JPH08122966A - Photosensitive material - Google Patents

Abstract

PURPOSE: To provide a silver halide photographic sensitive material free from a problem on residual dye stains and superior in aptitude to a sensor. CONSTITUTION: The photosensitive material contains at least one of compounds represented by formula I-III in which each of A1 and A2 is a carboxylate or sulfonate group; each of T<1> and T<2> is a 1-5C straight or branched alkylene group; Q is an optionally substituted phenyl group; each of G<1> -G<5> is H atom or the like; M is an ion for charge balancing; n is 0 or 1; each of R1 and R2 is an optionally substituted alkyl group; each of Z1 and Z2 is an atomic group necessary to form an optionally substituted benzene or naphthalene ring; L is a trivalent group comprising 7 methine group linked with each other in a conjugated double bond; X is an ion for charge balancing; and m is a number for charge balancing.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a light-sensitive material, and more particularly to a technique for imparting aptitude to a sensor for detecting conveyance or position.

[0002]

2. Description of the Related Art In recent years, there has been a growing need to speed up the processing of light-sensitive materials and to reduce the replenishment rate of processing solutions. Therefore, it is essential to reduce the amount of silver halide. At this time, the blocking ability of the sensor for detecting the conveyance or the position related to the control of the apparatus is lowered, resulting in poor control. Therefore, as disclosed in JP-A-3-211542, a method of improving by using a dye is disclosed, but it is still insufficient in terms of residual color.

[0003]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a light-sensitive material having sensor suitability without the problem of residual color.

[0004]

The above objects of the present invention have been achieved by a light-sensitive material containing at least one compound selected from compounds represented by the following general formulas (I), (II) and (III). General formula (I)

[0005]

Embedded image

Where A₁, A₂Is a carboxylate (-
COO^-) Or sulfonate (-SO₃ ^-)
Then T¹, T²Is a linear or branched chain having 1 to 5 carbon atoms
Represents a branched alkylene group, Q is a phenyl group or substituted
Represents a phenyl group, G¹, G ³Is a halogen atom,
Ano group, methanesulfonyl group, methoxycarbonyl group,
Ethoxycarbonyl group, alkyl having 1 to 4 carbon atoms
Represents an alkoxy group having 1 to 4 carbon atoms,
G², G^FourIs a hydrogen atom, a halogen atom, or a carbon atom
Alkyl group having 4 carbon atoms, alkoxy having 1 to 4 carbon atoms
Represents an Si group, and M represents an ion for maintaining charge balance.
I forgot. General formula (II)

[0007]

[Chemical 6]

[0008] represents in n is 0 or 1 formula, A _1, A ₂ are carboxylate groups (-COO ^-) or sulfonate group (-SO ₃ ^-) represents, T _1, T ₂ is C 1 -C 5 represents a linear or branched alkylene group, wherein G ¹ , G ² , G ³ and G ⁴ are hydrogen atom, halogen atom, cyano group, methanesulfonyl group, methoxycarbonyl group, ethoxycarbonyl group, carbon atom. Represents an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, G ⁵ represents a hydrogen atom, a halogen atom, a methyl group, or a halogen-substituted methyl group, and M represents an ion for maintaining charge balance. Represent. General formula (III)

[0009]

[Chemical 7]

In the formula, R ₁ and R ₂ are each an alkyl group which may have a substituent, and Z ₁ and Z ₂ are atoms each forming a benzene ring or a naphthalene ring which may have a substituent. Group, L is a trivalent group in which seven methine groups which may have a substituent are linked by a conjugated double bond, X is an ion for maintaining a charge balance, and m is a charge balance Represents the number for.

Preferred as the group represented by Q in the formula (I) are a phenyl group, a halogen-substituted phenyl group, a phenyl group substituted with an alkyl group having 1 to 4 carbon atoms, and an alkoxy group having 1 to 4 carbon atoms. A phenyl group substituted with a group, particularly preferably a phenyl group. Those in which at least one of A ₁ and A ₂ is a sulfonate group are preferable, and those in which both A ₁ and A ₂ are sulfonate groups are particularly preferable. Preferred among the alkylene group represented by _{T 1, T 2 - (CH} 2) 4 -,
_{-CH 2 CH 2 CH (CH 3} ) -, - CH 2 CH 2 - , and particularly preferably - (CH _{2) 4} - a. The group represented by G ¹ and G ³ is preferably a halogen atom or an alkyl group having 1 or 2 carbon atoms, and particularly preferably a chlorine atom or a trifluoromethyl group. Preferred as the groups represented by G ² and G ⁴ are a hydrogen atom, a halogen atom,
An alkyl group having 1 or 2 carbon atoms, particularly preferably a hydrogen atom, a fluorine atom, a chlorine atom or a trifluoromethyl group. Preferred as the ion represented by M are proton, alkali metal ion, alkaline earth metal ion, ammonium ion (for example, ammonium ion, methylammonium ion, piperidinium ion, triethylammonium ion, N, N-dimethylammonium ion, 1 , 4-diazabicyclo [2,2,2] octane-1-ium, tetrabutylammonium, trimethylbenzylammonium, etc.),
Immonium ion (eg pyridinium ion, 1-
Methylpyridinium ion, 1,3-diazabicyclo [5,4,0] undecenium ion and the like), but particularly preferred are tertiary ammonium ions such as proton, sodium ion, potassium ion and triethylammonium ion. Is.

Specific examples of the compound represented by formula (I) of the present invention are shown below, but the scope of the present invention is not limited to these.

[0013]

[Table 1]

N in the general formula (II) is preferably a case of completing a 1-membered, 6-membered ring. It is preferable that at least one of A ₁ and A ₂ is a sulfonate group.
It is particularly preferred that both ₁ and A ₂ are sulfonate groups. Preferred among the alkylene group represented by _{T 1, T 2 - (CH} 2) 4 -, - CH 2 CH 2 CH (CH 3) -, -CH 2 CH 2 - , and particularly preferably - (CH ₂ ) _4- . The group represented by G ¹ and G ³ is preferably a halogen atom or an alkyl group having 1 or 2 carbon atoms, and particularly preferably a chlorine atom or a trifluoromethyl group. G ² ,
The group represented by G ⁴ is preferably a hydrogen atom, a halogen atom or an alkyl group having 1 or 2 carbon atoms, and particularly preferably a hydrogen atom, a fluorine atom, a chlorine atom or a trifluoromethyl group. The group represented by G ⁵ is preferably a hydrogen atom, a halogen atom or a trifluoromethyl group, and particularly preferably a hydrogen atom. Preferred as the ion represented by M are a proton, an alkali metal ion, an alkaline earth metal ion, an ammonium ion (for example, an ammonium ion, a methylammonium ion, a piperidinium ion, a triethylammonium ion, an N, N-dimethylanilinium ion, 1,4-diazabicyclo [2,2,2] octane-1-ium, tetrabutylammonium, trimethylbenzylammonium, etc., immonium ions (for example, pyridinium ion, 1-methylpyridinium ion, 1,3-diazabicyclo [5,5] 4,0] undecenium ion and the like), and particularly preferred are tertiary ammonium ions such as proton, sodium ion, potassium ion and triethylammonium ion.

Specific examples of the compound represented by formula (II) of the present invention are shown below, but the scope of the present invention is not limited to these.

[0016]

[Table 2]

[0017]

[Table 3]

The alkyl group represented by R ₁ and R ₂ in the general formula (III) may have a substituent,
It is preferably an alkyl group having 1 to 8 carbon atoms. As the above-mentioned substituents, phenyl, naphthyl, -O
H, -COOH (or a salt thereof), SO ₃ H (or a salt thereof), carbon atoms of 1 to 4 alkoxy, -F, -Cl-
CN, carbonamide having 1 to 5 carbon atoms, carbamoyl having 1 to 5 carbon atoms, alkoxycarbonyl having 2 to 6 carbon atoms, acyloxy having 1 to 7 carbon atoms, amyl having 1 to 7 carbon atoms, carbon Preferred are alkanesulfonyl groups having 1 to 4 atoms and alkylthio groups having 1 to 4 carbon atoms. Among these, a particularly preferable substituent is -CO.
It is OH (or its salt) and -SO ₃ H (or a salt thereof). Further, at least one of R ₁ and R ₂ is —CO
It is preferably an alkyl group having 1 to 4 carbon atoms, which is substituted with OH (or a salt thereof) or —SO ₃ H (or a salt thereof).

The substituent on the benzene ring or naphthalene ring represented by Z ₁ and Z ₂ is a halogen atom (especially F
Or Cl), a methyl group, an ethyl group, a trifluoromethyl group or the like, and an alkyl group having 1 to 6 carbon atoms is preferable, and an alkyl group having 1 or 2 carbon atoms is particularly preferable. X
Is preferably a positive or negative monovalent or divalent organic or inorganic ion. m is R ₁ , R ₂ , Z ₁
And the number of X's required to balance the charge, including the cationic or anionic substituents present on Z ₂ , specifically 0, 1/3, 1/2, 1, 3/2, 2,
The numbers are 3, 4, etc.

Preferred substituents on the trivalent group represented by L include halogen atoms, alkyl having 1 to 8 carbon atoms such as methyl, ethyl and propyl, carbon atoms such as methoxy, ethoxy and propoxy. Number 1-8 alkoxy,
Phenoxy, 4-sulfophenoxy, 3,5-dichlorophenoxy, 4-ethylphenoxy and the like have 6 carbon atoms.
~ 12 aryloxy, phenyl, 6 to 6 carbon atoms
12-substituted aryl such as phenyl having 1 to 8 carbon atoms
And alkylphenyl, substituted phenylthio having 6 to 12 carbon atoms, and the like. These groups may be linked to each other to form a ring. Among these groups, the following groups are particularly preferable.

[0021]

Embedded image

R ₃ and R ₄ in the above formulas are hydrogen atoms, alkyl groups having 1 to 8 carbon atoms such as methyl, ethyl, isopropyl and cyclohexyl; carbon atoms such as methoxy, ethoxy, isopropoxy and butoxy. Number is 1-8
An alkoxy group of: phenyl, 4-chlorophenyl, 4-
Aryl group having 6 to 12 carbon atoms such as methoxyphenyl and 3-sulfophenyl; aryloxy having 6 to 12 carbon atoms such as phenoxy, 4-sulfophenoxy, 3,5-dichlorophenoxy and 4-methoxyphenoxy Group;

Amino group, mono- or di-substituted amino group (substituents in this case are methyl, ethyl, propyl,
An alkyl group having 1 to 12 carbon atoms such as isopropyl, butyl, hexyl, octyl, dodecyl; an alkoxycarbonylalkyl group such as methoxycarbonyl, methylethoxycarbonylmethyl, ethoxycarbonylethyl;
Phenyl, 4-methylphenyl, 3-methylphenyl,
Although aryl groups such as 4-chlorophenyl, 3-chlorophenyl, 3-methoxyphenyl, 4-ethoxyphenyl, 3-methoxyphenyl, 4-ethoxyphenyl, 3-propoxyphenyl and 3,5-dichlorophenyl can be exemplified, In the case of a di-substituted amino group, two substituents may combine with each other to form a ring. Examples of such a ring include a pyrrolidine ring, a piperidine ring, a morpholine ring, and a pyrazine ring. These rings may be rings having a substituent such as N-acetylpyrazine ring. ), F, Cl, Br, and other halogen atoms, methylthio, ethylthio, butylthio, sulfomethylthio, and other alkylthio groups; phenylthio, 4-sulfophenylthio, 3-carboxyphenylthio, and other arylthio groups.

Q is a non-metallic atomic group forming a 5- or 6-membered ring. Among the above groups, R ₃ is preferably a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an aryl group having 4 to 6 carbon atoms, and particularly isobutyl,
An alkyl group having 4 to 6 carbon atoms such as cyclohexyl and benzyl; and a substituted phenyl group such as phenyl group, 4-chlorophenyl, 4-methoxyphenyl, and 3-ethylphenyl are preferable.

R ₄ is preferably a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 12 carbon atoms, a disubstituted amino group or a halogen atom, and particularly, a hydrogen atom, It is preferably a di-substituted amino group substituted with an alkyl group having 1 to 4 carbon atoms such as a methyl group, a phenyl group or a lower alkoxycarbonylmethyl group.

Among the compounds represented by the general formula (III), a particularly preferred compound is represented by the following general formula (IV). General formula (IV)

[0027]

[Chemical 9]

R in the formula₁Is-(CH₂)_FourSO₃ ^-,-(C
H₂)₃SO₃ ^-,-(CH₂)₂SO ₃ ^-,-(CH₂)
₂(CH₃) SO₃ ^-, R_FourIs H, CH₃, Cl, Ph, P
h₂N-, P = 3, Y₁Is H, Cl, Y₂Is Cl, F,
Ph, X⁺Represents a cation capable of forming a salt. General formula
Specific examples of the compound represented by (IV) include the following compounds.
Things.

[0029]

[Table 4]

In the tables and chemical formulas, Ph represents a phenyl group. The synthesis of the compound represented by the general formula (III) is
"The Cyanine Soybeans" by FM HAMER
And Relayed Compounds (THE CYANINEDYE
S AND RELATED COMPOUNDS) "(Interscience
Publishers (INTERSCIENCE PUBLISHERS), N.M.
Y. , 1964) Page 55; Nikolai Chuturkov, Jürgen Fabian, Akim Merhorn,
Fritz Dietz, Aria Tajir (NIKOLAI TYUT
YULKOV, JUREGEN FABIAN, ACHIM MEHLHORN, FRITZDIETZ, AL
IA TADJER) co-authored “POLYMETHINE DY
ES) (St. KLIMENT OHRIDSKI UNIVERSITY PRES
S), SOPHIA (1992) 23-38.
PAGE; RESEARCH DISCL
OSURE), vol. 152, p. 48 (1976), U.S. Pat. No. 3,482,978 and the like.

Next, synthetic examples will be given, but the present invention is not limited thereto. Synthesis Example-1 Synthesis of Compound 1-3 4- (6-chloro-4-methyl-1-quinolinio) butanesulfonate 0.5 g, 3-benzyl-1,5-diphenyl-1,5-diaza-1, 0.28 g of 3-pentadiene hydrochloride was dissolved in 5 ml of methanol, and 0.46 ml of triethylamine and 0.24 of acetic anhydride were stirred at room temperature.
ml was added dropwise. The reaction mixture is heated to 50 ° C,
Stir for 30 minutes. Furthermore, 0.46 ml of triethylamine and 0.24 ml of acetic anhydride were sequentially added dropwise to the reaction mixture,
Stir for 30 minutes. The produced solid substance was collected by filtration and washed with methanol to obtain 0.13 g of compound 3. Yield 19.1%, λ _max = 827 nm (MeOH), melting point 2
50 ° C or higher

Synthesis Example-2 Synthesis of Compound 2-3 0.19 g of 4- (6-chloro-4-methyl-1-quinolinio) butane sulfonate and 1,7-diphenyl-3,3
5- (1,3-propylidene) -1,7-diaza-1,
0.1 g of 3,5-heptatriene hydrochloride was dissolved in a mixed solvent of (methanol-acetonitrile 2: 3 volume ratio),
Stir at room temperature. To the mixed solution, 0.17 ml of triethylamine and 0.8 ml of acetic anhydride were sequentially added dropwise, and the mixture was stirred at room temperature for 10 minutes. Then, the reaction mixture was heated to 50 ° C. and stirred for 1 hour. A methanol solution of 0.15 g of potassium acetate was added to the reaction mixture, the mixture was cooled to room temperature, and the formed solid product was collected by filtration and washed with methanol. Yield 0.12 g, yield 26.1% λ _max = 971 nm (MeOH) melting point 250 ° C or higher

Synthesis Example-3 Synthesis of Compound 3-3 In a mixed solution of 10 ml of acetonitrile and 2 ml of ethanol,
2.0 g of 4- (5-chloro-2-methyl-1-benzothiazolin-1-yl) butanesulfonate and 1.12 g of 2-chloro-3-phenylaminomethylidene-1-phenyliminomethylcyclohexene hydrochloride were added. Add
Further, 2.45 ml of triethylamine and 1.2 of acetic anhydride.
After adding 8 ml, the reaction is carried out by stirring at 50 ° C. for 45 minutes.

The reaction solution obtained was cooled to room temperature, filtered, washed successively with acetonitrile and ethanol, and dried under reduced pressure to obtain 1.92 g of the compound. The maximum absorption wavelength of the obtained compound in a methanol solution is 807 nm.
Is. The compound used in the present invention easily forms a so-called J-aggregate in a hydrophilic solvent, and the compound has a wavelength range of several tens nm to several hundreds of nm from the absorption maximum wavelength measured in an organic solvent. The absorption band derived from coalescence is shown.

Particularly preferable binders for the layer to which the present invention is added are those soluble in water, and among them, cellulose derivatives, gelatin or polyvinyl alcohol are preferable.

Fine particles insoluble in water may be added to the compound of the present invention. As such fine particles, fine particles of an inorganic compound are preferable. Specific examples thereof are silver halides,
Examples thereof include fine crystals such as zinc oxide, ore powders such as mica and talc, and colloidal silica. Colloidal silica is particularly preferable.

A surfactant may be added to the compound of the present invention, and it can be used by appropriately selecting from anionic, cationic or nonionic surfactants.
Specific examples thereof include sodium alkylbenzene sulfonate, sodium alkyl sulfate, dioctyl sodium sulfosuccinate, and polyalkylene glycol (eg, polyoxyethylene nonylphenyl ether).

The compound of the present invention can be solidified by cooling or drying. At this time, a compound capable of covalently crosslinking the binder molecule may be added.
Such a cross-linking agent can be selected, for example, with reference to the descriptions in the following documents. "The Theory of Photographic Process" edited by TH James, edited by "The Theory of Photographic Process"
Process "Macmillan Publishing Co. Inc.,
Description of Chapter 2, III, published in 1977, JP-A-60-25
8545 and JP-A-62-85247.
The addition amount of the compound of the present invention is 1 mg / m ^{2 to 2} g /
It is preferably m ² , especially 10 mg / m ^{2 to 1} g / m ² .
The place of addition of the compound of the present invention is not particularly limited,
It is preferably a layer other than the silver halide emulsion layer, and particularly preferably a back layer.

There are no particular restrictions on the various additives and the like used in the photographic light-sensitive material of the present invention. For example, those described in the following relevant parts can be used. Item Relevant part 1) Silver halide emulsion and JP-A-2-68539, page 8, lower right column, bottom thereof, manufacturing method, 6th line to 10th page, upper right column, 12th line, 3-24537, JP Page 2, lower right column, line 10 to page 6, upper right column, line 1; page 10, upper left column, line 16; page 11, lower left column, line 19; JP-A-4-107474. 2) Chemical sensitization method JP-A-2-68539, page 10, upper right column, line 13 to upper left column, line 16; Japanese Patent Application No. 3-105035. 3) Antifoggant JP-A-2-68539, page 10, lower left column 17, stabilizer Stabilizer, line 11 to page 11, upper left column, line 7 and page 3, lower left column, line 2 to page 4, lower left column . 4) Color tone improving agent JP-A-62-276539, page 2, lower left column, line 7 to page 10, left lower column, line 20; JP-A-3-94249, page 6, lower left column, line 15 to 1 Page 1, upper right column, line 19 5) Spectral sensitizing dye JP-A-2-68539, page 4, lower right column, line 4 to page 8, lower right column. 6) Surfactant, JP-A-2-68539, page 11, upper left column 14, antistatic agent line to page 12, upper left column, line 9 7) Matting agent, slipping agent, JP-A-2-68539, page 12, upper left column 10, plasticizer line to same upper right column, line 10; page 14 lower left column 10, line 10 to lower right column 1 line . 8) Hydrophilic colloid JP-A-2-68539, page 12, upper right column, line 11 to left lower column, line 16 9) Hardener JP-A-2-68539, page 12, lower left column, line 17 to page 13, upper right column, line 6 10) Support, JP-A-2-68539, page 13, upper right column, lines 7 to 20. 11) Crossover JP-A-2-264944, page 4, upper right column 20 From the cutting method line, page 14 upper right column. 12) Dyes and mordants JP-A-2-68539, page 13, lower left column, line 1 to page 14, lower left column, line 9 JP-A-3-24537, page 14, lower left column to page 16, lower right column. 13) Polyhydroxy JP-A-3-39948, page 11, upper left column, benzenes, page 12, lower left column, EP Patent No. 452772A. 14) Layer structure JP-A-3-198041. 15) Developing method JP-A-2-103037, page 16, upper right column, line 7 to page 19, left lower column, line 15 and JP-A-2-115837, page 3, lower right column, line 5 Page 6, upper right column, line 10

[0040]

EXAMPLES The present invention will now be described in more detail by way of examples, but the embodiments of the present invention are not limited thereto. Example 1 Preparation of Emulsion A 1200 ml of an aqueous gelatin solution (containing 18 g of deionized alkali-treated bone gelatin having a methionine content of about 40 μmol / g, pH 4.3) was placed in a reaction vessel, and while maintaining the temperature at 38 ° C., Ag- 1 solution (20 ml of AgNO _{3 in} 100 ml)
g, 0.8 g of the gelatin, 0.2 ml of HNO ₃ 1N solution) and X-1 solution (6.9 g of NaCl in 100 ml, 0.8 g of the gelatin, 0.3 ml of 1N NaOH solution).
Simultaneous addition of only 12 ml at 4 ml / min. After stirring for 2 minutes, Ag-2 solution (containing 2 g of AgNO ₃ in 100 ml, 0.8 g of the gelatin and 0.2 ml of HNO ₃ 1N solution) and X-2 solution (1.4 g of KBr in 100 ml, 31 ml of containing 0.8 g of gelatin and 0.2 ml of NaOH 1N solution)
At the same time, 20 ml of the mixture was simultaneously mixed and added. After stirring for 2 minutes,
The Ag-1 solution and the X-1 solution were simultaneously mixed and added at 36 ml at 48 ml / min. NaCl-1 solution (100 ml of NaCl
20 ml (including 10 g) was added to adjust the pH to 4.8 and the temperature was raised to 75 ° C. After aging for 20 minutes, raise the temperature to 60
After lowering the temperature to ℃ and adjusting the pH to 5.0, A at a silver potential of 130 mV
g-3 solution (containing 10 g of AgNO _{3 in} 100 ml) and X
-3 solution (containing 3.6 g of NaCl in 100 ml)
CDJ. (Controlled double jet) was added. The flow rate at the start of addition was 7 ml / min, and the flow rate was accelerated at 0.1 ml / min per minute, and 400 ml of Ag-3 solution was added. Subsequently, AgBr fine particles 0.0 having an average particle size of 0.04 μm
59 moles were added over 5 minutes. Thereafter, 8.5 cc of 2N potassium thiocyanate solution was added to complete the grain formation. The resulting grains were rectangular to square tabular grains having a (100) plane as the main surface, and were high silver chloride grains having a silver bromide content of 17.3 mol%.

A precipitating agent was added, the temperature was lowered to 30 ° C., the precipitate was washed with water, an aqueous gelatin solution was added, and the pH was adjusted to 6.
2, adjusted to pCl 3.0. A part of the emulsion was sampled, and an electron micrograph image of the grains was observed. The shape characteristic values of the particles were as follows. (Total projected area of (100) tabular grains having an aspect ratio of 2 or more / sum of projected areas of all AgX grains) = 0.91, and (10) having an aspect ratio of 2 or more (10
0) Average aspect ratio of tabular grains (average diameter / average thickness) = 3.7, average diameter of (100) tabular grains having aspect ratio of 2 or more = 0.75 μm, (edge ratio of 1 or more and edge ratio of 1 ˜1.4 total (100) tabular grain total projected area / total AgX grain projected area) = 0.86,
(When (100) tabular grains having an aspect ratio of 2 or more are taken out from the large one up to 70% of the total projected area, the variation coefficient of the diameter distribution of the grains) = 0.055, average thickness =
0.21 μm.

After that, soluble salts were removed by the coagulation sedimentation method. The temperature was again raised to 40 ° C., 7.5 g of gelatin, 0.6 g of phenoxyethanol and 0.2 g of sodium polystyrene sulfonate as a thickener were added, and the pH was adjusted to 6.2 and pAg of 7.8 with caustic soda. To the emulsion thus prepared, 1 × 10 ⁻⁵ mol / mol Ag of thiosulfonic acid compound-I was added while maintaining the temperature at 58 ° C. with stirring, and then 8 × 10 5 of sensitizing dye-I was added. ^-Four
Mol / mol Ag and sensitizing dye-II were added at 3 × 10 ⁻⁶ mol / mol Ag.

[0043]

[Chemical 10]

[0044]

[Chemical 11]

Sodium thiosulfate, selenium compound-I, chloroauric acid and potassium thiocyanate were added, optimally chemically sensitized and then cooled to 35 ° C. to prepare Emulsion A of the present invention.

[0046]

[Chemical 12]

Preparation of Support X Preparation of Undercoat Dye Dispersion A The following Dye-I was ball milled by the method described in JP-A-63-197943.

[0048]

[Chemical 13]

434 ml of water and 791 ml of a 6.7% aqueous solution of Triton X-200 surfactant (TX-200) were placed in a 2 liter ball mill. 20 g of the dye were added to this solution. Zirconium oxide (ZrO ₂ ) beads 4
00 ml (2 mm diameter) was added and the contents were milled for 4 days.
Thereafter, 160 g of 12.5% gelatin was added. After defoaming, the ZrO ₂ beads were removed by filtration. Observing the obtained dye dispersion, the particle size of the crushed dye has a wide range of diameters from 0.05 to 1.15 μm, and the average particle size was 0.37 μm. Furthermore, dye particles having a size of 0.9 μm or more were removed by centrifugation. Thus, Dye Dispersion A was obtained.

Preparation of support Corona discharge treatment was carried out on a biaxially stretched blue-colored polyethylene terephthalate film having a thickness of 175 μm, and a first undercoat liquid having the following composition was applied at an amount of 4.
It was coated with a wire bar coater so as to be 9 cc / m ² and dried at 185 ° C. for 1 minute. Next, a first undercoat layer was similarly provided on the opposite surface.・ Butadiene-styrene copolymer latex solution (solid content 40% butadiene / styrene weight ratio = 31 to 69) 158cc ・ 2,4-dichloro-6-hydroxy-s-triazine sodium salt 4% solution 41cc ・ Distilled water 300cc Above A second undercoat layer having the following composition on each side of the first undercoat layer on both sides so that the coating amount will be the amount described below, one side at a time, and 165 ° C by a wire bar coater method on both sides.
And dried.・ Gelatin 160 mg / m ²・ Dye Dispersion A (as dye solid content) 8 mg / m ²・ C ₁₂ H ₂₅ O (CH ₂ CH ₂ O) ₁₀ H 1.8 mg / m ²・ Proxel 0.27 mg / m ² Matting agent Polymethylmethacrylate having an average particle size of 2.5 μm 2.5 mg / m ^{2 In} this way, a support including a crossover cut layer was prepared.

Preparation of Emulsion Coating Solution The following chemicals were added to 1 mol of silver halide of the tabular emulsion A for coating.・ 2,6-Bis (hydroxyamino) -4-diethylamino-1,3,5-triazine 72 mg ・ Dextran (average molecular weight 39,000) 18.5 g ・ Sodium polystyrene sulfonate (average molecular weight 600,000) 1.8 g ・ Gelatin The addition amount of each coated sample was adjusted so that the coating amount of gelatin in the emulsion layer was 1.6 g / m ² . Hardener 1,2-bis (vinylsulfonylacetamide) ethane 3.2 g

[0052]

Embedded image

The sensor layer was prepared and prepared so that each component had the following amount. Sensor layer coating liquid-Gelatin 800g-Dye described in Table 4-Proxel 0.7g

The surface protective layer was prepared and prepared so that the amounts of the respective components were as follows. Protective layer coating liquid ・ Gelatin 800g ・ Dextran (average molecular weight 39,000) 200g ・ C ₁₆ H ₃₃ O (CH ₂ CH ₂ O) ₁₀ H 39g ・ C ₈ F ₁₇ SO ₂ N (C ₃ H ₇ ) (CH ₂ CH ₂ O) ₄ (CH ₂ ) SO ₃ Na 1.6 g ・ C ₈ F ₁₇ SO ₃ K 7 g ・ Polymethylmethacrylate particles (average particle size 3.7 μm) 91 g ・ Proxel 0.7 g ・ Sodium polyacrylate (average molecular weight 4.1 10,000 g) 45 g ・ Sodium polystyrene sulfonate (average molecular weight 600,000) 3 g ・ NaOH 1.6 g ・ C ₈ H ₁₇ C ₆ H ₄ (OCH ₂ CH ₂ ) ₃ SO ₃ Na 24 g

[0055]

[Chemical 15]

-Add distilled water to 14 liters and complete

Preparation of Photographic Material The emulsion prepared above and the coating solution for the surface protective layer were sequentially coated on both sides of the support X under the same conditions by the simultaneous extrusion method. The amount of gelatin in the sensor layer and the protective layer was 0.
3 g / m ² and 0.75 g / m ² . For the tabular emulsion A, the coated silver amount was 1.00 g / m ² per side of the support.
(2 g / m ² on both sides) was adjusted. Thus
Preparation of photographic material 1 was completed. The swelling ratio of the obtained photographic material was 180% when measured according to the means and definition described in JP-A-58-11193. Also,
U.S. Pat. Nos. 4,425,425 and 4,425,42
When the crossover light of the photographic material was measured according to the means and definition described in No. 6, it was 20%.

Automatic developing machine and processing agent As an automatic developing machine, a modified plate-making / plate-making processor FG360A manufactured by Fuji Photo Film Co., Ltd. was used. As shown in FIG. 1, a ceramic liquid heater was arranged in the lower part of the main body to prepare a waste liquid receiving tray capable of temperature control. A polyethylene sheet for holding and collecting the residue obtained by evaporating and solidifying the waste liquid was placed on the tray. In addition, a part of the dry air is passed through the upper part of the tray to be exhausted so as to prevent the space between the main body of the automatic developing machine and the tray from becoming close to the saturated steam pressure. The developing and fixing waste liquids were mixed and discharged to a pan, and the pan was kept at 38 ° C. at all times.

Processing Method The developing solution had the following composition, and was supplied to a container having a low oxygen permeability of high-density polyethylene, with one bag being 2.0 liters. In use, without diluting this composition,
I just replenished it. To start the operation of the automatic developing machine, the developing tank was filled with the main developer (I) as it was. Developer (I) Diethylenetriamine pentaacetic acid 4 g K ₂ CO ₃ 55.2 g Sodium sulfite 30 g Ascorbic acid 50 g KBr 0.5 g 5-Methylbenztriazole 0.06 g 4-Methyl-4-hydroxymethyl-1-phenyl-3-pyrazolidone 4 g

[0060]

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Acetic acid 4.8 g A total volume of 1.0 liter was prepared and adjusted to pH 9.5.

The fixing solution had the following composition and was supplied in a polyethylene container in a volume of 2.0 liters. In use, this composition was replenished as it was without dilution. In the operation of the automatic processor, the fixing tank was filled with the fixing solution as it was. Fixer (I) Ethylenediaminetetraacetic acid 0.025g Sodium thiosulfate 290g Sodium bisulfite 76g NaOH 2.4g Adjust the total volume to 1.0 liter and adjust to pH 5.6.

Running Conditions An automatic developing machine was prepared, filled with the developing solution and the fixing solution as described above, and running was performed under the following conditions. Processing speed Dry to Dry 98 seconds Development temperature 35 ℃ Development replenishment rate 100cc / m ² Fixing temperature 35 ℃ Fixation replenishment rate 100cc / m ² Washing water volume 3 liters per minute only when photographic material is processed 15 sheets / day, operating 5 days a week Photographic material has an average blackening rate of 40%, and the operating time of the automatic developing machine is 8 hours a day. To correct the water content that decreases due to rinsing water evaporation and photographic material processing. To prevent the increase of waste liquid due to the rinse water.

Evaluation of Photographic Performance Photographic materials to be processed every day were sandwiched with an HG-M screen manufactured by Fuji Photo Film Co., Ltd., and the blackening rate was 4%.
It was exposed to 0%. Sandwich the photographic material with the HG-M screen manufactured by Fuji Photo Film Co., Ltd.
The X-ray exposure amount was changed by the distance method, and stepwise exposure was performed with a width of logE = 0.15. The X-ray tube used was a DRX-3724HD manufactured by Toshiba Corp., using a tungsten target and a focal spot size of 0.6 mm × 0.6.
The X-ray is generated by passing through an aluminum equivalent material of 3 mm including a diaphragm and a diaphragm. A voltage of 80 KVp was applied to the three phases with a pulse generator, and an X-ray that passed through a filter of 7 cm of water having absorption almost equivalent to the human body was used as a light source.

Evaluation of Residual Color The unexposed photographic material was processed for 45 seconds in Dry to Dry, and the resulting material was visually evaluated. ○: Practical no problem ×: Practical problem

Sensor Detectability 10 sheets of each photographic material were inserted from the film insertion port of the automatic processor for sensor detectability test, and tested for detection. This automatic processor has a pair of infrared light emitting elements (1150 nm and 1300 nm) and a light receiving element at the film insertion port, and the inserted sample recognizes the insertion of the sample when the infrared ray is sufficiently blocked. Has a mechanism for starting and transporting the film to the developing tank.

[0067]

[Table 5]

From Table 4, it can be seen that the samples of the present invention are excellent.

Example-2 1. Preparation of silver halide emulsion a) Preparation of silver halide emulsion B 15 g of gelatin was added to 900 ml of distilled water at 40 ° C.
After dissolution, adjust the pH to 2.0 with phosphoric acid and use sodium chloride.
1.35 g of the rubber was added. 60g of silver nitrate is added to distilled water 12
Liquid dissolved in 0 ml and sodium chloride 21.6 g, K ₂I
rCl₆Completed 5 × 10 per mol of silver halide^-6Mole
And a solution of 120 ml of distilled water
Under the conditions, it was added and mixed to the above liquid for 2 minutes and 48 seconds. Continued
A solution of 15 g of silver nitrate dissolved in 30 ml of distilled water and sodium chloride.
Thorium 4.34g, potassium bromide 2.12g distilled water
Add the solution dissolved in 30 ml under the condition of 30 ℃ for 42 seconds.
Then, the mixture was added and mixed. Adjust pH to 3.5 after addition
4-hydroxy-6-methyl-1,3,3a, 7-
2 g of tetrazaindene was added. The resulting emulsion is charged
Observed under a microscope, the diameter of the circle equivalent to the projected area was 0.
As a coefficient of variation of particle size with a particle size of 05 μm, 1
It was an emulsion consisting of cubic grains having a value of 2%. This
After desalting the emulsion of, gelatin 37 g, proxel 34
pH, phenoxyethanol 1.3g, and pH 5.
9. Adjust to pAg 7.2 with sodium chloride and
Chemical sensitization was performed at 60 ° C. by the procedure.

First, 73 mg of potassium iodide was added, after 5 minutes, 18 mg of sodium thiosulfate was added, and further after 3 minutes, 22 mg of chloroauric acid was added, and then aged for 60 minutes, 4-hydroxy-6-methyl-1,3,3. Emulsion B was prepared by rapid solidification while adding 70 mg of 3a, 7-tetrazaindene. Emulsion B
Is silver chloride 96 mol%, silver bromide 4 mol%, silver iodide 0.01
It was silver chloroiodobromide consisting of mol%.

2. Preparation of emulsion coating liquid The following chemicals were added to Emulsion B per mol of silver halide to prepare an emulsion coating liquid.

(Formulation of Emulsion Coating Solution) a. Spectral sensitizing dye [1] 7.3 × 10 ⁻⁵ mol. Supersensitizer [2] 0.42 g c. Polyacrylamide (molecular weight 40,000) 9.2 g d. Trimethylolpropane 1.4 g e. Poly (ethyl acrylate / acrylic acid = 95/5) latex 20g

Spectral sensitizing dye [1]

[0074]

[Chemical 17]

Supersensitizer [2]

[0076]

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F. Compound (3) 0.38 g

[0078]

[Chemical 19]

G. Compound (4) 0.085 g

[0080]

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3. Preparation of Coating Solution for Surface Protecting Layer of Emulsion Layer The container was heated to 40 ° C., and the following chemicals were added to prepare a coating solution. I. Gelatin 100 g b. Polyacrylamide (molecular weight 40,000) 8.7 g c. Sodium polystyrene sulfonate (molecular weight 600,000) 0.8 g d. Polymethylmethacrylate fine particles (average particle size 2.5 μm) 2.4 g (average particle size 0.8 μm) 9.2 g e. Sodium polyacrylate 2.6 g f. Sodium t-octylphenoxyethoxyethane sulfonate 1.6 g. C ₁₆ H ₃₃ O- (CH ₂ CH ₂ O) ₁₀ -H 3.6 g h. C ₈ F ₁₇ SO ₃ K 176 mg Re. C ₈ F ₁₇ SO ₂ N (C ₃ H ₇ ) (CH ₂ CH ₂ O) ₄ (CH ₂ ) _4- SO ₃ Na 88 mg. NaOH 0.2 g ru. Methanol 83 cc. 1,2-bis (vinylsulfonylacetamide) ethane Prepared to be 2.5% by weight based on the total amount of gelatin in the emulsion layer and the surface protective layer. W. Compound (5) 56mg

[0082]

[Chemical 21]

4. Preparation of Backing Layer Coating Liquid The container was heated to 40 ° C. and the chemicals shown below were added to prepare a back layer coating liquid. I. Gelatin 65 g b. Dye (A) 2.1g

[0084]

[Chemical formula 22]

C. Sodium polystyrene sulfonate 1.26 g d. Phosphoric acid 0.4 g e. 2.2 g of latex of poly (ethyl acrylate / acrylic acid = 95/5) f. Compound (5) 42mg

(Preparation of Dye Dispersion L) 2.5 g of each of the following dye-I and oil-I and II was dissolved in 50 cc of ethyl acetate to prepare sodium dodecylbenzenesulfonate 1.
5 g and 0.18 g of methyl p-hydroxybenzoate
90 g of an 8% aqueous gelatin solution containing the mixture was mixed at 60 ° C., and the mixture was stirred at high speed with a homogenizer. After the high speed stirring was completed, the pressure was reduced at 60 ° C using an evaporator, and ethyl acetate was added to 92
wt% removed. Thus, a dye dispersion L having an average particle size of 0.18 μm was obtained.

[0087]

[Chemical formula 23]

G. Dye Dispersion L 18.7 g below. Oil dispersion of dye (B) described in JP-A-61-285445 is used as dye itself 65 mg Dye (B)

[0089]

[Chemical formula 24]

Re. Compound (6) 0.65 g

[0091]

[Chemical 25]

Nu. Compound (7) 0.55 g

[0093]

[Chemical formula 26]

Preparation of Sensor Layer The following chemicals were added to prepare a coating solution. I. Gelatin 100 g b. Dyes listed in Table 5

5. Preparation of coating solution for surface protective layer of backing layer The container was heated to 40 ° C and the following chemicals were added to prepare a coating solution.

B. Gelatin 100 g b. Sodium polystyrene sulfonate 0.78 g c. Polymethylmethacrylate fine particles (average particle size 4.7 μm) 3.1 g d. Sodium t-octylphenoxyethoxyethane sulfonate 2 g e. Sodium polyacrylate 1.8 g f. C ₁₆ H ₃₃ O- (CH ₂ CH ₂ O) ₁₀ -H 4.05 g To. C ₈ F ₁₇ SO ₃ K 396 mg Chi. _{C 8 F 17 SO 2 N (} C 3 H 7) (CH 2 CH 2 O) 4 (CH 2) 4 -SO 3 Na 52mg Li. NaOH 0.24 g j. Methanol 148 ml. 1,2-bis (vinylsulfonylacetamide) ethane Prepared to be 2.5% by weight based on the total amount of gelatin in the back layer and surface protective layer.ヲ. Compound (5) 52.5mg

6. Preparation of photographic material The back layer coating solution was applied to one side of the polyethylene terephthalate support colored blue together with the back layer surface protective layer coating solution, and the gelatin coating amount of the backing layer was
1.50 g / m ² , sensor layer gelatin coating amount 0.5 g
/ M ² , and the surface protective layer of the backing layer was coated such that the gelatin coating amount was 1.02 g / m ² . Subsequently, the above-mentioned emulsion coating solution and surface protective layer coating solution were applied to the opposite side of the support, and the coating Ag amount was 1.00 g / m ² and the gelatin coating amount of the emulsion layer was 0.93 g / m ² . The surface protective layer was coated such that the coating amount of gelatin was 1.09 g / m ² .

Evaluation was carried out in the same manner as in Example 1, except that the infrared light emitting device was set to 940 nm and the dry-to-dry process was carried out for 29 seconds.

[0099]

[Table 6]

From Table 5, it can be seen that the samples of the present invention are excellent.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI technical display location G03C 1/83

Claims (5)

[Claims] 1. The following general formulas (I), (II) and (III)
At least one compound selected from the compounds represented
A photosensitive material containing a compound. General formula (I)In the formula, A₁, A₂Is a carboxylate (-COO^-)
Or sulfonate (-SO₃ ^-), T¹, T²
Is a linear or branched alkylene having 1 to 5 carbon atoms
Q represents a phenyl group or a substituted phenyl group.
I, G¹, G ³Is a halogen atom, cyano group, methane
Sulfonyl group, methoxycarbonyl group, ethoxycarbo
Nyl group, alkyl group having 1 to 4 carbon atoms, 1 carbon atom
Represents an alkoxy group of 1 to 4 and G², G^FourIs hydrogen
Child, halogen atom, alkyl having 1 to 4 carbon atoms
Represents an alkoxy group having 1 to 4 carbon atoms,
Represents an ion for maintaining the balance of charge. General formula (II)In the formula, n represents 0 or 1, and A₁, A₂Is Carboxyra
Group (-COO^-) Or a sulfonate group (-S
O₃ ^-), T₁, T₂Is 1 to 5 carbon atoms
Represents a linear or branched alkylene group of
G¹, G², G³, G^FourIs a hydrogen atom, halogen atom,
Ano group, methanesulfonyl group, methoxycarbonyl group,
Ethoxycarbonyl group, alkyl having 1 to 4 carbon atoms
Represents a C 1 -C 4 alkoxy group,
G^FiveIs hydrogen atom, halogen atom, methyl group, halogen unit
Represents a substituted methyl group, and M represents an ion for maintaining charge balance.
Represents the General formula (III):Where R₁And R₂Are each optionally substituted
Kill group, Z₁And Z₂Each may have a substituent.
A group of atoms that form a benzene ring or naphthalene ring, L is
The methine group, which may have a substituent, is linked by a conjugated double bond.
It is a trivalent group with 7 units connected, and X keeps charge balance.
, And m is a number for maintaining charge balance. 2. A compound represented by the general formula (III) is
The feeling according to claim 1, which is represented by the general formula (IV).
Light material. General formula (IV):R in the formula₁Is-(CH₂)_FourSO₃ ^-,-(CH₂)₃SO₃
^-,-(CH₂)₂SO ₃ ^-,-(CH₂)₂(CH₃) SO₃
^-, R_FourIs H, CH₃, Cl, Ph, Ph₂N-, P =
3, Y₁Is H, Cl, Y₂Is Cl, F, Ph, X⁺Is salt
Represents a cation capable of forming 3. The light-sensitive material according to claim 1, wherein the silver halide has a silver content of 4 g / m ² or less. 4. The light-sensitive material according to claim 1, wherein the silver amount of silver halide is 3 g / m ² or less. 5. The light-sensitive material according to claim 4, wherein the silver halide has a Cl content of 50 mol% or more.