JPH03253841A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To prevent a change of sensitivity with the lapse of time or due to heat by incorporating a specified sensitizing dye and a specified compd. into a silver halide emulsion layer. CONSTITUTION:At least one silver halide emulsion layer is formed on at least one side of a base and at least one kind of sensitizing dye represented by formula I or II and at least one kind of compd. represented by formula III are incorporated into the emulsion layer. In the formulae I, II, each of Y11, Y12, Y21 and Y22 is a group of nonmetallic atoms required to complete a 5- or 6-membered N-contg. hetero ring, of R11, R12, R21 and R22 is alkyl, aryl, etc., and each of R13-R15 and R23-R26 is H, alkyl, etc. In the formula III, R31 is H or acetyl and each of R32-R35 is H or optionally substd. alkyl. A change of sensitivity with the lapse of time and due to heat is prevented and stability of sensitivity is obtd.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a silver halide photographic material, and more specifically, a silver halide photographic material that can prevent sensitivity fluctuations due to aging or heat and maintain stable sensitivity. Regarding materials.

[Background of the Invention] Recently, there has been an increasing demand for the development of high-sensitivity silver halide photographic materials, and among the high-sensitivity technologies using sensitizing dyes, seven
The formula [I-al and/or the formula [I-b] with good sensitivity from 00 nm to 800 nm
] The sensitizing dye represented by is attracting attention.

General formula (+-a) However, such - formula [I] and/or - formula [I-b
] Silver halide photographic materials using sensitizing dyes shown in the following table are susceptible to aging or exposure to heat (so-called thermo).
It was found that the sensitivity increased and the stable ft sensitivity did not last.

Therefore, the present inventors conducted extensive research to solve the problems in silver halide photographic materials using such sensitizing dyes, and as a result, these sensitizing dyes were formulated with the general formula [! 1
By using the compound represented by It was found that high sensitivity can be achieved, and the present invention has now been completed.

[Object of the Invention] Therefore, an object of the present invention is to provide a silver halide photographic light-sensitive material which is highly sensitive and exhibits sensitivity stability without fluctuations in sensitivity over time or due to thermostat.

[Structure of the Invention] A silver halide photographic material that achieves the above object of the present invention has at least one silver halide emulsion layer on at least one of the supports, and the silver halide emulsion layer includes Containing at least one of the sensitizing dyes represented by formulas [I-al and - formula [I-b], and - containing at least one compound represented by formula [1] That is.

General formula ([-a) General formula [I1] [In the formula, Y, , Y, 2, YH5Y22 each represent a nonmetallic atomic group necessary to complete a 5- or 6-membered nitrogen-containing heterocycle. , R11, R12, R21% R22 each represents a substituted or unsubstituted alkyl group, aryl group, or aralkyl group, R15, R14, R1s% R23, R24, R
25, R2 is a hydrogen atom, a substituted or unsubstituted alkyl group, an alkoxy group, a phenyl group, a benzyl group, an unsubstituted alkyl group (the number of carbon atoms in the alkyl portion is 1 to 18, preferably 1 to 4). ), represents an aryl group, and further Wl
and W2 can be linked to each other to form a 5-membered ring or a 6-membered ring.

X1 and X2 represent anion groups.

(XzI-)mt+ R3 represents a hydrogen atom or an acetyl group, R32, R3
3, R34 and R35 represent a hydrogen atom or a substituted or unsubstituted alkyl group.] Hereinafter, the present invention will be explained in more detail.

The silver halide photographic light-sensitive material of the present invention contains at least one layer of silver halide emulsion, and the type, crystal habit, grain size, etc. of silver halide used in the silver halide emulsion layer are not limited, but the present invention According to research by et al., the average particle size is 0.
Preferably, it is a silver halide photographic light-sensitive material in which an emulsion layer consisting of a silver halide emulsion containing silver halide grains of 0.05 to 0.5 μm and having a monodispersity of 20 or less is deposited on a support. It has been found that it is particularly preferred that the silver halide in the emulsion layer contains at least 50 mole percent silver chloride. A silver halide photographic light-sensitive material having such a silver halide emulsion layer is particularly suitable as a light-sensitive material for laser beams, and exhibits unprecedented resolution.

Next, the general formula [I-a] and the numerical formula [I-b] will be explained.

General formula [Ia] [In the formula, Yll, YI2, Y21 and Y22 each represent a group of nonmetallic atoms necessary to complete a 5- or 6-membered nitrogen-containing heterocycle, such as a benzothiazole ring, a naphthothiazole ring, etc. ring, benzoselenazole ring, naphthoselenazole ring, benzoxazole ring, naphthoxazole ring,
Examples include a quinoline ring, a 3,3-dialkylindolenine ring, a Benrai main dazole 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, , R,2, R21 and R72 each represent a substituted or unsubstituted alkyl group, aryl group or aralkyl group.

R+3, R14, R15, R23, R24, R25 and R26 are each a hydrogen atom, a substituted or unsubstituted alkyl group, an alkoxy group, a phenyl group, or a benzyl substituted or unsubstituted alkyl group (the number of carbon atoms in the alkyl portion is 1). ~18, preferably 1-4), represents an aryl group,
W and w2 can also be linked to each other to form a 5- or 6-membered nitrogen-containing heterocycle.

Further, R1 and R15 and R23 and R2S can be linked to each other to form a 5-membered ring or a 6-membered ring.

Y■, YI2, Y2IY22, R11, RI2, R13
, R]4, R]5, R2,, R22, R23, R24,
One of R25 and R26 is preferably an acid group (eg, carbonyl group, sulfonyl group, etc.) or a group substituted with an acid group. Represents X11 and xz+Gi anion.

If there is an acid group, ff1ll% 1L21 represents O; if there is no acid group, mll, m21 represents 1.

n++% n+2% n, 1 and n22 represent O or 1.

Next, specific examples of the sensitizing dye used in the present invention (hereinafter referred to as the sensitizing dye of the present invention) will be shown, but the present invention is not limited thereto.

Margin below ■ 1 -2 C! H5 C3H? ■0 ■ 1 -7 Iυ ■ ■ Q 3 -4 ■ -6 ■ 0 ■ 1 ■ 2 2 4 e 9 1'-3 ■ 13 ■ -14 ■ 5 -19 ■ 1 e O 5 zHs Lj 7 ■ -16 ■-17 ■Su■-18 C Snow Is e 6 ■-22 tHs C Tomi Hi e ■-23 4 8 The sensitizing dye used in the present invention preferably has an IB to 2 g1 per mole of silver halide. 5mg~1g
It is contained in silver halide photographic emulsions within the range of .

The sensitizing dye used in the present invention can be directly dispersed in the emulsion. Alternatively, they can be first dissolved in a suitable solvent such as 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 dye used in the present invention may be used alone,
Two or more types may be used in combination. 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 used in the present invention is disclosed in U.S. Pat.
No. 3776, British Patent No. 742112, French Patent No. 206
It can be easily synthesized with reference to No. 5662 and Japanese Patent Publication No. 40-2346.

Next, the compound represented by the general formula [II] used in the present invention will be exemplified below.

ll-11-phenyl-3-pyrazolidone ll-21-
Phenyl-4-methyl-3-pyrazolidone ll-31-phenyl-4,4-dimethyl-3-pyrazolidone 11-41-phenyl-5-methyl-3-pyrazolidone ll-51-phenyl-4-methyl-4'- Hydroxymethyl-3-pyrazolidone-61-phenyl-4,4-dihydroxymethyl-
3-Pyrazolidonell-71-phenyl-4,4-di-n-propyl-3
-Pyrazolidonell-81-phenyl-2-acetyl-4,4-dimethyl-3-pyrazolidone The above-mentioned formula [! ! Although the amount of the compound represented by 9 to be added is arbitrary, it is preferably used in an amount of up to 10 g per mole of silver halide contained in the silver halide photographic material of the present invention.

The silver halide used in the silver halide photographic light-sensitive material of the present invention may be any of silver bromide, silver iodobromide, silver chlorobromide, silver chloroiodobromide, etc. Silver chlorobromide or silver chloroiodobromide containing silver chloride is preferred. That is, from the viewpoint of high contrast, it is preferable that the content of silver chloride is 50 mol % or more. Further, the average grain size of the silver halide used is preferably in the range of 0.05 to 0.5 μm. That is, from the point of view of sensitivity, it is preferable that the average particle size is 0.05 μm or more, and from the point of view of obtaining practical concentration, it is preferable that the average particle size is 0.05 μm or more.
It is preferable that it is 5 μm or less.

When carrying out the invention, the photographic emulsion is, for example,
“Shemi” by Glafkides (P, Glafkides)
Chimle et Physique Ph
otogra.

hique; published by Paul Monte 1) 1967, G.F. Duffin
Author: “Photographic Emulsion Chemistry”
Published by The Focal Press (Photography
c Emulsion Ch0 emistry; Published by The Focal Press) 1966, V, L,
“Making and
Coating Photographic Emulsion” The
Published by Focal Press (Makingand Coa)
ting Photographic EmuIsio
n; published by The Focal Press, 1964, etc. can be used for adjustment. In other words, any of the acidic method, neutral method, ammonia method, etc. may be used, and any one-sided synthesis method, simultaneous mixing method, or a combination thereof may be used to react the soluble silver salt and the soluble halogen salt. .

Preferably used in the present invention is a combination of acidic and simultaneous mixing methods.

It is also possible to use a method in which particles are formed in an excess of silver ions (so-called back-mixing method).

As one type of simultaneous mixing method, a method in which PAg in the liquid phase in which silver halide is produced can be kept constant, that is, a so-called Chondrald double jet method can also be used. According to this method, so-called monodisperse silver halide grains having a regular crystal shape and a nearly uniform grain size can be obtained.

In the present invention, the grain size of silver halide grains is conveniently expressed as the principal dimension of cubic crystal grains, or in the case of non-cubic grains, the diameter of the projected area converted into a circle, and the average value thereof is defined as the average grain size (l). The degree of monodispersity is expressed as a value obtained by dividing the standard deviation of the particle size by the average particle size (r), multiplied by 100.

Here, if the degree of monodispersity is expressed as a formula, in a preferred embodiment of the present invention, it is important to adjust the silver halide grains so that this value is 20 or less, and if the degree of monodispersity exceeds 20. This is undesirable because the contrast may be impaired and the sharpness may deteriorate. Especially for helium lasers, neon lasers,
Such a monodisperse emulsion is more preferable as a photosensitive material for a helium-neon laser, and provides accurate halftone dot quality.

Here, the term "high contrast" refers to the degree of density difference between bright areas and dark areas in a photographic image. Also sharpness (Sh
The term "arpness" refers to the degree to which the boundaries of an image are clear and even minute details are shown.

The high-intensity single exposure characteristics of the silver halide photographic emulsion used in the present invention can be improved by using in combination a compound containing a metal of Group 8 of the periodic table.

Metals belonging to Group 8 of the periodic table include iron, cobalt,
It refers to nickel, ruthenium, rhodium, palladium, osmium, iridium, and platinum, and particularly preferred compounds containing these metals include ferric chloride, red blood salt, cobalt chloride, cobalt nitrate, and luteo salt. , nickel chloride, nickel sulfate, ruthenium chloride, ruthenium hydroxide, rhodium chloride, ammonium hexachlororhodate, sodium hexachlororhodate,
Potassium hexabromorhodate, palladium chloride, palladium nitrate, potassium hexachloropalladate, osclam chloride, iridium 34 chloride (IrCj23 and IrCu4), potassium hexachloroiridate, ammonium hexachloroiridate, potassium hexachloroplatinate, etc. .

The binder used in the silver halide emulsion layer and other hydrophilic colloid layers constituting the silver halide photographic light-sensitive material of the present invention is preferably gelatin. Sugar derivatives such as cellulose derivatives, sodium alginate, starch derivatives; polyvinyl alcohol, polyvinyl alcohol partial acetal, polyvinyl alcohol;
N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole,
A wide variety of synthetic hydrophilic polymeric materials can be used, such as single or copolymers such as polyvinylpyrazole.

In addition to lime-processed gelatin, acid-processed gelatin and Bulletin of Society of Science Op Photography of Japan (Bull
,Soc,Sci,Photo,Japan) ,No.
Oxygen-treated gelatin as described on page 16.30 [I966] may be used, and gelatin hydrolysates and oxygen-decomposed products may also be used. Examples of gelatin derivatives include gelatin, acid halides, acid anhydrides, isocyanates, bromoacetic acids, alkanesultones, vinyl sulfonate compounds, maleimide compounds, polyalkylene oxides, epoxy compounds, etc. Those obtained by reacting compounds are used.

In carrying out the present invention, various hydrophilic colloid layers such as the silver halide emulsion layer are used to prevent fogging during the manufacturing process, storage, or photographic processing of the light-sensitive material, or to stabilize photographic performance. The compound can be contained. Azoles such as benzothiazolium salts, nitroindazoles, triazoles, benzotriazoles, benzimidazoles (particularly nitro- or halogen-substituted); heteromercapto compounds such as mercaptothiazoles, mercaptobenzothiazoles, mercaptothiazoles; Captobenzoic dazoles, mercaptodeadiazoles, mercaptotetrazoles (especially 1
-phenyl-5-mercaptotetrazole), mercaptopyrin-based dines; the above-mentioned heterocyclic mercapto compounds having a water-soluble group such as a carboxyl group or a sulfone group; thioketo compounds such as oxazolinthione; azaindenes such as tetraazaindenes ( In particular, many compounds known as antifoggants or stabilizers can be added, such as 4-hydroxy-substituted-1,3,3a,7-tetrazaindenes); benzenethiosulfonic acids; benzenesulfinic acid; can.

Further, a polymer latex can be contained in the silver halide photographic emulsion used in the present invention. As the polymer latex, aqueous dispersions of homo or copolymers of methyl acrylate, methyl methacrylate, acrylic acid, methacrylic acid, glycidyl acrylate, styrene, vinyl chloride, vinylidene chloride, etc. are used.

The silver halide photographic emulsion used in the present invention includes commonly used chemical sensitizers, stabilizers, toning agents, hardeners, antifoggants, surfactants, thickeners, plasticizers, slip agents, and development inhibitors. agent, ultraviolet absorber, irradiation inhibitor (dye),
Heavy metals, matting agents, etc. can be further incorporated by conventional methods.

The silver halide photographic emulsion used in the present invention can be used on a suitable support, such as glass, cellulose derivative film such as cellulose triacetate, synthetic resin film such as polyethylene terephthalate, baryta paper, resin coated paper, synthetic paper, etc. can be applied in the usual way.

After exposure, the silver halide photographic material according to the present invention can be developed by various commonly used methods.

The black and white developer contains hydroxybenzenes, 1-phenyl-
It is an alkaline solution containing developing agents such as 3-pyrazolidones, aminophenols, and azaindenes, and may also contain other alkali metal salts such as sulfites, carbonates, bisulfites, bromides, and iodides.

[Example] Next, the present invention will be specifically explained by referring to an example. however,
The present invention is not limited thereby.

Example 1 A silver chlorobromide gelatin emulsion containing 35 mol % of silver bromide was prepared by a simultaneous mixing method at 45° C. for 100 minutes. To prepare the emulsion in this way, the emulsion was desalted, redispersed, and the average grain size was 0.2.
A monodisperse emulsion of 6 μm (monodispersity 15) was obtained. This emulsion contained 1.0 mol of silver halide. To this emulsion, 11 mg of sodium thiosulfate and 14 mg of chloroauric acid were added to 1 mol of AgX, and chemically sensitized at 57° C. for 90 minutes. This chemically sensitized emulsion was divided into 10 equal parts, and these were divided into 10 parts as shown in Table 1.
-b] and the compound of general formula [II] were added in respective amounts to prepare samples Nos. 1 to 10. Furthermore, samples Nos. 091 to 10 in Table 1 each contained 7 mR of 0.4% solution of 1-phenyl-5-mer-8 captotetrazole as an antifoggant and 6-methyl-4-hydroxy-1,3,3a as a stabilizer. , 7-
150 nl of 1% solution of tetrazaindene.

Are there any other spreading agents? ;20% saponin aqueous solution 101,
20% solution of hydroquinone as 1611 hardener 3
% formalin aqueous solution as a hardening agent,
0.8 g of sodium-2,6-dichloro-1,3,5-triazine-4-olate was added, and further 35 g of a polymer latex of ethyl acrylate was added.

Each of these emulsions was coated on a film support with a silver content of 4.
2g/m2, and further as a protective layer,
An aqueous solution of 500 g of inert gelatin and 80 ml of C5% formalin. 12g of amorphous silica with an average particle size of 2μm
, 1.2 g of polymethyl methacrylate with an average particle size of 3 μm
The above emulsion layer and this protective layer were simultaneously coated so that the amount of gelatin added was 0.7 g/m2.

Each of the 10 types of samples obtained in this way was
Stepwise exposure was performed using a semiconductor laser light source, and a developing solution with the following formulation was applied using a Konica automatic developing machine GR-26 (manufactured by Konica Corporation).
Developed at 38°C for 12.4 seconds using a fixer,
It took hold immediately.

[Developer prescription] Pure water (ion exchange water) approximately 800 mj2
Potassium sulfite 60g Ethylenediaminetetraacetic acid disodium salt 2g Potassium hydroxide 10.535-Methylbenzotriazole 150 mg Diethylene glycol 251-phenyl-4,
4-dimethyl-3-pyrazolidinone 300mg1
-Phenyl-5-mercapto 60mgTetrazole 60mgPotassium bromide 3.5gHydroquinone 20gPotassium carbonate 15gThe following [α] compound 25+ngPure water (ion-exchanged water) was added and heated to 1°C.

CH2CH2CIhNHCON)ICH2CHzSC2
Hs [Fixer prescription] (Composition A) Ammonium thiosulfate (72.5% W/V aqueous solution) 240m
A Sodium sulfite 17g
Sodium acetate trihydrate 6.5g Boric acid 6g Sodium citrate dihydrate 2g Acetic acid (90%
W/W aqueous solution) 13.6mJ2 (composition) Pure water (ion exchange water) ' 17m
A Sulfuric acid (50% W/W aqueous solution) 4.7
g Ammonium sulfate (^1203 equivalent content is 8.1%W)
/W aqueous solution) When using 26.5 g of fixer, the above composition A was dissolved in 500 ml of water in that order, and finished to IJl.

The pH of this fixer was about 4.3.

1 Sensitivity was measured for these treated samples, and the measurement results are shown in Table 1.

Note that the sensitivity is calculated by setting the reciprocal of the exposure amount of fog density (unexposed area) + 3.0 to the sensitivity immediately after coating sample No. 011 to 100.
It is expressed as a relative value. Further, a sample heat-treated at 55° C. for 3 days after coating and a sample heated 200 days after coating were also measured after the above-mentioned treatment.

2 As is clear from Table 1 below, the sensitivity of the silver halide photographic material of the present invention is extremely stable over time after coating and even during storage at high temperatures; It shows that it is excellent.

Example 2 The particle composition in Example 1 was kept as is, and the particle size was changed to 0.
Sample No. 36 μm was prepared in the same manner as in Example 1 except that the sensitizing dye and compound n used in the present invention were changed as shown in Table 2.

111-20 were produced. The developing solution and fixing solution used in the processing were also the same as in Example 1, and the processing was also the same. All other evaluations were made in the same manner as in Example 1. The results of these measurements are shown in Table 2. However, the sensitivity was expressed as a relative value, with the sensitivity of sample No. 11 immediately after coating being 100.

5. As is clear from Table 2, the silver halide photographic material of the present invention has high sensitivity and is stable over time after coating and during storage at high temperatures. Excellent sensitivity stability can be obtained due to thermometry.

[Effects of the Invention] According to the present invention, the formula [I-a] and the formula [I-
b] and the general formula [! By using the compound represented by I] in combination, a silver halide photographic material with high sensitivity and excellent sensitivity stability can be obtained, with no change in sensitivity due to aging or thermostat.

Claims (1)

[Scope of Claims] At least one of the supports has at least one silver halide emulsion layer, and the silver halide emulsion layer contains compounds of the general formula [I-a] and [I-b]. A silver halide photographic material comprising at least one of the sensitizing dyes represented by the following formulas and at least one compound represented by the general formula [II]. General formula [I-a] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ General formula [I-b] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ General formula [II] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [ In the formula, Y_1_1, Y_1_2, Y_2_1, Y_2
_2 each represents a nonmetallic atomic group necessary to complete a 5- or 6-membered nitrogen-containing heterocycle, R_1_1, R_1_2,
R_2_1 and R_2_2 each represent a substituted or unsubstituted alkyl group, aryl group, or aralkyl group, R_1_3,
R_1_4, R_1_5, R_2_3, R_2_4, R
_2_5, R_2_6 are hydrogen atoms, substituted or unsubstituted alkyl groups, alkoxy groups, phenyl groups, benzyl groups, ▲
There are mathematical formulas, chemical formulas, tables, etc. Represents ▼. Here W_1
, W_2 each represent a substituted or unsubstituted alkyl group (the number of carbon atoms in the alkyl moiety is 1 to 18, preferably 1 to 4), or an aryl group, and W_1 and W_2 are connected to each other to form a 5-membered ring. Or a 6-membered ring can be formed. X_1 and X_2 represent anion groups. R_3_1 represents a hydrogen atom or an acetyl group, R_3_
2, R_3_3, R_3_4, R_3_5 are hydrogen atoms,
Represents a substituted or unsubstituted alkyl group. ]