JPH0235445A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To improve the sensitivity of the title material against a semiconductor laser, and to lessen the change of the sensitivity of the material against the change of a wavelength by specifying the spectrally sensitive distribution of the material. CONSTITUTION:The sensitive material is composed of the photosensitive material which exposes it using a light source capable of changing the max. wavelength of an emission spectrum by the variance of a temp. and the production of the material. The spectrally sensitive distribution of the material is specified to within 0.2 (log E) against the standard value of a light source of + or -25nm, and is controlled to within the value by incorporating a prescribed sensitizing dye (such as a compd. shown by formula I) and a prescribed phenol resin or a compd. shown by formula II, in the material. In formula I, Y1 and Y2 are each an atomic group necessary for forming a prescribed ring, R1 and R2 are each a lower alkyl or alkyl group having sulfo group, etc., R3 is methyl or ethyl group, etc., X1 is an anion, (n1) and (n2) are each 1 or 2, (m) is 1 or 0. In formula II, A is an aromatic residual group, R1-R4 are each hydrogen atom or hydroxyl group, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a silver halide photographic material for light sources such as semiconductor lasers and light emitting diodes.

[Background of the invention]

One of the exposure methods for photographic light-sensitive materials is a so-called scanner, which scans an original image and exposes the silver halide photographic light-sensitive material based on the image signal to form a negative or positive image corresponding to the image on the original image. There are various recording devices that utilize a one-sided image forming method, and glow lamps, xenon lamps, mercury lamps, tungsten lamps, light emitting diodes, and the like have conventionally been used as recording light sources for these scanner devices. However, all of these light sources have practical problems such as low output and short lifespan. As a solution to these problems, there is a scanner that uses a coherent laser light source such as a helium-neon laser, an argon laser, a helium-cadmium laser, etc. as a scanner-only light source. Although these devices can provide high output, they are large and expensive, require a modulator, and use visible light, which limits the safe light of photosensitive materials, making them difficult to handle. There are problems such as.

In contrast, semiconductor lasers are small, inexpensive, easy to modulate, can change emission intensity by changing voltage, and have a longer lifespan than the above lasers.

Also, since it emits light in the infrared region, it has the advantage of being a bright safelight.

A method of image exposure by scanning a photosensitive material using a semiconductor laser as a light source such as a light emitting diode is described in Japanese Patent Application Laid-Open No. 57-1519.
No. 33, Proc, of 5PIE, 390. P149
-154 (1983), etc.

However, at present, the maximum wavelength of the laser emission spectrum varies by about ±20 nm due to manufacturing variations (variation in layer thickness), operating temperature, and the like.

Therefore, in order to avoid the influence of the fluctuation of the light source on the photosensitive material, for example, Japanese Patent Application Laid-Open No. 61-52642 proposes a method in which the maximum of the spectral sensitivity distribution of the photosensitive material is set on the longer wavelength side than the fluctuation range of the wavelength maximum of the emission spectrum. Proposed. However, this method cannot effectively utilize spectral sensitivity;
If only those with low sensitivity can be used and the fluctuation is ±20 nm or more, it is insufficient. Also, patent application No. 61-261165
The publication discloses a technique for suppressing fluctuations in sensitivity with respect to wavelength fluctuations of a light source by using a sensitizing dye of 780n11 or higher and a sensitizing dye of 780n11 or higher in combination. In the case of this technique, the difference in adsorption equilibrium between the dyes used causes deterioration in the stagnation of the coating solution and deterioration in storage stability, which is not desirable and also increases the cost.

[Purpose of the invention]

In order to solve the above-mentioned problems, an object of the present invention is to provide a silver halide photographic material that has high sensitivity to light emitting light sources, especially semiconductor laser light sources, and provides stable images even with wavelength fluctuations. .

[Structure of the invention]

The above-mentioned object of the present invention is to provide a silver halide photographic light-sensitive material that is exposed to light from a light source whose maximum wavelength of emission spectrum changes due to temperature and manufacturing variations, etc. ±25no
This is achieved by using a silver rhodanide photographic light-sensitive material, which is characterized in that it is within 0.2 (QogE) with respect to +.

Note that the standard value for light sources is 66 for light emitting diodes.
0nm, 670nm, 780nm, 670nm, 680nm, 780nm, 8 for semiconductors
Although 20 nm is generally used, it is not limited to this.

The present invention will be explained in detail below.

In the present invention, any method may be used to bring the spectral sensitivity distribution of the silver halide photographic material within 0.2 in terms of QogE, but the method described below is preferred.

That is, in the silver halide photographic light-sensitive material, dyes represented by [:I-a) and CI-b) or (II-a) and (n-b) are used as sensitizing dyes, and the compound ( II
I) is characterized by having a hydrophilic colloid layer containing at least one phenolic resin obtained by condensing phenols and aldehydes with acid or alkali or a compound represented by the following general formula [■]. be.

General formula (I-a) (XI'')n [However, in the above general formula, Yl and Y2 each form a benzothiazole ring, a benzoselenazole ring, a naphthothiazole ring, a naphthoselenazole ring, or a quinoline ring. Represents a necessary group of nonmetallic atoms, and these heterocycles may be substituted with a lower alkyl group, an alkoxy group, a hydroquine group, an aryl group, an alkoxycarbonyl group, or a halogen atom.R1 and R2 are each a lower alkyl group , represents an alkyl group having a sulfo group or an alkyl group having a carboxyl group.R3 is a methyl group, an ethyl group,
Represents a propyl group. Xl represents an anion. n I
+ n 2 represents l or 2. l represents ■ or 0, and when it is an inner salt, m=o.

General formula [:I-b). ZC'-02 [However, in the above general formula, Y and Y4 each represent an atomic group necessary to form a 5-membered ring and/or a 6-membered nitrogen-containing heterocycle. R6 and R5 each represent a saturated or unsaturated aliphatic group. Q and Q2 represent an atomic group necessary to form a 4-thiazolidinone, 4-oxasilidinone, 4-imigzolidinone, 5-thiazolidinone, 5-oxazolidinone or 5-imidazolidinone ring. Ll, L! and R3 represents a methine group, a substituted methine group, (-C-, where R6 represents an ethyl group, a methyl group, an ethoxy group, or an aryl group). X2 represents an anion. R13+
n represents an integer of 0 to 3. [ General formula (II-a) ring, quinoline ring, 3,3-dialkylindolenine ring,
Examples include a benzimidazole nucleus and a pyridine ring.

These heterocycles include lower alkyl groups, alkoxy groups, hydroxyl groups, aryl groups, alkoxycarbonyl groups,
It may be substituted with a halogen atom.

R++, R1□, R2, and R2□ each represent a substituted or unsubstituted alkyl group, aryl group, or aralkyl group.

R13+ R14+ R1s+ R23+ R
24+ R2G and R26 are each a hydrogen atom, a substituted or unsubstituted alkyl group, an alkoxy group, a phenyl group, a benzyl group, [in the formula, Y Il+ Y 121 Y
z+ and Y22 each represent an alkyl group (the number of carbon atoms in the alkyl moiety is 1-18, preferably 1-4) or an aryl group that is not necessary or unsubstituted to complete the 5- or 6-membered nitrogen-containing heterocycle. Wl and W2 can also be linked to each other to form a 5- or 6-membered nitrogen-containing heterocycle.

Furthermore, R13 and RIS and R2 and R2% can be linked to each other to form a 5-membered ring or a 6-membered ring.

X11 and X21 represent anions. n+++n+z
*n2+ and n'12 represent 0 or l. ] General formula [■] A.

503M [In the formula, -8- represents a divalent aromatic residue, and these are -
503M group [where M represents a hydrogen atom or a cation (eg, sodium, potassium, etc.) that provides water solubility. ] may be included.

A- is usefully selected from the following -A1- or -A2-, for example. However, R+, R2, Rs or R1
-A- is selected from the group -A, - when M is not included.

SO,M O3M Represents a cation.

-A, -: Rl+R2, Rs and R4 are each a hydrogen atom, a hydroxy group, a lower alkyl group (the number of carbon atoms is preferably 1 to 8. For example, a methyl group, an ethyl group, a low propyl group, n
-butyl group, etc.), alkoxy group (number of carbon atoms is 1
~8 are preferred, such as methoxy group, ethquine group, propoxy group, butoxy group), aryl group (e.g. phenoxy group, naphthoquine group, o-troquine group, p-sulfophenoxy group, etc.), halogen atom (e.g. chlorine atom, bromine atom, etc.), heterocyclic nucleus (e.g. morpholinyl group, piperidyl group, etc.), alkylthio group (e.g. methylthio group, ethylthio group, etc.), heterocyclylthio group (e.g. benzothiazolylthio group, benzimidazolylthio group) , phenyltetrazolylthio group, etc.), arylthio group (e.g. phenylthio group, tolylthio group), amino group, alkylamino group or substituted alkylamino group,
(For example, methylamine group, ethylamino group, propylamino group, dimethylamino group, diethylamino group, dodenylamino group, cyclohexylamino group, β-hydroxyethylamino group, di(β-hydroxyethyl)amino group, β-sulfoethyl amino group,) arylamino group,
or a substituted arylamino group (for example, anilino group, 0-sulfoanilino group, m-sulfoanilino group, m-anindino group, p-sulfoanilino group, o-toluidino group, m-
Toluidino group, p-toluidino group, 0-carboxyanilino group, m-carboxyanilino group, p-carboxyanilino group, 0-chloroanilino group, rrr-chloroanilino group, p1 loroanilino group, p-aminoanilino group,
0-anisidino group, p-anisidino group, 0-acetaminoanilino group, hydroxy7anilino group, disulfophenylamino group, naphthylamino group, sulfonaphthylamino group), heterocyclylamino group (e.g. 2- benzothiazolylamino group, 2-pyridyl-amino group, etc.), substituted or unsubstituted aralkylamino groups (e.g. benzylamino group, 0-anisylamino group, m-anisylamino group, p-anisylamino group, etc.), aryl group ( For example, phenyl group), mercapto group. RIR2, Rs.
, R4 may be the same or different from each other. -A
When m is selected from the group -A2-, R,,R,,R
, , R, at least one of which has one or more sulfo groups (
(It may be a free acid group or may form a salt.) W represents 100- or -N-, preferably -011- is used.

First, specific examples of the compound represented by the above general formula used in the present invention will be shown. However, the compounds used in the present invention are not limited to these.

Examples of compounds represented by the above general formula CI-a) I-a
-1 ■ -a-3 ■ (CH2), 5O3H (CH2)4SO3θ ■ ■ ■ ■ ■ ■ a-8 ■ ■ CH.

I しH28) υ3H ■ ■ ■ ■ CH.

(shiH2) 25s3″ ■ ■ ■ ■ SO3゜ ■ ■ ■ ■ ■ ■ ■ (Uli, ), btJ3- Shi wits ■ ■ ■ ■ ■ ■ ■ -b General formula above Examples of compounds covered by (The number at the bottom right of the structural formula is Mail Ta of nol solution Wavelength at the point where the optical absorption curve takes its maximum value λmax (unit: nm).

■ ■ b ■ λmax 98nm λmax 70nm λmax 88nm b-11 1-b b ■ λmax 95nm eOH λmax 604nm eOH λmax 588nm ■ eOH eOH λmax fi04nm eOH r0 eOH r0 Meat (λmax 658 nm Note that the above general formula CI − used in the present invention The compound represented by a) is known to those skilled in the art by referring to the specifications of U.S. Pat. It can be easily synthesized by engineers.

Next, a synthesis example of the compound represented by the above general formula (I-b) used in the present invention will be shown.

(Synthesis example) Synthesis of exemplified r-b-15 2-(2'-acetanilide vinyl)-3-ethylbenzothiazolium iodite (35 g) and l,3-diphenylrhodanine (2,2 g), methanol 800
After heating and dissolving in a mixed solution of 300 mQ of +n+2 mm-cresol, 25 g of triethylamine was added dropwise over about 30 seconds. After the dropwise addition, the mixture was reacted at about 50°C for 30 minutes, then returned to room temperature, and the precipitated crystals were collected by filtration to obtain melonanine pigment.

This melonanine dye (23 g) and methyl p-toluenesulfonate (65 g) were reacted at about 150°C for 20 minutes.

The temperature was returned to room temperature, 50 mQ of acetone was added, and the precipitated crystals were collected by filtration.

The crystals (25.7 g) obtained by the above operation and 3-ethyl-2-methyl-4,5-diphenylthiazolium.
Iodite (16.3 g) was dispersed in 600 mL of ethanol, and 1 g of triethylamine (12.1 g) was added under reflux.
It was dropped in 0 minutes. After refluxing for 1 hour, add sodium perchlorate (
A solution of 7.3 g) dissolved in 50 mQ of methanol was added, and the mixture was further refluxed for 1 hour. Return to room temperature, collect precipitated crystals by filtration, and recrystallize from ethanol to obtain exemplified dye (D-15) 5.
0 g (yield 30%) was obtained. The methanol solution of this sensitizing dye had a λmax of 604 nm.

As mentioned above, the above general formula [:I-a) or CI-
The compound represented by b) is used by being contained in at least one of the photographic constituent layers of the silver halide photographic light-sensitive material of the present invention.
When the compound represented by b) is used in a silver halide emulsion, it may be added after being dissolved in water or an organic solvent such as methanol, ethanol, acetone, etc. alone or in a mixture thereof.

As mentioned above, it can be added to non-photosensitive layers, and if necessary, it can also be added to layers adjacent to the silver halide emulsion layer, such as protective layers and intermediate layers, to the extent that it does not affect photographic performance. can do.

The amount of the compound represented by the above general formula CI-a) or CI-b) when added to a silver halide emulsion varies depending on the type of silver halide emulsion and the type of compound, but usually 5 mg to 1 per mole of silver
A range of 000 mg is preferable.

The above compound may be added to the silver halide emulsion at any time, but it is usually desirable to add it at any time during ripening or at any time after completion of ripening and immediately before coating.

Furthermore, the above general formula (I-a) or ['l
-b: The compound represented by l may be used alone, or 2
More than one type may be used in combination.

Specific examples of the general formula (■) are shown below, where ll-1 to 13 are the general formula [■-b) and I+-14-21 is the general formula CI [-a]
It is a compound represented by

／　　＼ Margin below C2H9 2H5 2Hs C,H.

■-7 ■-8 C. H, C, H.

CaO 4.

ll-10 CxHs C2H.

C82C820H ■ IΦ I(3 ■-15 C2H.

(2) 2H5 (e) The sensitizing dye of the present invention is preferably contained in the silver halide photographic emulsion in an amount of 1 mg to 2 g, more preferably 5 mg to 1 g per mole of silver halide.

The sensitizing dyes of the present invention can be directly dispersed into emulsions. They can also be first dissolved in a suitable solvent, such as evaporative methyl alcohol, ethyl alcohol, methyl cellosolve, acetone, water, pyridine, or a mixed solvent thereof, and then added to the emulsion in the form of a solution.

The sensitizing dyes of the present invention may be used alone or in combination of two or more. Furthermore, sensitizing dyes other than those of the present invention may be used in combination. When a sensitizing dye is used in combination, it is preferable that the total amount is the above content.

The sensitizing dye of the present invention can be easily synthesized with reference to US Pat.

Next, the phenolic resin according to the present invention contains phenols (phenol, catechol, ethylphenol, t-butylphenol, cyclohexylphenol, resorcinol, cresol, xylenol, [-octylcresol, resorcinol, pyrogallol, L-amylcresol, etc.) and aldehyde. It is a resin obtained by condensing esters (formaldehyde, acetaldehyde, acrolein, crotonaldehyde, furfural, balaformaldehyde, etc.) with an acid or an alkali.

When condensed with an acid, a novolac type resin is obtained, which can be further treated with excess formaldehyde, paraformaldehyde, hexamethylenetetramine, etc.
It can also be made harder.

When condensed using an alkali, resol, resitol, and resit are produced depending on the degree of condensation. Phenol resin can also be dissolved in a solvent such as alcohol or drying oil to form a festival.

Furthermore, the phenolic resin used in the present invention is composed of one or more types of phenols and one or more types of aldehydes.
It is a condensed phenolic resin with two or more different types of 7
It may be a mixture of enol resins, or a mixture of two different enol resins.
It may also be a product obtained by further condensing more than one type of 7-enol resin.

Regarding phenolic resin, "phenolic resin"
(Nikkan Kogyo Shimbun, Plastic Materials Course),
JP 54-123035, JP 55-105254, JP 55-105380, JP 55-153948,
They are described in Japanese Patent Publication No. 55-161250 and Japanese Patent Publication No. 56-20543, and all of these can be used in the present invention.

next. Specific examples of phenolic resins effective in the present invention are shown below. However, the present invention is not limited to these phenolic resins. However, Qlm,n indicates the polymerization molar ratio.

(Exemplary phenolic resin) (III-1) [■ 2] [■ 6] [■ 3] [:III-7) [■ 4] (III-8) [■ 9] CI[l-13] [I[ l-10) [■ 14] [lll-11) Cl-15) Cl-12) CI [[-16] n#5 ffl#20 n#2 m#3 n#5 m#15 These phenolic resins The degree of polymerization is 2 to 10,000, preferably 3
~1,000.

Specific examples of compounds of [general formula Sodium salt.

(TV-2) 4,4'-bis[4,6-di(benzothiazolyl-2-amino)pyrimidin-2-ylaminocostilbene-2,2'-disulfonic acid disodium salt.

[IV-3) 4,4'-bis[4,6-di(su7thi-2-ox7)pyrimidin-2-ylaminocostilbene-2,2'-disulfonic acid disodium salt.

(IV-4) 4,4'-bis[4,6-di(naphthyl-2-oxy)pyrimidin-2-ylamino]bipenzyl-2,2'-disulfonic acid disodium salt.

Zin-2-ylaminocostilbene-2,2'-disulfonic acid disodium salt.

(IV-6) 4.4'-His[4-chloro-6-(
2-naphthyloxy)pyrimidin-2-ylaminocobiphenyl-2,2'-disulfonic acid disodium salt.

(IV-7) 4.4'-bis[4,6-di(l-phenyltetrazolyl-5-thiopyrimidin-2-ylaminocostilbene-2,2'-disulfonic acid disodium salt).

[rV -8'] 4,4'-bis[4,6-di(
Benzimidazolyl-2-thio)pyrimidin-2-ylamitsuno]stibene-2,2'-disulfonic acid disodium salt.

(TV-9) 4.4'-bis(4,6-difecki/pyrimidin-2-ylamino)stilbene-2,2'
- Disulfonic acid disodium salt.

[:IV-10) 4.4'-His(4,6-cyphenylthiopyrimidin-2-ylamino)stilbene-
2,2'-(IV-5) 4,4'-bis[4,6-
Di(dianilinopyrimidisulfonic acid disodium salt.

(rV-11) 4.4'-bis(4,6-dimercabutovirimidin-2-ylamino)hyphenyl-2,
2'-disulfonic acid disodium salt.

(IV-12:l 4,4'-bis(4,6-dianilino-triazin-2-ylamino)stilbene-2
, 2'-disulfonic acid disodium salt.

(rv-13) 4.4'-bis(4-anilino-
6-Hydrooxytriazin-2-ylamino)stilbene-2,2'-disulfonic acid disodium salt.

[V-14] 4.4'-His(4-naphthylamino-6-anilino-triazin-2-ylamino)stilbene-2,2'-disulfonic acid disodium salt.

Among these specific examples, (rv-1) to (rV-12)
are preferable, especially [-1), (rV-2), (IV-3
), (IV-4), CIV-5), (rV-7), [r
v-12) is preferred.

The compound of general formula (IV) used in the present invention is advantageously used in an amount of about 0.01 to 5 grams per mole of silver halide in the emulsion.

The compound represented by the general formula (IV) used in the present invention can be directly dispersed into an emulsion, or can be dispersed in a suitable solvent (
For example, it can be dissolved in a solvent such as methyl alcohol, ethyl alcohol, methyl cellosolve, water, etc.) or a mixed solvent thereof and added to the emulsion. In addition, it can be added to the emulsion in the form of a solution or a dispersion in a colloid according to the method of adding sensitizing dyes. Also, Japanese Patent Publication No. 5040119
They can also be dispersed and added into the emulsion by the method described in the above publication.

Further, in the present invention, it is preferable to add compounds represented by the following general formulas (V) and (Vl) from the viewpoint of improving sensitivity and reducing fog.

General formula ('/) In the formula, 2 represents a group of nonmetallic atoms necessary to form a 5- or 6-membered heterocycle. However, the heterocycle does not contain a sulfo group or a carboxy group as a substituent. X represents a hydrogen atom, an alkali metal atom, an ammonium group, or an amine residue.

The 5-membered or 6-membered heterocycle represented by Z is preferably imidazole, thiazole, oxazole, pennoimitazole, benzothiazole, benzoxazole, oxadiazole, thiadiazole, triazole,
Mention may be made of tetrazole, pyrimidine, triazine, tetrazaindene and the like.

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

(Exemplary Compounds) These are the above-mentioned general formula CV that can be used in the present invention.
For example, the compound shown in US Pat. No. 3,615.50
No. 1, No. 2,324,123, No. 2,384.593
No. 2゜496.940, No. 3,137,578, No. 2,496.940, No. 3゜082.088,
3,473.924, 3,575,699, 3゜687.660, 2,271.229, 2
, 496,940, British Patent No. 1.141.773,
It can be easily synthesized by the method described in Japanese Patent No. 1,376.600 or similar thereto. You may also find The Chemistry of Organic Chemistry (edited by Fujio Kotake) (published by Asakura Shoten, 1971 edition) or The Chemistry of
Heterocyclic Co, 7 Bounds (A, Weiss
berger4he Chemistryor het
erocyclic compounds N, Y, I
interscience.

1950-1964), or according to the method described therein.

In order to use the compound represented by the general formula [■] in a silver halide emulsion, it is added and dissolved in a coating solution, or dissolved in water or an organic solvent such as methanol, ethanol, acetone, etc. alone or in a mixture thereof. It may be added to the coating solution at any time. Usually, it can be added at any time from before ripening to just before coating. Preferably, it is added to the silver halide emulsion layer. However, if necessary, it can also be added to layers adjacent to the silver halide emulsion layer, such as a protective layer and an intermediate layer, to the extent that it does not affect photographic performance.

The amount of the compound represented by the general formula [v] used in the present invention when added to a silver halide emulsion varies depending on the type of silver halide emulsion and the type of compound, but usually silver halide 1 5mg to 50 per mole
The optimal amount for obtaining appropriate effects can be arbitrarily selected over a wide range of 0 mg.

General formula (Vl) (R, , R2, R, , R, , R5, R6+, at least two sites are hydroxyl groups, and the remaining sites each have a hydrogen atom, a halogen atom, a sulfonic acid group, or a substituent. An alkyl group, an aryl group, an aralkyl group, a heterocyclic group, a carbonyl group which may have a substituent, for example, as a substituent for an alkyl group, an aryl group such as a hydroxyl group, an alkoxyl group, a sulfone group, etc. The substituents are
Substituents of aralkyl groups such as alkyl groups, hydroxyl groups, nitro groups, etc. are alkyl groups, hydroxyl groups, etc. Substituents of heterocyclic groups are substituents of carbonyl groups such as alkyl groups, hydroxyl groups, alkoxyl groups, amino groups, etc. is an alkyl group, a hydroxyl group, an alkoxyl group, etc., or represents -〇-R, or -SR7, R+, Rz,
Two adjacent sites among R3, R4, RS, and R may form a 5- or 6-membered carbocyclic ring or a heterocycle.

R2 is an alkyl group that may have a substituent, an aryl group,
When it is an aralkyl group or a heterocyclic group and has a substituent, for example, the substituent for an alkyl group is a hydroxyl group, an alkoxyl group, a sulfone group, etc., and the substituent for an aryl group is an alkyl group, a hydroxyl group, a nitro group, etc. The substituent of the aralkyl group is an alkyl group, a hydroxyl group, etc., and the heterocyclic group is an alkyl group, a hydroxyl group, an alkoxyl group, an amino group, etc.

Next, specific examples of the compound represented by the above general formula (VT) used in the present invention will be shown. However, as a matter of course, the compounds used in the present invention are not limited to these.

Table 1 shows examples of the compounds represented by the above general formula [VI].

Jj 1,000' Margin Compounds represented by the general formula (Vl) of the present invention are disclosed in, for example, U.S. Pat. No. 2,008,032, U.S. Pat. No. 529,
JP-A-49-129536, JP-A-50-93967
No. 1 and E. C. Armstrong et al.
m5tron4 et al) Jharna Jl/- American Chemical Society (J, Am, Chem.

Soc,) 82.1928-1935 (1960)
, D, E, Koalens
) Journal American Chemical Society 5
6.24713-2481 (1934), Pharmaceutical Journal 56
．． 814-828 (1936) and the like.

The amount of the compound of the general formula (Vl) used in the present invention is arbitrary, but it may be up to 10 g per mole of /'10 silver halide contained in the silver halide photographic light-sensitive material of the present invention. Preferably, it is used.

The compound represented by the general formula CVI'l can be dissolved in a suitable solvent such as water, methanol, ethanol, etc., and added to the constituent elements of the silver halide photographic light-sensitive material according to the present invention. The compound represented by the general formula CVI) is preferably added to the silver halide emulsion layer. However, if necessary, it can also be added to layers adjacent to the silver halide emulsion layer, such as a protective layer and an intermediate layer, to the extent that it does not affect photographic performance. Further, these compounds represented by the general formula (VI) can be added to the constituent elements of the silver halide photographic material at any time during the manufacturing process of the material.

In the silver halide emulsion used in the light-sensitive material of the present invention, any silver halide used in ordinary silver halide emulsions, such as silver iodobromide and silver chlorobromide, can be used.
The silver halide grains may be obtained by any of the acid method, neutral method, and ammonia method.

Silver halide grains may have a uniform silver halide composition distribution within the grain, or may be core/fell grains in which the silver halide composition differs between the inside and surface layer of the grain, and the latent image is mainly on the surface. It may be a particle that is formed inside the particle, or it may be a particle that is mainly formed inside the particle.

Any shape of the silver halide grains according to the present invention can be used. One preferable example is a cube having (1001 plane) as a crystal surface.

Also, U.S. Patent Nos. 4,183,756 and 4,225,6
No. 66, JP-A-55-26589, JP-A-55-42
737, etc., and The Journal of Photographic Science (J, Photgr, S
Particles having shapes such as an octahedron, a tetrahedron, a dodecahedron, etc. can be prepared by the method described in literature such as ci) -21, 39 (1973), and used. Furthermore, particles having twin planes may be used.

The silver halide grains according to the present invention may be of a single shape or may be a mixture of grains of various shapes.

Also, any grain size distribution may be used, and emulsions with a wide grain size distribution (referred to as polydisperse emulsions) may be used, or emulsions with a narrow grain size distribution (referred to as monodisperse emulsions) may be used. They may be used alone or in combination. or,
A polydisperse emulsion and a monodisperse emulsion may be mixed and used.

The silver halide emulsion may be a mixture of two or more separately formed silver halide emulsions.

In the present invention, monodisperse emulsions are preferred. As monodisperse silver halide grains in a monodisperse emulsion, the weight of silver halide contained within a grain size range of ±20% around the average grain size r is 60% or more of the weight of all silver halide grains. A certain amount is preferable, particularly preferably 70% or more, and still more preferably 80% or more.

Here, the average particle size r is the frequency ni of particles having particle size r1
Define the particle size aperture when the product niX ci3 of and ci3 is maximum.

(3 significant digits, round off the smallest digit.) The grain size here refers to the diameter in the case of spherical silver halide grains, and the projected image in the case of grains with shapes other than spherical. This is the diameter when the circumferential area is converted into a circular image.

The particle size can be obtained, for example, by photographing the particles with an electron microscope at a magnification of 10,000 to 50,000 times, and actually measuring the particle diameter or projected area on the print.

(The number of grains to be measured shall be 1000 or more indiscriminately.) Particularly preferred highly monodisperse emulsions of the present invention have a degree of monodispersity of 20 or less, more preferably 15 or less. be.

Here, the average particle diameter and particle diameter standard deviation shall be determined from ri defined above. Monodisperse emulsion is disclosed in Japanese Patent Application Laid-Open No. 54-4852.
No. 1, No. 5g-49938 and No. 60-122935
This information can be obtained by referring to the Publication No.

Although the photosensitive silver halide emulsion can be used as a so-called unripe (Pr1mltive) emulsion without chemical sensitization, it is usually chemically sensitized.

For chemical sensitization, the Glafkides or Z
elikman et al.'s book, or) 1. Frleser
Die Grundlagen der Fotografisien Prozesse Mid Zilber Halogennieden (Die
Grundlagen der Photograp
hischen Prozesse mit Silb
erhalogen+den, Akademich
e Verlagsgesellschaft, 19
68) can be used.

That is, a sulfur sensitization method using a sulfur-containing compound capable of reacting with silver ions or active gelatin, a reduction sensitization method using a reducing substance, and gold or other noble metal compounds can be used.

As the sulfur sensitizer, thiosulfates, thioureas, thiazoles, rhodanines, and other compounds can be used, specific examples of which are described in U.S. Pat. No. 1,574.944.
No. 2,410.689, No. 2,278,947, No. 2,728.668, and No. 3,656.955. As the reduction sensitizer, stannous salts, amines, hydrazine derivatives, formamidisulfinic acid, silane compounds, etc. can be used, and specific examples thereof are described in U.S. Pat. Nos. 2,487,850 and 2,419. ,97
No. 4, No. 2,518,698, No. 2,983,609
No. 2,983.610 and No. 2,694,637. For noble metal sensitization, in addition to total complex salts, complex salts of metals in group II of the periodic table, such as platinum, iridium, and palladium, can be used.
, No. 399.083, No. 2,448,060, British Patent No. 618.061, etc.

Further, the PHS pAg1Ag2O conditions during chemical sensitization are not particularly limited, but the pH value is preferably maintained at 4 to 9, particularly 5 to 8, and the pAg value is preferably maintained at 5 to IL, particularly 8 to 1O. The temperature is preferably 40 to 90°C, particularly 45 to 75°C.

In addition to the aforementioned sulfur sensitization and gold/sulfur sensitization, the photographic emulsion used in the present invention can also be subjected to reduction sensitization using a reducing substance, noble metal sensitization using a noble metal compound, or the like.

As the photosensitive emulsion, the above emulsion may be used alone,
Two or more emulsions may be mixed.

When carrying out the present invention, for example, 4-hydroxy-6-methyl-1,3,
3a, 7-chitrazaindene, 5-mercapto-1-7
Various stabilizers can also be used, including 22rutetrazole, 2-mercaptobenzothiazole, and the like.

Furthermore, if necessary, a silver halide solvent such as thioether,
Alternatively, a crystal habit control agent such as a mercapto group-containing compound or a sensitizing dye may be used.

The silver halide grains used in the emulsion of the present invention are formed by cadmium salts, zinc salts, lead salts, thallium salts, iridium salts or complex salts, rhodium salts or complex salts, iron salts, etc. Alternatively, metal ions can be added using complex salts and included inside the particles and/or on the particle surfaces.

In the emulsion of the present invention, unnecessary soluble salts may be removed after the growth of silver halide grains is completed, or they may be left contained. In the case of removing the salts, it can be carried out based on the method described in Research Disclosure No. 17643.

In the silver halide photographic material according to the present invention, a sensitizing dye may be further added and used in combination.

The pigments used include /Ayu 2 pigment, merocyanine pigment, composite cyanine pigment, composite merocyanine pigment, holopolar cyanine pigment, hemicyanine pigment, styryl pigment, and hemioxanol pigment. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes and complex merocyanine dyes. Any of the nuclei commonly used for cyanine dyes can be used as the basic heterocyclic nucleus for these dyes. That is, pyridine nucleus, oxazoline nucleus, thiazoline nucleus, virol nucleus, oxazole nucleus, thiazole nucleus, selenazole nucleus, imidazole nucleus,
Tetrazole nucleus, pyridine nucleus, etc. Nuclei in which an alicyclic hydrocarbon ring is fused to these nuclei, and nuclei in which an aromatic hydrocarbon ring is fused to these nuclei, i.e., indolenine nucleus, benzindolenine nucleus, indole nucleus , benzoxazole nucleus, naphthoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, benzoselenazole nucleus, benzimidazole nucleus, quinoline nucleus, etc. are applicable. These nuclei may be substituted on carbon atoms.

Merocyanine dyes or composite merocyanine dyes include a pyrazolin-5-one nucleus, a thiohydantoin nucleus, and a 2-thioxazolidine-2 nucleus having a ketomethylene structure.
, 4-dione nucleus, thiazolidine-2,4-dione nucleus, rhodanine nucleus, thiobarbic acid nucleus, etc. can be applied.

The sensitizing dye used in the present invention is used at a concentration equivalent to that used for ordinary negative-working silver halide.

In particular, it is advantageous to use the dye at a concentration that does not substantially reduce the inherent sensitivity of the silver halide emulsion.

Approximately 1.0% of sensitizing dye per mole of silver halide. OX 10-
6 to about 5 X 10-' moles of sensitizing dye are preferred, especially about 4 X 10-5 to 2 X moles of sensitizing dye per mole of silver halide.
Preferably, a concentration of 10-' molar is used.

The sensitizing dyes of the present invention can be used alone or in combination of two or more. More specific examples of the sensitizing dyes advantageously used in the present invention include the following.

That is, examples of the sensitizing dye used in the blue-sensitive silver halide emulsion layer include West German Patent No. 929,080, US Patent No. 2,231.658, US Patent No. 2,493.748, and US Patent No. 2,503.776. No. 2,519,001, No. 2
, No. 912.329, No. 3,656゜956, No. 3,
No. 672.897, No. 3,694.217, No. 4.0
No. 25゜349, No. 4,046,572, British Patent 1
, No. 242,588, Special Publication No. 44-14030, No. 5
No. 2-24844, JP-A-48-73137, JP-A No. 61
-172140 etc. can be mentioned. In addition, examples of sensitizing dyes used in green-sensitive silver halide emulsions include, for example, US Pat.
, No. 072,908, No. 2,739,149, No. 2,
Typical examples include cyanine dyes, merocyanine dyes, and complex anionine dyes as described in No. 945.763, British Patent No. 505,979, and Japanese Patent Publication No. 48-42172. Further, as sensitizing dyes used in red-sensitive and infrared-sensitive silver halide emulsions, for example, U.S. Pat.
No. 270,378, No. 2,442,710, No. 2,4
No. 54.629, No. 2,776.280, Special Publication No. 1977
-17725, JP-A No. 50-62425, JP-A No. 61.
Typical examples include cyanine dyes, merocyanine dyes, and composite cyanine dyes such as those described in No. 29836 and No. 60-80841.

These sensitizing dyes may be used alone or in combination. Combinations of sensitizing dyes are often used, especially for the purpose of supersensitization. Typical examples are U.S. Patent Nos. 2,688.545, 2,977.229, and 3
, No. 397.060, No. 3,522.052, No. 3,
No. 527.641, No. 3,617,293, No. 3,6
No. 28.964, No. 3,666.480, No. 3,67
No. 2.898, No. 3,679,428, No. 3,703
゜377, 3,769,301, 3,814,
No. 609, No. 3,837゜862, No. 4,026,7
07, British Patent No. 1,344.281, British Patent No. 1,507
, No. 803, Special Publication No. 43-4936, No. 53-123
No. 75, JP-A-52-110618, JP-A No. 52-109
No. 925, etc.

The silver halide photographic material according to the present invention may contain a water-soluble dye in the hydrophilic colloid layer as a filter dye or for various purposes such as preventing irradiation and halation. Such dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes, azo dyes, and the like. Among them, oxal dyes; hemioxanol dyes and merocyanine dyes are useful.

In the silver halide photographic material according to the present invention, when dyes, ultraviolet absorbers, etc. are included in the hydrophilic colloid layer, they may be mordanted with a cationic polymer or the like.

Various compounds can be added to the above-mentioned photographic emulsion in order to prevent a decrease in sensitivity and the occurrence of fog during the manufacturing process and storage of silver halide photographic materials. In other words, azoles, etc. Benzothiazolium salts, nitroindazoles, triazoles, benzotriazoles, benzimidazoles (especially nitro- or halogen substituted), heterocyclic mercapto compounds such as mercaptothiazoles, mercaptobenzimidazoles, mercaptothiazoles (especially l-7enyl-5-mercaptotetrazole)
, mercaptoviridines, the above-mentioned heterocycles having a water-soluble group such as a carboxyl group or a sulfone group, mercapto compounds, thioketo compounds such as oxazolinthione, azaindenes such as tetraazaindenes (especially 4-hydroxy substituted (1.3 Many compounds known as stabilizers can be added, such as .3a, 7) tetraazaindenes), benzenethiosulfonic acids, benzenesulfinic acids, etc.

An example of a compound that can be used is K. Mees, The Theory of the Photographic Process
Theory of the Photography
ic Process, 3rd edition, 1966), citing the original literature.

For more detailed examples and other methods of use, see, for example, U.S. Pat.
No. 82.947, No. 4,021,248 or Tokuko Sho 5
The description in No. 2-28660 can be referred to.

Further, the silver halide photographic light-sensitive material of the present invention includes U.S. Pat. No. 3,411,911 and U.S. Pat.
912, Japanese Patent Publication No. 45-5331, etc., may be included.

The silver halide photographic material of the present invention may contain the following various additives. As thickeners or plasticizers, for example, U.S. Pat.
No. 15, Belgian Patent No. 762.833, US Patent No. 3
, No. 767.410 and Belgian Patent No. 588.143, such as styrene-sodium maleate copolymer, dextran sulfate, etc. Hardening agents include aldehyde-based, epoxy-based, Various hardeners and ultraviolet absorbers such as ethyleneimine, active halogen, vinyl sulfone, isocyanate, sulfonic acid ester, carbodiimide, mucochloric acid, and acyloyl hardeners include, for example, U.S. Pat. No. 3,253,92.
No. 1, British Patent No. 1,309,349, particularly 2-(2'-hydroquine-5
-tertiary butylphenyl)henzotriazole, 2-(2
'-hydroxy-3',5'-di-tert-butylphenyl)benzotriazole, 2-(2-hydroxy-3
'-tertiary butyl-5'-butylphenyl)-5-chlorobenzo1-riazole, 2-(2'-hydroxy-3
', 5'-di-tertiary butylphenyl) 5-chlorobenzotriazole, and the like. Furthermore, coating aids, emulsifiers, permeability improvers for processing solutions, antifoaming agents, and surfactants used to control various physical properties of photosensitive materials are described in British Patent No. 548.
No. 532, No. 1,216.389, U.S. Patent No. 2,02
No. 6,202, No. 3,514,293, Special Publication No. 1977-
No. 26580, No. 43-17922, No. 43-179
No. 26, No. 43-3166, No. 48-20785,
French Painting Patent No. 202.588, Belgian Patent No. 773.4
Anionic, cationic, nonionic or amphoteric compounds described in No. 59, JP-A-48-101118, etc. can be used, and among these, anionic surfactants having a sulfone group, For example, succinic acid ester sulfonates, alkylbenzene sulfonates, and the like are preferred. In addition, as an antistatic agent,
No. 159, JP-A-48-89979, U.S. Patent No. 2,8
No. 82.157, No. 2,972,535, Japanese Unexamined Patent Publication No. 1972
-20785, 48-43130, 48-90
No. 391, Special Publication No. 46-24159, No. 46-393
No. 12, No. 48-43809, JP-A No. 47-3362
There are compounds described in each publication of No. 7.

In the manufacturing method of the present invention, the pH of the coating liquid is 5.3 to 7.
．． It is preferable that it is in the range of 5. For multi-layer coating,
It is preferable that the pH of the coating liquid obtained by mixing the coating liquids for each layer in the ratio of coating amounts is within the above range of 5.3 to 7.5. If the pH is less than 5.3, the progress of hardening is undesirable, and if the pH is greater than 7.5, it is undesirable because it adversely affects photographic performance.

In the light-sensitive material of the present invention, the constituent layers include matting agents, such as silica described in Swiss Patent No. 330.158, glass powder described in French Painting Patent No. 1,296,995, and British Patent No. 1.
．． Inorganic particles such as alkaline earth metals or carbonates such as cadmium, zinc, etc. as described in No. 173.181; starch as described in U.S. Pat. No. 2,322,037;
Starch derivatives described in No. 5,451 or British Patent No. 981,198, polyvinyl alcohol described in Japanese Patent Publication No. 44-3643, Swiss Patent No. 330.158 i:
Organic particles such as polystyrene or polymethyl methacrylate as described in US Pat. No. 3,079,257, polyacrylonitrile as described in US Pat. No. 3,022,169, and polycarbonate as described in US Pat.

In the photosensitive material I of the present invention, the constituent layers include slipping agents, such as U.S. Pat.
Higher aliphatic higher alcohol esters as described in No. 0, casein as described in U.S. Pat. No. 3,295,979, higher aliphatic calcium salts as described in British Patent No. 1, No. 263.722, British Patent No. 1,313,384 No. 3,04 U.S. Pat.
2.522 and 3,489,567, etc. may also be included.

Dispersions of liquid paraffin and the like can also be used for this purpose.

The photosensitive material of the present invention may further contain various additives depending on the purpose. These additives are described in more detail in Research Disclosure Volume 176.
+17643 (December 1978) and volume 187 ■
tem18716 (November 1979), and the relevant parts are summarized in the table below.

In carrying out the silver halide photographic material of the present invention, for example, the emulsion layer and other layers can be constructed by coating on one or both sides of a flexible support commonly used in photographic materials. Useful flexible supports include films made of semi-synthetic or synthetic polymers such as cellulose nitrate, cellulose acetate, cellulose acetate butyrate, polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, baryta layers or α-olefin polymers. (
Examples include paper coated with or laminated with polyethylene, polypropylene, ethylene/butene copolymer, or the like. The support may be colored using dyes or pigments. It may be made black for the purpose of blocking light. The surface of these supports is generally treated with an undercoat to improve adhesion with emulsion layers and the like. The undercoating treatment is as per JP-A-52-104913 and JP-A-52-104913.
No. 9-18949, No. 59-19940, No. 59-1
The treatments described in each publication of No. 8949 are preferred.

The surface of the support may be subjected to corona discharge, ultraviolet irradiation, flame treatment, etc. before or after the undercoating treatment.

In the silver halide photographic light-sensitive material according to the present invention, the photographic emulsion layer and other hydrophilic colloid layers can be coated on the support or on other layers by various coating methods. For coating, a dip coating method, a roller coating method, a curtain coating method, an extrusion coating method, etc. can be used.

The photographic processing of the silver halide photographic material according to the present invention is as follows:
There are no particular restrictions, and various methods can be used. For example, Research Disclosure
losure) No. 176, pages 28-30 (RD-17
Any of the various methods and various treatment liquids can be applied, such as those described in 643).

The treatment temperature is usually chosen between 18°C and 50°C, but it may also be below 18°C or above 50°C.

For example, the developer used in black-and-white photographic processing can contain a developing agent. As developing agents, dihydroxybenzenes (e.g. /S hydroquinone), 3-pyrazolidones (e.g. l-phenyl-3-pyrazolidone)
, amine phenols (for example, N-methyl-〇-aminophenol), etc. can be used alone or in combination.

The silver halide photographic material of the present invention may be photographically processed using a developer containing imidazoles as a 7X silver halide solvent as described in Japanese Patent Application No. 155489/1989. It is also possible to process with a developer containing a silver halide solvent and an additive such as indazole or triazole as described in Japanese Patent Application No. 136267/1982. The developing solution generally contains various other preservatives, alkaline agents, pH buffering agents, antifoggants, etc., and further contains dissolving aids, color toners, development accelerators, surfactants, antifoaming agents, etc. as necessary. , a water softener, a hardening agent, a viscosity imparting agent, and the like.

The photographic emulsion of the present invention can be subjected to a so-called "lith type" development process. "Lith type" development processing is a process in which dihydroxybenzenes are usually used as a developing agent and the development process is carried out at a low sulfite ion temperature for the photographic reproduction of line images or the photographic reproduction of halftone images using halftone dots. (Details are described in "Photographic Processing Chemistry" by Mason (1966), pp. 163-165.) As a special form of development processing, developing agent A method may be used in which the photosensitive material is contained in a light-sensitive material, for example, in an emulsion layer, and the light-sensitive material is processed in an alkaline aqueous solution to perform development. Among the developing agents, hydrophobic ones are described in Research Disclosure No. 169 (RD-16928), US Pat.
39.890, British Patent No. 813.253, and West German Patent No. 1,547,763. Such development treatment may be combined with silver salt stabilization treatment with thiocyanate.

As the fixer, one having a commonly used composition can be used. In addition to silver halides and thiosulfates, organic sulfur compounds known to be effective as fixing agents can be used as fixing agents.

The fixer may contain a water-soluble aluminum salt as a hardening agent.

Exposure for the photographic emulsion used in the present invention varies depending on the state of chemical sensitization, purpose of use, etc., but includes tungsten, fluorescent lamps, mercury lamps, arc lamps, xenon sunlight, xenon 7 run units, cathode ray tube flying spot, laser light, electronic Various types of light sources such as X-rays, X-rays, and fluorescent screens for X-ray photography can be used as appropriate.

As for the exposure time, in addition to normal exposure of 1/1000 to 100 seconds, short exposure of 1/10' to 1/10' second can be applied for xenon flash, cathode ray tube, and laser light.

〔Example〕

EXAMPLES The present invention will be explained below with reference to Examples, but the present invention is not limited thereto.

Example-1 (Preparation of emulsion) Solution A Water
9.7Q Sodium Chloride
20 g gelatin 10
5 g solution B water
3.8mff sodium chloride
380g gelatin 94
g Potassium bromide 420g 0.10% aqueous solution of potassium hexachloroiridate salt 28fflα
0.001% aqueous solution of potassium hexabromorodate salt 1.0 m (
2 solution C water
3.8mQ silver nitrate
1700. The above solution B and solution C were simultaneously added functionally over 60 minutes to the above solution A kept at 40 °C while maintaining pI (3) and pAg 7.7, and after continuing to stir for an additional 10 minutes. , the pH was adjusted to 6.0 with an aqueous sodium carbonate solution, and a 20% aqueous magnesium sulfate solution 2ρ and a 5% aqueous polynaphthalene sulfonic acid solution 2.
55f2 is added and the emulsion is flocculated at 40°C, decanted and washed with water to remove excess aqueous salt. Next, 3.7Q of water is added to disperse it, and 0.9Q of a 20% aqueous magnesium sulfate solution is added again to remove the excess salt in the aqueous solution.

Add 3.7Q of water and 141g of gelatin to it,
Disperse for 55°030 minutes. This allows silver bromide 35
Particles having a mol % of silver chloride of 65 mol %, an average particle size of 0.25 μm, and a monodispersity of 9 are obtained. Here, the monodispersity is a value expressed by 100 times the standard deviation of particle diameter divided by the average particle diameter.

120 mQ of 1% citric acid aqueous solution, 5 sodium chloride
% aqueous solution was added, pH 5.5, pAg 7.
To the emulsion adjusted to
2 and mature at 60°C to achieve maximum sensitivity.

The above emulsion was divided into 10 equal parts, 25 mQ of a 0.5% solution of compound (V-13) was added to each as an antifoggant, and 4-hydroxy-6-methyl 1,3.3a,7-
After adding 180 m of a 1% solution of chitrazaindene (2) and 400 m of a lθ% aqueous solution of gelatin to stop the ripening, the sensitizing dye and the compound (I [[) or [■]] were added as shown in Table 1 and further fogged. Compound CVI- as an inhibitor
Add 50mL of 10% solution of 1), 50mL of 5% solution of potassium bromide (2), add 19n+72° of 20% saponin aqueous solution as a spreading agent, and 4ml of styrene-male as a thickener.
11 4% aqueous solution of 59m+2, ethyl acrylate polymer latex 30g1 as a hardening agent.
- Hydroquine-3,5-dichlorotriazine sodium salt and formalin were added and the above emulsion was deposited on a subbed polyethylene terephthalate support at 4.2 g/m of silver.
Add 500g of gelatin as a protective layer.
100m of potassium bromide 10% aqueous solution! 2, 400 mQ of 1% aqueous solution of sodium l-decyl-2-(3-impentyl)succinate-2-sulfonate as a spreading agent, and 100 g of amorphous silica with an average particle size of 3.5 μ. The emulsion layer and the protective layer were coated at the same time so that the gelatin was dispersed to a concentration of 1.1 g/m2.

In order to determine the sensitivity of the sample obtained in this way, a light emitting diode (660 nm) and a semiconductor laser (680 nm) were used.
n111) and 660nm±25am
In order to determine the maximum and minimum sensitivity difference (1 ogE) at 680 nm f 25 nm using spectral sensitization characteristics, subvectorodram exposure was performed, and the image was exposed at 38° using a Sakura Automatic Processor GR-27 (manufactured by Konica) using a developer and fixer with the following composition. Developed for 20 seconds at C, fixed, washed with water,
After drying, the optical density was measured. The results are shown in Table 1.

From Table 1, it can be seen that the inventive device has high sensitivity and little sensitivity fluctuation with respect to changes in the wavelength of the light source.

<Developer formulation> Pure water (ion-exchanged water) approximately 800 mQ Potassium sulfite 60 g Ethylenediaminetetraacetic acid disodium salt 2 g Potassium hydroxide 10.5 g 5-methylbenzotriazole 300 mg Diethylene glycol 25 gl-Phenyl-4,4
-Dimethyl-3-pyrazolidinone 300 mg l-phenyl-5-mercaptotetrazole 60 ff1g Potassium bromide 3.5g Hydroquinone 20g Potassium carbonate
Add 15g of pure water (ion-exchange liquid water) to make 1,000+n12. The developer pH is l
It was 098.

<Fixer formulation> (Composition A) Ammonium thiosulfate (72.5% W/V aqueous solution) 240 mQ
Sodium sulfite 17 g Sodium acetate trihydrate 6.5 g Boric acid
6g sodium citrate dihydrate 2g acetic acid (90%W/
V aqueous solution) 13.6 mQ (composition) Pure water (ion exchange water) 17 mQ sulfuric acid (90% W/V aqueous solution) 4.7 g aluminum sulfate (aqueous solution with A12203 equivalent content of 8.1% W/W) 2
6.5 g When using a fixer, the above compositions were dissolved in 500 mQ of water in the order of composition A1 and finished to H.

The pFI of this fixer was about 4.3.

Example 2 Particles were prepared in the same manner as in Example 1, but the amounts of sodium chloride and potassium bromide in solution B were changed, and silver bromide was 20 mol%.
, silver chloride 80 mol%, average 0.27μ, monodispersity 12 grains were obtained. This emulsion was chemically ripened, prepared and coated in the same manner as in Example 1. However, the sensitizing dye and compound are (rV)
and compound [:V), (Vl) were added as shown in Table 2.

The sample thus obtained was heated using a semiconductor laser (780
Exposure processing was evaluated in the same manner as in Example 1 using 100 nm), and the results are shown in Table 2.

From Table 2, it can be seen that the device of the present invention has high sensitivity to changes in the wavelength of the light source and has little sensitivity fluctuation.

Furthermore, it can be seen that the sensitivity was even higher and the fog was lower when the compounds (V) and (Vl) were added.

Example 3 (1) Production of seed particles While keeping Solution A of the following formulation at 60°C, solutions B and C were adjusted to pH = 1.9. A silver iodobromide emulsion (composition: silver bromide 98 mol%, silver iodide 2-E, 1%) with an average grain size of 0°28 μm was prepared by a simultaneous mixing method in which EAg was added over 120 minutes while controlling EAg = 84 mV. , after completion of physical ripening, pH = 5.5. After setting EAg = -23 mV and repeating desalination water washing twice, gelatin for dispersion was added, and the
After dispersing at 5°0 for 30 minutes, it was finished to 5.95Q.

A liquid pure water Br GeQ.

B liquid pure water Br I GeQ.

C liquid pure water AgN0゜ 6% HNO.

2.09 g 6 g 6.5 a 1168.5 g 33.2 g 77.66 g 6.5 12 1700 g 195 cc (2) Particle growth While keeping solution A of the following recipe at 40°C, add solution B and C While changing the pH of the solution from 8.0 to 7.0, EAg
A silver iodobromide emulsion (composition: silver bromide 99.4 mol%, silver iodide 0.6 mol%) with an average grain size of 0.38 μm was prepared by a simultaneous mixing method in which the voltage was added for 30 minutes while controlling the voltage at +43 mV.
was prepared.

After physical ripening, pH=6.0. EAg=47
After repeating demineralization and water washing three times as mV, gelatin for dispersion was added, and after dispersing for 55°0130 minutes, it was finished to 6.8Q.

A liquid pure water 8.
7 QK B r 2.4
5gHAc 510cc28%
NH4OH384cc seed emulsion
2.35 Q B liquid GeQ, 30gKBr
728g o, oi% aqueous solution of potassium hexachloroiridate salt 0 mQ 0.01% aqueous solution of potassium hexabromorodate salt mQ Ce kgNOx 1049 g2
Finished with 8% NH4OH493cc pure water 3Q.

The emulsion obtained above was prepared and evaluated in the same manner as in Example 1, and it was confirmed that there was little sensitivity variation with respect to variation in emission wavelength. In addition, in another experiment, compound [v] or [■]
It was confirmed that by adding , the sensitivity was even higher and the fog was lower.

The processing was carried out using a developer having the composition shown below at 38 DEG Cl2O for 2 seconds, followed by fixation, washing with water, and drying.

(Developer composition) [Part A] Hydroquinone 25 g Boric acid
10 g potassium sulfite
65 g Potassium hydroxide 30 gED
Add TA-2NaO and 5g of pure water to make 300cc.

5 cc 1.1 g 0.08g [Part-B] acetic acid 1-722-3-pyrazolidone 5-Nitropenzimidazole 4-hydroxy-6-methyl- 1,3,3a,7-chitrazaindene potassium bromide 0.5 g g Add pure water to make 30cc.

Preparation method of working liquid: Part A 300cc and Part 8
Add water to 30cc to make 1.012.

〔Effect of the invention〕

According to the present invention, it was possible to provide a halogen-4 silver photographic material that has high sensitivity to light emitting light sources, particularly semiconductor laser light sources, and provides stable images even against wavelength fluctuations.

Claims (1)

[Claims] In a silver halide photographic light-sensitive material that is exposed to a light source whose maximum wavelength of emission spectrum varies due to variations in temperature and manufacturing, the spectral sensitivity distribution of the silver halide photographic light-sensitive material is within ±25 nm of the standard value of the light source. 0.2(
1. A silver halide photographic material, characterized in that it is within logE).