfactants (SU-1), (SU-2) and (SU-3) were added as coating aids to adjust the surface tension. In addition, an antifungal agent (F-
1) was added so that the total amount was 0.04 g / m ² .
The silver halide emulsion is shown by a value converted to silver. The structure of each layer is shown below.

Layer composition Addition amount (g / m ² ) Seventh layer Gelatin 1.00 (Protective layer) High boiling solvent (DIDP) 0.002 High boiling solvent (DBP) 0.002 Silicon dioxide 0.003 Sixth Layer Gelatin 0.40 (UV absorbing layer) Anti-irradiation dye (AI-1) 0.01 UV absorbing agent (UV-1) 0.12 UV absorbing agent (UV-2) 0.04 UV absorbing agent (UV- 3) 0.16 Stain inhibitor (HQ-5) 0.04 PVP 0.03 Fifth layer Gelatin 1.30 (Red-sensitive layer) Red-sensitive emulsion (Em-R1) 0.21 Cyan coupler (C- 1) 0.28 Dye image stabilizer (ST-1) 0.10 Stain inhibitor (HQ-1) 0.004 High boiling solvent (DBP) 0.10 High boiling solvent (DOP) 0.20 Fourth layer Gelatin 0.94 (purple Line absorbing layer) UV absorber (UV-1) 0.28 UV absorber (UV-2) 0.09 UV absorber (UV-3) 0.39 Irradiation prevention dye (AI-1) 0.02 Stain Inhibitor (HQ-5) 0.10 Third layer Gelatin 1.30 (Green photosensitive layer) Anti-irradiation dye (AI-2) 0.01 Green photosensitive emulsion (Em-G1) 0.15 Magenta coupler ( M-1) 0.20 Dye image stabilizer (ST-3) 0.20 Dye image stabilizer (ST-4) 0.17 High boiling solvent (DIDP) 0.13 High boiling solvent (DBP) 13 Second layer Gelatin 1.20 (Intermediate layer) Anti-irradiation dye (AI-3) 0.01 Stain inhibitor (HQ-2) 0.03 Stain inhibitor (HQ-3) 0.03 Stain inhibitor ( HQ-4) 0.0 Anti-stain agent (HQ-5) 0.23 High boiling solvent (DIDP) 0.04 High boiling solvent (DBP) 0.02 Optical brightener (W-1) 0.10 First layer gelatin 1.20 (blue) Photosensitive layer) Blue photosensitive emulsion (Em-B1) 0.29 Yellow coupler (Y-1) 0.70 Dye image stabilizer (ST-1) 0.10 Dye image stabilizer (ST-2) 0 .10 Dye image stabilizer (ST-5) 0.10 Stain inhibitor (HQ-1) 0.01 Image stabilizer A 0.15 High boiling solvent (DBP) 0.10 High boiling solvent (DNP) 05 Support polyethylene laminated paper

The structures of the additives used in the preparation of the photosensitive material are shown below. SU-1: sodium tri-i-propylnaphthalenesulfonate SU-2: di (2-ethylhexyl) sulfosuccinate sodium salt SU-3: di (2,2,3,3,4,4, sulfosuccinate)
5,5-octafluoropentyl) sodium salt H-1: tetrakis (vinylsulfonylmethyl) methane H-2: 2,4-dichloro-6-hydroxy-s-triazine sodium DBP: dibutyl phthalate DIDP: diisodecyl phthalate DOP : Dioctyl phthalate DNP: dinonyl phthalate PVP: polyvinylpyrrolidone HQ-1: 2,5-di-t-octylhydroquinone HQ-2: 2,5-di-sec-dodecylhydroquinone HQ-3: 2,5-di- sec-tetradecylhydroquinone HQ-4: 2-sec-dodecyl-5-sec-tetradecylhydroquinone HQ-5: 2,5-di (1,1-dimethyl-4-hexyloxycarbonyl) butylhydroquinone Image stabilizer A : Pt-octylphenol

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[0130]

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In the preparation of the light-sensitive material 101, the blue light-sensitive emulsion (Em-B1) of the first layer was added to each of (Em-B1).
B2) to (Em-B10), except that photosensitive materials 102 to 110 were prepared in the same manner.

The light-sensitive materials 101 to 101 thus prepared
110 was subjected to the following scanning exposure and processing. Scanning exposure was performed by using a semiconductor laser (oscillation wavelength: 680 nm) as a red light source, a He—Ne gas laser (oscillation wavelength: 544 nm) as a green light source, an Ar gas laser (oscillation wavelength: 454 nm, 477 nm) as a blue light source, and a solid laser crystal LiSrAlF6 to LiB3O5. What was taken out by combining SHG elements (oscillation wavelength 430n
m) and a light emitting diode (main wavelength 410 nm),
The photosensitive material is fixed on the outer periphery of the cylindrical drum, and the light beam is irradiated by rotating the drum while modulating the amount of light for each light beam by the AOM based on the image data. Simultaneously with the scanning, the light source was moved perpendicularly to the rotation direction of the drum to perform sub-scanning. Dmax is status A (R, G,
B) = (2.35, 2.30, 2.20). At this time, the exposure time was 10 ^-6 seconds per pixel. Further, it was confirmed using a beam monitor that the beam diameter was 100 μm for each of B, G, and R. Using this device, 1cm x 1cm patch images are gray, yellow,
Scanning exposure was performed at a resolution of 381 dpi while adjusting the exposure amount of each color so that magenta and cyan could be reproduced, and then processing was performed in the following development processing step 1. The reflection density of each step of the four-color patch image thus obtained was measured using a densitometer X-Rite.

A fine line image having a width of one pixel was exposed in parallel with the main scanning direction with the same exposure amount as that for outputting a patch image for each of the four color steps.

A fine line image obtained by exposing the fine line image at the same exposure amount as that for obtaining Dmax was obtained by using a microdensitometer PDM-5AR (manufactured by Konica Corporation) in a direction perpendicular to the fine line. And aperture size 2μm × 1
Scanning measurement was performed at a sampling pitch of 2 μm assuming 00 μm to obtain density profile data of a fine line. As the output image, in addition to the above-mentioned patches and fine lines, landscape images and portraits photographed by a digital camera, and rectangular wave patterns and lattice images, which are repetitions of fine line images, were also included as part of the subject evaluation.

(Development Processing Step 1) Processing Temperature Time Color Developer (CD-1) 37.0 ± 0.5 ° C. 45 seconds Bleach-fixer (BF-1 35.0 ± 2.5 ° C. 45 seconds) Stabilizing solution 25-39 ° C 45 seconds Drying 60-80 ° C 30 seconds

Color developer (CD-1) Pure water 800 ml Triethylenediamine 2 g Diethylene glycol 10 g Potassium bromide 0.02 g Potassium chloride 4.5 g Potassium sulfite 0.25 g N-ethyl-N- (β-methanesulfonamidoethyl) -3 -Methyl-4-aminoaniline sulfate 4.0 g N, N-diethylhydroxylamine 5.6 g Triethanolamine 10.0 g Sodium salt of diethylenetriaminepentaacetic acid 2.0 g Potassium carbonate 30 g Water was added to bring the total volume to 1 liter. Alternatively, the pH is adjusted to 10.1 with potassium hydroxide.

Bleach-fix solution (BF-1) Pure water 700 ml Diethylenetriaminepentaacetate ammonium ferric dihydrate 65 g Diethylenetriaminepentaacetic acid 3 g Ammonium thiosulfate (70% aqueous solution) 100 ml 2-amino-5-mercapto-1,3,4 -Thiadiazole 2.0 g Ammonium sulfite (40% aqueous solution) 27.5 ml Add water to make the total volume 1 liter, and adjust the pH to 5.0 with potassium carbonate or glacial acetic acid.

Stabilizing liquid Pure water 800 ml o-phenylphenol 1.0 g 5-chloro-2-methyl-4-isothiazolin-3-one 0.02 g 2-methyl-4-isothiazolin-3-one 0.02 g diethylene glycol 1 0.0 g Optical brightener (Tinopearl SFP) 2.0 g 1-hydroxyethylidene-1,1-diphosphonic acid 1.8 g Magnesium sulfate heptahydrate 0.2 g Polyvinylpyrrolidone 1.0 g Nitrilotriacetic acid trisodium salt 1. Add 5 g of water to make the total volume 1 liter, and adjust the pH to 7.5 with sulfuric acid or potassium hydroxide.

The print image thus obtained was evaluated by the half-value width of the fine line density profile, the blue density, green density and red density of the maximum density yellow patch, the density of the unexposed area, and the subjective evaluation of 30 subjects. did.

The half-value width of the fine line density profile is represented by the distance of a point indicating a half value of the peak density in the density profile obtained by the above method. The smaller the half width, the smaller the thickness of the thin line image, and the more clearly the outline appears, indicating that the image expression is performed with a sharp feeling. The subject's subjective evaluation was performed with emphasis on the reproducibility of fine lines (tightness of each color, cut edges, etc.) and character reproducibility (color shift of character outlines, presence or absence of white spots, etc.). received. The higher the image quality, the higher the score (up to 100)
The average score was calculated.

The results of each exposure method were used to determine the sensitivity of the blue photosensitive layer, the blue density of the maximum density yellow patch, the green density and red density, the half line width of the thin line, the density of the unexposed area,
Tables 3 to 5 collectively show the evaluation of subjects and the like.

The sensitivity of the blue photosensitive layer is represented by a value obtained by multiplying the logarithm of the amount of exposure irradiated to obtain a yellow image having a density of 0.8 by -1. An Ar gas laser having a wavelength of 454 nm is used as a blue light source. The sensitivity of the light-sensitive material 101 in the case of using is set to 0, and the difference from this is obtained as a relative value.

[0144]

[Table 3]

[0145]

[Table 4]

[0146]

[Table 5]

From the results shown in Tables 3 to 5, in the light-sensitive materials 102 to 110 satisfying the conditions of the present invention, the comparative light-sensitive materials 1
01, there is no particular difference in the density of the unexposed portion, but each exposure method having a different exposure wavelength, particularly 410 nm
When blue light having a relatively short wavelength such as 430 nm or 430 nm is used, the half line width of the fine line shows a small value stably, and it can be seen that an image expression with less blur and good sharpness is achieved. In addition, the green density and red density of the maximum density yellow patch are stably low.
It can be seen that a vivid yellow image with little turbidity is stably reproduced up to a high density range. These evaluation results faithfully appear in the subject evaluation. From these facts,
The photosensitive materials 102 to 110 exhibit stable and good print quality with respect to various digital exposure apparatuses, indicating that this is a preferred embodiment of the present invention.

Example 2 The amount of addition in the silver halide photographic light-sensitive material indicates grams per 1 m ² unless otherwise specified. Incidentally, silver halide and colloidal silver are shown in terms of silver, and photosensitive dyes are shown in moles per mole of silver halide in the same layer.

(Preparation of Halogenated Photographic Emulsion) <Preparation of Seed Emulsion-1> Seed Emulsion-1 was prepared as follows. A1 ossein gelatin 100 g potassium bromide 2.05 g 11.5 liter with water B1 ossein gelatin 55 g potassium bromide 65 g potassium iodide 1.8 g 0.2N sulfuric acid 38.5 ml 2.6 liters with water 75 g C1 ossein gelatin 75 g Potassium bromide 950g Potassium iodide 27g Water 3.0L D1 Silver nitrate 95g Water 2.7L E1 Silver nitrate 1410g Water 3.2L

The A1 solution kept at 60 ° C. in the reaction vessel was charged with B1
Solution and D1 solution by the control double jet method.
The solution was added over 0 minutes, and then the C1 and E1 solutions were added over 105 minutes by the control double jet method.
Stirring was performed at 500 rpm.

The flow rate was such that no new nuclei were generated with the growth of the particles and so-called Ostwald ripening was performed, and the flow rate was such that the particle size distribution did not spread. At the time of adding the silver ion solution and the halide ion solution, pAg was adjusted to 8.3 ± 0.05 using an aqueous potassium bromide solution, and pH was adjusted to 2.0 ± 0.1 using sulfuric acid.

After the addition, the pH was adjusted to 6.0, and then extraneous salts were removed to remove extraneous salts.
A desalting treatment was performed by the method described in No. 6.

When this seed emulsion was observed with an electron microscope, a cubic monodisperse emulsion having an average grain size of 0.27 μm and a grain size distribution of 17% and having a slightly chipped corner was obtained. <Preparation of Em-C> A monodisperse core / shell emulsion was prepared using Seed Emulsion-1 and the following seven kinds of solutions.

A2 ossein gelatin 10 g ammonia water (28%) 28 ml glacial acetic acid 3 ml seed emulsion-1 0.119 mol equivalent 11.5 liter with water B2 ossein gelatin 0.8 g potassium bromide 5 g potassium iodide 3 g with water 110 ml C2 ossein gelatin 2.0 g potassium bromide 90 g with water 240 ml D2 silver nitrate 9.9 g ammonia water (28%) 7.0 ml with water 110 ml E2 silver nitrate 130 g ammonia water (28%) 100 ml with water 240 ml F2 potassium bromide 94 g 165 ml with water G2 9.9 g silver nitrate 7.0 ml ammonia water (28%) 7.0 ml with water 110 ml

The solution A2 was kept at 40 ° C., and 800
Stirring was performed at rpm. The pH of Solution A2 was adjusted to 9.90 using acetic acid, and Seed Emulsion-1 was collected and dispersed and suspended.
Thereafter, the G2 solution was added at a constant speed over 7 minutes, and pAg was added to the mixture at 7.
Three. Further, solution B2 and solution D2 were added simultaneously over 20 minutes. At this time, the pAg was kept constant at 7.3. Furthermore,
Using potassium bromide aqueous solution and acetic acid for 10 minutes, p
After adjusting H = 8.83 and pAg = 9.0, C2 solution,
Solution E2 was added simultaneously over 30 minutes.

At this time, the flow ratio between the start of addition and the end of addition was 1:10, and the flow rate was increased with time.
Further, the pH was lowered from 8.83 to 8.00 in proportion to the flow rate ratio. Further, when the C2 solution and the E2 solution were added in only ／ of the total amount, the F2 solution was additionally injected and added at a constant speed over 8 minutes. At this time, the pAg was 9.0 to 11.
It has risen to zero. Further, acetic acid was added to adjust the pH to 6.0.

After completion of the addition, precipitation and desalting were carried out using an aqueous solution of Demol (manufactured by Kao Atlas) and an aqueous solution of magnesium sulfate to remove excess salts.
5, an emulsion having an average silver iodide content of about 2.0 mol% at pH 5.85 was obtained at 40 ° C.

When the obtained emulsion was observed with an electron microscope, the average particle size was 0.55 μm and the particle size distribution was 14%.
This was a rounded tetradecahedral monodisperse core / shell emulsion.

<Preparation of Seed Emulsion-2> Seed emulsion-2 was prepared as follows. A3 Ossein gelatin 24.2 g Water 9657 ml Polypropyleneoxy-polyethyleneoxy-disuccinate sodium salt (10% ethanol aqueous solution) 6.78 ml Potassium bromide 10.8 g 10% nitric acid 114 ml B3 2.5 N silver nitrate aqueous solution 2825 ml C3 Potassium bromide 824 g Potassium iodide 23.5 g 2825 liters with water D3 1.75 N aqueous solution of potassium bromide Silver potential control amount below

At 35 ° C., JP-B-58-58288, 5
Solution A using a mixing stirrer described in JP-A-8-58289.
464.3 ml of the solution B3 and 464.3 ml of the solution C3 were added to the sample No. 3 by the simultaneous mixing method over 2 minutes to form nuclei.

After stopping the addition of the solution B3 and the solution C3, it takes 60 minutes to raise the temperature of the solution A3 to 60 ° C., adjust the pH to 5.0 with a 3% KOH aqueous solution, and then again. The solution B3 and the solution C3 were added at a flow rate of 55.4 ml / min for 42 minutes by the simultaneous mixing method. The silver potential (measured with a silver ion selective electrode using a saturated silver-silver chloride electrode as a reference electrode) during the temperature rise from 35 ° C. to 60 ° C. and the re-simultaneous mixing with the solutions B3 and C3 was +8 mV using the solution D3. And +16 mV.

After completion of the addition, p
H was adjusted to 6, and immediately desalting and washing were performed. In this seed emulsion, 90% or more of the total projected area of silver halide grains is composed of hexagonal tabular grains having a maximum adjacent side ratio of 1.0 to 2.0,
It was confirmed with an electron microscope that the average thickness of the hexagonal tabular grains was 0.06 μm and the average particle size (in terms of salt diameter) was 0.59 μm.

<Preparation of Em-D> A tabular emulsion was prepared using Seed Emulsion-2 and the following three kinds of solutions. A4 ossein gelatin 5.26 g Polypropylene oxy-polyethylene oxy-disuccinate sodium salt (10% aqueous solution of ethanol) 1.4 ml Seed emulsion-2 equivalent to 0.094 mol 569 ml with water B4 ossein gelatin 15.5 g Potassium bromide 114 g Potassium iodide 3.19 g with water 658 ml C4 silver nitrate 166 g with water 889 ml

The B4 solution and the C4 solution were added to the A4 solution stirred vigorously at 60 ° C. for 107 minutes by the double jet method. During this time, the pH was kept at 5.8 and the pAg was kept at 8.7 throughout.
The addition rates of the B4 solution and the C4 solution were linearly increased so that the initial and final addition rates were 6.4 times.

After completion of the addition, precipitation and desalting were carried out using an aqueous solution of Demol (manufactured by Kao Atlas) and an aqueous solution of magnesium sulfate to remove excess salts.
5, an emulsion having an average silver iodide content of about 2.0 mol% at pH 5.85 was obtained at 40 ° C.

Observation of the obtained emulsion with an electron microscope revealed that 82% of the projected area had a mean grain size of 0.98 μm, a broad grain size distribution of 15%, and a tabular halide having a mean aspect ratio of 4.5. It was silver particles. The average of the ratio (t / l) of the distance between twin planes (l) to the thickness (t) of tabular grains is 11
Met. The crystal plane was composed of a (111) plane and a (100) plane, the main planes were all (111) planes, and the ratio of the (111) plane to the (100) plane in the edge plane was 78:22.

These emulsions were adjusted to pH 5.8 and pAg 7.0 with citric acid and sodium chloride.
Several kinds of dyes shown in Table 6 below were added, and after optimal chemical ripening at 60 ° C. using ammonium thiocyanate, sodium thiosulfate pentahydrate and chloroauric acid, 4-hydroxy-6-methyl- The ripening was stopped by adding 1.0 g of 1,3,3a, 7-tetrazaindene per mole of silver. (Preparation of silver halide photographic light-sensitive material) One side (front side) of a triacetylcellulose film support is subjected to an undercoating process, and then the surface opposite to the undercoated process (back side) with the support interposed therebetween. A layer having the following composition was formed sequentially from the support side.

Back surface first layer Alumina sol AS-100 (aluminum oxide) (manufactured by Nissan Chemical Industries, Ltd.) 0.8 g Back surface second layer Diacetyl cellulose 100 mg Stearic acid 10 mg Silica fine particles (average particle size 0.2 μm) 50 mg Subbing process On the surface of the triacetylcellulose film support, each layer having the following composition was sequentially formed from the support side to form a color photographic light-sensitive material (Sample Nos. 201 to 201).
208). First layer: Antihalation layer (HC) Black colloidal silver 0.15 g UV absorber (UV-1) 0.20 g Dye (CC-1) 0.02 g High boiling solvent (Oil-1) 0.20 g High boiling solvent (Oil-2) 0.20 g gelatin 1.6 g second layer: intermediate layer (IL-1) gelatin 1.3 g third layer: silver halide photosensitive layer silver halide emulsions C and D 0.9 g sensitizing dye ( Table 6) Magenta coupler (M-2) 0.30 g Magenta coupler (M-3) 0.13 g Colored magenta coupler (CM-1) 0.04 g DIR compound (D-1) 0.004 g High boiling solvent (Oil) -2) 0.35 g gelatin 1.0 g Fourth layer: first protective layer (Pro-1) Fine grain silver iodobromide emulsion (average particle size 0.08 μm) 0.3 g UV absorber (UV-1) 07g UV absorption Absorbent (UV-2) 0.10 g Additive 1 (HS-1) 0.2 g Additive 2 (HS-2) 0.1 g High boiling solvent (Oil-1) 0.07 g High boiling solvent (Oil-3) 0.07 g Gelatin 0.8 g Fifth layer: second protective layer (Pro-2) Additive 3 (HS-3) 0.04 g Additive 4 (HS-4) 0.004 g Polymethyl methacrylate (average particle size) 3 μm) 0.02 g Methyl methacrylate: ethyl methacrylate: methacrylic acid copolymer (3: 3: 4 weight ratio) (average particle size 3 μm) 0.13 g gelatin 0.5 g

Incidentally, the above-mentioned coated sample was further provided with an activator SA.
-2, SA-3, viscosity modifier, hardener H-2, H-3,
Stabilizers ST-3, ST-4, ST-5 (weight average molecular weight of 10,000 and 1,100,000),
Dyes F-4 and F-5 and an additive HS-5 (9.4 mg /
m ² ).

[0170]

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[0171]

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[0172]

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[0173]

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[0174]

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Each of the prepared samples was divided into two parts, one of which was left as it was, and the other was left for 3 days in an atmosphere of 80% RH and 40 ° C. in order to evaluate the stability under high temperature, and forcibly. Deteriorated.

[Evaluation of Photographic Performance] Each of the obtained samples was exposed to a wedge with white light for 1/100 second, and then subjected to development, bleaching and fixing according to the following processing steps. The density of the processed sample was measured using an optical densitometer (PDA-65 manufactured by Konica). The sensitivity was defined as the reciprocal of the exposure at fog density +0.03.
The relative values were set to 0. When the increase in fog (ΔFog) of the sample after the forced deterioration treatment with respect to the sample immediately after coating and drying and the sensitivity before aging of the sample immediately after coating and drying are S1, and the sensitivity value after aging of the sample after forced deterioration is S2. Sensitivity variation ΔS
= S2 / S1 x 100 (%).

The results are shown in Table 6. (Processing step) Step Processing time Processing temperature Replenishment amount * Color development 3 minutes 15 seconds 38 ± 0.3 ° C. 780 ml Bleaching 45 seconds 38 ± 2.0 ° C. 150 ml Fixing 1 minute 30 seconds 38 ± 2.0 ° C. 830 ml Low Constant 60 seconds 38 ± 5.0 ° C. 830 ml Drying 60 seconds 55 ± 5.0 ° C.-* The replenishment amount is a value per 1 m 2 of the photosensitive material.

<Preparation of Processing Agent> (Composition of Developer) Water 800 ml Potassium carbonate 30 g Sodium hydrogen carbonate 2.5 g Potassium sulfite 3.0 g Sodium bromide 1.3 g Potassium iodide 1.2 mg Hydroxyamine sulfate 2.5 g 4 -Amino-3-methyl-N-ethyl-N- (β-hydroxyethyl) aniline sulfate 4.5 g Diethylenetetraaminepentaacetic acid 3.0 g Potassium hydroxide 1.2 g Water was added to make up to 1.0 liter, Adjust the pH to 10.06 with potassium hydroxide or 20% sulfuric acid.

(Development replenisher composition) Water 800 ml Potassium carbonate 35 g Sodium hydrogen carbonate 3.0 g Potassium sulfite 5.0 g Sodium bromide 0.4 g Hydroxyamine sulfate 3.1 g 4-Amino-3-methyl-N-ethyl N -(Β-hydroxyethyl) aniline sulfate 6.3 g Diethylenetetraamine pentaacetic acid 3.0 g Potassium hydroxide 2.0 g Water was added to make up to 1.0 liter, and the pH was adjusted to 10 using potassium hydroxide or 20% sulfuric acid. Adjust to 18.

(Composition of bleaching solution) Water 700 ml 1,3-Diaminopropanetetraacetic acid iron (III) ammonium 125 g ethylenediaminetetraacetic acid 2 g sodium nitrate 40 g ammonium bromide 150 g glacial acetic acid 40 g PH 4 with water or glacial acetic acid. Adjust to 4.

(Composition of bleach replenisher) Water 700 ml 1,3-diaminopropanetetraacetic acid iron (III) ammonium 175 g ethylenediaminetetraacetic acid 2 g sodium nitrate 50 g ammonium bromide 200 g glacial acetic acid 56 g PH 4 using ammonia water or glacial acetic acid. Adjust to 0.

(Formulation of Fixing Solution) Water 800 ml Ammonium thiocyanate 120 g Ammonium thiosulfate 150 g Sodium sulfite 15 g Ethylenediaminetetraacetic acid 2 g Water was added to make up to 1.0 liter, and the pH was adjusted to 6.0 with ammonia water or glacial acetic acid. Adjust to 2.

(Formulation of Fixing Replenisher) Water 800 ml Ammonium thiocyanate 150 g Ammonium thiosulfate 180 g Sodium sulfite 20 g Ethylenediaminetetraacetic acid 2 g Water was added to make up to 1.0 liter. Adjust to 5.

(Preparation of Stabilizing Solution and Stabilizing Replenishing Solution) Water 900 ml p-octylphenol-ethylene oxide-10 mol adduct 2.0 g dimethylolurea 0.5 g hexamethylenetetramine 0.2 g 1,2-benzoisothiazolin-3-one 1 g Siloxane (UCC L-77) 0.1 g Ammonia water 0.5 ml Water is added to make up to 1.0 liter, and the pH is adjusted to 8.5 using ammonia water or 50% sulfuric acid.

[0185]

[Table 6]

From Table 6, it can be seen that the silver halide photographic light-sensitive material of the present invention has high sensitivity both on the same day and over time (thermo substitution) and good photographic performance in which fog and sensitivity fluctuation are suppressed as compared with the comparative sample. Also, it is found that the residual color contamination is excellent.

Embodiment 3

[0188]

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J. Org. Chem. , 1943, 40
2-amino-4- obtained by the method described in 6-412
(2-Pyridyl) phenol (5.0 g) and compound 3-2a (5.0 g) were added to 100 ml of methanol, heated under reflux for 1 hour, and then the solvent was distilled off with a rotary evaporator. The residue was extracted with 50 ml of ethyl acetate, washed with saturated sodium bicarbonate and brine, dried over magnesium sulfate, and the solvent was distilled off with a rotary evaporator. The residue was purified by column chromatography to obtain a colorless liquid (4.5 g). NMR
The spectrum and mass spectrum confirmed that the target compound was obtained.

Embodiment 4

[0191]

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2-Amino-4- (2-pyridyl) phenol (5.0 g) and compound 3-4a (4.5 g) were added to 200 ml of ethanol, heated under reflux for 8 hours, and then the solvent was evaporated with a rotary evaporator. Was distilled off. The residue was dissolved in 200 ml of water, adjusted to pH 6 with acetic acid, and the precipitate was collected by filtration. The precipitate was recrystallized from EtOH to give red crystals (5.1 g). NMR spectrum and m
The product was confirmed to be the target product by an ass spectrum.

Embodiment 5

[0194]

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Compound 3-2 (2.0 g) and 1,3-
Propane sultone (1.5 g) was heated at 130 ° C. for 1 hour, cooled to room temperature, dispersed and washed with acetone, and acetone insolubles were collected by filtration to obtain brown crystals (2.8 g).
The product was confirmed to be the target product by NMR spectrum and mass spectrum.

Embodiment 6

[0197]

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Compound 3-4 (2.0 g) and 1,3-
Propane sultone (2.7 g) was heated at 130 ° C. for 1 hour, cooled to room temperature, dispersed and washed with acetone, and acetone insolubles were collected by filtration to obtain brown crystals (3.6 g).
The product was confirmed to be the target product by NMR spectrum and mass spectrum.

Embodiment 7

[0200]

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Compound 4-2 (2.0 g) and Compound 4
-4 (2.8 g) in 50 ml of acetonitrile,
While stirring, 5 ml of triethylamine was added, and the mixture was heated under reflux for 2 hours. After cooling to room temperature, the precipitate was collected by filtration,
The crystals were recrystallized from tOH to obtain single yellow crystals (1.8 g). N
The product was confirmed to be the target by the MR spectrum and the mass spectrum.

Embodiment 8

[0203]

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The compound (6-6) (2.0 g) and the compound (5-
5) 1.4 g and 4.0 g of propane sultone at 150 ° C.
For 2 hours. After cooling to room temperature, ethanol 2
0 ml and 2 ml of triethylamine were added, and the mixture was heated under reflux for 1 hour. After cooling to room temperature, the precipitate was filtered to obtain 5.1 g of a pale yellow solid. The product was confirmed to be the target product by NMR spectrum and mass spectrum.

Embodiment 9

[0206]

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2.0 g of compound (6-1) and compound (5-
5) 1.6 g and 5.0 g of butane sultone were heated at 150 ° C. for 2 hours. After cooling to room temperature, ethanol 20
Then, 2 ml of pyridine and 2 ml of pyridine were added, and the mixture was heated under reflux for 1 hour. The mixture was cooled to room temperature, and the precipitate was filtered.
g was obtained. The product was confirmed to be the target product by NMR spectrum and mass spectrum.

Embodiment 10

[0209]

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Compound (6-1) (2.0 g), compound (5-
4) 2.0 g and 7.5 p-toluenesulfonate ethyl
g was heated at 150 ° C. for 2 hours. After cooling to room temperature,
20 ml of ethanol and 1 ml of triethylamine were added, and the mixture was heated under reflux for 1 hour. After cooling to room temperature, the precipitate was filtered to obtain 4.5 g of a yellow solid. The product was confirmed to be the target product by NMR spectrum and mass spectrum.

[0211]

According to the present invention, in each of the exposure methods having different exposure wavelengths, in particular, when blue light having a relatively short wavelength such as 410 nm or 430 nm is used, the half line width of the thin line shows a stable small value. Able to achieve good image expression with less bleeding and sharpness, the green density and red density of the maximum density yellow patch show a stable low value, and a vivid yellow image with little turbidity is stably reproduced up to the high density area, A silver halide photographic light-sensitive material, an image forming method, a compound and a method for synthesizing the same, which stably show good print quality for various digital exposure apparatuses, can be provided.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C07D 403/14 C07D 403/14 4H056 413/04 413/04 413/14 413/14 417/04 417/04 417/06 417/06 417/14 417/14 421/04 421/04 421/14 421/14 C09B 23/00 C09B 23/00 ML G03C 1/00 G03C 1/00 B 1/035 1/035 C 1/16 1/16 5/08 5/08 F term (reference) 2H016 AC00 BA00 BB04 BD02 2H023 AA02 BA02 CA07 CA14 4C031 JA05 4C056 AA01 AB01 AC02 AD03 AE03 CA28 4C063 AA01 AA03 AA05 BB01 BB02 BB03 CC10 CC62 CC62 CC52 CC52 CC52 CC52 CC52 CC62 CC62 CC75 CC78 CC92 CC98 DD04 DD06 DD12 DD14 DD22 DD26 DD29 DD43 DD52 DD62 EE10 4H056 CA01 CA04 CC02 CC08 CE03 CE06 DD19 DD23 FA05

Claims (20)

[Claims] 1. A silver halide photographic light-sensitive material applied to an image forming method in which digitized image information is developed after imagewise exposure and contains at least one compound represented by the following general formula (1). A silver halide photographic light-sensitive material comprising: Embedded image (Wherein, R ¹ and R ² each represent an aliphatic group or an aromatic group, R ³ , R ⁴ , and R ⁵ each represent a hydrogen atom or a monovalent substituent, and at least one of R ⁴ and R ⁵ Represents a heteroaromatic ring, Z ¹ and Z ² each represent a group of nonmetal atoms necessary to form a 5- or 6-membered nitrogen-containing heterocyclic ring, and n ¹ and n ² each represent 0
Or 1 represents, X is an ion necessary to neutralize the molecular charge, n ³ represents the number of ions necessary for neutralizing the charge. ) 2. The method according to claim 1, wherein the digitized image information is displayed after imagewise exposure.
Silver halide photographic material applicable to image forming method
Of the compound represented by the following general formula (2)
Silver halide photography characterized by containing at least one kind
True photosensitive material. Embedded image(Where A¹, A²Is O, S, Se, NR²², CR
²³, R²⁴And R ¹¹, R¹², R²²,
R²³, R²⁴Represents an aliphatic group or an aromatic group,
R¹³~ R²¹Represents a hydrogen atom or a monovalent substituent, respectively.
Then R¹⁴~ R²¹At least one has a heteroaromatic ring
Represent. X represents an ion required to neutralize the charge in the molecule.
Then n³Indicates the number of ions required to neutralize the charge.
You. ) 3. A silver halide photographic material applied to an image forming method in which digitized image information is developed after imagewise exposure with an exposure time of 10 ^-3 seconds or less per pixel,
A silver halide photographic light-sensitive material comprising at least one compound represented by formula (1) or (2). 4. A silver halide photographic material which is applied to an image forming method in which digitized image information is developed after imagewise exposure with an exposure time of 10 ^-3 seconds or less per pixel,
A compound represented by the above formula (1) or (2), which has at least one layer of an image forming silver halide emulsion layer containing a silver halide emulsion having an average silver chloride content of 95 mol% or more on a support; A silver halide photographic material comprising a silver halide emulsion sensitized with at least one of the following. 5. Digital image information is converted to 10 ^-3 per pixel by at least three kinds of light having different wavelengths.
In a silver halide photographic light-sensitive material applied to an image forming method of developing after imagewise exposure with an exposure time of not more than second, a silver halide emulsion having an average silver chloride content of at least 95 mol% of at least one layer is formed on a support. Having a yellow image forming silver halide emulsion layer, a magenta image forming silver halide emulsion layer, and a cyan image forming silver halide emulsion layer, wherein at least one of the compounds represented by formula (1) or (2) is used. A silver halide photographic light-sensitive material containing a color-sensitized silver halide emulsion. 6. Digital image information is converted to 10 ^-3 per pixel by at least three kinds of light having different wavelengths.
In a silver halide photographic light-sensitive material applied to an image forming method of developing after imagewise exposure with an exposure time of not more than second, a silver halide emulsion having an average silver chloride content of at least 95 mol% of at least one layer is formed on a support. A yellow image forming silver halide emulsion layer, a magenta image forming silver halide emulsion layer and a cyan image forming silver halide emulsion layer, wherein the compound represented by the general formula (1) or (2) pAg =
When it is added to a silver halide emulsion having an average silver chloride content of 6.0 to 7.7 and 95 mol% or more, it is 380 to 430 nm.
A silver halide photographic material comprising a silver halide emulsion which is color-sensitized with at least one compound having a spectral absorption maximum in a wavelength region up to nm. 7. The halogenation according to claim 1,
In a silver photographic light-sensitive material, R of the general formula (1)⁴, R⁵so
A heteroaromatic ring represented by the general formula (2): ¹⁴~ R
²¹Is a 5- or 6-membered heteroaromatic ring
Silver halide photosensitivity characterized by being an aromatic ring
material. 8. The silver halide photographic light-sensitive material according to claim 1, wherein the heteroaromatic ring represented by R ⁴ or R ⁵ in the general formula (1) or R in the general formula (2). ^{1 4 ~R
A} silver halide photographic material, wherein the heteroaromatic ring represented by ²¹ is a thiophene ring, a furan ring, a pyrrole ring or a pyridine ring. 9. The silver halide photographic light-sensitive material according to claim 1, wherein a semiconductor laser having an oscillation wavelength λ between 380 nm and 430 nm and a second harmonic are used as a blue light source. An image forming method, comprising performing imagewise exposure by a scanning exposure method using a combination of a generating element (SHG element), and then developing. 10. An image characterized by imagewise exposing the silver halide photographic material according to claim 1 to an exposure time of 10 ⁻⁶ seconds or less per pixel, and thereafter developing. Forming method. 11. A compound represented by the following general formula (3). Embedded image(Where R¹, R²Represents an aliphatic group or an aromatic group, respectively.
Then R³, R³¹, R ³²Is a hydrogen atom or monovalent
Represents a substituent, R³¹, R³²At least one of which contains nitrogen
Represents a 6-membered heteroaromatic ring. Z¹, Z²Contains 5 or 6 members
Represents a group of non-metallic atoms necessary to form a nitrogen heterocycle,
n¹, N²Represents 0 or 1, respectively, and X represents the charge in the molecule.
Represents the ion required for neutralization, n³Neutralizes the charge
Represents the number of ions required for ) 12. A compound represented by the following general formula (4). Embedded image(Where A¹, A²Is O, S, Se, NR⁵², CR
⁵³R⁵⁴And R^{4 1}, R⁴², R⁵², R⁵³,
R⁵⁴Each represents an aliphatic group or an aromatic group; ⁴⁴~
R⁵¹Each represents a hydrogen atom or a monovalent substituent;⁴⁴
~ R⁵¹At least one has a nitrogen-containing heteroaromatic 6-membered ring
Represent. X represents an ion required to neutralize the charge in the molecule.
Then n³Indicates the number of ions required to neutralize the charge.
You. ) 13. The compound represented by the general formula (3) according to claim 11,
^31. A compound, wherein at least one of R ³¹ and R ³² is a pyridine ring. 14. A compound of the formula (4) R ^{44 according} to claim 12,
To at least one of R ⁵¹ is a pyridine ring. 15. A silver halide photographic material comprising a compound represented by the formula (3) or (4). 16. A silver halide photographic material containing a compound represented by the general formula (3) or (4), wherein a semiconductor laser having an oscillation wavelength λ between 380 nm and 430 nm is used as a blue light source. An image forming method, comprising: performing imagewise exposure by a scanning exposure method using a combination of a semiconductor laser and a second harmonic generation element (SHG element); 17. A compound represented by the following general formula (5). Embedded image (Wherein, R ⁶¹ is a hydrogen atom, an aliphatic group, an aromatic group, SR
⁶⁶ , R ^{62 to} R ⁶⁶ represent a hydrogen atom or a monovalent substituent, and at least one of R ^{62 to} R ⁶⁵ represents a pyridine ring. ) 18. A compound represented by the following general formula (6). Embedded image (Wherein, R ⁷¹ is a hydrogen atom, an aliphatic group, an aromatic group, SR
Represents ^{74, R 72} represents an aliphatic group, an aromatic radical, R
⁷³ represents a pyridine ring, n ⁴ represents 0 or 1, Z ¹
Represents a non-metallic atomic group necessary for forming a nitrogen-containing heterocyclic ring 5 or 6-membered, X is an ion necessary to neutralize the molecular charge, n ³ to neutralize the charge Indicates the number of ions required. ) 19. A compound represented by the general formula (9), wherein the compound represented by the following general formula (7) and the compound represented by the general formula (8) are reacted with an alkylating agent in the same system. A method for producing the represented monomethine cyanine compound. Embedded image In the formula, Z ¹ and Z ² represent a group of atoms necessary to form a 5- or 6-membered nitrogen-containing heterocyclic ring, R ⁸¹ represents a hydrogen atom or a monovalent substituent, and R ⁸² and R ⁸³ Represents an aliphatic group, n ¹ and n ² each represent 0 or 1, X represents a charge neutralizing ion, and n ³ represents a number necessary to maintain the charge balance of the whole molecule. 20. An acid or a base after reacting the compound represented by the general formula (7) and the compound represented by the general formula (8) according to claim 19 with an alkylating agent in the same system. A method for producing a monomethine cyanine compound, comprising obtaining a compound represented by the general formula (9) in the presence of: