JPS63239434A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To improve the tone of a silver image, and to reduce the pressure desensitization and the pressure fogging of the titled material by using a silver chlorobromide particle or silver chloride particle which has a specified particle size distribution curve and is composed of a cubic crystal, for the titled material. CONSTITUTION:The particle size distribution curve of the silver halide particle contd. in an emulsion layer has >=2 peaks, and one or more of the interval between the mode of the each peaks and the mode of its adjacent peaks is >=0.05mum respectively. And, said particle is substantially composed of the cubic crystal of the silver chlorobromide or the silver chloride. In case that the peak of the particle size distribution is >=3, two or more mode intervals having >=0.05mum may present. Said emulsion is composed from a mixture of the plural emulsions, and is preferably prepared by mixing with 3 or more kinds of monodisperse emulsions. Thus, even if the high concn. part of said particle has a warm tone, while the low concn. part of said particle has a cold tone, as the whole, the image having the preferable color tone is obtd., and the pressure desensitization and the pressure fogging of the titled material are reduced.

Description

Detailed Description of the Invention (Industrial Application Field) The present invention relates to a silver halide photographic light-sensitive material, and particularly to a silver halide black-and-white photographic light-sensitive material for observing silver images, which has excellent color tone and excellent pressure resistance. This invention relates to a silver halide photographic material for black and white printing.

(Prior Art) In silver halide black-and-white photographic materials for observing silver images, the color tone (color of the silver image) is very important. To adjust this, various color toning agents have been used in the past. That is, LnFi, which is a compound having a mercapto group,
These include nitrogen-containing heterocyclic compounds.

In general, the larger the size of the silver halide grains, the cooler the temperature.
On the other hand, the smaller the size, the better the temperature control. In addition, it is generally preferable that the low-density areas of the image formed are cool-toned and the high-density areas are warm-toned, which makes the highlights look neat and makes the whole look calm. This change in color tone has hitherto been achieved by using polydisperse emulsions. However, conventional polydisperse emulsions have a mixture of various crystal habits, have many defects inside the grains, and are affected by the pressure applied before development.
Desensitization (pressure desensitization) or blackening (pressure staining) easily occurs in those areas, so that sufficient care must be taken when handling the photosensitive material.

(Object of the Invention) An object of the present invention is to provide a silver halide photographic material for black-and-white printing for observing silver images, which has excellent overall color tone, has little pressure desensitization and pressure fog, and is easy to handle. The purpose of this invention is to provide a silver black and white photographic material.

Furthermore, it is an object of the present invention to provide a silver halide photographic light-sensitive material capable of forming a silver image having a cool tone in a low density area and a temperature tone in a high density area.

(Structure of the Invention) The above object of the present invention is to provide a photographic light-sensitive material having at least seven light-sensitive silver halide emulsion layers on a support.
The grain size distribution curve of silver halide grains in the emulsion layer is 2.
It has more than one peak, and the distance between the mode of the winter mountain and the mode of the adjacent mountain.

This was achieved in a silver halide photographic light-sensitive material in which at least seven grains have a grain size of 0.0 jμ or more, and the silver halide emulsion grains are silver chloride or silver chlorobromide consisting essentially of cubic crystals. Here, "particles consisting essentially of cubic crystals" means that all or a majority of their surfaces are (10
0) refers to a particle that is a plane. In the present invention, the mode spacing is 0.0. tμ or more, but o, or ~ 0° Qμ, especially o, or ~ 0. /! Preferably, it is tμ. If there are three or more peaks in the particle size distribution, there may be two or more mode spacings of o, orμ or more.

With the above configuration, silver halide groups with a large particle size distribution curve (Mode C mode) have a large grain size, and the sensitivity is high and the resulting image is a cold image. ) can be controlled to a cool tone,
Those in which the mode of the grain size distribution curve is small, that is, the small grain size silver halide group Fi sensitivity is low, resulting in images with a warm tone, so the color tone of high density areas (shadows) can be controlled in a warm tone, which is preferable overall. A toned image is obtained.

The above-mentioned emulsion with a grain size distribution curve having two or more peaks and consisting essentially only of cubic crystals may be a mixture of multiple emulsions, or may be obtained by adding seed grains midway through the manufacturing process of one emulsion. It may also be prepared by adding a method. Alternatively, multiple emulsions may be used for multilayer coating. Preferably, a mixture of a plurality of monodisperse emulsions is used. More preferably, a mixture of three or more types of monodispersed emulsions is used. The monodisperse emulsion referred to here refers to one in which the dispersion coefficient C (standard deviation of the grain size divided by the average grain size) is less than or equal to 04I. Preferably it is 1 rqh or less.

In the present invention, known silver halide solvents such as ammonia and thioether compounds can be used during grain formation. These silver halide emulsions contain at least one of the following salts (soluble salts): iridium, thallium, noradium, rhodium, zinc, nickel, cobalt, uranium, thorium, strontium, tungsten, and platinum. Preferably. Addition position 1
time) is arbitrary.

The silver halide in the halogenated photosensitive material used in the present invention is silver chloride or silver chlorobromide, which has high solubility in a developer and has a high speed of development.

Silver chlorobromide contains no or substantially no iodine (
(more than 1 mole) consisting of silver halide grains.

Preferably, the proportion of silver chloride is equal to or greater than the molar width of three layers.

The number of halogen pairs of particles corresponding to the Fuyuyama mode may be the same or different.

In an emulsion made of silver iodobromide or silver bromide having a grain size distribution similar to that of the silver halide emulsion of the present invention, both the low-density part and the high-density part of the obtained silver image have a cool tone, and the overall image g1h It becomes undesirable.

The size of the silver chloride or silver chlorobromide particles of the present invention is 0°2 to 1
．． Qμ, particularly preferably 0.3 to 0.7μ.

In the present invention, when the silver halide grain size distribution consists of λ peaks, the grains belonging to the larger peak have a width of 70 to It is preferable.

Also, when there are three mountains, the particles belonging to the maximum particle size (7) mountains have the total r~Job<heavy! -), especially 10N, and the particles belonging to the smallest particle size pile are l! ~Aj4, especially Ko. The silver halide emulsion is preferably 604 to 604.Although a so-called primitive emulsion without chemical sensitization can be used, it is usually chemically sensitized. For chemical sensitization, the above-mentioned book by Glafkides or Zellkman et al.
Rundlagen der Photograp
hischenProzesse mit Silb
erhalogeniden.

(Akademische Verlagsgesel
lschaft.

/ri+r) can be used.

That is, a sulfur sensitization method using compounds such as thiosulfates, thioureas, thiazoles, and rhodanines, and activated gelatin, and using stannous salts, amines, hydrazies, formamidine sulfines, silane compounds, etc. It can be used alone or in combination with a reduction sensitization method, a noble metal sensitization method using complex salts of metals of Group I of the periodic table, such as platinum, iridium, /g radium, etc. in addition to total complex salts. However, from the viewpoint of fogging, it is preferable that no noble metal sensitization be applied to the sensitive material for printing.

Further, for the purpose of increasing sensitivity, increasing contrast, or accelerating development, it may contain, for example, thioether compounds, thiomosphorins, quaternary ammonium salt compounds, urethane derivatives, urea derivatives, imidazole derivatives, 3-pyrazolidones, and the like.

Although it is advantageous in the present invention to use gelatin as the binder or protective colloid in the photographic emulsion, other hydrophilic colloids can also be used.

For example, cellulose attractants such as hydroxyethyl cellulose, sugar derivatives such as starch derivatives; single or copolymer materials such as polyvinyl alcohol, polyhinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polyacrylamide, etc. A wide variety of synthetic hydrophilic polymeric materials such as polymers can be used.

In addition to lime-treated gelatin, acid-treated gelatin may be used for gelatin processing, and gelatin hydrolysates and gelatin enzymatically decomposed products may also be used.

In the present invention, the support is preferably a water-impermeable support. A water-impermeable support refers to a support to which no or very little water permeates. Examples of such a support include a whitened plastic film prepared by coating a transparent plastic film such as cellulose triacetate or polyethylene terephthalate with a white pigment such as titanium white dispersed in a binder such as gelatin, or a hydrophobic polymer such as polyethylene. Double-sided laminated paper support etc. Preferably 20% due to the ease of printing failures.
The thickness is 0μ or more.

The photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material of the present invention may contain coating aids, antistatic properties, improvement of slipperiness, emulsification dispersion, prevention of adhesion and improvement of photographic properties (for example, acceleration of development, increase in contrast, It may contain various known surfactants for various purposes such as sensitization), such as saponin, polyoxyethylene compounds, glycidol derivatives (such as alkenylsuccinic acid polyglycerides), fatty acid esters of polyhydric alcohols, and sugars. alkyl ester m, also a nonionic surfactant such as urethanes or ethers;
triterpenoid saponins, alkyl carboxylates,
Anionic surfactants such as alkylbenzene sulfonates, alkyl sulfates, alkyl phosphates, N-acyl-N-alkyl taurines, sulfosuccinates, sulfoalkyl polyoxyethylene alkylphenyl ethers, diamino acids, amino acids, etc. Double-faced surfactants such as alkyl sulfonic acids, aminoalkyl sulfuric acid or phosphoric acid esters, alkyl betaines, amine imides, amine oxides, etc.; Cationic surfactants such as heterocyclic ammonium salts and aliphatic or heterocyclic phosphonium sulfonium salts can be used. Fluorine-containing surfactants are preferably used for the purpose of preventing static electricity.

In the photographic light-sensitive material of the present invention, the photographic emulsion layer and other hydrophilic colloid layers may contain a dispersion of a water-insoluble or sparingly soluble synthetic polymer for the purpose of improving dimensional stability. For example, a polymer containing as a monomer component alkyl (meth)acrylate, glycidyl (meth)acrylate, etc. alone or in combination, or a combination of these with acrylic acid, methacrylic acid, etc. can be used.

The silver halide emulsion of the present invention can be spectrally sensitized with a merocyanine dye, a cyanine dye, or the like.

For example, in the regular area, Tokukai Sho! ! -2714
Same issue! ! -/4t74t3, and in the ortho region, JP-A-Sho≠ff-14442j, same! /-J/ko 21r, special public show≠7-ko! As described in Japanese Patent No. 372, they can be used alone or in combination.

Furthermore, spectral sensitization on the long wavelength side is possible, for example, in JP-A-Sho! /
This can be carried out using the cyanine dye having a longer methine chain described in Publication No. -726/μQ, and supersensitization can also be carried out arbitrarily using a combination of dyes. The sensitizing dye may be added at any point during silver halide grain formation, during water washing, before chemical sensitization, during chemical sensitization, or after chemical sensitization and before coating.

The photographic material of the present invention may contain an inorganic or organic hardener in the photographic emulsion layer or other hydrophilic colloid layer.

For example, chromium salts, aldehydes (formaldehyde, geltaraldehyde, etc.), N-methylol compounds, activated vinyl compounds (/.

3, j-) cyclolyloyl-hexahydro-3-triazine, bis(hinylsulfonyl) methyl ether, etc.)
, active halogen compound (2,≠-dichloro-6-hydroxy-5-)riazinato), mucohalogenic acid, etc. can be used alone or in combination.

The photosensitive material of the present invention contains water-soluble dyes (such as oxonol dyes, hemioxonol dyes, styrene dyes, merocyanine dyes, cyanine dyes, and azu dyes) for use as filter dyes in the hydrophilic colloid layer or for various purposes such as preventing irradiation. .) may be contained.

The silver halide photosensitive material of the present invention may contain a known toning agent, antifoggant or stabilizer.

Color toning agents, antifoggants or stabilizers that may be contained include:
Mercaptos, benzothiacilium salts, nitroindazoles, nitrobenztriazoles, chlorobenzimidazoles, bromobenzimidazoles, aminotriazoles, benztriazoles, nitrobenztriazoles, benzenethiosulfonic acids, benzenesulfinic acids, Benzene sulfonic acid amide, azaindenes [e.g. triazaindenes, tetraazaindenes (%VC4A-hydroxy substituted (/, J, 3a).

7) Tetraazaindenes], etc. Preferably, as a color toning agent or an antifoggant, JP-A No. 7-///10, JP-A No. 4t7-JJJtJ, JP-A-Kokai Sho! 7-/≠! The photosensitive material contains a compound containing an S atom such as a thione group or a mercapto group as described in No. 3. More preferably, a compound containing an S atom that changes the color is incorporated into the photosensitive material from 2'1.10-' to 100% per mole of Ag. You can follow the usual method.

Exposure times range from 7,710 seconds to 100 seconds, which is normally used with a milling machine, as well as exposure times shorter than 7,710 seconds, and exposure times using, for example, xenon flash lamps or cathode ray tubes.
Exposures of /10' to //106 seconds can be used, or exposures longer than 100 seconds can be used. Like [
7〈 is used with an exposure time of l/10 seconds to ioo seconds.

Even better than the exposure accuracy of a normal milling machine/
It is used with an exposure time of /≠ seconds to 100 seconds.

For the photographic processing of the light-sensitive material of the present invention, any of the known photo-processing methods for forming silver paintings can be used.

The present invention will be explained in more detail with reference to Examples below.

Examples/(1) Preparation of photosensitive silver halide emulsion Polydisperse emulsion I was prepared as follows. That is, potassium bromide / / 1. Sodium chloride t.

Otsu? An aqueous solution containing 209 silver nitrate was added instantaneously to an acidic (pH=≠) aqueous solution containing 1tt2 gelatin while stirring vigorously, and an aqueous solution containing potassium bromide J4Cf, sodium chloride 24tf and an aqueous solution containing silver nitrate rot were added in an instant. was added using a double jet method to obtain an average particle size of 0. ≠t
μ spherical polydisperse emulsion (silver bromide 10 molar ratio, dispersion coefficient 22
(in charge) and mourning. Thereafter, it was washed with water using a conventional precipitation method, and further sulfur sensitized to obtain a polydisperse emulsion I.

Monodispersed emulsions (1), (2) and (2) were prepared as follows: 1, ie, sodium chloride≠, 4tp.

Potassium bromide Je is added to an acidic (pH=≠) aqueous solution containing
? , an aqueous solution containing 22 tf of sodium chloride.

The following three types of cubic monodisperse emulsions [silver bromide!
θmol staff>tv! 4 were made.

Average grain size Dispersion coefficient 0, tμ /A ratio → Emulsion π O0 Hiroj /≠悌 → Emulsion ■o, 3s
/34 →The emulsion layer is then υ by the usual precipitation method.
After washing with water and further sulfur sensitization, monodisperse emulsion II, m,
Illll yield dispersion emulsions V and M were prepared in the same manner as π, ■, and ■ by changing the ratio of 1 lium bromide to sodium chloride.

Silver bromide ratio Average particle size Dispersion coefficient Ao mole 4 0. jta 74% -+emulsion■4
4 0.3 to cO%! /74 −+emulsion layer (
21 Preparation of coating samples Samples 1 to 7 were prepared by applying each layer of the following formulation sequentially from the support side to a paper support laminated on both sides with polyethylene (thickness 200μ) and applying pressure.

(Emulsion layer) Binder: Gelatin≠, 7f/m2 Amount of silver coated: Listed in Table 1 including the type of milkyelitis O9 Hirofn
g/m2 (Surface retention 1111) Binder: Gelatin 2.097m2 Coating aid: Dodecylbenzenesulfonic acid) IJum to/m2
, colloidal silica θ, 397 m2 (average 0.0j) t) H film agent: 4A
-Cyclolobe-Hydroxy/.

j, j-) Riazine sodium salt 0.01rf7m2 (3) Evaluation of coated samples These sample tubes were coated at a temperature and humidity of 50ctz% RH.
Stored for days. Evaluate each sample using the following method. The evaluation results are shown in Table 1.

A) Color tone evaluation Neono 1! /Presto 4100 (Fuji Photo Film■
These coated samples were printed through the Tsubamebai negative image obtained by photographing and developing using Fuji Nobitol developer (manufactured by Fuji Photo Film Co., Ltd.) and diluted with water to /:/. After developing and stopping at 2o'C for 20 seconds using
With Fuji Fix (manufactured by Fuji Photo Film)! After fixing for a minute, washing with water, and drying, the color PAt of the image was evaluated.

O: Preferable for low concentration part cold and high concentration part @ tone.

X...Unfavorable.

B) Evaluation of pressure property Each sample was exposed to light (arz
Before or after 4A0y, 7 seconds exposure to %1ioo lux tungsten light, scratch the sample with a Q, YR sapphire needle with a load of -C109-V2009, then develop, stop, fix, After washing with water and drying, the scratched area was evaluated for pressure desensitization and the degree of pressure fog.

○...No practical problem.

×...It is a practical problem.

As can be seen from Table 1, it can be seen that Sample Yahiro-7 to which the present invention was applied had excellent pressure resistance and a desirable image tone.

Patent Applicant: Fuji Photo Film Co., Ltd., June 2-2, 1939, Commissioner of the Patent Office, Trademark 1, Indication of Case: 1986 Patent Application No. 731Pl No. 2,
Title of the invention Silver halide photographic light-sensitive material 3, Relationship to the case of the person making the amendment Patent applicant contact information 〒10
6 4, 2-26-30 Nishi-Azabu, Minato-ku, Tokyo, Subject of amendment: ``Detailed explanation of the invention'' column 5 of the specification, Contents of the amendment The description of the ``Detailed explanation of the invention'' section of the specification is as follows. Correct as shown.

After "Contained in the 2XIO light-sensitive material" on page 13, line it, "The photographic light-sensitive material of the present invention contains stilbene in the photographic emulsion layer, other hydrophilic colloid layers, or the undercoat layer of the support." The whitening agent may contain a whitening agent such as a triazine type, an oxazole type, or a coumarin type.These whitening agents may be water-soluble, or a water-insoluble whitening agent may be used in the form of a dispersion. Specific examples of fluorescent brighteners are described in U.S. Patent λ, 6J.
2.70/issue, IerJ3. /1,9. rll-0 issue,
Same J, J! ? , No. 10, British patent rj2.075,
It is described in J/J, No. 763, etc. In the reflective photosensitive material of the present invention, the whiteness of the white background is increased,
Highlight '(rElimination 2) Page 1A, line λ, "O1zμ" tro, toμ'' is corrected.

3) Page 14, line 3 [o,uB@ "0.≠jμ" and correct it.

4) Page 76 "0, J JJ "o, ssμ" and correct it.

5) 1st page/Ith row ro, ryd ro, zjiμ” and correct it.

6) Page 76/row [o, 3z, J "o, 3rμ" and correct it.

7) Page 17/line 7 and correct it.

8) Page 1, line Q "Print on these coated samples" "Expose these coated samples to light" and correct it.

9) Replace the full text on page 20 with the full text on Attachment-1.

Claims (1)

[Claims] In a photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer on a support, the grain size distribution curve of silver halide grains in the emulsion layer has two or more peaks, and the mode of each peak is and an adjacent mountain mode is 0.005μ or more, and the silver halide emulsion grains are silver chlorobromide or silver chloride consisting essentially of cubic crystals. A silver halide photographic light-sensitive material.