JP2844069B2 - Silver halide photographic materials for laser light sources - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a silver halide photographic material for a laser light source.

BACKGROUND OF THE INVENTION Attempts have been made to capture a radiation image for medical diagnosis as a digital value, perform image processing using a computer to make the image more suitable for diagnosis, and then reproduce the image by exposing with a laser beam. . In particular, argon, helium-neon,
Helium-cadmium and the like have been put to practical use. However, all of these lasers have shortcomings such as short lifetime, large size, and the need for complicated devices for modulating the emission intensity. On the other hand, in recent years, research on semiconductor lasers has progressed, and power-up and long life have been realized. Semiconductor lasers have the advantages of being inexpensive, having a long life, being small in size and capable of direct modulation, and requiring no modulation group, as compared with conventional argon or helium-neon lasers.

However, since the emission wavelength of the semiconductor laser having the above characteristics is in the near infrared region of 750 to 1500 nm, it is necessary for the recording material to have a photosensitive region in the near infrared region.

Methods for spectrally sensitizing silver halide to the near infrared region include, for example, The Theory of the Photographic Technology.
Process (The Theory of the Photographic Process)
As described in Third Edition (Macmillan 1966), pp. 198 to 201, a method using a long-chain Sinian dye is known.

However, these light-sensitive materials have poor storage stability, and have the drawback that if they are not stored in a refrigerator, they will be greatly desensitized.

In order to improve the sensitivity decrease during storage, the silver ion concentration and the hydrogen ion concentration of the photographic emulsion used for the photosensitive material are increased, the amount of the inhibitor is reduced, and further, a combination thereof is used. Increase fog. Also,
On the other hand, in order to improve the fog increase, there are the reverse of the above, that is, the silver ion concentration is reduced, the hydrogen ion concentration is reduced, the amount of the inhibitor is increased, or a combination thereof, but there is a disadvantage of lowering the sensitivity. . That is, the increase in fog during storage and the improvement in decrease in sensitivity are mutually incompatible.

[Object of the Invention] An object of the present invention is to provide a silver halide photographic light-sensitive material for a laser light source which improves the increase in fog and the decrease in sensitivity during storage.

[Constitution of the Invention] A silver halide photographic light-sensitive material for a laser light source, which achieves the object of the present invention, comprises a sensitizing dye represented by the following general formula (1).
A silver halide photographic light-sensitive material for a laser light source having at least one silver halide emulsion layer which has been spectrally sensitized to 0 nm or more, wherein the silver halide emulsion is dissolved in a solution containing a protective colloid with a water-soluble silver salt solution. A silver halide emulsion is obtained by aggregating silver halide particles formed by adding a neutral halide solution together with a protective colloid with the following aggregating polymer agent and removing dissolved substances.

General formula (1) In the formula, Z ₁ and Z ₃ represent a benzothiazole nucleus optionally having a substituent, a benzoxazole nucleus, a naphthothiazole nucleus, a nonmetallic atom group necessary for forming a naphthoxazole nucleus, and R ₁ and R ₂ Represents a saturated or unsaturated aliphatic group, respectively.

Z ₂ represents a carbon atom ring 5- to 6-membered, A is Z ₂ is 6
In the case of a member, it represents a hydrogen atom. In the case of a 5-membered ring, the general formula (1
-A).

(General formula 1-a) R ₃ and R ₄ each represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a halogen atom, an alkoxy group having 1 to 4 carbon atoms, and R ₅ and R ₆ each represent an alkyl group having 1 to 12 carbon atoms, R ₇ represents an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an alkoxycarbonyl having an alkoxy group having 1 to 4 carbon atoms. Represents a group.

When Z ₂ is a 6-membered ring, it is represented by the general formula (Ib).

General formula (Ib) Where R₈Is a hydrogen atom or a methyl group, R₉Is hydrogen field
Represents an alkyl group of 1 to 4 carbon atoms and a monocyclic aryl group.
You. Χ Represents an anion, and n is 1 or 2 (internal salt is
When formed, n is 1).

[Aggregating polymer agent] An aggregated gelatin agent in which at least 50% or more of the amino groups of the gelatin molecule are substituted with acyl, carbamoyl, sulfonyl, thiocarbamoyl, alkyl and / or aryl groups, or from the following A and B chains A polymer compound represented by the general formula [II]:

General formula [II] In the formula, R ¹ and R ₂ represent an aliphatic group, which may be different or the same. R ₃ is a hydrogen atom, an aliphatic group, an aryl group,
Or an aralkyl group. Χ is -O- or -NH
-, M ⁺ represents a cation. n takes a value of 10 to 10 ⁴ .
The two connecting hands of the B chain may be connected to either side of the tertiary carbon to which R ₁ and R ₂ of the A chain are arranged. Also Χ
There the case of -NH- may form a nitrogen-containing ring together with R _3.

 Hereinafter, the present invention will be described in detail.

First, the general formula (1) which can be preferably used in the present invention
The infrared sensitizing dye represented by the formula will be described.

In the general formula (1), Z ₁ and Z ₃ represent a nonmetallic atom group necessary for forming a benzothiazole nucleus, a benzoxazole nucleus, a naphthothiazole nucleus, and a naphthoxazole nucleus which may have a substituent. Examples of the group include a halogen atom, an alkyl group having 1 to 4 carbon atoms, and an alkoxy group having 1 to 4 carbon atoms.

R ₁ and R ₂ each represent a saturated or unsaturated aliphatic group (for example, a methyl group, a methyl group, a 2-hydroxyethyl group, a 2-methoxyethyl group, a 2-acetoxyethyl group, a salboxoxymethyl group, a 2-carboxyethyl group , 3-carboxypropyl, 4-carboxybutyl, 2-sulfoethyl, 3-sulfopropyl, 3-sulfobutyl, 4-
Sulfobutyl group, vinylmethyl group, benzyl group, phenethyl group, p-sulfophenethyl group, n-propyl group, isopropyl group, n-butyl group, etc.).

Z ₂ represents a carbon atom ring 5- to 6-membered, A is Z ₂ is 6
In the case of a member, it represents a hydrogen atom. In the case of a 5-membered ring, the general formula (1
-A).

In the general formula (1-a), R ₃ and R ₄ each represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a halogen atom, and 1 to 4 carbon atoms.
Wherein R ₅ and R ₆ each have 1 to 12 carbon atoms
Alkyl group, alkoxycarbonylalkyl group (for example, methoxycarbonylmethyl group, ethoxycarbonylethyl group, etc.), and optionally substituted aryl group (for example, phenyl group, m-tolyl group, p-tolyl group, m-chlorophenyl) Group, p-chlorophenyl group, m-, p-alkoxyphenyl group having an alkoxy group having 1 to 4 carbon atoms, etc.)
Wherein R ₇ is an alkyl group having 1 to 12 carbon atoms, 6 to 10 carbon atoms.
And an alkoxycarbonyl group having an alkoxy group having 1 to 4 carbon atoms.

When Z ₂ is a 6-membered ring, it is represented by the general formula (Ib).

 In the general formula (Ib), R₈Is hydrogen or methyl
Group, R₉Is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms,
Represents an aryl group. Χ Represents an anion (eg salt
Elementary ion, bromide ion, iodine ion, perchloric acid, ben
Zensulfonate, p-toluenesulfonate, methyl
Sulphate, ethyl sulphate, tetrafluorophore
Acid).

n represents 1 or 2 (n is 1 when an internal salt is formed).

Next, typical specific examples of the compound represented by formula (I) will be described.

The use amount of these dyes of the present invention is preferably from 0.003 g to 0.3 g, more preferably from 0.005 g to 0.15 g, per mol of silver halide.

These dyes of the present invention are described in U.S. Pat.Nos. 2,734,900 and 3,4,900.
Compounds can be easily synthesized according to the methods described in Nos. 82,978 and 3,758,461.

The dye of the present invention can be directly dispersed in an emulsion. These can be first dissolved in a suitable solvent, for example, methyl alcohol, ethyl alcohol, methyl cellosolve, acetone, water, pyridine or a complex solvent thereof, and added to the emulsion in the form of a solution. Also, ultrasonic waves can be used for dissolution. Further, as a method for adding the dye of the present invention, as described in U.S. Pat.No. 3,469,987, the dye is dissolved in a volatile organic solvent, the solution is dispersed in a hydrophilic colloid, and this dispersion is dispersed in an emulsion. As described in JP-B-46-24185, a method of dispersing a water-insoluble dye in a water-soluble solvent without dissolving it and adding this dispersion to an emulsion; U.S. Pat. No. 3,822,135 A method of dissolving a dye in a surfactant and adding the solution to an emulsion as described in Japanese Patent Application Laid-Open No. 51-74624; As described in JP-A-50-80826, a method in which a dye is dissolved in an acid substantially free of water and the solution is added to the emulsion is used. Other additions to emulsions include U.S. Pat.
912,343, 3,342,605, 2,986,287, 3,429,8
The method described in No. 35 is also used.

The dyes of the present invention may be uniformly dispersed in the silver halide emulsion before being coated on a suitable support, but may of course be dispersed in any step of the preparation of the silver halide emulsion. It is.

The silver halide photographic light-sensitive material of the present invention has at least one light-sensitive silver halide emulsion layer on one side of a support.

The silver halide photographic light-sensitive material of the present invention protects silver halide grains formed by adding a water-soluble silver salt solution and a water-soluble halide solution to a solution containing a protective colloid, with an aggregating polymer agent. It contains a silver halide emulsion obtained by coagulation with a colloid and removing dissolved substances (hereinafter, appropriately referred to as “emulsion according to the present invention”).

The emulsion according to the present invention may be contained in at least one of the emulsion layers of the light-sensitive material of the present invention, but preferably includes many emulsion layers, and more preferably all of the emulsion layers according to the present invention. Is contained.

The emulsion according to the present invention is prepared, for example, by adding a water-soluble silver salt solution and a water-soluble halide solution to a solution containing a protective colloid, and then forming the resulting silver halide particles with an aggregating polymer agent. It is obtained by coagulating from a suspension together with a protective colloid and removing dissolved substances in the suspension.

Here, the aqueous solution containing a protective colloid refers to an aqueous solution in which a protective colloid is formed in an aqueous solution by gelatin or another substance capable of forming a hydrophilic colloid (a substance capable of serving as a binder). It is an aqueous solution containing.

When gelatin is used as the protective colloid in the practice of the present invention, the gelatin may be either lime-treated or acid-treated.
The details of the method for producing gelatin are described in Arthur Weiss, The Macromolecular Chemistry of Gelatin (Academic Press, 1964).

Examples of hydrophilic colloids other than gelatin that can be used as protective colloids include gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and kazenin: hydroxyethyl cellulose, alkoxymethyl cellulose, cellulose sulfates, and the like. Cellulose derivatives such as, sodium alginate,
Sugar derivatives such as starch derivatives: Polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, etc. There are synthetic hydrophilic polymer substances.

In the case of gelatin, jelly strength 200
It is preferable to use the above.

In the light-sensitive material of the present invention, gelatin is advantageously used as a hydrophilic colloid that can be used for a photographic component layer such as a protective layer, a backing layer, and an intermediate layer that are formed as necessary. Other hydrophilic colloids described above can be used alone or together with gelatin.

The water-soluble silver salt solution and the water-soluble halide solution are reacted to obtain a desired silver halide, and are appropriately selected and combined according to a desired silver halide composition.

The aggregating polymer agent refers to a polymer substance capable of aggregating silver halide particles together with a protective colloid.
Usually, a step (so-called desalination step) of aggregating and gelatinizing the protective colloid, such as gelatin, with such an aggregating polymer agent and removing dissolved substances such as soluble salts in the liquid is performed.

In the present invention, it is preferable that the aggregated polymer agent is an aggregated gelatin agent in which at least 50% or more of the amino groups of the gelatin molecule are substituted with various kinds of acyl, carbamoyl, sulfonyl, thiocarbamoyl, alkyl and / or aryl. Also preferred alongside this,
A polymer compound represented by the general formula [II] consisting of the following A chain and B chain can be mentioned.

General formula [II] In the formula, R ₁ and R ₂ represent an aliphatic group, which may be different or the same. R ₃ is a hydrogen atom, an aliphatic group, an aryl group,
Or an aralkyl group. Χ is -0- or -NH
-, M ⁺ represents a cation. n takes a value of 10 to 10 ⁴ .
The two connecting hands of the B chain may be connected to either side of the tertiary carbon to which R ₁ and R ₂ of the A chain are arranged. In the case Χ is -NH- may form a nitrogen-containing ring together with R _3.

Examples of substituents for the amino group of gelatin are described in U.S. Pat.
No. 691,582, 2,614,928 and 2,525,753.

Examples of useful substituents include (1) an acyl group such as alkylacyl, arylacyl, acetyl and substituted and unsubstituted benzoyl; (2) a carbamoyl group such as alkylcarbomoyl and arylcarbamoyl; and (3) alkylsulfonyl and aryl. A sulfonyl group such as a sulfonyl group, (4) a thiocarylbamoyl group such as an alkylthiocarbamoyl group and an arylthiocarbamoyl group, (5) a linear or branched alkyl group having 1 to 18 carbon atoms, and (6) a substituted or unsubstituted group. And aryl groups such as phenyl, naphthyl and aromatic heterocycles such as pyridyl and furyl.

Among them, preferred modified gelatin is an acyl group (-CO
R ¹ ) or a carbamoyl group It is due to.

R ¹ is a substituted or unsubstituted aliphatic group (for example, having 1 to 1 carbon atoms)
18 alkyl groups, allyl groups), aryl groups or aralkyl groups (for example, phenethyl group), and R ² is a hydrogen atom, an aliphatic group, an aryl group, or an aralkyl group.

Particularly preferred is a case where R ¹ is an aryl group and R ² is a hydrogen atom.

Hereinafter, specific examples of the aggregated gelatin agent that can be used as the aggregated polymer agent in the present invention will be exemplified by an amino group substituent, but the present invention is not limited thereto.

Exemplary flocculated gelatin agent (amino group substituent): When a flocculant gelatin agent is used for removing dissolved substances (desalting), the amount of the flocculant is not particularly limited, but is 0.3 to 10 times (weight) the substance (preferably gelatin) contained as a protective colloid at the time of removal. Is suitable, and particularly preferably 1 to 5 times (weight).

When an agglomerated gelatin agent is used, the pH can be adjusted after the addition of the agglomerated gelatin agent to cause the silver halide emulsion to coagulate. PH for coagulation
The acid used for pH adjustment is preferably 5.5 or less, particularly preferably 4.5 to 2, but is not particularly limited, but organic acids such as acetic acid, citric acid, and salicylic acid, and inorganic acids such as hydrochloric acid, nitric acid, sulfuric acid, and phosphoric acid are preferable. Used. Heavy metal ions, for example, magnesium ions, cadmium ions, lead ions, zirconium ions, etc. may be added in combination with the aggregating gelatin agent.

The removal of dissolved substances (desalting) may be repeated once or several times. When repeated several times, an agglomerated gelatin agent may be added each time it is removed, or only the agglomerated gelatin agent may be added first.

Next, the case where the polymer compound represented by the general formula [II] is used as the aggregation polymer agent in the present invention will be described. This molecular compound has a high molecular weight of preferably 1 × 10 ³ to 1 × 10 ⁶ , more preferably 3 × 10 ³ to 2 × 10 ^5.
The addition amount is preferably 1/50 to the protective colloid (preferably gelatin) contained in the emulsion in a weight ratio.
It is 1/4, more preferably 1/40 to 1/10. The method of use is in accordance with the agglomerated gelatin agent.

Hereinafter, specific examples of the polymer compound represented by the general formula [II] will be described, but the invention is not limited thereto.

Exemplary polymer compound represented by the general formula [II]: In the present invention, the temperature of the silver halide emulsion at the time of addition of the aggregating polymer agent is preferably 30 ° C. or higher. Particularly preferred are those having a silver halide emulsion temperature in the range of 30 to 60 ° C.

Further, it is preferable that the pH in the reaction vessel at the time of the addition of the aggregating polymer agent is 2 or more. More preferably, the pH is in the range of 2 to 6. The pAg in the reactor is preferably 5 or more, and more preferably the pAg is in the range of 10 to 12.

In addition, it is preferable that the concentration of the silver halide emulsion is 20% or more when the above-mentioned flocculant is added. Particularly preferably, the concentration of the silver halide emulsion is preferably from 20 to 50%.
Here, the concentration of the silver halide emulsion means the weight% of the silver halide emulsion in the reaction solution.

The emulsion according to the present invention is obtained by preparing an emulsion containing a seed crystal and growing grains from the seed crystal, and may be obtained without using a seed crystal. When the seed crystal is used, when the emulsion containing the seed crystal itself is the emulsion according to the present invention using the aggregating polymer, all the emulsions obtained therefrom correspond to the emulsion according to the present invention. However, the seed crystal emulsion for obtaining the emulsion according to the present invention does not necessarily need to be the emulsion according to the present invention. It is preferable to use a seed crystal emulsion, which is the emulsion according to the present invention, as the seed crystal, and to use the emulsion according to the present invention obtained by using the aggregating polymer agent according to the present invention even during the seed crystal growth. .

The silver halide composition of the emulsion according to the present invention is optional,
For example, any silver halide that can be used includes silver chloride, silver bromide, silver iodide, silver chlorobromide, silver iodobromide, silver chloroiodide, silver chloroiodide, and mixtures thereof. Included,
Particularly when silver iodobromide is used, in which silver iodobromide is preferably used, the content of silver iodide is not particularly limited, but the average silver iodide content in the whole silver halide grains is 10 mol% or less. Preferably, it is 6 mol% or less, more preferably 0.2 to 6 mol%.

In this case, it is desirable that silver iodide be concentrated inside.

Preferred silver halide grains contained in the emulsion according to the present invention include silver halide grains having a multilayer structure and tabular grains.

Tabular grains can be obtained by adding certain drugs such as thioethers during grain growth.
For tabular grains, see, for example, JP-A-58-113927,
Nos. 58-113928 and JP-A-59-105636
252-253, 60-147727.

Here, the particles having a multilayer structure are those provided with a coating layer made of an arbitrary halogen composition outside the inner core,
So-called core / shell particles can be used. The coating layer may be only one layer, two or more layers, for example, three layers,
It may be laminated with four layers. Preferably it has five or less layers.

Silver bromide, as silver halide in the inner core and the coating layer,
Although silver iodobromide and silver iodide are preferably used, a mixture with a small amount of silver chloride (specifically, a mixture containing preferably about 10 mol% or less, more preferably about 5 mol% or less of silver chloride) ).

Preferably, silver iodobromide grains having layers formed by different silver iodide contents may be used.

The surface layer is preferably substantially silver bromide or substantially silver iodobromide (silver iodide content: 10% or less), and may contain less than several% of chlorine atoms.

The emulsion according to the present invention, in a solution containing a protective colloid,
A silver halide grain is prepared by adding a water-soluble silver salt solution and a water-soluble halide solution, and various techniques can be used as a forming means in this case.

The grain size of the silver halide grains is not particularly limited, but preferably has an average grain size of 0.05 to 2 μm. More preferably, it is 0.1 to 1 μm.

The emulsion according to the present invention can effectively exhibit the effects of the present invention regardless of whether it is a monodisperse emulsion or a polydisperse emulsion.

 The emulsion according to the present invention can be chemically sensitized.

In case of chemical sensitization, normal sulfur sensitization, reduction sensitization,
Noble metal sensitization and combinations thereof are used. More specific chemical sensitizers include allylthiocalibamide (Al
lyl thiocarbamide), thiourea, thiosulfate,
Sulfur sensitizers such as thioether and cystine: Potassium chloroaurate, Auras, thiosulfate and Potassium chloro palladate
Noble metal sensitizers such as: reduction sensitizers such as tin chloride, phenylhydrazine, and reactone.

The silver halide light-sensitive material according to the present invention is a photographic hardener usually used in the coating solution thereof, for example, an aldehyde-based hardening agent.
Aziridine-based (eg, PB Report 19,921; U.S. Pat.
950,197, 2,964,404, 2,983,611, 3,271,1
No. 75, JP-B-46-40898, JP-A-50-91315
), Isoxazoles (for example, those described in U.S. Pat. No. 331,609) and epoxys (for example, U.S. Pat. No. 3,047,394, West German Patent 1,085,6)
No. 63, British Patent 1,033,518, Japanese Patent Publication No. 48-354
No. 95), vinyl sulfone type (for example,
PB Report 19,920, West German Patent 1,100,942, UK Patent 1,2
51,091, Japanese Patent Application Nos. 45-54236, 48-110996, U.S. Patent Nos. 353,964, and 3,490,911), acryloyl-based (for example, Japanese Patent Application No. 48-27949,
U.S. Pat. No. 3,938,892), carbodiimides (e.g., U.S. Pat.
JP-B-46-38715 and JP-A-49-15095), and maleimide, acetylene, methanesulfonate, triazine and polymer hardeners can be used. Also, as a thickener, for example, US patent
3,167,410, those described in the specifications of Belgian Patent 558,143, polyols as gelatin plasticizers (for example, U.S. Pat.No. 2,960,404, JP-B-43-4939,
JP-A Nos. 48-623715) and US Pat. Nos. 766,979 and 1,395,5 as latex.
Nos. 44 and 43, and JP-B-48-43125, and matting agents described in British Patent 1,221,980 can be used.

In the constituent layer of the silver halide photographic light-sensitive material according to the present invention, a desired coating aid can be used. For example, as a saponin or sulfosuccinic acid-based surfactant, for example, British Patent No. 548,532, Japanese Patent Application No. No. 47-89630, or as an anionic surfactant, for example, JP-B-43-18166, U.S. Pat.
Those described in the specifications of French Patent 2,025,688 and JP-B-43-10247 can be used.

Various compounds can be added to the above-mentioned photographic emulsion in order to prevent a reduction in sensitivity and the occurrence of fog during the production process, storage or processing of the photographic material. Those compounds are 4-
Hydroxy-6methyl-1,3,3a, 7-tetrazaindene,
Many heterocyclic compounds including 3-methyl-benzothiazole, 1-phenyl-5-mercaptotetrazole,
An extremely large number of compounds such as mercury-containing compounds, mercapto compounds, and metal salts have been known for a long time.

One example of a compound that can be used is K. Mees
Author, The Theory of the Photographic Process
(3rd ed., 1966) with the original documents listed, and JP-A-49-81024, JP-A-50-6306, and JP-A-50-194.
Any of the well-known antifoggants in the art, such as those described in US Pat. No. 29, US Pat. No. 3,850,639, can be used.

In addition, in carrying out the present invention, various techniques used in photographic techniques can be applied.

[Effects of the Invention] According to the present invention, it is possible to provide a silver halide photographic light-sensitive material for a laser light source which improves the increase in fog and the decrease in sensitivity during storage.

[Examples] Hereinafter, examples of the present invention will be described in detail.

Example 1 (i) Preparation of Emulsion (A) Preparation of Seed Crystals T-1 and T-2 While controlling at 60 ° C., pAg = 8 and pH = 2.0, an iodine having an average particle size of 0.15 μm was obtained by a double jet method. Monodispersed cubic grains of silver iodobromide containing 2 mol% of silver iodide were prepared. The reaction liquid containing the obtained particles was divided into two parts, and each was subjected to desalting as described below, to obtain two kinds of species (T-1 and T-2).

Desalting method of T-1: The mixed reaction solution was heated to 40 ° C., and a condensate of sodium naphthalenesulfonate and formalin (compound 1) and magnesium sulfate MgSO ₄ were each added in an amount of 15 g / AgΧ1 mol, 6 mol.
0 g / AgΧ1 mol was added and stirred for 3 minutes. Then let it stand,
Excess salt is removed by decantation. afterwards,
After adding pure and 2.1 l / Ag @ 1 mol at 40 ° C and dispersing,
After adding 30 g / Ag モ ル 1 mol of gSO ₄ and stirring for 3 minutes, the mixture was allowed to stand and decanted. Thereafter, post-gelatin was added, kept at 55 ° C., stirred for 20 minutes and redispersed.
I got

Desalting method of T-2 (corresponding to the dissolved matter removing means for obtaining the emulsion according to the present invention): The reaction solution after completion of mixing is kept at 60 ° C. as an aggregating polymer agent, and the aggregating gelatin agent G-3 exemplified above. (90% replacement)
Was added and stirred for 3 minutes. Thereafter, 0.13 g of potassium hydroxide KOH / AgΧ1 mol is added to adjust the pH to 4.0, and the mixture is allowed to stand and decanted. Then, 2.1 l of pure water at 40 ° C
/ AgΧ1 mol, then add KOH 0.25g / Agg1 mol,
Adjust the pH to 5.8 and stir for 5 minutes. Then, nitric acid HNO ₃ (1.7
Addition of 1.5ml / Ag を 1mol, pH to 4.3,
Decant. Then, after gelatin and KOH0.2
g / AgΧ1 mol, pH was adjusted to 5.8, redispersed, and T-
2 was obtained.

Since this seed crystal emulsion T-2 is an emulsion according to the present invention,
The emulsion obtained from this is according to the present invention.

(B) Growth from seed crystal The following particles were grown using the above-mentioned T-1 and T-2 seed crystals. First, this seed crystal T-1 was dissolved in a solution 8.5 (corresponding to a solution containing a protective colloid) containing protective gelatin kept at 40 ° C. and, if necessary, ammonia, and the pH was adjusted with acetic acid. Using this solution as a mother liquor, a 3.2 N aqueous ammonia silver ion solution was added as a water-soluble silver salt solution by a double jet method. in this case,
The pH and EAg were changed as needed depending on the silver iodide content and the crystal habit. That is, the pAg was controlled to 7.3 and the pH to 9.7, and a layer having a silver iodide content of 35 mol% was formed. Next, the pH was changed from 9 to 8 to 95% of the particle size, and the pAg was maintained at 9.0 to grow the cells. Thereafter, a potassium bromide solution as a water-soluble halide solution was added by a nozzle over 8 minutes, the pAg was dropped to 11.0, and the mixing was completed 3 minutes after the addition of the potassium bromide. PH with next acetic acid
Dropped to 6.0. This emulsion was monodisperse grains having an average grain size of 0.30 μm and a silver iodide content of about 2 mol% in the whole grains. Next, this reaction solution is divided into two parts, and excess soluble salts are removed (corresponding to the removal of dissolved substances) by the following two desalting methods (a) and (b). Was.

Desalting method (a): 1. The compound I was added to the mixed reaction solution at 40 ° C.
5.5 g / Ag (1 mol) and 8.5 g / Ag (1 mol) of MgSO ₄ were added, and the mixture was stirred for 3 minutes, allowed to stand, and decanted.

After adding 1.8 l / Ag @ 1 mol of pure water at 2.40 ° C and dispersing,
gSO ₄ was added at 20 g / AgΧ1 mol, stirred for 3 minutes, and allowed to stand.
Perform decantation.

3. Repeat the above step 2 once more.

4. After adding 15g / Ag モ ル 1mol of gelatin and water, 450ml / AgΧ1
After finishing to molar, stir and disperse at 55 ° C. for 20 minutes.

 Thus, Emulsion 1-1 was obtained.

Desalting method (b): 1. The reaction mixture after mixing is kept at 40 ° C., and the above-exemplified agglomerated gelatin agent G-3 as an agglomerated polymer agent is 50 g / Agg1.
Then, the pH was lowered to 5.0 by adding 56% by weight of HAC acetate 100 ml / AgΧ1 mol, and the mixture was allowed to stand still, followed by secantation.

After adding 1.8 l / Ag @ 1 mol of pure water at 2.40 ° C, KOH 6.8 g / Ag
Add 1 mole, bring the pH to 6.0, and disperse. After well dispersing, 56 wt% HAC acetate 70 ml / Ag / 1 mol was added to adjust the pH to 4.
Set at 5, leave still and decant.

3. Repeat the above step 2 once more.

4. Then, add 15 g / AgΧ1 mol KOH1 g / AgΧ1 mol of post-gelatin and water to make 450 ml / AgΧ1 mol.

 Thus, Emulsion 1-2 was obtained.

The above desalting method (b) corresponds to a dissolved substance removing means for obtaining the emulsion according to the present invention.

Similarly, grains are grown using the seed crystal T-2, and the emulsions 2-1 and 2-2 are obtained by the two kinds of desalting methods described above.
I got

(Ii) Preparation and Evaluation of Samples (ii-1) Preparation of Samples The four emulsions obtained in (i) above were chemically sensitized. That is, ammonium thiocyanate and chloroauric acid were added to hypo and gold-sulfur sensitization was performed.

After completion of the chemical sensitization, 4-hydroxy-6-methyl-
150 mg of 1,3,3a, 7-tetrazaindene were added per mole of Ag. Thereafter, as shown in Table 1, spectral sensitization was performed by adding spectral sensitizing dyes.

In addition, 9 g of trimethylolpropane was added to 1 mol of the silver halide, 30 mg of nitrophenyltriphenylphosphonium chloride, 1 g of ammonium 1,3-dihydroxybenzene-4-sulfonate, and 2-mercaptobenzimidazole-5-mol. Sodium sulfonate 10mg, 2
-10 mg of mercaptobenzothiazole The following compounds were added as additives for the protective layer.

That is, per 1g of gelatin (Iii) Preparation of Coating Sample A backing layer solution composed of 400 g of gelatin, 2 g of polymethyl methacrylate, 6 g of sodium dodecylbenzenesulfonate, 20 g of the following antihalation dye and glyoxal was prepared as a backing layer, and 50 wt.
%, Methyl acrylate 10wt%, butyl methacrylate
One side of a polyethylene terephthalate base coated with an aqueous dispersion of a copolymer obtained by diluting a copolymer composed of three types of monomers of 40% by weight so that the concentration becomes 10% by weight as a subbing liquid is coated on one side of a polyethylene terephthalate base. , A matting agent, sodium dodecylbenzenesulfonate, and a protective layer solution comprising glyoxal to prepare a support for a backing agent obtained by coating. The coating amount backing layer, 2.5 g / m ² of protective layer as each amount with gelatin, 2.0 g / m ^2.

7 mg of a matting agent composed of polymethyl methacrylate having an average particle size of 5 μm, and colloidal silica 70 having an average particle size of 0.013 μm
mg and the like were added.

Further, 2 ml of formalin (35%) and 1.5 ml of an aqueous glyoxal solution (40%) were added as hardeners.

(Iv) Evaluation method of sample The obtained sample was subjected to a storage stability test.

Storage test 1.23 ° C. 55% RH 3 days 2.50 ° C. 80% RH 3 days 3.55 ° C. 20% RH 3 days The sample thus obtained was cut into 3.5 cm widths, and a 820 nm interference filter was used with a xenon flash light source. The wedge statue was burned in ^10-5 seconds. The film was further processed by a Konica Lay automatic developing machine (trade name: Konica Lay automatic developing machine K-500).

The processing solution was carried out at a developer temperature of 35 ° C. using Konica Corporation's developer for Ray automatic developing machine (product name: ΔD90) and fixing solution (product name: ΔF).

 Table 1 clearly shows the effect of the present invention.

Example 2 Particles were grown using the seed crystal T-2 in the same manner as in Example 1, and the agglomerated gelatin G-3 was replaced with G-1, G-2 and G- 5, G-7, G-8, G
Emulsions 3 to 8 were obtained in exactly the same manner except that each was changed to -11. Emulsions 9 to 12 were obtained in exactly the same manner, except that the example of agglomerated gelatin G-3 50 g / AgΧ1 mol was changed to P-1, P-3, P-6, and P-7 1 g / AgΧ1 mol. Was.
Samples of these emulsions were prepared in the same manner as in Example 1 and evaluated. Table 2 shows the results.

As is clear from Table 2, the same effects as in Example 1 were observed.

Claims (1)

(57) [Claims] 1. A sensitizing dye represented by the following general formula (1):
A silver halide photographic light-sensitive material for a laser light source having at least one spectrally sensitized photosensitive silver halide emulsion layer, wherein the silver halide emulsion is mixed with a water-soluble silver salt solution and a water-soluble solution in a solution containing a protective colloid. A silver halide emulsion obtained by adding a protective halide solution to a silver halide particle produced by adding a neutral halide solution together with a protective colloid using the following aggregating polymer agent and removing the dissolved substance. Silver halide photographic material. General formula (1) In the formula, Z ₁ and Z ₃ represent a benzothiazole nucleus optionally having a substituent, a benzoxazole nucleus, a naphthothiazole nucleus, a nonmetallic atom group necessary for forming a naphthoxazole nucleus, R ₁ , R ₂ represents a saturated or unsaturated aliphatic group, respectively. Z ₂ represents a 5- to 6-membered carbon atom ring, and A represents a hydrogen atom when Z ₂ is 6-membered. In the case of a 5-membered ring, the general formula (1-
a). General formula (1-a) R ₃ and R ₄ each represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a halogen atom, an alkoxy group having 1 to 4 carbon atoms, and R ₅ and R ₆ each represent an alkyl group having 1 to 12 carbon atoms, R ₇ represents an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an alkoxycarbonyl having an alkoxy group having 1 to 4 carbon atoms. Represents a group. When Z ₂ is a 6-membered ring, it is represented by the general formula (1-b). General formula (1-b) In the formula, R ₈ is a hydrogen atom or a methyl group, R ₉ is a hydrogen atom,
Represents an alkyl group having 1 to 4 carbon atoms or a monocyclic aryl group.
Chi ^- represents an anion, n represents 1 or 2 (when forming an intramolecular salt n is 1). (Aggregating polymer agent) From an aggregated gelatin agent in which at least 50% or more of the amino groups of the gelatin molecule are substituted with acyl, carbamoyl, sulfonyl, thiocarbamoyl, alkyl and / or aryl groups, or from the following A chain and B chain A polymer compound represented by the general formula (2): General formula (2) In the formula, R ₁ and R ₂ represent an aliphatic group, which may be different or the same. R ₃ is a hydrogen atom, an aliphatic group, an aryl group,
Or an aralkyl group. Χ is -O- or -NH
-, M ⁺ represents a cation. n takes a value of 10 to 10 ⁴ . The two connecting hands of the B chain may be connected to either side of the tertiary carbon to which R ₁ and R ₂ of the A chain are arranged. Also,
In the case of NH- may form a nitrogen-containing ring together with R _3.