JPS63231444A - Silver halide black-and-white photographic sensitive material having satisfactory antistatic performance and fine silver tone - Google Patents

Abstract

PURPOSE:To obtain a sensitive material having superior antistatic performance and a fine silver tone by incorporating specified compds. and a fluorinated surfactant. CONSTITUTION:At least one kind of compd. represented by formula I, at least one kind of compd. represented by formula II and at least one kind of fluorinated surfactant are incorporated into an emulsion layer or other constituent layer on a supporting body. In formula I, each of R1 and R2 may be the same or different with each other and is hydroxyl, hydroxyamino, amino, alkylamino, arylamino, aralkylamino, alkoxy, phenoxy, alkyl, aryl, alkylthio or phenylthio group. In formula II, R3 is H atom or 1-3C unsubstd. alkyl group, each of (l) and (m) is an integer of 1-3 and (n) is an integer of 0-2. A sensitive material having superior antistatic performance and a fine silver tone can be obtd.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a silver halide black-and-white photographic material, and more specifically, to a silver halide black-and-white photographic material that has excellent antistatic properties and a good color tone of a silver image. Regarding materials.

[Conventional technology]

Since silver halide photographic materials generally consist of an electrically insulating support and photographic constituent layers, they are easily charged by friction or peeling under low humidity conditions, and the discharge causes the photosensitive emulsion layer to be exposed to light, resulting in a starburst. Problems such as dendritic or feather-like fog called tick marks may occur, dust particles may adhere to the surface of the photosensitive material due to accumulated electrostatic charge, and coating may not be uniform.

As a means to prevent such charging, attempts have been made to include hygroscopic substances, water-soluble inorganic salts, surfactants, etc. in the constituent layers of photosensitive materials, but among these methods, the following are useful: A method is known in which a polyalkylene oxide type or fluorine-containing surfactant is incorporated into the surface layer (JP-A-52-55521, JP-A-81-479).
No. 48, Special Publication No. 56-44411, etc.).

However, if only these surfactants are used, the stability of antistatic performance against changes in temperature and humidity is poor, so as a technique to improve this drawback, a technique that uses various polyols and various other surfactants in combination is proposed. Special Public Service
It is known from No. 9626. However, a drawback of this technique is that the color tone (silver tone) of the silver image (developed silver) obtained by the development process becomes yellowish, and this phenomenon is noticeable when observed using reflected light. Further, a light-sensitive material having an emulsion layer containing tabular silver halide grains has a particularly strong yellow tinge.

Such a yellowish tone of the developed silver is not desirable in a black-and-white photographic material in which the developed silver is directly observed as an image. For example, in the case of a medical X-ray film, since it may be observed not only by transmitted light but also by reflected light, such a yellowish image silver color gives an unpleasant impression to the observing doctor.

As a technique for improving silver tone, for example, Japanese Patent Application Laid-Open No. 1983-1989. 1
No. 58436 is known, but it is insufficient and further improvements are desired.

[Purpose of the invention]

Accordingly, an object of the present invention is to provide a silver halide black and white photographic light-sensitive material which has excellent antistatic properties and a good silver tone.

[Structure of the invention]

As a result of intensive research, the present inventors found that the above-mentioned object of the present invention can be achieved by the following silver halide black and white photographic light-sensitive material. That is, the silver halide black-and-white photographic light-sensitive material of the present invention has, on at least one surface of the support,
In a black and white photographic material having at least one silver halide emulsion layer, at least one compound represented by the following general formula ([) is contained in the emulsion layer or other constituent layers, and is represented by the following general formula (II). It is characterized in that it contains at least 1 m of the represented compound and at least one fluorinated surfactant.

In the formula, R1 and R2 may be the same or different from each other, and each represents a hydroxyl group, a hydroxyamino group, an amino group, an alkylamino group, an arylamino group, an aralkylamino group, an alkoxy, a phenoxy group, an alkyl group, an aryl group, an alkylthio group. or phenylthio group.

General formula [■] (CH2)--On In the formula, R3 represents a hydrogen atom or an unsubstituted alkyl group having 1 to 3 carbon atoms. 1 and . . . represent an integer of 1 to 3, and n represents an integer of 0 to 2.

The present invention will be explained in detail below.

-a In formula [l), the alkylamino group represented by R1 and R2 is preferably a mono- or di-substituted amine group of an alkyl group having 1 to 5 carbon atoms, and the arylamino group is preferably an aryl group having 6 to 10 carbon atoms. The group is a substituted amine group, and the aralkylamino group preferably has 7 to 7 carbon atoms.
11, an alkoxy group preferably has 1 to 5 carbon atoms, an alkyl group preferably has 1 to 5 carbon atoms, an aryl group preferably has 6 to 10 carbon atoms, and an alkylthio group preferably has 1 to 10 carbon atoms. 1 to 5.

The alkyl moiety in each group represented by R7 and R2 is a hydroxyl group or an alkoxy group (preferably a carbon number of 1 to 4).
, especially those of 1 to 2), amino groups, alkylamino groups (
It may have a substituent such as a mono- or di-substituted amino group, preferably an alkyl group having 1 to 4 carbon atoms, particularly 1 to 2 carbon atoms.

In each group represented by R3 and R2 above, the aryl or phenyl moiety is a hydroxyl group, an amine group, an alkylamino group (preferably 1 to 4 carbon atoms, particularly 1 to 2 carbon atoms).
mono- or di-substituted amino groups of alkyl groups), alkyl groups (preferably those having 1 to 4 carbon atoms, especially those having 1 to 2 carbon atoms), alkoxy groups (preferably those having 1 to 4 carbon atoms, especially those having 1 to 2 carbon atoms), etc. General formula [1] which may have a substituent
Among the compounds represented by the formula, either R1 or R2 is a hydroxyamino group, and the other is an alkylamino group. Particularly preferred are those in which R3 and R2 are both an alkoxy group or an alkylamino group.

General formula (1) preferably used in the present invention below
The following compounds are exemplified.

Below margin (g I -101-tt
I-12113l-1
4 (15[-16 [-171-18 [-191-20) These compounds are described in Journal of the Organic Chemistry, Volume 27, page 4054 (1962)
Journal of the American Chemical Society, Vol. 73, p. 2981 (1951), Special Publication No. 49-1
It can be synthesized by the synthesis method described in Publication No. 0692 and the like.

These compounds are added as aqueous, hydrochloric acidic or methanol solutions to hydrophilic colloid solutions for forming photographic emulsion layers or other constituent layers. The amount of the triazine compound represented by the general formula [I] to be added is preferably o, otg to 1011, and 0.1 g to 1011 per mole of silver halide.
0.01 per mole of silver halide, particularly preferably 1 g
．． If it is less than 10 g, the color tone of the developed silver will be insufficiently improved, and if it is more than 10 g, the sensitivity will decrease.

The triazine compound represented by the above general formula [I] can be used in combination with the hexahydrotriazine compound represented by the following general formula [(')].

General formula [1'] R1 1'1S [In the formula, R1 and Rs represent a hydrogen atom or a substituent] Specific examples of the compound represented by the general formula [1'] are listed below.

1'-11'-2 1'-31'-4 ■'-5 So, H ■ Below ° Margin Preferred specific examples of the compound (polyol) represented by the general formula [II] in the present invention are shown below.

■-3■-4 CI(2-CI(,OR) The amount of the polyol compound represented by the general formula [■] is preferably 0.04 to 0.25 per mole of silver halide. If it is less than 0.2, the storage stability against changes in temperature and humidity will deteriorate and the antistatic performance will deteriorate over time).
If it is 59 or more, a shoe-stick failure will occur.

The timing of adding the triazine compound represented by general formula [I] and the polyol compound represented by general formula (II) is not particularly limited, but it is preferable to add them after chemical ripening and immediately before coating. In addition to the silver halide emulsion layer, these compounds may be contained in coated layers such as an intermediate layer, a filter layer, and a protective layer on the side of the support having the silver halide emulsion layer.

As a fluorinated surfactant, Japanese Patent Publication No. 56-44411
The ones described on pages 58 to 61 of the publication and JP-A-49-
No. 46733, No. 51-32322, No. 56-190
No. 42, No. 57-11341, No. 55-7782,
No. 56-34858, No. 54-111330, No. 6
No. 1-47948, Special Publication No. 52-25087, No. 47
-9303, U.S. Patent No. 3,775,126, U.S. Patent No. 3,589,906, Research Disclosure
<Re5search Disclosure-re) 16
It is preferable to use those described in No. 630.

Among these, particularly preferred ones are listed below as typical examples.

m I CllF23S03 to IH3fl+cFz)s C112-OCl12Cl
lzCtlzSOJa111-4 C2
11゜1l-5 H+CF2)s C0NII CH2CL O5
OJa■-8 CH.

CH.

1l-9 CH.

411° ■-10 C.O.

CiF+* CHz CI CI+2 (l(CH
2C1hO)-ncsH+*■” 721+.

CtF+ 5cON +CHaCLO)Y+cllt)
The ysOsNa fluorinated surfactant may be added to at least one of the coating solutions for the coating layer on the side of the silver halide emulsion layer on the support, but it is preferably added to the coating solution for the protective layer. The amount of activator added is 1 part of the coating solution for the protective layer.
0.4 g to 1.5 g per liter is preferable; if it is less than 0.4 y/l, the antistatic performance will be insufficient, and if it exceeds t, sg/l, the improvement in the color tone of developed silver will be insufficient.

In the present invention, it is also possible to use surfactants other than fluorinated surfactants in combination.1For example, polyethylene oxide surfactants include JP-A Nos. 48-87828 and 5
No. 1-3219, No. 52-55521, No. 53-12
No. 9823, No. 58-208743, No. 81-479
Preferred are those disclosed in No. 48 and the like.

A specific example is shown below.

I n C+ol1g+ 0 (CH
tCHtO! allOn C1oH*+ 0
(CH2CHiOFsSJNaha n C1oH
*+ 0 (CIIiCH20)-scIIt
5O3N&) C,, +1. , C0NH(CH2
CH2O), HCl1゜force C+oLCtlt CHC)It O→C
HzCHiO)'n5OsNaThe silver halide emulsion used in the light-sensitive material of the present invention contains silver bromide, silver halide,
Any materials used in conventional silver halide emulsions, such as silver iodobromide, silver iodochloride, silver chlorobromide, and silver chloride, can be used, and the silver halide grains can be prepared by an acid method or a neutral method. Silver halide grains, which may be obtained by either the ammonia method or the ammonia method, are produced by cadmium salts, zinc salts, lead salts, thallium salts, iridium salts (including complex salts) during the process of grain formation and/or growth. ), rhodium salts (including complex salts), and iron salts (including complex salts) to add metal ions and contain these metal elements inside the particles and/or on the surface of the particles. The core/shell grains may have a uniform silver halide composition distribution within the grain, or they 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 the latent image is mainly formed on the surface, or may be such that the latent image is mainly formed inside the grain.

Silver halide grains may have regular crystal shapes such as cubes, octahedrons, and dodecahedrons, or may have irregular crystal shapes such as spherical or tabular shapes. In the 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 silver halide emulsion may have any grain size distribution. It may be an emulsion with a wide grain size distribution (referred to as a polydisperse emulsion) or an emulsion with a narrow grain size distribution (referred to as a monodisperse emulsion) either singly or in combination. Alternatively, a polydisperse emulsion and a monodisperse emulsion may be mixed and used.

The silver halide emulsion may be a mixture of two or more separately formed silver halide emulsions.

Silver halide emulsions can be chemically sensitized by conventional methods. That is, a sulfur sensitization method, a selenium sensitization method, a reduction sensitization method, a noble metal sensitization method using gold or other noble metal compounds, etc. can be used alone or in combination.

Silver halide emulsions can be optically sensitized to a desired wavelength range using dyes known in the photographic industry as sensitizing dyes. The sensitizing dye may be used alone or in combination of two or more, and together with the sensitizing dye, it is a dye that itself does not have a spectral enhancement effect, or a compound that does not substantially absorb visible light, A supersensitizer that enhances the exacerbating effect of the exacerbating dye may be included in the emulsion.

Silver halide emulsions are used during the manufacturing process of photosensitive materials, during storage,
Alternatively, for the purpose of preventing fog during photographic processing or maintaining stable photographic performance, photographic Compounds known in the art as antifoggants or stabilizers can be added.

Binder (or protective colloid) for silver halide emulsions
Although it is advantageous to use gelatin, synthetic hydrophilic materials such as gelatin derivatives, graphite polymers of gelatin and other polymers, other proteins, sugar derivatives, cellulose derivatives, monopolymers or copolymers, etc. Hydrophilic colloids such as polymeric substances can also be used.

The photographic emulsion layer and other hydrophilic colloid layers of the light-sensitive material of the present invention can be hardened by using one or more hardeners that crosslink binder (or protective colloid) molecules and increase 111 strength. can.

Plasticizers (for example, research,
Disclosure (Research Di-sc I)
Compounds described in A of Section 2 of No. 17643 can be added.

The photographic emulsion layer and other hydrophilic colloid layers of the light-sensitive material may contain a dispersion (latex) of a water-insoluble or sparingly soluble synthetic polymer for the purpose of improving dimensional stability.

In addition to the above, the photographic emulsion layer and other hydrophilic colloid layers of the light-sensitive material may contain additives commonly used in silver halide black-and-white photographic materials.

〔Example〕

The present invention will be further explained below with reference to Examples.

It goes without saying that the present invention is not limited to the examples.

Example 1 2 mol% silver iodide, 0.2 silver chloride with an average grain size of 0.18 μm
An inner core of monodispersed silver chloroiodobromide containing mol %, and a silver iodobromide layer with a ratio of 40 mol % silver iodide and 60 mol % silver bromide on the outside thereof to form 0.5 μ- grains. A silver iodobromide layer was grown to a diameter of 0.85 μm at a ratio of 1 mol % silver iodide and 99 mol % silver bromide to form a slightly rounded dodecahedral halide. Silver particles were obtained.

Chlorauric acid salts, rhodanammonium, sodium thiosulfate, and thiourea compounds were added to these particles, and after chemical ripening, an emulsion coating solution containing the following additives was prepared. The emulsion coating solution was coated simultaneously on a polyethylene terephthalate support at a coating speed of 150 m/sin so that the amount of silver was 4.8 g/m 2 and the amount of gelatin was 1.0 g/m 2 for the protective layer solution on a polyethylene terephthalate support and dried.

(Composition of emulsion coating solution) Per 1 p of coating solution (a) 51 g of lime-treated ossein gelatin (b
)5-Methyl-1,3,4,7a-tetrazaindene-
7-ol 0.8 g (c) Silver halide grains 0.6 mol (d) (e) Nitron 0.05 g (
f) Copolymer fine particles of styrene and butadiene (average particle size 0.03 μs) z, 5. I(g
) Copolymer of styrene and maleic acid 1.58 (h)
Triazine compounds listed in Table 1 (compounds represented by general formula [I]) (i) Polyol compounds listed in Table 1 (protective layer liquid composition) 41 lime-treated inert gelatin per coating solution i1 68 g, acid-treated gelatin 2g ha,
CHI C00C,. 821■ Na0=S C1(C00Csll+ +
1 g 2, polymethyl methacrylate, matting agent with a projected area average particle size of 3.2 μm 1.1 g e, Ludox AM (colloidal silica, manufactured by DuPont) 30 g, 2,4-
Aqueous solution (2%) of dichloro-6-hydroxy-1,3,5-triazine sodium salt (hardener) 15mZ 1~. Formalin aqueous solution <35%) (hardening agent) 1.
8ml Thiglyoxal aqueous solution (40%) (Hardening agent) 0.9...l Surfactant (antistatic agent) listed in Table 1 for nail fixing
- Humidify the unexposed sample at 23°C and 23% relative humidity for 2 hours,
After rubbing the sample with a rubber roller in a dark room under the same conditions,
Automatic processor G X-300 (manufactured by Konishiroku Photo Industry Co., Ltd.) and
After developing at 35° C. using developer D-90 (manufactured by the same company), the degree of static marks generated was visually determined. The evaluation was performed as follows.

A　°: Does not occur at all B: Occurs a little C: Occurs quite often D: Appears on almost the entire surface The results are shown in Table 1.

Going straight to 1nJL? -, tL The transmitted light density of the sample prepared as above after development was 1.
After exposure to 0, automatic processor KX-500 (
Using developer solution
90 (manufactured by the same company), development, fixing, washing, and drying were performed in 90 seconds.

The developed sample thus obtained was observed on a Scherkasten, and the silver tone determined by transmitted light was visually determined.

The evaluation was performed as follows.

A: Black B: Slightly reddish black C: Reddish black D = Black with a slight yellowish reddish tinge E: Yellowish reddish black The results are shown in Table 1.

Table 1 As shown in Table 1, samples No. 18 to No. 1 of the present invention
, 30 improved the color tone of developed silver while maintaining antistatic properties.

Example 2 An emulsion having tabular silver iodobromide grains with an average grain diameter of 1.71 μm and an asbec I ratio of about 30:1 was prepared by the method described in Example 2 of JP-A-58-113927. Prepared. These grains account for 70% or more of the projected area of silver iodobromide grains.

Chlorauric acid salt, rhodanammonium and sodium thiosulfate were added to the emulsion thus obtained and chemically ripened, and then the following sensitizing dyes were added and allowed to adsorb at 55°C for 15 minutes. An emulsion coating solution was prepared using the same additives as in Example 1, and the same protective layer solution as in Example 1 was used, and the photosensitive material samples were coated and dried under the same conditions as in Example 1. However, the types and amounts of the added triazine compound, polyol compound, and surfactant are as shown in Table 2.

White (sensitizing dye) The samples obtained in the above manner were evaluated in the same manner as in Example 1, with the amount added per mole of AgX being higher than that of white (sensitizing dye). The results are shown in Table 2.

Margin below Table 2 As shown in Table 2, samples No. 10 to No. of the present invention.

In No. 23, the color tone of developed silver was improved while maintaining antistatic performance. However, if the added wall of the polyol compound represented by the general formula (H) is less than 4 g (No. 16), the antistatic performance deteriorates over time, and if it is 25 g or more (No. 18), the film will suffer from sticking failure.

〔Effect of the invention〕

According to the present invention, the instability of antistatic performance due to changes in temperature and humidity when a fluorinated surfactant is used as an antistatic agent is improved, and silver images in conventional techniques for improving this instability are improved. The defect that the color tone is yellowish is improved.

Therefore, according to the present invention, a silver halide black and white photographic material having excellent antistatic properties and a good silver tone can be obtained.

・Applicant Konishiroku Photo Industry Co., Ltd. Procedural Amendment Statement March 10, 1986 Dear Commissioner of the Patent Office
U11 Pal Δ′- ■, Indication of the case 1988 Patent Application No. 66876 2, Name of the invention Silver halide black and white photographic light-sensitive material with good antistatic performance and silver tone 3, Person making the correction Relationship with the case Patent applicant address: 1-26-2 Nishi-Shinjuku, Shinjuku-ku, Tokyo Contact address: Konica Corporation, 1 Sakura-cho, Hino-shi, Tokyo, 191 Japan (Telephone: 0425-83-1521) 5
, "Detailed Description of the Invention" column of the specification to be amended.

6. Contents of amendment The detailed description of the invention is amended as follows.

(1) "In particular" on page 7, line 11 of the specification is amended to "especially."

(2) On page 8 of the same page, the structural formula of I-4 in the compound example of general formula CI) is corrected as follows.

(3) The structural formula of Compound Example 1-8 on page 15 of the same page is corrected as follows.

(4) The structural formula of Compound Example 2 on page 17 of the same page is corrected as follows.

(5) The structural formula of compound example (e) on page 17 of the same page is corrected as follows.

(6) On page 17 of the same, the structural formula of the compound example is corrected as follows.

r 5H (9) Sample No. 29 and N in Table 1 on page 27
Correct the column o, 30 as follows.

10) Correct the columns from Sample No. 16 to No. 23 in Table 2 on page 30 as follows.

(11) On page 31, insert the following between lines 6 and 7.

Example 3 In Example 1, samples No. 19, No. 2 in Table 1
0, No., and 21 triazine compounds I-6, respectively.
-7, l-14, l-18, and l-21, the effect of the present invention was also obtained.

Also, sample No. 19, No. 20. Polyol compound n-2 of No. 21 was ll-1, ll-4, respectively.
The effect of the present invention was also obtained by changing to I+-5.

Claims (1)

[Scope of Claims] A black and white photographic material having at least one silver halide emulsion layer on at least one surface of a support, in which the emulsion layer or other constituent layers is represented by the following general formula [I]. A silver halide black-and-white photographic light-sensitive material comprising at least one compound, at least one compound represented by the following general formula [II], and at least one fluorinated surfactant. General formula [I] ▲ Numerical formulas, chemical formulas, tables, etc. It represents an aralkylamino group, an alkoxy group, a phenoxy group, an alkyl group, an aryl group, an alkylthio group, or a phenylthio group. ] General formula [II] ▲ Numerical formulas, chemical formulas, tables, etc. are available▼ [In the formula, R_3 represents a hydrogen atom or an unsubstituted alkyl group having 1 to 3 carbon atoms. l and m represent an integer of 1 to 3, and n represents an integer of 0 to 2. ]