JPH05165147A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain a silver halide photographic sensitive material capable of forming a neutral black silver image by incorporating a dye specified in absorption maximum wavelength in the photosensitive material in a state of being dissolved in a specified solvent. CONSTITUTION:This photographic sensitive material is provided on a transparent support with at least one silver halide emulsion layer, and this layer or another hydrophilic colloidal layer contains the dye having the absorption max wavelength 500700nm and dissolved in the organic solvent represented by formula in which R1 is H, alkyl, cycloalkyl, aryl, or alkoxy-carbonyl; R2, is halogen, alkyl, cycloalkyl, aryl, alkoxy, or aryloxy; and k is an integer of 0-3.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a silver halide photographic light-sensitive material, and more particularly to a technique for improving the color tone of a silver image of a black-and-white silver halide photographic light-sensitive material such as an X-ray film.

[0002]

2. Description of the Related Art The covering power of silver halide emulsions is of great interest to light-sensitive material manufacturers. This is because the use of an emulsion having a high covering power can save the amount of silver necessary for maintaining a constant optical density.
However, although the color tone of developed silver in emulsion grains having such a high covering power almost always depends on the grain size and grain thickness, it is yellowish and gives an image observer discomfort. This yellowish tint is due to the fact that the size and thickness of developed silver also decreases as the grain size and grain thickness decrease, and the scattering of blue light components increases, resulting in strong yellowish light.

As a countermeasure against this, a neutral black color is obtained by incorporating a dispersion of a dye having an absorption maximum at 500 to 700 nm in a light-sensitive material.
-285445, JP-A-62-276539, JP-A-60-243654, JP-A-2-100044,
JP-A-2-297539, JP-A-3-94249,
It is shown in JP-A-3-100645. In these, the adjustment of the color tone for obtaining a neutral black color depends on the type of dye to be added and the addition amount thereof. When adjusting the color tone according to the type of dye, if the desired color tone cannot be obtained with the existing dye, it is necessary to synthesize a new dye, and what kind of color tone can be obtained before it is synthesized It is not clear that, unlike dyes used in other industries, the dyes used in the photographic industry must not have adverse photographic effects such as desensitization due to impurities or the dyes themselves. However, it is very difficult to put a new dye into practical use, and a method capable of easily adjusting the color tone of a dye dispersion without relying on the synthesis of a new dye has been desired.

[0004]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to provide a silver halide photographic light-sensitive material capable of forming a silver image having a neutral black color.

[0005]

As a result of earnest research, the inventor of the present invention has at least one photosensitive silver halide emulsion layer on a transparent support and has an absorption maximum value of 50 in a light-sensitive material.
It was found that the above object can be achieved by a silver halide black and white photographic light-sensitive material characterized in that a dye having a wavelength of 0 nm to 700 nm is dissolved and dispersed in an organic solvent represented by the following general formula (1). ..

[0006]

[Chemical 2]

The phenolic oil represented by the general formula (1) is not described in any of the above-mentioned patents as a color-controlling dye dispersion oil, and its specific solvent effect on the absorption of the dye is It was found by the inventor.

In the general formula (1), when R ₁ or R ₂ is an alkyl group or a group containing an alkyl group, the alkyl group may be linear or branched, and may have an unsaturated bond. Or may have a substituent (for example, a halogen atom, a hydroxyl group, an epoxy group, an aryl group, an alkoxy group, an aryloxy group, an acyloxy group, an alkoxycarbonyl group). R ₁ or R
_{When 2} is a cycloalkyl group or a group containing a cycloalkyl group, the cycloalkyl group is a 3- to 8-membered ring, may contain an unsaturated bond in the ring, and may also have a substituent (for example, a halogen atom, a hydroxyl group, Epoxy group, alkyl group,
It may have an aryl group, an alkoxy group, an acyl group) or a cross-linking group (for example, methylene, ethylene, isopropylidene). When R ₁ or R ₂ is an aryl group or a group containing an aryl group, the aryl group may be a condensed ring (eg, naphthyl group) or a substituent (eg, halogen atom, alkyl group, aryl group, alkoxy group, aryloxy). Group, an alkoxycarbonyl group). k
When R is plural, plural R ₂ may be the same or different.

Among the compounds represented by the formula [1], the compounds more preferable in the present invention will be explained below. In the formula [1], R ₁ is the total number of carbon atoms (hereinafter C
Number) 1 to 24 (preferably 1 to 18) alkyl groups [eg methyl, isopropyl, t-butyl, 2-butyl, n-pentyl, t-pentyl, 2-pentyl, t
-Hexyl, 2-hexyl, t-octyl, 2-ethylhexyl, 2-octyl, nonyl (branched), n-decyl, n-dodecyl, dodecyl (branched), 2-dodecyl,
n-pentadecyl, t-pentadecyl, 2-hexadecyl, benzyl], C number 3-18 (preferably 5-12)
A cycloalkyl group (for example, cyclopentyl, cyclohexyl), an aryl group (for example, phenyl, p-tolyl) having a C number of 6 to 32 (preferably 6 to 24) or a C number of 2
24 (preferably 5 to 17) alkoxycarbonyl group (for example, n-butoxycarbonyl, 2-ethylhexyloxycarbonyl, n-dodecyloxycarbonyl), R ₂ is a halogen atom (F, Cl, Br, I, preferably F or Cl) C number 1 to 24 (preferably 1 to 1)
8) alkyl group (for example, the alkyl group mentioned above for R ₁ ), C number 3-18 (preferably 5-17) cycloalkyl group (for example cyclopentyl, cyclohexyl), C number 6-32 (preferably 6-). 24) aryl groups (eg phenyl, p-tolyl, o-tolyl, p-methoxy), C 1-24 (preferably 1-18) alkoxy groups (eg methoxy, n-butoxy, 2-ethylhexyloxy, Benzyloxy, n-dodecyloxy, n-hexadecyloxy) or an aryloxy group having a C number of 6 to 32 (preferably 6 to 24) (for example, phenoxy, pt-butylphenoxy, pt-octylphenoxy, m). -Pentadecylphenoxy, p-dodecyloxyphenoxy), and k is 0 to 2 (preferably 1).
Or it is an integer of 2). Here, when k is 2, neither R ₂ is at both ortho positions of the hydroxyl group. Also, R
The sum of C numbers of ₁ and (R ₂ ) _k is 10 to 54.

The substituent R ₁ in the formula [1] is particularly preferably an alkyl group or a cycloalkyl group, and R ₂ is particularly preferably a halogen atom, an alkyl group or a cycloalkyl group. Specific examples of the phenolic oil represented by the formula [1] are shown below.

[0011]

[Chemical 3]

[0012]

[Chemical 4]

[0013]

[Chemical 5]

[0014]

[Chemical 6]

Here,

[0016]

[Chemical 7]

Is a cyclopentyl group,

[0018]

[Chemical 8]

Is a cyclohexyl group and C ₈ H ₁₇ (t) is

[0020]

[Chemical 9]

C ₁₂ H ₂₅ (sec) is

[0022]

[Chemical 10]

C ₁₆ H ₃₃ (sec)

[0024]

[Chemical 11]

C ₉ H ₁₉ (branch)

[0026]

[Chemical 12]

C ₁₂ H ₂₅ (branched)

[0028]

[Chemical 13]

A mixture of C ₁₅ H ₃₁ (t)

[0030]

[Chemical 14]

Represents a mixture containing as a main component.
Specific examples of the phenolic oil represented by the formula [1] other than the above and / or methods for synthesizing these compounds are described in, for example, US Pat. No. 2,835,579 and JP-A-59-1022.
34, 62-79451 and 62-24736.
No. 4 etc. are described.

The dyes of this invention are dissolved in the phenolic oils of this invention, which can be used in combination with high boiling organic solvents such as those described in US Pat. No. 2,322,027. .. The content of the phenolic oil of the present invention is 20- of the total amount of the phenolic oil of the present invention and the high boiling point organic solvent of 160 ° C. or higher.
100wt% is desirable. More preferably, 40-1
It is 00 wt%. The phenolic oil of the present invention is
It can be used in combination with an organic solvent-soluble polymer as described in JP-A-63-800,723. The desirable amount of the phenolic oil of the present invention used is 30-100 wt% of the total amount of the phenolic oil of the present invention and the organic solvent-soluble polymer. A more preferable amount used is 50-100 wt%.
The amount of the phenolic oil of the present invention used is 1/10 to 50 times that of the dye of the present invention. More preferably 1-2
It is 0 times.

Phenolic oils of the invention and 500
A dispersion of dyes having absorption at -700 nm is prepared as follows. The phenolic oil of the present invention and the dye of the present invention are completely dissolved together in a low boiling organic solvent, and this solution is then dissolved in water, preferably in a hydrophilic colloid aqueous solution, more preferably in a gelatin aqueous solution. , With the aid of a dispersant, disperse into fine particles by ultrasonic waves, colloid mill, etc. Alternatively, water or a hydrophilic colloid aqueous solution such as a gelatin aqueous solution is added to a low boiling point organic solvent containing a dispersion aid such as a surfactant, the phenolic oil of the present invention, or the dye of the present invention to form an oil-in-water solution with phase inversion. It may be a droplet dispersion. The low boiling point organic solvent may be removed from the prepared dispersion by a method such as distillation, washing with noodles, and ultrafiltration.

As the low-boiling organic solvent, lower alcohol acetates such as ethyl acetate and butyl acetate, propionsanethyl, secondary butyl alcohol, methyl ethyl ketone, methyl isobutyl ketone, methyl carbitol propionate, cyclohexanone, methyl alcohol, ethyl are used. Examples thereof include alcohol, acetone, tetrahydrofuran and the like. The particle size of the oil droplets of the dispersion thus obtained is 0.04 μm to 1.5 μm, and more preferably 0.04 μm to 0.4 μm.
This particle system can be measured by a measuring device such as Nanosizer manufactured by Coulter Counter.

As the surfactant used in the present invention,
There is no particular limitation, and the Handbook of Surfactants (Sangyo Tosho 1966
, Etc.) can be used.

The dye used in the present invention is 500-70.
Any material having an absorption maximum at 0 nm in the light-sensitive material may be used, and preferably anthraquinone, azo,
Azomethine, indoaniline and pyrazolotriazole dyes are used. More preferably, a dye represented by the following general formula (2) or (3) is used. The dyes in the present invention can be used in combination.

The amount of the dye used in the present invention varies depending on the absorption of the dye, but is 0.5 mg / m ² -150 mg.
/ M ^{2 and} more preferably 1-100 mg / m ² .

[0038]

[Chemical 15]

The general formula (2) will be described. Where R
²¹ represents a substituted or unsubstituted aryl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted heterocyclic group, R ²⁶ represents a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group, and R ²⁵ and R ²⁶ may be the same or different and each represents a substituted or unsubstituted alkyl group, and R ²⁵ and R
²⁶ may be connected to each other to form a ring. R ²²
Represents a hydrogen atom, an alkyl group or a halogen atom, and R
²³ represents a hydrogen atom, an alkyl group or an acylamino group (R ²² and R ²³ may combine with each other to form a ring), and Z ²¹ represents —CONH—, —NHCO— or —NH.
Represents CONH-. The alkyl group represented by R ²¹ is
A linear or branched alkyl group having 1 to 20 carbon atoms, which is a substituent (for example, a halogen atom, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, a hydroxyl group, an acylamino group, a carbamoyl group, a sulfamoyl group). Group, cyano group, etc.).

The aryl group represented by R ²¹ (eg, phenyl group, α to β-naphthyl group, etc.) has at least one substituent (eg, alkyl group, alkoxy group, aryloxy group, halogen atom, alkoxycarbonyl group, Acylamino group, carbamoyl group, alkylcarbamoyl group,
Arylcarbamoyl group, alkylsulfonamide group,
Arylsulfonamide group, sulfamoyl group, alkylsulfamoyl group, cyano group, nitro group, etc.).

The heterocyclic group represented by R ²¹ (for example, a pyridyl group, a quinolyl group, a furyl group, a benzothiazolyl group, an oxazolyl group, an imidazolyl group, etc.) may have the substituents enumerated above for the aryl group. good. R
^The alkyl group represented by ²⁴ is a group having 1 to 20 carbon atoms and has the same meaning as the alkyl group represented by R ²¹ .

The alkyl group represented by R ²² and R ²³ is an alkyl group having 1 to 3 carbon atoms (eg, methyl group, ethyl group,
Propyl group). As a preferred example of the case where R ²² and R ²³ form a ring, a case where R ²² and R ²³ form a benzene ring can be mentioned. Preferred among the halogen atoms for R ²² is a chloro atom. The acylamino group of R ²³ is preferably an acylamino group having 10 to 30 carbon atoms which is substituted with an alkoxy group or an aryloxy group (which may be substituted with an alkyl group or the like).

The alkyl group represented by R ²⁵ and R ²⁶ is an alkyl group having 1 to 6 carbon atoms (eg, methyl group, ethyl group, n-butyl group, isopropyl group, n-hexyl group), total carbon number. 2-10 substituted alkyl groups (as a substituent, a hydroxyl group, a sulfonamide group, a sulfamoyl group,
Alkoxy group, halogen atom, acylamino group, carbamoyl group, ester group, cyano group, etc.) are preferable. R
Examples of ²⁵ and R ²⁶ linked together to form a ring include a piperidine ring, a pyrrolidine ring, and a morpholine ring.

Specific examples of the dye represented by the general formula (2) are shown below, but the present invention is not limited thereto.

[0045]

[Table 1]

[0046]

[Chemical 16]

The general formula (3) will be described. In the general formula (3), each group of R _{31 to} R ₃₈ may be the same or different, and is a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group, an aryl group, a heterocyclic group, a cyano group, an amino group or a nitro group. Base,
Sulfonic acid group, carboxylic acid group, OR ₄₁ , NR ₃₉ R ₄₀ , C
OOR ₄₁ , COR ₄₁ , SO ₂ R ₄₁ , NR ₄₀ COR ₄₁ , N
R ₄₀ SO ₂ R ₄₁ , NR ₄₀ COOR ₄₁ , NR ₃₉ CON
R ₄₀ , CONR ₃₉ R ₄₀ , SO ₂ NR ₃₉ R ₄₀ , OCOR ₄₁
Or R ₃₁ and R ₃₂ or R ₃₂ and R ₃₃ , R ₃₃
And R ₃₄ , R ₃₅ and R ₃₆ , R ₃₆ and R _37, or R ₃₇ and R ₃₈ represent a nonmetallic atomic group necessary for forming a 5- or 6-membered ring.

Each group of the general formula (3) will be described. R
_The alkyl group represented by _{31 to} R ₄₁ is preferably an alkyl group having 1 to 30 carbon atoms, and a substituent (for example, a hydroxyl group, a carboxylic acid group, a cyano group, an alkoxy group, an aryloxy group,
Halogen atom, sulfamoyl group, sulfonamide group,
It may have an alkoxycarbonyl group, an acyl group, a sulfonyl group, a carbamoyl group, an amino group, an aryl group). Specifically, methyl, ethyl, n-propyl, isopropyl, t-butyl, n-hexyl, n-octyl, cyclohexyl, 2-ethylhexyl, 2-carboxyethyl, 2-cyanoethyl, 2-hydroxyethyl, 2-dimethyl. Aminoethyl, carboxymethyl, isopropyloxycarbonylmethyl, butoxycarbonylmethyl, 2-methanesulfonamidoethyl, 2-methoxyethyl, benzyl, 2-acetoxyethyl, 5-carboxypentyl, 2- (2-carboxybenzoyloxy) ethyl, Each group such as chloromethyl may be mentioned.

The aryl group represented by R _{31 to} R ₄₁ is preferably an aryl group having 6 to 14 carbon atoms and has a substituent (for example, a carboxylic acid group, a sulfonic acid group, an alkyl group, a sulfonamide group, a sulfamoyl group, an acyl group). Group, amide group,
Carbamoyl group, alkoxycarbonyl group, alkoxy group, cyano group, hydroxyl group, nitro group, alkoxycarbonyl group, halogen atom, amino group).
Specifically, phenyl, naphthyl, 2-carboxyphenyl, 3-carboxyphenyl, 5-carboxyphenyl, 2,4-dicarboxyphenyl, 3,5-dicarboxyphenyl, p-tolyl, 4-methoxyphenyl, 2
Each group such as -chlorophenyl, 4-methanesulfonamidophenyl, 2-hydroxy-5-carboxyphenyl, 2-methoxy-5-carboxyphenyl, 4-nitrophenyl, 4-dimethylaminophenyl and the like can be mentioned.

The heterocyclic group represented by R _{31 to} R ₄₁ is preferably a 5- or 6-membered heterocycle, and may be a condensed ring. Specific examples thereof include 2-pyridyl, 3-pyrrolyl, 5-carboxybenzoxazol-2-yl, 3-pyrazolyl, 1-indolyl and the like, which may have a substituent. Examples of the substituent include an alkyl group and a substituent which the above-mentioned alkyl group may have.

Examples of the halogen atom represented by R _{31 to} R ₃₈ include fluorine, base, bromine and iodine.

R ₃₁ and R ₃₂ , R ₃₂ and R ₃₃ , R ₃₃ and R ₃₄ , R
_The 5- or 6-membered ring formed by linking ₃₅ and R ₃₆ , R ₃₆ and R ₃₇ , R ₃₇ and R ₃₈ includes a double bond of an anthraquinone ring to which each group is bonded, and a succinimide ring. , Benzene ring, naphthalene ring, indole ring, pyridine ring and the like.

Examples of the 5- or 6-membered ring formed by connecting R ₃₉ and R ₄₀ or R ₄₀ and R ₄₁ include a pyrrolidine ring, a piperidine ring, morpholinic acid and a pyrrolidone ring.

Preferred of the general formula (3) are R _{31 to} R
_At least one of ₃₈ represents COOR ₄₁ (R ₄₁ has the same meaning as defined above), or R ₃₁ and R ₃₂ or R _32.
And R ₃₃ are linked to form a 5- or 6-membered ring.
Specific examples of the dye represented by the general formula (3) are shown below, but the present invention is not limited thereto.

[0055]

[Chemical 17]

[0056]

[Chemical 18]

[0057]

[Chemical 19]

[0058]

[Chemical 20]

[0059]

[Chemical 21]

[0060]

[Chemical formula 22]

[0061]

[Chemical formula 23]

The location of addition of the dye of the present invention is not particularly limited, and the dye can be added to either the silver halide emulsion layer or the non-photosensitive hydrophilic colloid layer (eg, intermediate layer or back layer). The addition amount is 1 to 1 per square meter
It is 00 mg, especially 10 to 50 mg.

The emulsion grains used in the present invention are preferably tabular grains. As the tabular photosensitive silver halide emulsion used in the present invention, silver chloride, silver chlorobromide, silver bromide, silver iodobromide and silver chloroiodobromide can be used, but the odor is high in view of high sensitivity. Silver iodide or silver iodobromide is preferred,
Particularly, the iodide content is preferably 0 mol% to 3.5 mol%. The projected area diameter of the tabular emulsion of the present invention is 0.3-2.
It is preferably 0 μm, particularly 0.5 to 1.5 μm. The distance between parallel planes (particle thickness) is 0.0
It is preferably 5 μm to 0.5 μm, particularly preferably 0.1 to 0.25 μm. As a method for producing tabular silver halide grains,
This can be achieved by appropriately combining methods known in the art. The tabular silver halide emulsion is described in JP-A-58-12.
7,921, JP-A-58-113,927, JP-A-58
-113,928, the method described in U.S. Pat. No. 4,439,520 and the like can be easily prepared. Also, p
A seed crystal is formed in which the tabular grains are present in an amount of 40% or more by weight in an atmosphere having a relatively low pBr value of Br1.3 or less, and the seed crystal is added while simultaneously adding a silver and halogen solution while maintaining the same pBr value. It is obtained by growing. During this grain growth process, it is desirable to add silver and halogen solutions so that new crystal nuclei are not generated.

The size of the tabular silver halide grains is determined by selecting the kind and amount of the temperature controlling solvent, the silver salt used during grain growth,
It can be adjusted by controlling the addition rate of the halide and the like. Further, among the tabular silver halide grains, monodisperse hexagonal tabular grains are particularly useful grains. The details of the structure and manufacturing method of the monodisperse hexagonal tabular grain according to the present invention are described in JP-A-63-151618.
For the present invention, so-called halogen conversion type (conversion type) particles as described in British Patent 635,841 and US Pat. No. 3,622,318 can be used particularly effectively. The degree of halogen conversion is 0.2 mol% to 2 mol%, especially 0.2 mol% to silver.
0.4 mol% is good. In silver iodobromide, grains having a structure having a high iodine layer inside and / or on the surface thereof are particularly preferable. By converting the surface of the tabular silver halide grains of the present invention, a silver halide emulsion having higher sensitivity can be obtained.

As a method for halogen conversion, an aqueous halogen solution having a smaller solubility product with silver than the halogen composition on the grain surface before halogen conversion is usually added. For example, potassium bromide and / or potassium iodide aqueous solution is added to silver chloride or silver chlorobromide tabular grains, and potassium iodide aqueous solution is added to silver bromide or silver iodobromide tabular grains. To convert.
The concentration of the aqueous solution to be added is preferably thin, 30% or less, and more preferably 10% or less. Furthermore, 1 per minute per mol of silver halide before halogen conversion
It is preferred to add the converted halogen solution at a rate of less than or equal to mol%. Further, during the halogen conversion, a part or all of the sensitizing dye and / or the silver halide adsorbing material of the present invention may be present, and instead of the converted halogen aqueous solution, silver bromide or silver iodobromide is used. Alternatively, fine silver halide grains of silver iodide may be added. The size of these particles is
0.2 μm or less, preferably 0.1 μm or less, particularly 0.0
It is preferably 5 μm or less. The halogen conversion method of the present invention is not limited to any one of the above methods and may be used in combination depending on the purpose. The silver halide composition on the grain surface before conversion to halogen is preferably an iodine content of 3 mol% or less.
It is particularly preferably 1.0 mol% or less. When halogen conversion is carried out by the above method, the method in which a silver halide solvent is present is particularly effective. Preferred solvents include thioether compounds, thiocyanates, and tetra-substituted thioureas. Among them, the thioether compound and the thiocyanate are particularly effective, and it is preferable to use 0.5 g to 5 g of the thiocyanate and 0.2 g to 3 g of the thioether per mol of silver halide.

In the present invention, the tabular silver halide emulsion may be a mixture of two or more kinds of silver halide emulsions. The grain size, halogen composition, sensitivity, etc. of the emulsions to be mixed may be different. For example, a spherical or potato-shaped photosensitive emulsion or a photosensitive silver halide emulsion composed of tabular grains having a grain diameter of 3 times or more the grain thickness is used in the same layer or different as described in JP-A-58-127921. You may use it for a layer. When used in different layers, the light-sensitive silver halide emulsion consisting of tabular grains may be on the side closer to the support or conversely on the far side. Coexist with cadmium salt, zinc salt, lead salt, thallium salt, iridium salt or its complex salt, rhodium salt or its complex salt, iron salt or iron complex salt in the process of silver halide grain formation or physical ripening during the production of silver halide. You may let me.
A so-called silver halide solvent such as thiocyanate, thioether compound, thiazolidineethione or tetra-substituted thiourea may be allowed to be present at the time of grain formation. Among them, thiocyanate, tetrasubstituted thiourea and thioether are preferred solvents for the present invention.

There are no particular restrictions on the emulsion sensitizing method and various additives used in the light-sensitive material of the present invention.
It is possible to use those described in the following relevant parts of Japanese Patent No. 68539. Item This section 1 Chemical sensitization method JP-A-2-68539, page 10, upper right column 13, line 3 to left lower column, line 16 2 Antifoggants / stabilizers, page 10, lower left column, line 17 to page 11, upper left column, line 7 and page 3, lower left column, line 2 to page 4, lower left column. 3 Spectral sensitizing dyes, page 4, lower right column, line 4 to page 8, lower right column, 4 surfactants and antistatic agents, page 11, upper left column, line 14 to page 12, upper left column, line 9 .. 5 Matting agents, slip agents, plasticizers, page 12, upper left column, line 10 to upper right column, line 10 Page 14, lower left column, line 10 to lower right column, line 1 of the same. 6 Hydrophilic colloid, page 12, upper right column, line 11 to lower left column, line 16 7 Hardener, page 12, lower left column, line 17 to page 13, upper right column, line 6 8 Supports, page 13, upper right column, lines 7 to 20. 9 Dyes / mordanting agents, page 13, lower left column, line 1 to page 14, lower left column, line 9 10 Development processing method JP-A-2-103037, page 16, upper right column, line 7 to page 19, lower left column, line 15 And from Japanese Patent Publication No. 2-115837, page 3, lower right column, line 5 to page 6, upper right column, line 10.

[0068]

EXAMPLES Next, the present invention will be described in detail based on examples. Example 1 (Preparation of Dye Emulsion According to the Present Invention) With respect to 40 cc of ethyl acetate, a high boiling point organic solvent and an amount shown in Table 2, and
The dye dissolved. This solution was kept at 60 ° C., 110 g of 18% gelatin aqueous solution and 0.1% of 2-phenoxyethanol.
7 g and 2 g of sodium dodecylbenzenesulfonate were added, and the mixture was emulsified and dispersed using a homogenizer. Comparative solvents A to D were used as comparative examples of high boiling point organic solvents. Polymer A was used as an example of the combined use of organic solvent-soluble polymers.

[0069]

[Chemical formula 24]

(Preparation of tabular grains T-1) In 1 liter of water, 4.5 g of potassium bromide, 12.0 g of gelatin, thioether HO (CH ₂ ) ₂ S (CH ₂ ) ₂ S (CH ₂ ) ₂ OH. 5% aqueous solution 2.5
1. Add cc and stir into a container kept at 55 ° C. while stirring 37 cc of silver nitrate aqueous solution (3.43 g of silver nitrate) and potassium bromide.
33cc aqueous solution containing 97g and 0.363g potassium iodide
Was added by the double jet method in 37 seconds. Next, an aqueous solution of 0.9 g of potassium bromide was added, and the temperature was raised to 70 ° C., and 53 cc of an aqueous silver nitrate solution (4.90 g of silver nitrate) was added to 13
Added over minutes. Here, 8 cc of 25% aqueous ammonia solution was added, and after physically aging for 10 minutes at the same temperature, 7 cc of 100% acetic acid solution was added. Subsequently, an aqueous solution of 133.3 g of silver nitrate and an aqueous solution of potassium bromide were added to pAg.
3 by control double jet method while keeping at 8.5
Added over 5 minutes. Next, 10 cc of 2N potassium thiocyanate solution and AgI fine particles having a diameter of 0.07 μm were added in an amount of 0.05 mol% with respect to the total amount of silver. After physically aging for 5 minutes at the same temperature, the temperature was lowered to 35 ° C. Thus, monodisperse tabular grains having a total silver iodide content of 0.31 mol%, an average projected area diameter of 0.61 μm, a thickness of 0.120 μm and a variation coefficient of 16.5% were obtained. After this, the soluble salts were removed by the sedimentation method. The temperature was raised to 40 ° C. again, and 30 g of gelatin, 2.35 g of phenoxyethanol and 0.8 of sodium polystyrene sulfonate as a thickener.
g, and pH 5.90 with caustic soda and silver nitrate solution,
The pAg was adjusted to 7.90. 5 while stirring this emulsion
Chemical sensitization was performed while maintaining the temperature at 6 ° C. First, 0.043 mg of thiourea dioxide was added, and the mixture was held as it was for 22 minutes for reduction sensitization. Next, 250 mg of Sensitizing Dye A was added. Subsequently, sodium thiosulfate The following selenium sensitizer A was added at a molar ratio of 6: 4.

[0071]

[Chemical 25]

Subsequently, chloroauric acid and potassium thiocyanate were added, and 40 minutes later, the mixture was cooled to 35 ° C. In this way, preparation of tabular grains T-1 was completed. (Preparation of emulsion layer coating solution) The following chemicals were added to 1 mole of silver halide of tabular grains T-1 to prepare an emulsion layer coating solution.・ 2,6-bis (hydroxyamino) -4-diethylamino-1,3,5-triazine 72 g ・ Gelatin 69 g ・ Dextran (average molecular weight 39,000) 18.5 g ・ Sodium polystyrene sulfonate (average molecular weight 600,000) 1.8g-Hardener 1,2-bis (vinylsulfonylacetamide) ethane Addition amount adjusted so that the swelling ratio would be 230%.

[0073]

[Chemical formula 26]

[0074]

[Chemical 27]

Snowtex C (manufactured by Nissan Kagaku Co., Ltd.) 9.6 g as solid content Dextran (average molecular weight of 39,000) 5.8 g (manufactured by adjusting surface protective layer of emulsion layer) The surface protective layer of the emulsion layer is Each component was prepared and prepared so that the coating amount was as follows. Gelatin 0.48 g / m ² · Sodium polyacrylate (average molecular weight 400,000) 0.018g / m ² · 4- hydroxy-6-methyl-1,3,3a, 7 - tetrazaindene 0.003 g / m ² -Polymethylmethacrylate (average particle size 2.5μm) 0.05g / m ² · Proxel 0.0005g / m ²

[0076]

[Chemical 28]

The pH was adjusted to 7.2 with NaOH. The prepared emulsion layer coating solution and surface protective layer coating solution were simultaneously extruded onto a polyethylene terephthalate film having a thickness of 183 μm which had been biaxially stretched and pre-coated with an undercoat layer. , Coated on one side. Coating silver amount is 2.55
It was adjusted to be g / m ² . The polyethylene terephthalate used was one containing 0.04 wt% of the dye having the following structure.

[0078]

[Chemical 29]

(Preparation of Antihalation Layer) An antihalation layer and a surface protection layer of the antihalation layer were coated on the side on which the emulsion layer and the surface protection layer were coated, and on the side opposite to the support. Each layer was prepared so as to have the following coating amount. (Antihalation layer) ・ Gelatin 1.5 g / m ²・ Phosphoric acid 5.2 g / m ²・ Snowtex C (Nissan Chemical Co., Ltd.) Solid content 0.5 g / m ²・ Potassium polystyrene sulfonate (average molecular weight) 600,000) 25 mg / m ² · Polymer latex (poly (ethyl acrylate / methacrylic acid) = 97/3) 0.53 g / m ² · Dye emulsion according to the present invention Table 2

[0080]

[Chemical 30]

[0081]

[Chemical 31]

(Surface protection layer of antihalation layer) Gelatin 1.05 g / m ² Polymethylmethacrylate (average particle size 3.5 μm) 65 g / m ²

[0083]

[Chemical 32]

C ₈ F ₁₇ SO ₃ K 1.7 mg / m ² · potassium polystyrene sulfonate (average molecular weight 600,000) 2 mg / m ² · NaOH 2.5 mg / m ² antihalation layer and its surface protective layer The simultaneous extrusion method was applied and dried simultaneously. The result of measuring the swelling ratio of the antihalation layer and the surface protection layer by the cryo-SEM method 2
It was 30%.

(Evaluation of Photographic Performance) Each sample of photographic materials 1 to 5 was exposed to light from both sides for 0.05 seconds by using X Ray Orthoscreen HR-4 manufactured by Fuji Photo Film Co., Ltd. Was evaluated. After the exposure, the following processing was performed. The sensitivity was defined as the reciprocal of the ratio of the exposure amount that gives a density of 1.0 with the photographic material 1 being 100. The obtained results are shown in Table 2.

[Treatment] Automatic developing machine ... The transport speed was increased by modifying the drive motor and gear of SRX501 manufactured by KONICA. <Developer concentrate> Potassium hydroxide 56.6 g Sodium sulfite 200 g Diethylenetriaminepentaacetic acid 6.7 g Potassium carbonate 16.7 g Boric acid 10 g Hydroquinone 83.3 g Diethylene glycol 40 g 4-Hydroxymethyl-4-methyl 1-phenyl-3-pyrazolidone 22.0 g 5-methylbenzotriazole 2 g Make up to 1 liter with water (pH adjusted to 10.60). <Fixing liquid concentrate> Ammonium thiosulfate 560 g Sodium sulfite 60 g Ethylenediaminetetraacetic acid / disodium dihydrate 0.10 g Sodium hydroxide 24 g Water is adjusted to 1 liter (pH is adjusted to 5.10 with acetic acid). When the development processing was started, each tank of the automatic processor was filled with the following processing solutions. Developing tank: 333 ml of the above concentrated developer solution, 667 ml of water and 10 ml of a starter containing 2 g of potassium bromide and 1.8 g of acetic acid were added to adjust the pH to 10.25. Fixing tank: 200 ml of the above-mentioned fixing liquid concentrate and 800 ml of water Processing speed ... Dry to Dry 30 seconds Development temperature ... 35 ° C. Fixing temperature ... 32 ° C. Drying temperature ... 55 ° C.

(Measurement of Dye Light Absorption) The above treatment was carried out with the coated sample left unexposed to give an "unexposed sample" and a density of 0.5.
The sample was subjected to the above-mentioned treatment and was subjected to the uniform exposure so that the “exposed portion sample” was obtained. The dye absorption peaks of these samples were measured using a U-3410 transmission spectroscopic absorption measuring device manufactured by Hitachi Ltd. The obtained results are shown in Table 2.

[0088]

[Table 2]

Example 2 Preparation of tabular grains 6 g of potassium bromide and 7 g of gelatin were added to 1 liter of water, and 37 cc of silver nitrate aqueous solution (4.00 g of silver nitrate) and potassium bromide were added to a container kept at 55 ° C. with stirring. 38 cc of an aqueous solution containing 5.7 g was added by the double jet method in 37 seconds. Then, after adding 18.6 g of gelatin, 70
89 cc of silver nitrate aqueous solution (4.90 g of silver nitrate)
Was added over 22 minutes. Here, 7 cc of 25% aqueous ammonia solution was added, and after physically aging for 10 minutes at the same temperature, 6.5 cc of 100% acetic acid solution was added. Subsequently, an aqueous solution of 153 g of silver nitrate and an aqueous solution of potassium bromide were added over 35 minutes by the control double jet method while maintaining the pAg at 8.5. Next, 15 cc of 2N potassium thiocyanate solution was added. After physically aging for 5 minutes at the same temperature, the temperature was lowered to 35 ° C. Monodispersed pure silver bromide tabular grains having an average projected area diameter of 1.10 μm, a thickness of 0.165 μm and a variation coefficient of diameter of 18.5% were obtained. After this, the soluble salts were removed by the sedimentation method. The temperature was raised to 40 ° C again, and 30 g of gelatin and 2.3 of phenoxyethanol were used.
Add 5 g and 0.8 g of sodium polystyrene sulfonate as a thickener, and add pH with caustic soda and silver nitrate solution.
It was adjusted to 5.90 and pAg 8.25. This emulsion was chemically sensitized while being kept at 56 ° C. with stirring. First, 0.043 mg of thiourea dioxide was added, and the mixture was held as it was for 22 minutes for reduction sensitization. Then 4-hydroxy-6
-Methyl-1,3,3a, 7-tetrazaindene 20 mg
Then, 400 mg of the sensitizing dye A was added. Further, 0.83 g of calcium chloride was added. Subsequently, 1.3 mg of sodium thiosulfate, 2.7 mg of the selenium sensitizer A, 2.6 mg of chloroauric acid and 90 mg of potassium thiocyanate were added, and 40 minutes later, the mixture was cooled to 35 ° C. Thus tabular grains T
-2 was prepared. Preparation of Coating Samples Coating samples 16 to 33 were prepared by adding the following chemicals per mol of T-2 silver halide to prepare coating solutions.・ Gelatin (including Gel in emulsion) 65.6 g ・ Trimethylolpropane 9 g ・ Dextran (average molecular weight 39,000) 18.5 g ・ Sodium polystyrene sulfonate (average molecular weight 600,000) 1.8 g ・ Hardener 1 , 2-Bis (vinylsulfonylacetamide) ethane Addition amount is adjusted so that the swelling rate is 230%.

[0090]

[Chemical 33]

Dye Emulsion of the Present Invention Table 3 A surface protective layer was prepared and prepared so that each component had the following coating amount. Contents coating weight Gelatin 0.966 g / m ² · sodium polyacrylate surface protective layer (average molecular weight 400,000) 0.023 - 4-hydroxy-6-methyl-1,3,3a, 7- Tet Razainden 0. 015

[0092]

[Chemical 34]

Polymethylmethacrylate (average particle size 3.7 μm) 0.087 Proxel (adjusted to pH 7.4 with NaOH) 0.0005 Preparation of support (1) Preparation of dye D-1 for undercoat layer Was dyed by a ball mill according to the method described in JP-A-63-197943.

[0094]

[Chemical 35]

434 ml of water and 791 ml of a 6.7% aqueous solution of Triton X-200 surfactant (TX-200) were placed in a 2 liter ball mill. 20 g of dye were added to this solution. Zirconium oxide (ZrO) beads 4
00 ml (2 mm diameter) was added and the contents were crushed for 4 days. After this, 160 g of 12.5% gelatin was added. After defoaming, the ZrO beads were removed by filtration. Observation of the obtained dye dispersion revealed that the crushed dye had a wide range of particle diameters from 0.05 to 1.15 μm, and the average particle diameter was 0.37 μm. Further, a centrifugation operation was performed to remove dye particles having a size of 0.9 μm or more. Thus, Dye Dispersion D-1 was obtained. (2) Preparation of support Corona discharge treatment was performed on a polyethylene terephthalate film having a thickness of 183 μm that was biaxially stretched, and a coating amount of the first undercoat liquid having the following composition was adjusted to 5.1 cc / m ^2. It was applied with a wire bar coater and dried at 175 ° C. for 1 minute. Next, a first undercoat layer was similarly provided on the opposite surface. The polyethylene terephthalate used was one containing 0.04 wt% of the dye having the following structure.

[0096]

[Chemical 36]

Butadiene-styrene copolymer latex solution (solid content 40% butadiene / styrene weight ratio = 31/69) 79 cc

[0098]

[Chemical 37]

2,4-Dichloro-6-hydroxy-s-triazine sodium salt 4% solution 20.5 cc distilled water 900.5 cc A second undercoat having the following composition on the above-mentioned first undercoat layers. Layers are coated on each side so that the coating amount is as described below, and 150 ° C on both sides by the wire bar coater method.
It was applied and dried.・ Gelatin 160 mg / m ²・ Dye Dispersion D-1 (26 mg / m ² as a solid dye component)

[0100]

[Chemical 38]

Matting agent Preparation of polymethylmethacrylate 2.5 mg / m ² photographic material having an average particle diameter of 2.5 μm The above emulsion layer and surface protective layer were coated on both sides of the prepared support by the simultaneous extrusion method. The coated silver amount per one side was 1.75 g / m ² . Photographic performance evaluation and spectral absorption experiment were conducted in the same manner as in Example 1, and the obtained results are shown in Table 3.

[0102]

[Table 3]

As is clear from Tables 2 and 3, the use of the phenolic oil of the present invention can effectively change the absorption maximum value of the dye having the absorption maximum in the range of 500 to 700 nm, while the comparison solvent does not. , It can be seen that the absorption maximum has hardly changed. From this, it can be seen that the absorption of the dye emulsion can be easily adjusted by the phenolic oil of the present invention.

Claims (1)

[Claims] 1. A photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer on a transparent support, wherein the emulsion layer or another hydrophilic colloid layer has a maximum absorption value in the light-sensitive material. A silver halide photographic light-sensitive material characterized in that a dye having a particle size of 500 nm to 700 nm is dissolved and contained in an organic solvent represented by the following general formula (I). [Chemical 1]