JPS62148942A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To improve sensitivity in the infrared spectral region and storage stability of a photosensitive material by specifying the average particle diameter of a matting agent to be added to the emulsion layer of the photosensitive material spectrally sensitized in the infrared region and/or to other hydrophilic colloidal layers. CONSTITUTION:The maximum sensitivity of the silver halide photographic sensitive material is controlled to the wavelength region longer than 700nm by adding an optional IR sensitizing dye, preferably, in an amount of 5X10<-7>-X10<-3>mol per mol of silver halide to the silver halide emulsion layer. The matting agent to be used as an average particle diameter of, preferably, 1-10mum, if over that range, moire is caused, and if below it, slidability and antistaticness are deteriorated. It is used, preferably, in an amount of 5-100% of the binder of the layer to be added on the dry weight basis, thus permitting moire trouble in the longer wavelength region to be prevented, and the obtained photosensitive material to have no static trouble and appropriate slidability.

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention relates to a silver halide photographic material that is spectrally sensitized in the infrared region, and in particular has improved sensitivity and storage stability in the infrared region. This invention relates to silver halide photographic materials.

[Conventional technology]

One of the exposure methods for photographic light-sensitive materials is a so-called scanner that 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. An image forming method based on this method is known. There are various types of recording devices that utilize a scanner-type image forming method, and the recording light sources for these scanner-type recording devices have traditionally been glow lamps, xenon lamps, mercury lamps, tungsten lamps, light-emitting diodes, etc. However, all of these light sources have the practical problem of low output and short lifespan.To solve these problems, coherent lasers such as Ne-Ne laser, argon laser, HQ-Cd laser, etc. There are scanners that use a laser light source as a scanner-only light source.These can obtain high output, but they are large and expensive, require a modulator, and are not sensitive to light because they use visible light. There are problems such as the -L-flight of the monthly interest is limited and the handling is poor.

On the other hand, semiconductor lasers are small, inexpensive, easy to modulate, and have a longer lifespan than the lasers mentioned above. Furthermore, since it emits light in the infrared region, a bright safelight can be used, which has the advantage of improving handling efficiency.

The wavelength of this semiconductor laser is long-wavelength infrared light of 700 nm or more, and when a photographic light-sensitive material is exposed to infrared light of 700 nm or more, moiré tends to occur if the surface of the photographic light-sensitive material has irregularities. Note that moire is a phenomenon well known to those skilled in the art, and is a phenomenon in which an image appears striped.

Further, photographic light-sensitive materials used in image forming methods using a single scanner usually contain a matting agent in an emulsion layer or a layer above the emulsion layer. The purpose of including the man-nod agent in this way is to (al) prevent the static that tends to occur when pulling out the required amount of film from a roll-shaped film, (bl)
This is to create appropriate slipperiness and (C) to prevent sticking.

Therefore, even if a matting agent is contained in a photographic light-sensitive material, it is necessary to prevent moire from occurring.

[Purpose of the invention]

The purpose of the present invention is to eliminate the problems of the prior art mentioned above,
An object of the present invention is to provide a silver halide photographic light-sensitive material that has maximum sensitivity on the longer wavelength 14 side than 700 nm, does not cause moiré, and has excellent handling properties such as no static failure during handling and appropriate sliding properties. .

[Structure and operation of the invention]

The above object is to provide a silver halide photographic material having at least one light-sensitive silver halide emulsion layer on a support. The maximum sensitivity of 1 is 7
This can be achieved by a structure in which the photosensitive halogenated emulsion layer and/or other hydrophilic colloid layer of the photographic light-sensitive material contains a matting agent having a wavelength longer than 00 nm and having an average diameter of 10 μm or less. .

Preferably the maximum sensitivity is between 700 nm and 900 nm. The matting agent preferably has an average particle size of 0/1m to 1μ
It is m. (In this specification, the average particle diameter of Pine 1 agent is that of several groups.) As mentioned above, in order to make the maximum sensitivity of the silver halide photographic light-sensitive material to the longer wavelength side than 700 nm, , adding an infrared sensitizing dye, etc. can be used.

The infrared sensitizing dye used in this case may be any dye;
For example, the following general formulas (I a), (I b) and (I
A compound represented by c) is preferably used.

General formula (Ia) (x-) n-1 General formula (I b) RI R2 General formula (Ic) In the formula, R1 and R2 may each be the same or W, and each is an alkyl group (preferably Number of carbon atoms: 1~
8. For example, methyl group, ethyl group, propyl group, butyl group, pentyl group, heptyl group, etc.), substituted alkyl group (substituent such as carboxy group, sulfo group, cyano group, halogen atom (for example, fluorine atom, chlorine atom) , bromine atom, etc.), hydroxy group, alkoxycarbonyl group (8 or less carbon atoms, e.g. methoxycarbonyl group, ethoxycarbonyl group, benzyloxycarbonyl group, etc.), alkoxy group (7 or less carbon atoms, e.g. methoxy group, ethoxy group) , propoxy Jl (butoxy group, benzyloxy group, etc.), aryloxy group (e.g. phenoxy group, p-tolyloxy group, etc.), acyloxy group (3 or less carbon atoms, e.g. acetyloxy group, propionyloxy group, etc.), Acyl group (8 or less carbon atoms, such as acetyl group, propionyl group, hendiyl group, mesyl group, etc.),
Carbamoyl group (e.g. carbamoyl group, N,N-dimethylcarbamoyl group, morpholinocarbamoyl group, piperidinocarbamoyl group, etc.), sulfamoyl group (e.g. sulfamoyl group, N,N-dimethylsulfamoyl group, morpholinosulfonyl group, etc.), An alkyl group (the number of carbon atoms in the alkyl moiety is 6 or less) substituted with an aryl group (for example, a phenyl group, p-hydroxyphenyl group, p-carboxyphenyl group, p-sulfophenyl group, α-naphthyl group, etc.). Two or more of these substituents may be condensed and substituted with an alkyl group. ).

R represents a hydrogen atom, a methyl group, a methoxy group, or an ethoxy group.

R1 is a hydrogen atom, a lower alkyl group (e.g. methyl group, ethyl group, propyl group, etc.), a lower alkoxy group (e.g. methoxy group, ethoxy group, propoxy group, butoxy group, etc.)
, phenyl group, benzyl group, carbon atoms 1 to 18, preferably 1 to 4, such as methylnor, ethyl group, propyl group, butyl group, hensyl group, phenylethyl group), Ororinor, 1. % (e.g. phenyl group, naphthyl'+4,
Tolyl J%, p-chlorophenyl group, etc.), Wl
and W2 can also be linked to each other to form a 5- or 6-membered nitrogen-containing heterocycle.

D represents a group of atoms necessary to complete a divalent ethylene bond, e.g. ethylene or triethylene, and this ethylene bond is replaced by one, two or more suitable groups, e.g. 4 alkyl group (e.g. methyl group,
Ethylene, (, propyl group, isopropyl group, butyl group, etc.), halogen atom (e.g. chlorine atom, bromine atom, etc.), or alkoxy group (1 to 4 carbon atoms, e.g. mel-oxy group, ethoxy group, propoxy even if substituted with a group, isoproboxyno(, butoxy, etc.)
;stomach.

Dl represents a hydrogen atom. However, Dl can also form a divalent ethylene bond as defined in I-.

Z and Zl each represent a nonmetallic atomic group necessary to complete a 5- or 6-membered nitrogen-containing heterocycle, such as a thiazole nucleus [e.g., benzothiazole, 4-chlorobenzothiazole, 5-chlorobenzothiazole, 6- Chlorbenzothiazole, 7-chlorobenzothiazole, 4-methylbenzothiazole, 5-methylbenzothiazole, 6
-Methylbenzothiazole, 5-bromobenzothiazole, 6-bromobenzothiazole, 5-iodobenzothiazole, 5-phenylbenzothiazole, 5-methoxybenzothiazole, 6-methoxybenzothiazole,
5-Ethoxybenzothiazole, 5-carboxybenzothiazole, 5-ethoxycarbonylbenzothiazole, 5-phenethylbenzothiazole, 5-fluorobenzothiazole, 5-trifluoromethylbenzothiazole, 5゜6-simethylbenzothiazole, 5- Hydroxy-6-methylbenzothiazole, tetrahydrobenzothiazole, 4-phenylbenzothiazole, naphtho(
2,1-d) thiazole, natu[1°2-d]thiazole, naphtho(2,3-d)thiazole, 5-methoxynaphtho(1,2-d)thiazole, 7-nitoxynaphtho(2,ld)thiazole , 8-methoxynaphtho (2,1
-d) Thiazole, 5-methoxynaphtho(2,3-d)
thiazole etc.], selenazole cores [e.g. benzoselenazole, 5-chlorobenzoselenazole, 5-methoxybenzoselenazole, 5-methylbenzoselenazole,
5-hydroxybenzoselenazole, naphthoC2,1-
d) selenazole, naphtho(1,2-d) selenazole, etc.], oxazole nucleus [benzoxazole, 5-chlorobenzoxazole, 5-methylbendiogizazole, 5-bromobenzoxazole, 5-fluorobenzoxazole, 5- Phenylbendiogizazole, 5-
Methoxybenzoxazole, 5-1-lifluoropenzoxazole, 5-hydroxybenzoxazole, 5-carboxybenzoxol 1-→Seal, 6-
Methylbenzoxazole, 6-chlorobenzoxazole, 6-medoxybenzoxazole, 6-hydroxybenzoxazole, 4゜6-dimethylbenzoxazole, 5-ethoxybenzoxazole, naphtho(2
, 1-d) oxazole, naphtho(1,2-d)oxazole, naphtho(2,3-d)oxazole, etc.], quinoline nucleus [e.g. 2-quinoline, 3-methyl-2-quinoline, 5-ethyl-2 -quinoline, 6-methyl-2-quinoline, 8-fluoro-2-quinoline, 6-medoxy 2
-quinoline, 6-hydroxy-2-quinoline, 8-chloro-2-quinoline, 8-fluoro-4-quinoline, etc.),
3.3-dialkylindolenine core (e.g. 3.3-
Dimethylindolenine, 3.3-diethylindolenine, 3゜3-dimethyl-5-cyanoindolenine, 3.3
-dimethyl-5-methoxyindolenine, 3.3-dimethyl-5-methylindolenine, 3.3-dimethyl-
5-chlorindolenine, etc.), imidazole nuclei (e.g., 1-methylbenzimidazole, I=ethylbenzimidazole, 1-methyl-5-chlorobenzimidazole, 1-ethyl-5-chlorobenzimidazole, 1-
Methyl-5゜6-dichlorobenzimidazole, ■-ethyl-5.6-dichlorobenzimidazole, 1-alkyl-5-methoxybenzimidazole, 1-methyl-
5-cyanobenzimidazole, I-ethyl-5-cyanobenzimidazole, 1-methyl-5-fluorobenzimidazole, 1-ethyl-5-fluorobenzimidazole, 1-phenyl-5,6-dichlorobenzimidazole, ■ -Allyl-5,6-dichlorobenzimidazole, 1-allyl-5-chlorobenzimidazole,
1-phenylbenzimidazole, 1-phenyl-5-
chlorobenzimidazole, 1-methyl-5-trifluoromethylbenzimidazole, 1-ethyl-5-trifluoromethylbenzimidazole, 1-ethylnaphtho(1,1-d)imidazole, etc.), pyridine nuclei (e.g. pyridine, 5- Methyl-2-pyridine, 3-methyl-4
-pyridine, etc.). Among these, thiazole nuclei and oxazole nuclei are preferably used. More preferably, a benzothiazole nucleus, a naphthothiazole nucleus, a naphthoxazole nucleus, or a benzoxazole nucleus is advantageously used.

X represents an acid anion.

n represents 1 or 2.

q represents 2 or 3.

A particularly useful 4-quinoline nucleus-containing dicarbocyanine dye that can be used in the present invention is represented by the following general formula (Tl).

General formula (I[) (X+-)n,-+ In the formula, R4,l and R6 represent R+ and Rz, respectively.

R6 represents the same meaning as R3. However, R6 is preferably a lower alkyl group or a benzyl group.

■ is a hydrogen atom, a lower alkyl group (e.g. methyl group, ethyl group, propyl group, etc.), an alkoxy group (e.g. methoxy group, ethoxy group, butoxy group, etc.), a halogen atom (e.g. fluorine atom, chlorine atom, etc.), substituted alkyl It does not represent a group (e.g. trifluoromethyl group, carboxymethyl group, etc.).

Z2 represents the same meaning as Z and Z.

Xl represents the same meaning as X.

m, R6 and p each represent 1 or 2.

Examples of the infrared sensitizing dye used in the present invention are shown below (I-
1) ~(I-20), (II-1) ~(l]-2
0), (]II-1), (I[[-2) not shown. However, the present invention is not limited to these infrared sensitizing dyes.

lI Cz Hs C31
(q I -1l 1- CZH3CH□C0OH CZI+5 (CH2
) 3503-(T-5) (I-7) czars (
C1l□)2COO-(I-9) 1 1
I-CJs
CJs (I-12) 1 1do CJs
CZII5 (I-14) (I-15) H5C6C6115 (I-16) H-17) (I-18) C+(3 (I-20) H5C6CH+ (II-1) C211.

(II-2) (II-5) (ff-6) (II-7) (II-8) (n-9) (n-13) (CI(z)3SO3- (II-1,7) C511 ,,Ci,, - (Iff-1) II C2H5CZH5F (CHz)3SO3-C2H5 The above-mentioned infrared sensitizing dye used in the present invention preferably has a concentration of 5X10"' mol to 5XIO-
'mol, more preferably lXl0-6 mole-lX10-
3 mol, particularly preferably 2×10−6 mol−5×10−
It is contained in a silver halide photographic emulsion in a proportion of 4 moles.

The infrared sensitizing dye used in the present invention can be directly dispersed into the emulsion. In addition, these can be prepared using a suitable solvent,
For example, it can be dissolved in methyl alcohol, ethyl alcohol, methyl cellosolve, acetone, water, pyridine, or a mixed solvent thereof, and added to the emulsion in the form of a solution.

Ultrasonic waves can also be used for dissolution. ) 1; However, the method for adding the infrared sensitizing dye described above is described in U.S. Patent No. 3.
, 469,987, etc., a method in which a dye is dissolved in a volatile organic solvent, the solution is dispersed in a hydrophilic colloid, and this dispersion is added to an emulsion, Japanese Patent Publication No. 4
6-24185, etc., in which a water-insoluble dye is dispersed in a water-soluble solvent without dissolving it, and this dispersion is added to an emulsion; US Pat. No. 3,822.13.
A method of dissolving a dye in a surfactant and adding the solution to an emulsion as described in the specification of No. 5: JP-A-51-746
A method of dissolving a red-shifting compound as described in No. 24 and adding the solution to an emulsion; JP-A-5
A method such as that described in No. 0-80826 is used, in which a dye is dissolved in an acid substantially free of water, and the solution is added to an emulsion. In addition, 1 o U.S. Patent 2 for addition to emulsions
, No. 912,343, No. 3.3112.605, No. 2.996,287, No. 3,429.835, etc. can also be used. Further, the infrared sensitizing dye of the above general formula (1) may be uniformly dispersed in the silver halide emulsion before being coated on a suitable support, but it is of course possible to disperse the infrared sensitizing dye in any step in the preparation of the silver halide emulsion. It can also be distributed.

The infrared sensitizing dye used in the present invention can be used in combination with other sensitizing dyes. For example, U.S. Patent No. 3,70
No. 3,377, No. 2,688,545, No. 3, 3
No. 97.060, No. 3,615,635, No. 3.
628.964, British Patent No. L242,588, British Patent No. 1,293,862, Japanese Patent Publication No. 43-4936, Japanese Patent Publication No. 44-14030, Japanese Patent Publication No. 43-10773, U.S. Patent No. 3,416,927 , Japanese Patent Publication No. 43-4930, U.S. Patent No. 3,615,613, U.S. Patent No. 3,615,63
No. 2, No. 3,617,295, No. 3,635,7
Sensitizing dyes described in No. 21 and the like can be used.

Each layer of the photographic material of the present invention can contain a matting agent. For example, using finely divided inorganic powders such as silica, barium sulfate, calcium sulfate, zinc oxide, titanium oxide, desensitized silver halide, zinc carbonate in various forms dispersed in natural or synthetic vehicles. These are U.S. Patent Nos. 2,192,241, 1,201,905, and 3,257,206.
No. 3,437. /18. ! Kano, same No. 3.322,
No. 555, No. 3,411,907, No. 3.353
．． No. 958, No. 3,370,951, No. 3+61
5+55 April, British Patent No. 1,260,772, British Patent No. 3.635.714, British Patent No. 3.769,020, British Patent No. 4,029,504, British Patent No. 4,021,245,
West German Publication Box No. 2,529,321, British Patent No. 76
No. 0,775, U.S. Pat. No. 3,523,022, and U.S. Pat. No. 3,062,649.

Finely divided organic powders and beads can also be used, such as calcium organic salts, starches containing starch esters, wheat flour, arrowroot powder, india gum, talc, hardened deionized or demineralized gelatin, zein, Other composite materials such as various forms of cellulose, α,β-ethylenically unsaturated mono- and dicarboxylic acids, esters, halfesters and their sulfonic acid analogues (especially acrylic acid, methacrylic acid and their methyl esters), styrene , acrylonitrile, fluorinated ethylene polymers, and also materials such as polycarbonate and polyvinyl alcohol can be used as matting agents.

Regarding these, U.S. Pat. No. .005, No. 2.992.101,
Same No. 2,391,181, Same No. 2.701゜245, Same No. 3.516.832, Same No. 3,079,257
No. 3,443,946, No. 3,262,78
No. 2, British Patent No. 1,055,713, U.S. Patent No. 3
, 754.924 and 3.767.448.

The average particle size of the matting agent is preferably 10 μm to 1 μm. If the particle size of the matting agent is 10 μm or more, moiré may occur, which is not preferable. Moreover, if the thickness is less than 1 μm, the slipperiness and static property will be poor, which is not preferable. The amount used is 0.05 to 1.0, more preferably 0.05 to 0.5 in terms of dry weight ratio to the binder of the layer to which it is added.

In practicing the invention, the photographic emulsion may be
Chimi, by Glafkicles (P.)
e et Physique Photogra
phique (published by 1'au1Monte1, 19
1967), G. F. Duffin
Photographic Emuls
ionChemistry: The Focal
MakiB and Coat, published by Press, 196, 966, V, L, Zellkman et al.
ingPhotographic Emulsion
; The Focal Prass, 1964)
It can be prepared using the method described in et al. That is, any of the acidic method, neutral method, ammonia method, etc. may be used, and the method for reacting the soluble silver salt and soluble halogen salt may be any one-sided mixing method, simultaneous mixing method, or a combination thereof.

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 the 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, a silver halide emulsion having a regular crystal shape and a nearly uniform grain size can be obtained.

Two or more types of silver halide emulsions formed separately may be mixed and used.

Silver halides that can be used in the present invention include silver chloroiodide, silver iodobromide, silver chloride, silver chlorobromide, silver bromide, silver chloroiodobromide, etc., which are commonly used in silver halide photographic emulsions. It is optional. Silver chloroiodide or silver chlorobromide having a silver chloride content of 50 mol % or more is preferred.

In the process of silver halide grain formation or physical ripening,
A cadmium salt, a zinc salt, a lead salt, a thallium salt, an iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, an iron salt or a complex salt thereof, etc. may be present together.

In order to remove soluble salts from the emulsion after precipitation or physical ripening, the Tardel water washing method, which involves gelling gelatin, may be used. A precipitation method (flocculation) using gelatin derivatives (eg, acylated gelatin, carbamoylated gelatin, etc.) may also be used.

The silver halide emulsion is used after chemical ripening as usual.

For chemical ripening, for example Friese
r) ed. Die Grundl+igander
Photography prozess
e mit Silhor-halogeniden
(Yakademische VerlagsgeS
ellschaft.

(1968) pp. 675-734) can be used.

The silver halide grains used in the present invention can be subjected to reduction ripening at any point during production.

Reductive ripening may be carried out by stirring the emulsion under low pA, g conditions, ie by silver ripening, or by using a suitable reducing agent such as tin chloride, dimethylamine borane, hydrazine or thiourea dioxide.

In the practice of this invention, antihalation dyes and/or
Alternatively, an anti-irradiation dye can be used. Examples of such dyes include oxonol dyes, hemioxonol dyes, merocyanine dyes, cyanine dyes, and azo dyes, which have substantial absorption at long wavelengths of 700 nm or more. Specifically, among the dyes represented by the following general formulas (II/a) to (red), dyes having substantial absorption in long wavelength light of 700 nm or more are advantageously used.

General formula (IVa) R.

General formula (IVb) General formula (■d) In the formula, Q and Q may be the same or different,
Each represents an atomic group necessary to complete pyrazolone, barbylic acid, thiobarbylic acid, isooquinacylone, 3-oxythionaphthene, or 1,3-indanedione. Q2 represents an atomic group necessary to complete pyrazolone, barbylic acid, thiobarbylic acid, isoxacilone, 3-oxynaphthene, 1,3-indanedione, 2-thioxazolidione, rhodanine, and thiohydantoin. Z4 represents a nonmetallic atomic group necessary to complete benzothiazole, naphthothiazole, benzoxazole, and naphthoxazole. Ro is a hydrogen atom,
Represents a halogen atom or lower alkyl group. RI5 represents a substituted or unsubstituted alkyl group. Wo, Wl, W2
, W, and R4 each represent a hydrogen atom, an alkyl group, a substituted alkyl group, a nitro group, a cyano group, a halogen atom, an alkoxy group, a sulfo group, or a carboxy group. However, Wl
and W2, and W3 and W may be connected to each other to form a benzene ring. Vl, V2 and ■.

may be the same or different, and each represents an alkyl group or a substituted alkyl group. V4 represents a sulfo group or a carboxy group. R2 is 2 or 3, R3 is 1 or 2, n is 3 or 4, n, and R6 is 1.2 or 3, n.

represents 2.3 or 4, respectively.

Among the above dyes, the dye represented by (IVd) is particularly preferred.

In addition to the dyes represented by the above general formulas (IVa) to (IVd), other dyes may be used in combination. b) 1 As the dye used, for example, U.S. Patent No. 2.2711°78
Pyrazolone oxonol dyes described in US Pat. No. 2, diarylazo dyes described in US Pat. No. 2,956,879, US Pat.
styryl dyes and butadienyl dyes described in No. 7, merocyanine dyes described in U.S. Pat. No. 2,527,583,
U.S. Patent No. 3,486,897, U.S. Patent No. 3,652,2
84, merocyanine dyes and oxonol dyes described in U.S. Patent No. 3,718,472, U.S. Patent No. 3,976.6
Enaminohemioxonol dyes described in No. 61 and British Patent No. 584.609, British Patent No. 1,177.429, JP-A-115130-115130, British Patent No. 49-99620
No. 49-114420, U.S. Patent No. 2,533,
No. 472, No. 3,148,187, No. 3,177
゜078, same No. 3,247.127, same No. 3,54
No. 0,887, No. 3,575,704, No. 3,6
The dyes described in No. 53,905 may be used.

In addition, the silver halide photographic light-sensitive material of the present invention includes polyoxyethylene derivatives (British Patent No. 981°470,
Special Publication No. 31-6475, U.S. Patent No. 2,716,06
2), polyoxypropylene derivatives, and derivatives having a quaternary ammonium group.

Various compounds can be added to the photographic light-sensitive material of the present invention in order to prevent a decrease in sensitivity and the occurrence of fog during the manufacturing process, storage or processing of the light-sensitive material.

These compounds are nitrobenzimidazole, ammonium chloroplatinate, 4-hydroxy-6-methyl-1,3,3a, ? - Tetraazaindene, 1-phenyl-5-mercaptotetrazole, many heterocyclic compounds, mercury-containing compounds, mercapto compounds, metal salts, and many other compounds have been known for a long time. An example of a compound that can be used is the book by K. Mees: The Theory of Photography.
y of the Photo-graphics (3rd edition, 1966) pages 344 to 349, and other compounds include, for example, U.S. Patent No. 2,131,038 and the same. No. 2.694.7
Thiazolium salts described in US Pat. No. 16, etc.; azaindene salts described in US Pat. No. 2,886,437, US Pat.
．． Urazoles described in U.S. Patent No. 135, etc.; Sulfocatechols described in U.S. Patent No. 3,236,652, etc.; Oximes described in British Patent No. 623.448, etc.; U.S. Patent No. 2 , 403,927, 3,266.897, 3,397,987, etc., nitrones; nitroindazoles; U.S. Patent No. 2,839,40
Polyvalent metal salts (Polyvale
nt metalsalts) ; U.S. Patent No. 3,22
Thiuronium salt (th
iuronjum 5 alts) ; U.S. Patent No. 2,5
Examples include salts of palladium, platinum, and gold, which are described in No. 66.263, No. 2,597,915, and the like.

In carrying out the present invention, the silver halide photographic light-sensitive material may include a developing agent such as hydroquinone, catechols, etc.
Aminophenols; 3-virazolidones; ascorbic acid and its derivatives; reductones
s), phenylenediamines, or a combination of developing agents. The developing agent is used in the silver halide emulsion layer and/or other photographic layers (e.g. protective layer, interlayer, filter layer, antihalation layer, bank layer, etc.)
can be placed in The developing agent may be dissolved in a suitable solvent or used as described in U.S. Patent No. 2+592+368 or Buddhist Patent No. 1.
．． 505,778 in the form of a dispersion.

As a development accelerator, for example, U.S. Pat. No. 3,288.6
No. 12, No. 3.333.959, No. 3,345,
No. 1.75, No. 3i708.303, British Patent No. L
O98,748, West German Patent No. L14L531,
Compounds described in the same No. 1,183.78.1 etc. can be used.

Hardening of the emulsion can be carried out according to conventional methods. Examples of curing agents include aldehyde compounds such as formaldehyde and glutaraldehyde, ketone compounds such as diacetyl and cyclobentanedione, bis(2-chloroethyl urea), and 4,6-dichloro- 1,3,5-1-Ryazine, etc. U.S. Pat. No. 3,288.775, U.S. Pat. No. 2.732,
303, British Patent No. 974.723, British Patent No. L1 (
Compounds containing reactive halogens such as those shown in i7.207'T3-, divinylsulfone, 5-acetyl-1,3-'; acryloylhexahydro-1,3,5-1-riazine, Additionally, U.S. Patent No. 3,635,718, U.S. Patent No. 3,232
, No. 763, compounds with reactive olefins such as those shown in British Patent No. 994,869, N-hydroxymethylphthalimide, and other U.S. Patent Nos. 2 and 7.
N-methylol compounds such as those shown in U.S. Pat. No. 32,316, U.S. Pat.
Isocyanates such as those shown in US Pat. No. 3,017,280 and US Pat. No. 2.983.6, etc.
] Aziridine compounds as shown in No. 1 etc., U.S. Patent Nos. 2,725,294 and 2,725,29
Acid derivatives such as those shown in U.S. Pat.
．． 100.70, 1, etc., epoxy compounds as shown in U.S. Pat. No. 3,09L537, etc., U.S. Pat.
Isoxazole compounds as shown in No. 32L313 and No. 3,543,292, halogenocarboxaldehydes such as mucochloric acid, dioxane derivatives such as dihydroxydioxane and dichlorodioxane, or inorganic hard Film agents include chloramypan and zirconium sulfate. Moreover, instead of the above-mentioned compounds, compounds in the form of precursors such as alkali metal bisulfite aldehyde adducts, methylol derivatives of hydantoin, primary aliphatic nitroalcohols, etc. may be used.

A surfactant may be added alone or in combination to the photographic material of the present invention.

Although they are used as coating aids, they are sometimes applied for other purposes, such as emulsification and dispersion, improvement of sensitized photographic properties, antistatic properties, antiadhesion, and the like. These surfactants include natural surfactants such as Zabonin, nonionic surfactants such as alkylene oxides, glycerin, and glycidol, higher alkylamines, quaternary ammonium salts, and heterocycles such as lysine. , cationic surfactants such as phosphonium or sulfoniums, carboxylic acids, sulfonic acids, phosphoric acids, sulfuric acid ester groups, anionic surfactants containing acidic groups such as phosphoric ester groups, amino acids, aminosulfonic acids, sulfuric or phosphoric acids of amino alcohols. It is divided into amphoteric active agents such as esters.

In addition to gelatin as a protective colloid, the silver halide photographic emulsion used in the present invention contains acylated gelatin such as phthalated gelatin and malonated gelatin, cellulose compounds such as hydroxyethyl cellulose and carboxymethyl cellulose; Soluble starches: hydrophilic polymers such as polyvinyl alcohol, polyvinylpyrrolidone, polyacrylamide and polystyrene sulfonic acid may be added. In this case, the present invention preferably uses polyalkylene oxide compounds such as alkylene oxides having 2 to 4 carbon atoms, such as ethylene oxide, propylene-1,2-oxide, butylene-1,2-oxide, etc., preferably at least 10% of ethylene oxide. A condensate of a polyalkylene oxide consisting of units and a compound having at least one active hydrogen atom such as water, an aliphatic alcohol, an aromatic alcohol, a fatty acid, an organic amine, a hexitol derivative, or a block of two or more polyalkylene oxides. Copolymers and the like can be used.

Also, U.S. Patent No. 3.41L911, U.S. Patent No. 3,411,
No. 912, No. 3.142.568, No. 3.325
, No. 286, No. 3,547,650, Special Publication No. 1973-
Alkyl acrylates described in No. 5331 etc.
A polymer latex consisting of a homo- or copolymer of alkylmethacrylate-1-, acrylic acid, glycidyl acrylate, etc. can be included for the purpose of improving the dimensional stability of the photographic material, improving the physical properties of the film, etc.

The silver halide photographic material may also contain antistatic agents, plasticizers, optical brighteners, air fog inhibitors, toning agents, and the like.

The present invention can be applied to the sensitization of silver halide emulsions used in various color light-sensitive materials as well as black and white photographic emulsions.

The silver halide photographic emulsion is coated on a support together with other photographic layers if necessary. That is, it can be coated by a variety of coating methods including dip coating, air knife coating, curtain coating, or extrusion coating using a popper as described in U.S. Pat. No. 2,681,294.

U.S. Patent No. 2.76L791, U.S. Patent No. 3, as necessary.
No. 508.947, and No. 2,941,898AJ
It is also possible to apply two or more layers at the same time by the method described in, for example, Japanese Patent No. 3,526,528.

The emulsion is coated on a suitable support. Typical flexible supports include cellulose nitrate film, cellulose acetate film, cellulose acetate butyrate film, cellulose acetate film, polystyrene film, and polyethylene terephthalate film, which are commonly used in photographic materials. , polycarbonate film, other laminates of these, thin glass film, paper, etc. Baryta or α-olefin polymers, especially polyethylene, polypropylene,
Ethylene butene copolymer, etc., charcoal! α- of atoms 2 to 10
paper coated or laminated with olefin polymers;
By roughening the surface as shown in Japanese Patent Publication No. 47-19068, the adhesion with other polymeric substances is improved,
Supports such as plastic films that have improved printability also give good results.

These supports may be transparent or transparent depending on the purpose of the photosensitive material.
Make choices that are opaque. In addition, when it is transparent, it is not only colorless and transparent, but also dyes and pigments can be added to make it colored and transparent. This has been done for a long time with X-ray films, and is also described in the Journal of Varnish.
MPT E (J. SMPTE. Vol.
67, P296.

1958), etc.

Exposure to obtain a photographic image may be carried out using a conventional method. That is, any of various light sources including infrared light such as natural light (sunlight), tungsten electric lamp, cathode ray tube flying spot, light emitting diode, laser light (e.g. gas laser, YAG laser, dye laser, semiconductor laser, etc.) may be used. I can do it. Alternatively, exposure may be performed using light emitted from a phosphor excited by electron beams, Y-rays, Y-rays, α-rays, or the like. The exposure time is not only the 1/1000 second to 1 second exposure time normally used with a camera, but also the exposure time shorter than 1/1000 second, such as 1/10 to 1/106 second exposure using a xenon flash lamp or cathode ray tube. You can also do that. Exposures longer than 1 second can also be used. If necessary, the spectral composition of the light used for exposure can be adjusted using a color filter.

The silver halide photographic material of the present invention is suitable for use in a scanner using a semiconductor laser on the back.

Various methods can be used for the photographic processing of the silver halide photographic material of the present invention. Various types of processing liquids can be used. Processing temperature is usually 18℃ to 50℃
℃, but temperatures below 18°C or above 50°C may be used.

Development processing to form silver images depending on the purpose (black and white photographic processing)
Alternatively, any color photographic process consisting of a development process to form a dye image can be applied.

Developers used in black-and-white photographic processing can contain various developing agents. As developing agents, dihydroxybenzenes (e.g. hydroquinone), 3-pyrazolidones (e.g. 1-phenyl-3-pyrazolidone), aminophenols (e.g. N-methyl-p-aminophenol), 1-phenyl-3- Pyrazolines, ascorbic acid, and heterocyclic compounds such as a fused 1゜2.3.4-tetrahydroquinoline ring and intrene ring described in U.S. Pat. Can be used. The developing solution generally contains various other preservatives, alkaline agents, pH buffering agents, antifoggants, etc., and if necessary, a solubilizing agent, a color toning agent, a development accelerator, a surfactant, and an antifoaming agent. , a water softener, a hardening agent, a viscosity 1=J agent, and the like.

The photographic emulsion of the present invention can be subjected to a so-called [lith type-1 development process]. [Lith type-1 development processing is a process in which dihydroxybenzenes are usually used as a developing agent and under a low sulfite ion concentration for photographic reproduction of line images or halftone dots of LSI halftone images. , refers to a developing process in which the developing process is carried out contagiously.
(For details, see Mason, ``FoI Graphic Processing Rate Tree J (1966), pp. 163-165.
(described on the page).

As the fixer, one having a commonly used composition can be used.

As the fixing agent, in addition to thiosulfate and diocyanate, organic sulfur compounds known to be effective as fixing agents can be used.

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

When forming a dye image, conventional methods can be applied.

Negative-positive method (for example, Journal of the Society of Motion Picture and Television Engineers, “Journal of the
5ociety of Motion Picture
e and Televi-sion Engineering
RS, Vol. 61 (1953), pp. 667-701), developed in a developer containing a black and white developing agent to produce a negative silver image, followed by at least one uniform exposure or other suitable A color reversal method in which a dye-positive image is obtained by performing a fog treatment followed by color development, and a silver image is created by developing a photographic emulsion layer containing a dye after exposure.
A silver dye bleaching method or the like is used in which the dye is bleached using this as a bleaching catalyst.

For details of these color developing agents, see L, F, A.

Photographic Processing Chemistry by David Mason
Ssing Chemi-stry, Focal P
ress-London (published in 1966), 226~
It is described on page 229 etc. It is also possible to use it in combination with 3-pyrazolidones.

Various additives are added to the color developing solution as necessary.

Silver halide photographic emulsions are fixed according to post-development techniques, and in some cases are bleached. Bleaching can be done simultaneously with fixing or separately. When bleaching and fixing are carried out at the same time, a bleach-fixing bath may be prepared by adding a bleaching agent and a fixing agent.

The present invention can also be applied to light-sensitive materials with a low silver content, in which the amount of silver halide in the emulsion is a fraction to one-hundredth of that of conventional light-sensitive materials.

〔Example〕

Hereinafter, the present invention will be specifically explained with reference to Examples. However, the present invention is not limited to these.

Example 1 Emulsion preparation solution A Water 9.7
1 Inert gelatin 104g solution B Water 3.7β
Inert gelatin 550g Sodium chloride 935g Potassium bromide
415g 0.01% aqueous solution of hexachloroiridate potassium salt 20 mj!
0.01% aqueous solution of potassium hexabromorodate 1.5 ml
Solution C Water 3.7
ll silver nitrate 1700 g
pH 3.5, p, Ag7 in solution A kept at 40°C
Add solutions B and C simultaneously over a period of 60 minutes while maintaining the temperature at 1000 ml and continue stirring for an additional 10 minutes before adding 2C of a 20% aqueous solution of magnesium sulfate and 2.55 J of a 5% aqueous solution of polynaphthalene sulfonic acid. , emulsion at 40℃
The solution is flocculated, decanted, and washed with water to remove excess salt from the aqueous solution. then 3.7
Add β water and disperse, then add 141 g of inert gelatin and disperse. As a result, cubic crystal grains consisting of 35 mol % of silver bromide, 65 mol % of silver chloride, and (100) planes with an average grain size of 0.23 μm are obtained.

Add 150 mff of 0.1% sodium thiosulfate aqueous solution and 50 ml of 0.2% chloroauric acid aqueous solution,
The emulsion is aged for 120 minutes at a temperature of 0.degree. C. and a pH of 6.0 + pAg 7.0 for maximum sensitivity.

11. A 0.025% solution of a compound represented by chemical formula (I-3) as an infrared sensitizing dye was added to this emulsion. OOmn, 4-hydroxy-6-methyl-1,3°3a as a stabilizer,
7-1% of Chitrazaindene? liquid 11 (lomn, 1
-0.5% of phenyl-5-mercaptothi-1-razole
? 20ml of liquid, 500ml of 5% hydroquinone liquid
l! , add 1.00 mj+ of a 5% solution of potassium bromide, and further add 200 m of a 20% solution of saponin as a spreading agent.
l, 4 of styrene-maleic acid copolymer as a thickener
% solution 300mA, 4g of polyethylene glycol (number average molecular weight 3000) as a development accelerator, 300g of high molecular weight latex polymer of ethyl acrylate, 1% of 1-hydroxy-3,5-dichlorotriazine sodium salt as a hardening agent. Add 150ml 12 of solution.

This was coated on a support to obtain an emulsion layer.

Furthermore, 200 g of inert gelatin was added as a protective film forming solution.
Sodium dodecylbenzenesulfonate 1% solution 100
mjl! , 2000 mj2 of a solution containing 40 m12 of 5% formalin solution was prepared. This was divided into 10 equal parts, and as shown in Table 1, one without a matting agent (Arashi 1), and one with 0.00% amorphous silica with an average particle size of 1 to 20 μm as a matting agent.
A total of 10 types of protective film forming solutions containing 1 to 0.3 g of additive (2 to 10) were prepared, and each of these solutions was applied onto the above emulsion layer to form a protective film. I got the material.

The emulsion layer contains 4.0 mg/m of silver and 2.0 g/m of gelatin.
Two protective layers were simultaneously applied so that the gelatin content was 1.0 mg/%. Using a semiconductor laser having a wavelength of 780 nm, 10 kinds of photographic materials coated with the protective layers shown in columns 1 to 10 of Table 1 were image-exposed, respectively.
The degree of moiré was observed.

In addition, each sample was made into a roll and heated at 23'C.

After being left in a 20% RHO room for one day, the end of the roll was held and the state of static generation was observed. Furthermore, each sample was formed into a sheet, stacked, and the top layer sample was pulled to observe the slipperiness. Measurement Table 2 ×: Significant occurrence △: Slight occurrence ○: Total occurrence The development process was performed using Sakura Automatic Processor "J'G R-27" using the following developer and the following fixer.
(manufactured by Konishiroku Photo Industry KK) at 38° C. for 30 seconds, fixing, washing with water, and drying.

<Developer formulation> Pure water (ion-exchanged water) Approximately 800 β Potassium sulfite 60 g Ethylenediaminetetraacetic acid disodium salt g Potassium hydroxide 10.5 g 5-Methylbenzotriazole 300 mg Gl-tyrene glycol 25 gl-Phenyl-4,4-
Dimethyl-3=pyrazolidinone 300
mgl-phenyl-5-mercaptotetrazole 0
mg potassium bromide 3.5 g hydroquinone 20 g potassium carbonate
15 g of pure water (ion-exchanged water) was added to make up to 1,000 mg. When using the developer, the entire amount of the above developer was dissolved in 31 parts of pure water (ion-exchanged water).

The pH of the developer before dilution with water was about 11.4, and the pH of the developer after dilution with water was about 10.8.

Fixer formulation> (Composition A) Ammonium thiosulfate (72.5% W/V aqueous solution) 24
0 mj! Sodium sulfite 17 g Sodium acetate trihydrate 6.5 g Boric acid
6 g Sodium citrate dihydrate
2 [Acetic acid (90% W/W aqueous solution)
13.6m j! (IIJl) Pure water (ion exchange water) 17 m7! Sulfuric acid (50% W/W aqueous solution) 4. '1g aluminum sulfate (aqueous solution with hep203 equivalent content of 8.1% W/W)G-
When using a 5tr fixer, the above N2H composition A was dissolved in the order of the composition in 500 mp of water, and the solution was finished to 11. The pH of this fixer was about 4.3.

As shown in Table 2, those containing no matting agent (lVkL
l) is significantly inferior in both static and slippery properties, and the average particle size of the matting agent is larger than 10 μm (NO, 5,
6, 10), moiré is noticeable. Matting agents with a particle size of 10 to 1 μm (Numbers 2 to 4, Numbers 7 to 9) do not cause moire and have good static and slippery properties.

Example 2 An emulsion layer was prepared in the same manner as in Example 1, but this emulsion was silver chloroiodobromide containing 70 mol% of bromine and 0.1 mol% of iodine. As the sensitizing dye, a compound represented by the chemical formula (■-17) was used instead of the compound represented by the chemical formula (■-3). The rest is the same as in Example 1.

The emulsion prepared as described above was coated on a support to obtain an emulsion layer. Furthermore, as shown in Table 3, those without adding a matting agent (teeth, 11), those with an average particle size of 1 to 20 as a matting agent.
0.2-0.4g of μm polymethyl methacrylate
A total of 10 types of protective film forming solutions were prepared, each consisting of the additives (12 to 20), and each of these solutions was applied onto the above emulsion layer to form a protective film, and 10 types of photographic light-sensitive materials were prepared. I got it.

O As shown in Table 4, those containing no matting agent (, Itl
l) has significantly poor static and slip properties, and the particle size of the matting agent is larger than 10 μm (N[Li2゜19,
20), the occurrence of moiré is significant. The particle size of the matting agent is 10
μm to 1 μm (Nos. 12 to 14. No. 16 to 18)
There is no moiré, and the static and slippery properties are also good.

Table 4 [Effects of the Invention] As stated above, according to the present invention, the maximum sensitivity is 70
It is on the longer wavelength side than 0 nm and does not cause moiré, and
A silver halide photographic material with excellent handling properties such as no static failure during handling and appropriate slipping properties can be obtained.

Claims (1)

[Claims] A silver halide photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer on a support, wherein the maximum sensitivity of the silver halide photographic light-sensitive material is on the longer wavelength side than 700 nm, and the above-mentioned photographic light-sensitive material 1. A silver halide photographic material comprising a matting agent having an average grain size of 10 μm or less in a photosensitive silver halide emulsion layer and/or another hydrophilic colloid layer.