JPS63292125A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain a silver halide photographic sensitive material having increased sensitivity in an infrared region of >=700nm, especially >=750nm wavelength of semiconductor laser light by using a silver halide emulsion contg. a specified compd. added at an arbitrary time after the end of physical aging. CONSTITUTION:When a photographic sensitive material having a silver halide emulsion layer chemically sensitized with a sensitizing dye having max. spectral sensitivity at >=700nm is produced, a silver halide emulsion contg. a compd. represented by formula I and added at an arbitrary time after the end of physical aging is used. In formula I, each of R1 and R2 is H, alkyl, aryl, aralkyl, alkenyl, amino, acylamido or sulfonamido and the total number of C atoms in R1 and R2 is >=3. Various hydrophilic colloids may be used in the sensitive material and hydrophilic colloid used as a vehicle for the photographic emulsion layer and/or other photographic constituent layer may be gelatin, colloidal albumin, casein or a cellulose deriv. such as CMC or hydroxyethylcellulose.

Description

DETAILED DESCRIPTION OF THE INVENTION (A) Field of Industrial Application The present invention relates to a silver halide photographic material that is spectrally sensitized in the infrared region.

(B) Prior art and its problems With the recent development of rapid information transmission systems, silver halide photographic materials are increasingly required to have high sensitivity. Examples include high-speed phototypesetting systems that immediately display information output from a computer as characters or graphics on a cathode ray tube, and press facsimile systems that quickly send newspaper manuscripts to remote locations.

The characteristics required of silver halide photographic materials for such uses include a light source of 10-4 seconds or less using a light source such as a cathode ray tube (C-T), a laser such as helium-neon gas, or a light emitting diode (LED). So-called high-intensity short-time exposure (
It requires high sensitivity for flash exposure (referred to as flash exposure), as well as characteristics such as high contrast and high resolution.

A method using a laser light source such as helium-neon or argon as a scanner type light source can provide high output, but has disadvantages such as large and expensive equipment and low power consumption efficiency. On the other hand, semiconductor lasers have advantages such as being inexpensive, easy to modulate, and long-life. For semiconductor lasers, Ga/As/P:Ga/At
/As: Ga/As: In/P: In/
A type of semiconductor such as A @ is used, and the wavelength of this laser light is generally longer than 700 nm, especially 750 nm.
There are many wavelengths in the nm range.

Therefore, since a bright safelight can be used, it also has the advantage of improving handling workability.

However, infrared light-sensitive materials generally have problems such as insufficient sensitivity and poor storage stability, and various proposals have been made to date. For example, a technique called the so-called supersensitization effect has been proposed, in which the spectral sensitivity is significantly increased by adding a second mass of specifically selected organic compounds to the spectral sensitizing dye. , for example, U.S. Patent Nos. 2,785,058 and 3,695,888
Triazine derivatives described in US Pat. No. 3,457, etc.
Mercapto compounds having an electronegative group as described in JP-A-51-81613, quaternary salts as described in JP-A-59-191032, and others in JP-A-61-69063. , 1986-27
No. 884, etc. can be referred to. However, the reality is that these supersensitization techniques often give unsatisfactory results such as insufficient sensitization, increased fog, and poor storage stability.

The present inventors have conducted extensive research into silver halide photographic materials for use with semiconductor laser light that are free from such problems and have found that certain compounds are extremely effective for this purpose.

(C) Purpose of the Invention The purpose of the present invention is to provide a silver halide photographic material having increased sensitivity in the infrared region such as a semiconductor laser of 700 nm, particularly 750 nm or more.

Another object of the present invention is to have no problems with fogging, storage stability, etc.
An object of the present invention is to provide a silver halogenide photographic material with enhanced sensitivity in the infrared region.

CD) Structure of the Invention The above object of the present invention is to provide a light-sensitive material having a silver halide emulsion layer optically sensitized with a sensitizing dye having a maximum spectral sensitivity of 70 G nm or more, after the completion of physical ripening of the silver halide emulsion. This was achieved by a silver halide photographic material characterized by containing a compound represented by the following general formula (1) added at any time.

General formula (1) (wherein 几1 and 几2 are a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, and an alkeni group, respectively.

represents a group, an amino group, an acylamido group, or a sulfonamide group, and the sum of the carbon numbers of R1 and R2 is 3 or more. ) Specific examples of the compound of general formula (1) used in the present invention are shown below. However, only R1 and R2 in general formula (i) are shown.

Compounds used for comparison are shown below.

(Comparison a) (Comparison b) (Comparison C) (Comparison D) The compound of general formula (1) used in the present invention can be used at any time after the physical ripening of the silver halide emulsion is substantially completed until coating. At the same time, one kind or two or more of them are added, but in some cases, they may be diffused from the adjacent hydrophilic colloid layer during coating.

The amount added is from 95 x 10 mmol to 5 mmol, preferably from 1 x 10 mmol to 1 mmol per mole of silver halide.
It is in the mmol range. For addition, a suitable solvent,
It is advantageous to add it as a solution, for example in methanol, ethanol, globanol, acetone, dimethylformamide, etc.

The sensitizing dye having maximum spectral sensitivity in the long wavelength region (700 nm) used in the present invention is disclosed in, for example, U.S. Pat.
No. 095,854, same! No. 2.095,856, same No. 2
．． No. 955.939, No. 3,482.978, No. 3,552,974, No. 3,573,921, No. 3.582,344, No. 3,623,881 It can be something written in a book, etc.

Preferably, dyes represented by the following general formulas (1) to (IV) are used.

(Left below) Feeling general formula (
In 1) to (IV), zl and zl may be the same or different, and each represents an atomic group necessary to form a 5- or 6-membered nitrogen-containing heterocycle.几1 and R
2 may be the same or different, and each represents an alkyl group or an alkenyl group. R5 is an alkyl group,
Represents an alkenyl group or an aryl group.几4～R10 are
Each may be the same or different, and each hydrogen atom,
Represents a halogen atom, alkyl group, aryl group, or alkoxy group. However, R6 and R7 or R8 and R9 can also be linked to each other to form a 5- or 6-membered ring. R
11 and R12 may be the same or different,
Each represents an alkyl group or an aryl group, and R'1t and R11 can also be linked to each other to form a 5- or 6-membered ring. Y is a sulfur atom, an oxygen atom, N-Rng
(Rlg is an alkyl group).

X represents an acid anion. L, m, n, p and q each represent 1 or 2.

Specific examples of zll and zl include thiazole, benzothiazole, na7) C1,2-α]thiazole, na7
) (2,1-α]thiazole, naphtho[2,3-α
] Thiazole, selenazole, benzoselenazole, naphtho[2,1-a]selenazole, nand(1,2-α
] Selenazole, oxazole, benzoxazole,
Naphtho[1,2-a)oxazole, naphtho[2,
1-α]oxazole, nut[2,3-α]oxazole, 2-quinoline, 4-quinoline, 3,3-dialkylindolenine, imidazole, benzimidazole,
Examples include nitrogen-containing heterocycles such as naph) [1,2-α]imidazole and pyridine. These heterocycles are
Alkyl groups (e.g. methyl, ethyl, butyl, trifluoromethyl, etc.), aryl groups (e.g. phenyl, tolyl, etc.), hydroxy groups, alkoxy groups (e.g. methoxy, ethoxy, butoxy), carboxy groups, alkoxycarbonyl groups (e.g., methoxycarbonyl, ethoxycarbonyl, etc.), halogen atoms (e.g., fluorine,
chlorine, bromine, iodine), aralkyl groups (e.g. benzyl, phenethyl, etc.), cyano groups, alkenyl groups (e.g.
may have one or more substituents such as allyl), etc.

In Rt and R2, the alkyl group includes lower alkyl groups such as methyl, ethyl, propyl, butyl, hydroxyalkyl groups such as β-hydroxyethyl and γ-hydroxyglobil, β-methoxyethyl, γ-methoxypropyl, etc. alkoxyalkyl group, β-acetoxyethyl, T-
Acyloxyalkyl groups such as acetoxyglobil and β-benzoyloxyethyl, carboxyalkyl groups such as carboxymethyl and β-carboxyethyl, alkoxycarbonylalkyl groups such as methoxycarbonylmethyl, ethoxycarbonylmethyl and β-ethoxycarbonylethyl, β- Examples of the alkenyl group include sulfoalkyl groups such as sulfoethyl, γ-sulfopropyl and -sulfobutyl, aralkyl groups such as benzyl, phenethyl and sulfobenzyl, and allyl.

Examples of R5 include alkyl groups and alkenyl groups as described above for R1 and R2, and aryl groups such as phenyl, tolyl, methoxyphenyl, chlorophenyl, and naphthyl.

R4 to R1G are hydrogen atoms, halogen atoms (e.g. chlorine, bromine, iodine, fluorine), alkyl groups and aryl groups as described in 几1 and R2, or alkoxy groups having alkyl as described in 几1 and R2. (i.e. 0R1ft)
The 5-membered or 6-membered negative ring formed by R6 and R7 or R8 and 19 may be substituted with a lower alkyl group or the like.几11 and R12 represent an alkyl group or an aryl group as described for R, R2, and R11 and R12
can also be linked to each other to form a 5-membered or 6A ring. Examples of RIA include an alkyl group as described in R1 and 几2.

Examples of the acid anion of It does not exist when it has a betaine-like structure.

Specific examples of the sensitizing dye used in the present invention are illustrated below.

O11 80° C2H5L:2H5 C2) 15- ■ sos- C)1. Building 505- ch, ((defense 505- I-sos 〼 C2) 15 knee (30) So.

Hs D. The sensitizing dye used in the present invention can be synthesized by methods known to those skilled in the art. The addition to the silver halide emulsion can be at any time before the emulsion is coated, and may be before, after, or simultaneously with the addition of the compound of general formula (1).

The amount of the sensitizing dye used in the present invention is in the range of #) IXlo" mol to 1X10" mol, preferably from 5.times.10"' mol to 5.times.10" mol, per mol of silver halide.

Sensitizing dyes can be dispersed directly in the emulsion or dissolved in water-miscible solvents such as methanol, ethanol, pyridine, methylcellosolve, acetone, dimethylformamide, etc. (or mixtures thereof), and in some cases They can be diluted with water, or in some cases dissolved in water, and added to the emulsion in the form of these solutions. The dye solution can be added using ultrasonic vibration or by the method described in U.S. Pat. No. 3,469,987 and Japanese Patent Publication No. 46-24185. Furthermore, U.S. Patent No. 2.912
．． No. 345, No. 3,342,605, No. 2,996,
The methods described in Nos. 287 and 3,425,835 can also be used.

The silver halide emulsion used in the present invention can be prepared by any known method.

The silver halide emulsion used in the present invention may be prepared using either the so-called single jet method or the double jet method, but it is preferable to use a monodisperse emulsion prepared using the latter method. Moreover, the crystal habit of the silver halide crystal used in the present invention may be cubic, octahedral, dodecahedral, or tabular.

The halogen composition of the silver halide used in the present invention may be silver chloride, silver bromide, silver chlorobromide, or any of these including silver iodide.

Metals such as rhodium and iridium can also be used during precipitation or physical ripening of silver halide.

These emulsions can be subjected to chemical ripening by known methods. That is, U.S. Patent No. 1,574,944;
278.947, 2,410,689, 3.1
89.458, No. 3,501,313, etc., or sensitized region gelatin containing a sulfur compound can be subjected to shear-off sensitization. Also, U.S. Patent No. 2.597,856, U.S. Patent No. 2.597.915, U.S. Pat.
It is also possible to perform gold sensitization using a gold compound as described in, for example, No. 399,083.

Also, U.S. Patent No. 2.51 s, a 9 s,: 2.5
21,925, 2,487,850, 2,694,
Reduction sensitization can also be performed as described in No. 637. These sensitization methods can be used not only alone but also in combination.

The photographic emulsion used in the present invention can also be sensitized using quaternary ammonium salts, thioether compounds, polyethylene oxide conductors, diketones, and the like. These methods are described in U.S. Pat.
No. 046,132, No. 3,046.133, No. 3,0
No. 46,134, No. 3,046,135, British Patent No. 939.357, etc.

Various hydrophilic colloids are used in the photographic material of the present invention, and hydrophilic colloids used as vehicles for photographic emulsions and/or other photographic constituent layers include gelatin, colloidal albumin, casein, carboxymethyl Cellulose W conductors such as cellulose and human tetraxyethylcellulose, sugar conductors such as agar, sodium alginate, and starch conductors, synthetic hydrophilic colloids such as polyvinyl alcohol, polyhevinylpyrrolidone, polyacrylic acid copolymers, and polyacrylamide. or derivatives thereof,
Examples include partial hydrolysates. If desired, compatible mixtures of two or more of these colloids are used. Among these, gelatin is the most commonly used, but gelatin can be partially or completely replaced with synthetic polymeric substances, and gelatin can also be replaced with so-called gelatin enzyme conductors, i.e., amino-7 as a functional group contained in the molecule. or imino groups, hydroxyl groups, and carboxyl groups treated or modified with a reagent having one group that can react with them, or by replacing them with graft polymers bonded with molecular chains of other polymeric substances. It's okay.

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 (chromium alum, chromium acetate, etc.), aldehydes (formaldehyde, glyoxal, geltaraldehyde, etc.), N-methylol compounds (dimethylol urea, methylol dimethylhydantoin, etc.)
, dioxane derivatives (2,3-dihydroxydioxane, etc.), active vinyl compounds (1,3,5-)lyacryloyl-hexahydro-8-)riazine, 1,3-vinylsulfonyl-2-glopanolnato), active halogen compounds ( 2,4-dichloro-6-hydroxy-8-triazine 1"), mucohalogen [1 (mucochloric acid, mucophenoxychloroic acid, etc.), etc.] can be used alone or in combination.

The photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material of the present invention may contain various surfactants for various purposes such as coating aids, antistatic properties, improving slipperiness, emulsification dispersion, and preventing adhesion.

For example, saponins (steroids), alkylene oxide derivatives (such as polyethylene glycol, polyethylene glycol/polypropylene glycol condensates, polyethylene glycol alkyl ethers or polyethylene glycol alkyl aryl ethers, polyethylene glycol esters, polyethylene glycol sorbitan esters, Po!J alkylene glycol alkyl amines or amides, polyethylene oxide adducts of silicone), glycidol derivatives (e.g. alkenylsuccinic acid polyglycerides, argylsenols polyglycerides), fatty acid esters of polyvalent alkyls, alkyl esters of sugars. Nonionic surfactants such as alkyl carboxylates, alkyl sulfonates, alkylbenzene sulfonates, alkylnaphthalene sulfonates, alkyl sulfates, alkyl phosphates, N-acyl-N-alkyl taurines , sulfosuccinates, sulfoalkylpolyoxyethylene alkylphenyl ethers, polyoxyethylene alkyl phosphates, etc., with acidic groups such as carboxy groups, sulfo groups, phospho groups, sulfate ester groups, and phosphate ester groups. Containing anionic surfactants; amphoteric surfactants such as amino acids, aminoalkyl sulfonic acids, aminoalkyl sulfates or phosphates, alkyl betaines, and amine oxides: alkylamine salts, aliphatic or aromatic quaternary ammonium salts Cationic surfactants such as heterocyclic quaternary ammonium salts such as , pyridium, imidazolium, and phosphonium or sulfonium salts containing aliphatic or heterocycles can be used. It is also possible to add latex polymer or the like to modify the physical properties of the gelatin film, silica, starch powder, colloidal silica, glass powder, etc. to make the film surface matte.

The photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material of the present invention contains the general formula described above for the purpose of preventing fog during the manufacturing process, storage or photographic processing of the light-sensitive material, or stabilizing the photographic performance. Various compounds other than the compound (1) can be contained. Azoles such as benzothiazolium salts, nitroindazoles, triazoles, benzotriazoles, benzimidazoles (especially nitro- or halogen substituted); heterocyclic mercapto compounds such as mercaptothiazoles, mercaptobenzothiazoles, Mercaptobenzimidazoles, mercaptothiadiazoles, mercaptotetrazoles (1-phenyl-5-mercaptotetrazole at 411F), mercaptovirimidines: the above 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, especially 4-hydroxy-substituted (1,3,
Many compounds known as antifoggants or stabilizers can be added, such as (3a, 7) tetraazaindenes): benzenethiosulfonic acids: benzenesulfinic acid: etc.

The light-sensitive material of the present invention may contain various compounds other than those mentioned above, such as antistatic agents, ultraviolet absorbers, plasticizers, developing agents, carbon dioxide inhibitor dyes, fluorescent dyes, development accelerators, couplers, etc. .

In the photographic light-sensitive material of the present invention, any support that is normally used as a support for photographic light-sensitive materials can be used. Examples include cellulose nitrate film, cellulose acetate film, cellulose acetate butyrate film, cellulose acetate glopionate film, polystyrene 7° film, polyethylene terephthalate film, polycarbonate film, laminates thereof, and paper. Baryta or α-olefin polymers, especially polyolefins of 2 to 10 carbon atoms such as polyethylene and polypropylene! Paper coated or laminated with Supports such as films are also suitable.

Further, the coating method for the hydrophilic colloid layer of the present invention includes air doctor, blade coating, squeeze coating, air knife coating, reverse roll coating, and casting.
Methods such as coating, extrusion coating, etc. are used.

The coating amount is 1 to 15 μm, more preferably 2 to 10 μm.
It is preferable to set it to μm.

The light-sensitive material of the present invention is useful as a black-and-white photographic light-sensitive material for semiconductor lasers and a lithographic printing plate using a silver complex diffusion transfer method, but it can also be used for other purposes.

(E) Examples Example 1 Silver chlorobromide (10 mol of silver bromide emulsion) with an average grain size of about 0.23 μm was prepared by the controlled double jet method of AT, and after precipitation, washing with water and redissolving, Gelatin to iron 0.6
Sulfur + gold sensitization was performed to match the ratio of 1.0 to 1.0. After finishing, add 1 mole of silver halide to 1 x exemplified dye (1) as a sensitizing dye.
10° 4 mol was added, and a hardener and a surfactant were added. This emulsion was divided into 10 equal parts and finished by adding 1 mol of the compound shown in Table 1 per 1 mol of silver halide.] The emulsion was finished.

A sample was prepared by coating these emulsions together with a protective layer (gelatin 1υ) on a polyester film in a layered manner so that silver was 6 f/lri.

These samples were sensitometrically exposed for 10"5 seconds through a 780 nm interference filter, developed with PQ developer, fixed, washed with water, dried and characterized.

The results are shown in Table 1. Sensitivity is shown as a relative value with Sample 1 as 100.

Table 1 Example 2 In Example 1, a silver iodobromide emulsion containing 2 mol of silver iodide was prepared in the same manner as in Example 1, and the exemplified compound was
The second result was obtained in the same manner except that 1 mole of 0" was added.
Shown in the table.

Table 2 Example 3 Example 1 was followed except that the sensitizing dye was replaced with Exemplified Dye (25), and the results shown in Table 3 below were obtained.

, Table 3 Example 4 Exemplary dyes (15) and (23) in place of Exemplary dye (25)
The same procedure as in Example 3 was performed except that (28) was used.

Similar results to Example 3 were obtained.

(F) Effects of the Invention According to the present invention, the sensitivity of a sensitizing dye having maximum spectral sensitivity in the infrared region of 700 nm, particularly 750 nm or more can be increased by a specific mercapto compound, and fog can be reduced. Therefore, it is possible to obtain a highly sensitive silver halide photographic material suitable for use in conductor lasers.

procedure? mm self-written) August 17, 1986

Claims (1)

[Claims] (1) In a light-sensitive material having a silver halide emulsion layer optically sensitized with a sensitizing dye having maximum spectral sensitivity at 700 nm or more, the following general formula is added at any time after the completion of physical ripening of the silver halide emulsion. A silver halide photographic material containing a compound represented by (I). General formula (I) ▲ Numerical formulas, chemical formulas, tables, etc. and R_
The sum of the carbon numbers of 2 is 3 or more. )