JPH0444029A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To greatly improve safe light resistance and to prevent the generation of rubbing flaws and static marks so that a red sensitive paper having excellent practicability is obtd. by using silver halide particles which are subjected to red sensitization by desalting processing in the presence of a flocculating gelatin agent. CONSTITUTION:The silver halide photosensitive material provided with at least one kind of silver halide emulsion layers on a paper base which is red sensitive paper and is coated with a polyolefin resin on both surfaces is so color sensitized as to have the max. absorption wavelength at 600 to 750nm. In addition, the silver halide particles are subjected to the desalting processing in the presence of the flocculating gelatin agent. The generation of fogging against a safe light having the max. transmittance at 480 to 570nm is lessened by using the silver halide particles which are subjected to the desalting processing in the presence of he flocculating gelatin agent then to the red sensitization in such a manner. The silver halide photographic sensitive material which has the excellent safe light resistance and whiteness and does not generate static marks and rubbing flaws is obtd. in this way.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention provides a paper carrier having at least one silver halide emulsion layer provided on a panchromatically sensitized paper carrier whose both sides are coated with a polyolefin resin. This invention relates to a silver halide photosensitive material, so-called red-sensitive paper.

[Background of the invention]

So-called red-sensitive papers having a maximum absorption wavelength of 600 to 750 nm have been developed.

As a safelight for handling such red-sensitive paper, one with maximum transmittance in the range of 480 to 570 nm (region where silver halide has no photosensitivity) (Konica 1 to 5D) is used. There is.

On the other hand, on the sensitive material side, a dye (Mazenk dye) having a maximum absorption wavelength of 520 to 600 nm is added to the protective film to reduce fog caused by safelight. However, the current situation is that the safelight property is still not sufficient and the workability is very poor.

In addition, many of the pigments used in red-sensitive paper are water-insoluble, resulting in residual color after processing, which significantly impairs the whiteness of the paper.

On the other hand, in the computerized phototypesetting market, static marks and scratches occur due to static electricity generated by contact and friction between the phototypesetting machine and the photosensitive material, which can significantly impair image quality. As a countermeasure to this problem, the use of anionic, nonionic, and other surfactants has been studied. Conventional anionic, nonionic, and other surfactants are somewhat effective against static marks, but they are not always satisfactory. Further, it had almost no effect on scratches.

[Purpose of the invention]

Therefore, the present invention provides a paper that is used as a red-sensitive paper.
The object of the present invention is to provide a silver halide photographic light-sensitive material that has excellent safelight resistance and white skin, and is free from static, 7-marks and scratches.

[Structure of the invention]

The above object of the present invention is to provide a silver halide photosensitive material in which at least one silver halide emulsion layer is provided on a paper support coated with a polyolefin resin on both sides.
Achieved by a silver halide photographic material which is color sensitized to have a maximum absorption wavelength in the range from 0 to 750 nm, and which is characterized in that the silver halide grains are desalted in the presence of an agglomerating gelatin agent. Ru.

By using red-sensitized silver halide grains that have been desalted in the presence of an agglomerated gelatin agent, 480
In contrast to safelight, which has maximum transmittance at ~570 nm,
The occurrence of fog is reduced.

In addition, by adding other Mazenk dyes, especially by adding them to the outside of the emulsion layer, the safelight resistance can be further improved significantly.

Furthermore, by adding an oil-soluble fluorescent whitening agent to any of the constituent layers of the silver halide photographic light-sensitive material, residual color peculiar to red-sensitive paper is improved and a good white skin can be obtained.

Furthermore, by adding a fluorine-based surfactant to one of the constituent layers of a silver halide photographic light-sensitive material, the occurrence of static marks and scratches can be significantly improved. and,
- Layer effective.

The present invention will be explained in detail below.

The silver halide photographic light-sensitive material of the present invention has a molecular weight of 600 to 750.
It is a so-called red-sensitive paper that has been panchromatically sensitized to nm.

The sensitizing dye used in the present invention has the following general formula (1
) are preferred.

(XI)m In the general formula (1), Yl and Y2 each represent a group of nonmetallic atoms necessary to form a benzothiazole ring, a benzoselenazole ring, a naphthothiazole ring, a naphthoselenazole ring, and a quinoline ring, These heterocycles may have substituents, and these substituents include lower alkyl groups (
For example, methyl group, ethyl group, etc.), alkoxy group (for example, methoxy group, ethoxy group, etc.), hydroxy group, aryl group (for example, phenyl group, etc.), alkoxycarbonyl group (
Examples include methoxycarbonyl group, etc.), and halogen atoms (eg, chlorine atom, bromine atom, etc.).

R+, Rz are lower alkyl groups (e.g. methyl group, ethyl group, propyl group, methyl group, etc.), alkyl groups having a sulfo group (e.g. β-sulfoethyl group, γ-sulfopropyl group, δ-sulfobutyl group, sulfoethoxyethyl group) basis,
sulfopropoxyethyl group, etc.), and an alkyl group having a carboxyl group (for example, β-carboxyethyl group, γ-carbogyciprobyl group, δ-carboxybutyl group, carboxymethyl group, etc.).

R3 represents a methyl group, an ethyl group, or a propyl group.

X represents an anion commonly used in cyanine dyes (eg, halogen ion, Hensensulfonic acid ion, p-toluenesulfonic acid ion, etc.).

m represents 1 or O, and in the case of an inner salt, m=Q.

Next, specific examples of the compound represented by the two-layer general formula (1) will be shown. However, the compounds used in the present invention are not limited to these.

Margin below ■ ■ 　2HS C2I+.

■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ O3e (C11□)2COOI+ (C1l 2) 2COOe (C1lz) zcOo e ■ ■ ■ ■ The sensitizing dye represented by the general formula (1) is preferably a halogen 1 mg to 2 g per mole of silveride, more preferably 5 g
It is contained in the silver halide photographic emulsion layer in the range of 1 g to 1 g.

The sensitizing dye represented by the general formula [■] can be directly dispersed into the emulsion. Alternatively, they can be first dissolved in a suitable solvent such as methyl alcohol, ethyl alcohol, methyl cellosolve, acetone, water, hyridine, or a mixed solvent thereof, and then added to the emulsion in the form of a solution.

The sensitizing dye represented by the general formula (1) may be used alone or in combination of two or more. Moreover, sensitizing dyes other than the sensitizing dye represented by general formula (1) can also be used in combination. When a sensitizing dye is used in combination, it is preferable that the total amount amounts to two layers.

The above-mentioned sensitizing dyes are disclosed in US Pat. No. 2,503,776,
British Patent No. 742112, French Painting Patent No. 2065662,
It can be easily synthesized with reference to Japanese Patent Publication No. 40-2346.

In the silver halide photographic light-sensitive material of the present invention, the agglomerated gelatin agent used in the desalting treatment is preferably modified gelatin in which 50% or more of the amino groups of the gelatin molecules are substituted.

Examples of substituents for amino groups in gelatin are given in U.S. Pat.
, No. 691,582, No. 2,614,928, and No. 2,525,753, substituents useful in the present invention include (1) alkylacyl, arylacyl, Acyl groups such as acetyl and substituted or unsubstituted benzoyl; (2) carbamoyl groups such as alkylcarbamoyl and arylcarbamoyl; (3) sulfonyl groups such as alkylsulfonyl and arylsulfonyl; (4) alkylthiocarbamoyl and arylthio. Thiocarbamoyl group such as carbamoyl, (5) carbon number 1-
(6) aryl groups such as substituted or unsubstituted phenyl, naphthyl, pyridyl, aromatic heterocycles such as furyl, and the like.

Among these, preferred modified gelatin has an acyl group (-
COR') or carbamoyl group (-CON(11')R
2).

In addition, R1 is a substituted or unsubstituted aliphatic group (e.g., an alkyl group having 1 to 18 carbon atoms, an allyl group), an aral group, or an aralkyl group (e.g., a phenethyl group), and R2 is a hydrogen atom, an aliphatic group, or an aralkyl group (e.g., a phenethyl group). group, aryl group, or aralkyl group.

Particularly preferred is the case where R1 is an aryl group and R2 is a hydrogen atom.

It is desirable that the amine group-substituted agglomerated gelatin agent be used only during desalting treatment, and specific examples of such amino group-substituted agglomerated gelatin agents will be exemplified by amino group substituents, but the present invention is not limited thereto. It's not something you can do.

: Exemplary agglomerated gelatin agent (amino group substitution) 20-I
G-2 COC4Hq (t) C0CH5(,
-7 In addition, when using the above-mentioned flocculated gelatin agent during desalting treatment (removal of dissolved substances), there is no particular restriction on the amount added, but the substance contained as a protective colloid (
Preferably, the amount (weight) is 0.1 to 10 times that of gelatin (gelatin), particularly preferably 0.2 to 5 times (weight).

In the present invention, silver halide grains are agglomerated together with a protective colloid using an aggregating gelatin agent.
When a silver halide emulsion is coagulated, pi+ is adjusted. The pH for coagulation is 5.5.
Below, 4.8-2 is particularly preferable. The acid used for pH adjustment is not particularly limited, but organic acids such as acetic acid, citric acid, and salicylic acid, and inorganic acids such as hydrochloric acid, nitric acid, sulfuric acid, and phosphoric acid are preferably used. Heavy metal ions such as magnesium ions, cadmium ions, lead ions, zirconium ions, etc. may also be added to the aggregated gelatin agent.

The desalting step may be repeated once or several times. When repeating several times, an agglomerated gelatin agent may be added each time the removal is performed.

Note that the desalting treatment of silver halide grains using the amino group-substituted agglomerated gelatin agent, that is, the removal of soluble salts, may be carried out during the preparation of seed crystals, during growth, or after the completion of growth (after physical ripening). .

The fluorescent brightener contained in at least one of the photographic constituent layers including the hydrophilic colloid layer on the support is represented by the following general formula (
Compounds represented by II-a), (n-b), (n-c) (IT-d) can be preferably used.

(II-a) 2, 22 \ / [■] [■] (II-d) General formula (II-a), (II-b), (II-c), (
In II-d), Y and Y2 represent an alkyl group. 2. and Z2 represents a hydrogen atom or an alkyl group. n is 1 or 2. R+, Rz, R4 and RS are an aryl group, an alkyl group, an alkoxy group, an aryloxy group, a hydroxy group, an amino group, a cyano group, a carboxyl group, an amide group, an ester group, an alkylcarbonyl group, an alkylsulfo group, or a dialkylsulfonyl group. Does not represent a group or a hydrogen atom.

R6 and R1 represent a hydrogen atom or an alkyl group (methyl group, ethyl group, etc.).

RI6 represents a phenyl group, a halogen atom or an alkyl-substituted phenyl group, and R+s represents an amino group or an organic or secondary amine.

Next, general formula [■-a], (II-b), (II-c)
Specific examples of the compound represented by (II-d) will be listed, but the invention is not limited thereto.

[■ 3] H2 Ctl+ [■ 8] [■ 10] [■ 11] [■ 16] 113C-C-Ctla H3 [■ 17] [■ 18] [■ 19] [■ 13] [ ■ 14〕 [■ 15] (II-20) (II-21) the-C-CHz (II-22) [■ 23] (II-24) (II-25) (II-26) Amount of the above fluorescent whitening agent used preferably ranges from 1 mg/m to 200 mg/n (and more preferably from 5 mg/l to 50 mg/m) in the finished red-sensitive paper.

The above-mentioned fluorescent brighteners may be used alone or in combination of two or more. Further, fluorescent brighteners other than the above-mentioned fluorescent brighteners may be used in combination.

When a fluorescent brightener is used in combination, it is preferable that the total amount is the above content.

The layer to which the fluorescent brightener is added may be in any of the photographic constituent layers including the antihalation layer on the support, but it is preferably added to both the silver halide emulsion layer and the antihalation layer.

The method of adding the fluorescent brightener of the present invention is to dissolve it in a high boiling point organic solvent together with a low boiling point solvent if necessary, mix it with an aqueous gelatin solution containing a surfactant, and use a colloid mill, homogenizer, or ultrasonic dispersion device. It is added as an emulsified dispersion using an emulsifying device such as.

The fluorosurfactant used in the present invention contains one or more lipophilic hydrocarbon chains with 3 to 30 carbon atoms, as described in Belgian Patent No. 742,680; and contains at least one hydrophilic anion group, hydrophilic nonionic group, or hydrophilic hetain group, and all or part of the hydrogen atoms of one or more of the above hydrocarbon groups are substituted with fluorine. be.

The fluorine-based surfactant used in the present invention is represented by, for example, the following general formula (III).

General formula (III) RF-A-X In the formula, R4 represents a partially or fully fluorinated hydrocarbon group containing at least 3 fluorine atoms, A is a chemical bond or a divalent hydrocarbon group, Preferably an aliphatic group,
Represents an aromatic group, an aliphatic group, and an aromatic group, which includes oxygen, an ester group (-Coo-), and an amide group (-CO
NRI9- and -SO□NRI9-1 where RI9 includes a divalent hydrocarbon group interrupted by a heteroatom such as a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.

X is a hydrophilic group, for example (CIlzCIIzO)n6Rzo (Rzo is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, such as a methyl group,
n6 represents a number of 5 to 2i. ) (this polyoxyethylene group may be interrupted by one or more isopropyleneoxy groups).

), hydrophilic hequine groups, such as R2□ and (where ik represents an alkylene group having 1 to 5 carbon atoms, such as methylene, ethylene, propylene, butylene) , R21 represents an alkyl group having 1 to 5 carbon atoms, such as a methyl group or an ethyl group), a hydrophilic anion group, such as -
303M, -0303M represents a monium group or an organic ammonium group, such as jetanolammonium, morpholinium, pyridinium, etc., and R2□ represents an alkyl group or the same group as the above RF.

represents.

base RF The number of fluorine atoms in and R4 and charcoal in A The sum of the number of elementary atoms is 1 It is preferably 0 or more.

Best results are obtained using fluorosurfactants with terminal trifluoromethyl groups.

Representative examples of fluorosurfactants suitable for use in the present invention and corresponding to the above general formula include the following.

■-11 CI”＋ (CF2)? Cow SO□-N-C11゜CI (20-P-011■-15 (CFZ)6 CHz-0-CHz-Ctlz-Cflz-5OJa■ (CF2).

CI□-〇-Cllz-CI+z-CHz03Na (CF2)6 C1lz-O20:+Na ■ ↑ (CF2) 6-CHz-0-P-OffH ■ ■ 1゛(CF2) a-Cllz-0-P-Ot1■ I( ↑ (CFz)IQ-CH2-0-P-011■-17 (CFz) Io-Ctlz-0-CHz-CIlz-
CHz-3OJa■ CF3 (CF2) b-Ctlz-0-CHz-CHz-Cl
lz-SO3NaI1 ■ zHs CFz-C-0-CHz-CHz-CHz-3OJaC
211゜■-21 CF3 (CFz)z-COO-CHz-CHz-C)Iz-3
O3Na■ (CF2)+o-Coo-CHz-CHz-Ctlz-
5OJa■-23 (CFz) 6-CHz-00C-CHz-CHz-S
OJa(CF,)z-COO (C11□CIIzO)? -CL (CFz)? -3o□ N-(CIIZCII□O) 4 days Z115 (CFz) z-CtlzO (CII□CIl□0), ■ CH.

(CFz) 6-CONII-CIlzCHz-0-3
OJaC+ 61L+:+-CH-Coo-CHz-C
F3SO, Na C+ 61(:++-CH-C0NII-CHz-CI
'z-C)IFzSO:lH ■-40 CF3-(CF2) 7-8O□-N-CIIzCOO
I102+15 (CFz) 7-3Oz-N-Cllz-Cllz-0
-3(hllC2II 5 Na03S-CIl-COO-Cllz (CF2CF
2) 311C11z-C00-CIlz (CF2Ch
lzll■-44 (CF2CF2) t-CI(z-0-(C)IzCI
lzO)z. 11NaOzS-Cll-Coo((:
1lzcIIzO) zctlz(CFzCFz) z
llCIl□-COOC2115 I( ■-46 (CF2CF2) 3 Hz-0-CHz-CI-CHz-0CHz (CJIzCH20) z□H As the anionic surfactant particularly preferably used in the present invention, the following general 2 (IVA ), (rVB),
Compounds represented by l:■c) and (IVD:l) can be mentioned.

General formula (rVA) R+ 0COCII2 R20COCII Rs General formula (1'VB) R4-0COCII□ Rs 0COCII R60COCHR7 General formula CIVC) ■ (:9F, 9-0 (CIizCllzO) IocHzcHz-OH General formula in the above formula, R+, R2 , R4, Rs, Rb, Re
, R7 and RIG may be the same or different, and each represents a halogen atom, such as a chlorine atom, a bromine atom, an alkyl group, such as a methyl group, an ethyl group, a butyl group, an isobutyl group, a pentyl group, a hexyl group, an octyl group, nonyl group,
It represents a decyl group, a dodecyl group, or an octadecyl group, and may be linear or branched, and preferably has 1 to 32 carbon atoms. These alkyl groups are halogen atoms (
For example, chlorine atom, bromine atom), aryl group (for example, phenyl group, naphthyl group), etc. may be substituted with any substituent. Further, R3 and R7 represent an alkali metal salt of a carboxyl group, a sulfo group, or a phosphonic acid group. nI and R2 represent integers of 1 to 3.

Specific compounds represented by the general formulas (IVA) to CIVD) are illustrated below, but the compounds of the present invention are not limited thereto.

■ ■ ■ ■ ■ Below margin■ ■ ■ C5111□0OCCHzCHz C6III+0OCCHzCll-3OJaC1l:+
(CHz) 00C-Cll-3O:+Na ■ Csl++ +0OC-C1lz oHz+00cmCl-3OJa ■-18 ■ C113 (CHz) ? oco-cth Cll3 (Cll2) 7-OCO-CHCIl:l
(CH2) , -0CO-C)I-3OJaC311 COOCtl-3OJa C1b(CH2) 3-00C-CH-3OJaC1h
(Cll2) a-C1l (CJs) CHz-00
C-CH-3O3Na■-23C,H6CzIfs Examples of the polyethylene oxide nonionic surfactant used in the present invention include compounds represented by the following general formula.

General formula % Formula % General formula (VB) In the formula, A represents a group, a group, or a COO SO□N-R16 group (here, RI6 represents a hydrogen atom or a substituted or unsubstituted alkyl group).

R11 represents a substituted or unsubstituted hydrocarbon group.

R52 and RI3 are a hydrogen atom, a substituted or unsubstituted alkyl group, an aryl group, an alkoxy group, a halogen atom,
It represents an acyl group, amide group, sulfonamide group, carbamoyl group or sulfamoyl group.

RI4 and R15 represent a hydrogen atom, a substituted or unsubstituted alkyl group, or an aryl group. RI4 and RI5 may be linked to each other to form a substituted or unsubstituted ring.

R3, na, and R5 are average degrees of polymerization, R3 and R4 are 2 to 50, and R5 is 0 to 30.

Moreover, m is an average degree of polymerization, and is 2 to 50.

Preferred examples of the polyethylene oxide nonionic surfactant will be described below.

Preferred as R11 are alkyl groups, alkenyl groups, and alkylaryl groups having 4 to 24 carbon atoms, particularly hexyl groups, dodecyl groups, isostearyl groups, oleyl groups, t-butylphenyl groups, and 24-di-t -butylphenyl group, 2,4-di-t-pentylphenyl group, p-dodecylphenyl group, m-pentadecaffenyl group, L-octylphenyl group, 2,4-dinonylphenyl group, octylnaphthyl group, etc. are preferred.

Preferred examples of RIZ and R13 are a hydrogen atom, a methyl group, an ethyl group, an i-propyl group, a t-butyl group, and a t-
Amyl group, t-hexyl group, t-octyl group, nonyl group, decyl group, dodecyl group, trichloromethyl group, tribromomethyl group, 1-phenylethyl group, 2-phenyl group
Substituted or unsubstituted alkyl group having 1 to 20 carbon atoms such as 2-propyl group, substituted or unsubstituted aryl group such as phenyl group, p-chlorophenyl group, -OR+7 (RI7
represents a substituted or unsubstituted alkyl group or aryl group having 1 to 20 carbon atoms. same as below. ), a substituted or unsubstituted alkoxy group, a halogen atom such as a chlorine atom or a bromine atom, an acyl group represented by CORlq,
-NR11ICOR+7 (R+s represents a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms. The same applies hereinafter.

), an amide group represented by N R+ e S Oz R
It is a sulfonamidoyl group represented by I7.

Preferred examples of RI4 and RI5 are a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, and an n-propyl group.
Substituted or unsubstituted alkyl groups such as -heptyl group, -ethyl amyl group, n-undecyl group, trichloromethyl group, tribromomethyl group, phenyl group, naphthyl group,
p-chlorophenyl group, p-methoxyphenyl group, m-
It is a substituted or unsubstituted aryl group such as a nitrophenyl group.

Further, as a substituted or unsubstituted ring formed by R+a and R15 connected to each other, for example, a cyclohexyl ring can be mentioned.

Among these, those that are particularly preferable as R5 and RI5 are:
They are a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, and a phenyl group.

R3 and R4 are particularly preferably 5 to 30.

Next, specific examples of polyethylene oxide type (PEO type) nonionic surfactants preferably used in the present invention will be shown.

Margin below-I V-2 ■-18 C + lH 2 3COO (Cll□CHzO)s
tlC+slh+C00(CH2CH20)+sllC
+JasCOO(Cll□CHzO)+sHC. +11
70 (C112CH□0)? +1C+2HzsO(Ct
hCHzO) +. HC+6i1+:+O(CHzCl
+zO) +zllC1811270(CH2CH20
) 161102□H4SO(C12CH□0)z51
1CH3 CHzCIIzO (C)IzCIlzO) r□I!
a+b-15 ■-30 The silver halide emulsion used in the present invention includes conventional silver halide such as silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide, silver chloroiodobromide, and silver chloride. Any of those used in silver halide emulsions can be used.

The silver halide grains may have a uniform silver halide composition distribution within the grain, or may be core/shell grains in which the silver halide composition differs between the inside of the grain and the surface layer.

The silver halide grains may be such that a latent image is mainly formed on the surface, or may be such that a latent image is mainly formed inside the grain.

The silver halide grains may have a regular crystal shape such as a cube, octahedron, or dodecahedron, or may have an irregular crystal shape such as a spherical shape or a plate shape. In these particles, any ratio of the (100) plane to the (1111 plane) can be used.

Further, the particles may have a composite form of these crystal forms, or particles of various crystal forms may be mixed.

The grain size of silver halide grains is 0.05 to 3
0μ, preferably 0.1 to 20μ can be used.

The silver halide emulsion may have any grain size distribution. An emulsion with a wide grain size distribution (referred to as a polydisperse emulsion) may be used, or an emulsion with a narrow grain size distribution (referred to as a monodisperse emulsion) may be used alone or in combination.

Further, a polydisperse emulsion and a monodisperse emulsion may be mixed and used.

The silver halide grains used in the emulsion of the present invention are formed by cadmium salts, zinc salts, lead salts, thallium salts, iridium salts or complex salts, rhodium salts or complex salts, iron salts, etc. Alternatively, it is preferable to add a metal ion using a complex salt and include it inside the particles and/or on the particle surface, and it is particularly preferable that the rhodium salt or complex salt is present in an amount of 10-8 to 10-6 mol per mol.

In the emulsion of the present invention, unnecessary soluble salts may be removed after the growth of silver halide grains is completed, or they may remain contained.

Although the photosensitive silver halide emulsion can be used as a so-called primitive emulsion without chemical sensitization, it is usually chemically sensitized.

Chemical sensitization can be carried out either alone or by sulfur sensitization using active gelatin or a sulfur-containing compound that can react with silver ions, reduction sensitization using reducing substances, and noble metal sensitization using gold or other noble metal compounds. Can be used in combination. As the sulfur sensitizer, thiosulfates, thioureas, thiazoles, rhodanines, and other compounds can be used.

There are no particular restrictions on the conditions such as pH, pAg, temperature, etc. during chemical sensitization, but the pH value is preferably 4-9, especially 5-8, and the pAg value is kept at 5-11, especially 8-10. is preferable. In addition, the temperature is 40°C to 90°C.
°C1 Particularly preferred is 45°C to 75°C.

In addition to the aforementioned sulfur sensitization and gold/sulfur sensitization, the photographic emulsion used in the present invention can also be subjected to reduction sensitization using a reducing substance, noble metal sensitization using a noble metal compound, or the like.

As the photosensitive emulsion, the above emulsion may be used alone,
Two or more emulsions may be mixed.

When carrying out the present invention, for example, 4-hydroxy-6-methyl-1,3,
Various stabilizers can also be used, including 3a,7-tetrazaindene, 5-mercapto-1-phenyltetrazole, 2-mercaptobenzothiazole, and the like.

The sensitizing dye used in the present invention is used at a concentration equivalent to that used in ordinary negative-working silver halide emulsions. In particular, it is advantageous to use the dye at a concentration that does not substantially reduce the inherent sensitivity of the silver halide emulsion. A concentration of about 1.0XIO-' to about 5X10-' mole of sensitizing dye per mole of silver halide is preferred, particularly for use at a concentration of about 4X10-5 to 2X10-' mole of sensitizing dye per mole of silver halide. is preferred.

One type of sensitizing dye or a combination of two or more types can be used, and sensitizing dyes other than those mentioned above may be used in combination.

A color coupler can be added to the silver halide photographic material of the present invention, if necessary, and for example, at least one of a cyan coupler, a magenta coupler, and a yellow coupler is added.

The silver halide photographic material according to the present invention may contain water-soluble dyes other than those mentioned above as filter dyes in the hydrophilic colloid layer or for various purposes such as preventing irradiation and halation.

Such dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes, azo dyes, and the like.

Among them, oxonol dyes, dihemioxonol dyes, and merocyanine dyes are useful.

In the silver halide photographic material according to the present invention, when dyes, ultraviolet absorbers, etc. are included in the hydrophilic colloid layer, they may be mordanted with a cationic polymer or the like.

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

The silver halide photographic light-sensitive material of the present invention contains antifoggants, ultraviolet light inhibitors, antistatic agents, capping agents, surfactants, thickeners, plasticizers, hardeners, and coating aids that are commonly used in light-sensitive materials. Agents, emulsifiers, modifiers, antifoaming agents, clotting agents, slipping agents, toning agents, etc. can be used.

In the manufacturing method of the present invention, the pH of the coating liquid is 5.3 to 7.
．． It is preferable that it is in the range of 5. For multi-layer coating,
It is preferable that the pH of the coating liquid obtained by mixing the coating liquids for each layer in the ratio of coating amounts is within the above range of 5.3 to 7.5. If the pH is less than 5.3, the progress of hardening is slow, which is undesirable, and if the pH is more than 7.5, it often has an adverse effect on photographic performance (which is not preferred).

The photosensitive material of the present invention may further contain various additives depending on the purpose.

These additives are described in more detail in Research Disclosure Vol. 176 Item/7643 (1978, 1
February) and Volume 187 Item /8716 (19
(November 1979).

In carrying out the silver halide photographic material of the present invention, for example, the emulsion layer and other layers can be constructed by coating on one or both sides of a flexible support commonly used in photographic materials.

Useful flexible supports include films made of semi-synthetic or synthetic polymers such as cellulose nitrate, cellulose acetate, cellulose acetate butyrate, polyethylene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, etc.
Baryta layer or alpha olefin polymer (e.g. polyethylene, polypropylene, ethylene/butene copolymer)
paper coated or laminated with etc. Preferably, the paper is coated or laminated with a baryta layer or an α-olefin polymer (for example, polyethylene, polypropylene, ethylene/butene copolymer) on one or both sides. The support may be colored using dyes or pigments.

It may be black for the purpose of blocking light. The surface of these supports is generally treated with an undercoat to improve adhesion with emulsion layers and the like.

The surface of the support may be subjected to corona discharge, ultraviolet irradiation, flame treatment, etc. before or after the undercoating treatment.

In the silver halide photographic light-sensitive material according to the present invention, the photographic emulsion layer and other hydrophilic colloid layers can be coated on the support or on other layers by various coating methods. For coating, a dip coating method, a roller coating method, a curtain coating method, an extrusion coating method, etc. can be used.

The photographic processing of the silver halide photographic material according to the present invention is as follows:
Various methods can be used without particular limitations.

For example, research disclosure (Research
Any of various methods and various treatment liquids can be applied, such as those described in No. 176, pp. 28-30 (RD-17643). The treatment temperature is usually chosen between 18°C and 50°C, but it may also be below 18°C or above 50°C.

For example, the developer used in black-and-white photographic processing can contain a developing agent. As developing agents, dihydroxybenzenes (e.g. hydroquinone), 3-pyrazolidones (e.g. 1-phenyl-3-pyrazolidone),
Aminophenols (for example, N-methyl-0-aminophenol) and the like can be used alone or in combination.

Developing solutions generally contain various preservatives, alkaline agents, and p.
Contains H buffering agent, antifogging agent, etc., and further contains dissolving aid, color toning agent, development accelerator, surfactant, antifoaming agent, etc. as necessary.
It may also contain a water softener, a hardening agent, a viscosity imparting agent, and the like.

The photographic emulsion of the present invention can be subjected to a so-called "lith type" development process.

As the fixer, one having a commonly used composition can be used. As the fixing agent, in addition to thiosulfates and thiocyanates, organic sulfur compounds known to be effective as fixing agents can be used. The fixer may contain a water-soluble aluminum salt as a hardening agent.

Exposure for the photographic emulsion used in the present invention varies depending on the state of chemical sensitization, purpose of use, etc., but includes tungsten, fluorescent lamp, mercury lamp, arc lamp, xenon sunlight, xenon flash, cathode ray tube flying spot, laser light, electronic Various types of light sources can be used as appropriate, such as X-rays, X-rays, and fluorescent screens for X-ray photography.

As for the exposure time, in addition to normal exposure of 1/1000 to 100 seconds, short exposure of 1/10' to I/10' second can be applied with xenon flash, cathode ray tube, and laser light.

〔Example〕

Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these Examples.

Example-1 (Preparation of emulsified dispersion of fluorescent brightener) 0.8 g of oil-soluble fluorescent brightener (II-13) was mixed with 25 ml of talesyl diphenyl phosphate and 12 ml of 1-butanol.
To mA? The solution was mixed with 260 m6 of a 5% aqueous gelatin solution containing 0.5 g of triisopropylnaphthalene sulfonic acid sodium salt, and an emulsified dispersion was prepared by ultrasonic dispersion.

(Preparation of coating solution for silver halide emulsion layer) (i) Preparation of emulsion Bm-A ■Preparation of silver halide grains■ Solution 1 Ossein gelatin aqueous solution 2 AgNO.

Aqueous solution 3 8gC7! Br Aqueous solution 4 Br l Water Ammonia water (28%) 0g 400 mβ 8g 1g 150m7! 0g 50mA 2g 0.6g 00mA 0m11 Solution 5 1% KsRhBr6 1 m
j! 25% KBr solution 1999nl solution 6 0.5% Kz (Ir(IV)CL,)
0.75g water
36.75mj! Solution of solution 1, 2 ml of solution 5 (
The amount of rhodium salt added is 4.2X1 per mole of silver halide.
After 2 minutes, solutions 2 and 3 were simultaneously injected over 5 minutes, and after aging for 10 minutes, solution 4 was injected over 1 minute. Solution 6
to 0.25 mA (the amount of iridium salt added is halogen (1
2.9 x 10-7 moles per 11 moles) were taken and added.

After aging for 60 minutes after addition of solution 6, acetic acid (20%)
was added to adjust the pH to 5.7.

(2) Desalting step Next, Solution 7 below was added to this prepared solution and stirred for 5 minutes.

Solution 7 Agglomerated gelatin agent G-8 (amino group substituted -CONH (D modification rate 90%) 12g water 100n+
j2 Thereafter, the pH was adjusted to 4.4 with acetic acid to flocculate and precipitate the gelatin, and the supernatant liquid was drained.

Next, add pure 3ρ, then add NaOH to pH 4,
90 and stirred and dispersed. Thereafter, the pH was adjusted to 4.60 again with acetic acid to flocculate and precipitate the gelatin, and the supernatant liquid was drained.

This operation was repeated to desalinate a total of 3 times, and then 100% of phenol and 4% of the following compound [a] were added as antipyretic agents.
(2) was added, and the pH was finally adjusted to 5.90 to obtain emulsions E and -A having an average silver halide grain size of 0.67 μm and a monodispersity of 16.0%.

Compound (a) r HOCHHz CCH20)1 O2 (ii) Preparation of emulsions E and -B In the preparation of E and -A, the aging time after addition of solution 6 was set to 2
Emulsions E and -B having an average silver halide grain size of 0.54 μm and a monodispersity of 12.0% were obtained by using the same desalting process.

(iii) Preparation of Emulsions E and -C In the preparation of EII-A (7), the aging time after addition of solution 6 was set to 20 minutes to form grains, and the desalting step was performed as follows. That is, 15 m of a 10% polynaphthalic acid solution was added to the adjustment solution adjusted to 9115.7 obtained in the silver halide grain forming step (2) of emulsions E and -A. and 10 mβ of a 30% magnesium sulfate solution were added to flocculate and precipitate the gelatin, and the supernatant liquid was drained.

Next, pure water 3! was added and stirred, and further, 7.5 mj2 of 30% magnesium sulfate solution was added to flocculate and precipitate the gelatin again, and the supernatant liquid was drained.

This operation was repeated to desalinate a total of 3 times, and then phenol 300■ and the following compound (e) 11 were added as antifungal agents.
③ was added, the pH was finally adjusted to 5.90, and emulsion E
, -C was obtained. The average silver halide grain size and monodispersity were the same as those of Emulsions E and -B.

(2) Preparation process of coating solution for silver halide emulsion layer Emulsions EIl-A, E, -B thus obtained.

E and -C were kept at 59°C, 250 μl of calcium chloride and 1 mol of Ag were added, and 1 mol of KBr was added to 270 μl.

Ammonium thiocyanate 240nw 1 mol Ag, chloroauric acid 10 mol Ag and sodium thiosulfate 6 mol/^
Optimal chemical sensitization was performed using 8 and 8.

Then sensitizing dye: Example 1-12 10 tng 1 mol A
gDiethylene glycol 20g/mole 8g
, and then the fluorescent brightener emulsion prepared above was added as shown in Table 1, styrene-maleic anhydride copolymer was added as a thickener, and tetrakis(vinylsulfonylmethyl) was added as a hardener. Methane and taurine potassium salt 1:
A coating solution for a silver halide emulsion layer was prepared by adding 0.25 mol of the reaction product at 30 μm per gram of gelatin and adjusting the pH to 5.5 with citric acid.

(Preparation of coating solution for protective layer) Add a capping agent in the gelatin binder with an average particle size of 3.
5 μm polymethyl methacrylate was added at 70 μm/M, and a surfactant was added as shown in Table 1. Add formalin at 25 μm per gram of gelatin as a hardening agent, add 1 μg of 1 phenyl-5-mercaptotetrazole as an antifoggant, adjust PL+ to 5.5 with citric acid, and apply for protective layer. A liquid was prepared.

(Coating) The silver halide emulsion layer coating solution and the protective layer coating solution thus prepared were coated in multiple layers on a 110 μm thick polyethylene coated paper having a hydrophilic colloid soaking layer and an undercoat layer. Also, immediately before application (within 10 seconds), apply 1-
Phenyl-3-pyrazolidone (0.7 g per mole of silver)
) and a compound represented by the following compound (i) (5 g per mole of silver) was added to the coating solution for a silver halide emulsion layer.

Compound (i) HOCHzSO3Na The amount of silver coated was 1.5 g/I.

(Exposure) The thus prepared sample was exposed to light for 10 −6 seconds from an LED laser light source through an optical wedge.

(Processing) After the above exposure, development was performed using a developer having the composition shown below, followed by fixing, washing with water, and drying. Automatic developing machine GR-2 is used for development.
6 (manufactured by Konica Corporation) (development temperature: 38° C1 development time: 20 seconds).

<Developer prescription> Pure water (ion exchange water) Approximately 800ml Potassium sulfite 60g Ethylenediaminetetraacetic acid disodium salt 2g Potassium hydroxide
10.5g 5-methylbenzotriazole 300ml! diethylene glycol
25g 1-phenyl-4,4-dimethyl 3-pyrazolidone 300ml l11
-Phenyl-5-mercaptotetrazole 60m j
! Potassium bromide 3.5g Hydroquinone 20g Potassium carbonate 15g Add pure water (ion exchange water) to make a final solution of 1000 mβ. The pH of the developer was approximately 1018.

<Fixer formulation> (Composition A) Ammonium thiosulfate (72.5% W/V aqueous solution) 24
0ml sodium sulfite 17
g Sodium acetate trihydrate 6.5g Boric acid 6g Sodium citrate dihydrate 2g Acetic acid (90% W/W aqueous solution) 13.6m j! (Composition) Pure water (ion exchange water) 11ml 1l
Sulfuric acid (50% W/W aqueous solution) 4.7
g Aluminum sulfate (1!203 equivalent content is 8.1%W
/W aqueous solution) When using 26.5 g of the fixer, it was dissolved in 500 mj2 of water in the order of the above composition A and the composition and finished to 1β before use.

The pl+ of this fixer was about 4.3.

Sakura Digital Densitometer PDA measures the reflection density of the sample after processing.
-65 model (manufactured by Konica Corporation) to evaluate photographic properties.

The sensitivity was expressed as the reciprocal of the exposure amount required to obtain a blackening density of 1.0, and was expressed as a relative sensitivity, with the sensitivity of Sample 3 being 100. Further, T indicates the slope of the linear portion of the characteristic curve, and the larger T indicates the higher contrast.

In addition, the sharpness and white discoloration were visually evaluated on a 5-level sensory evaluation. A larger value indicates better results. Safelight resistance was evaluated by irradiating a safelight using an Ib5D filter (manufactured by Konica Corporation) from 2 m above the sample and measuring the time until the fog density increased by 0.04.

For static marks, place the unexposed sample at 23°C1RH.
The sample was left in a 20% dark room for one day and night, and the surface was brought into frictional contact with a neoprene rubber roll 20 times for development, and the degree of static marks generated was evaluated by sensory evaluation.

For scratches, the unexposed sample was left in a dark room at 23°C and R1+48% for one day and night, and the surface was rubbed 20 times with a stainless steel metal piece, developed, and the degree of scratches that occurred was evaluated by sensory evaluation. evaluated.

<Sensory evaluation level> 5: Not occurring at all 4: Occurring slightly, but no problem in practical use Level 3
...Level 2, which is the bare minimum for practical use...Level which cannot be used depending on the usage conditions■...Level which cannot be used at allAs can be seen from Table-1, the sample of the present invention was desalted in the presence of a condensed gelatin agent. Untreated emulsion E.

The safelight resistance was significantly improved compared to sample 1k13.14 using C.

Furthermore, compared to sample 1k12.14 without a fluorescent brightener, the sample to which a fluorescent brightener was added had improved whitening.

The sample of the present invention using a fluorine-based surfactant is excellent in safelight resistance, scratches, and static marks.

In addition, as seen in sample No. 4゜11, the use of an anionic or nonionic surfactant in combination was more effective than the samples No. 5 and 6 where a fluorine-based surfactant was used alone.
The improvement effect of static marks is significant.

As can be seen from sample numbers 7 and 8 and sample m9.10, when an anionic surfactant or a nonionic surfactant is used alone, the static mark is improved as the amount added increases.

〔Effect of the invention〕

As described above, safelight resistance can be significantly improved by using silver halide grains that have been desalted and red-sensitized in the presence of an agglomerated gelatin agent, and
Good whitening can be obtained by using a fluorescent brightener in combination, and further by using a fluorine-based surfactant, especially a fluorine-based surfactant and an anionic or/and nonionic surfactant. It is possible to provide a red-sensitive paper which can prevent the occurrence of scratches, static marks, and has excellent practicality.

applicant

Claims (1)

[Scope of Claims] 1. A silver halide photographic material comprising at least one silver halide emulsion layer on a paper support coated with a polyolefin resin on both sides, wherein
1. A silver halide photographic light-sensitive material, which is color sensitized so as to have a maximum absorption wavelength, and wherein silver halide grains are desalted in the presence of an agglomerated gelatin agent. 2. The silver halide photographic material according to claim 1, wherein the silver halide grains are color sensitized with a sensitizing dye of general formula [I]. General formula [I] ▲Mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, Y_1 and Y_2 are benzothiazole rings,
It represents a group of nonmetallic atoms necessary to form a benzoselenazole ring, a naphthothiazole ring, a naphthoselenazole ring, and a chirinone ring, and these heterocycles may have a substituent. R_1 and R_2 represent a lower alkyl group, an alkyl group having a sulfo group, or an alkyl group having a carboxyl group. R_3 represents a methyl group, an ethyl group, or a propyl group. X
_1 represents an anion commonly used in cyanine dyes. m represents 1 or 0, and in the case of an inner salt, m=0. 3. Claim 1 or 2 containing an oil-soluble fluorescent whitening agent
The silver halide photographic material described above. 4. The silver halide photographic material according to claim 1, 2 or 3, which contains a fluorine surfactant.