JPH0656476B2 - Silver halide black and white photographic material - Google Patents

Description

The present invention relates to a silver halide black-and-white photographic light-sensitive material, and more specifically, it is a silver halide black-and-white photographic material containing a developing agent internally, which blocks and glosses the surface of the photographic light-sensitive material. The present invention relates to a silver halide black-and-white photographic light-sensitive material having improved film reduction and physical properties suitable for processing in an automatic processor.

(Prior Art) Acceleration of development processing of silver halide black-and-white photographic light-sensitive materials (hereinafter simply referred to as black-and-white light-sensitive materials) has been strongly desired, and an alkaline processing solution containing no developing agent (hereinafter referred to as activator) has been strongly desired. ) Rapid black-and-white photographic materials are also strongly desired. A large amount of developing agent is required in the black-and-white light-sensitive material in order to carry out rapid processing including these allycitors. Therefore, if 0.3 mol or more of a developing agent (for example, hydroquinone) is internally added to 1 mol of silver in a black-and-white light-sensitive material, the hardening of gelatin is hindered, and further blocking of the coated emulsion surface and the back surface of the support and poor gloss occur. , Becomes a big problem in production and practical use.

With respect to the problem of poor gloss, the physical properties of gelatin are often involved, for example, JP-A-60-3621.
As disclosed in US Pat. No. 5,968,839, a technique of using gelatin having excellent gloss has been proposed. However, even in this case, the improvement in gloss was not always satisfactory with the silver halide-gelatin system containing a large amount of hydroquinone and the like. The present inventors have found that in these problems, there is a close relationship between a gelatin layer containing a large amount of hydroquinone and the like and a hardening agent. In the gelatin layer containing these hydroquinones and the like and containing silver halide, a hardener capable of guaranteeing the quality of the photographic material is required.

It is generally known that an inorganic hardener or an organic hardener is added to a gelatin binder layer as a method for hardening a photographic light-sensitive material. Inorganic hardeners such as chrome alum have recently been used only in special cases, and most of them are organic hardeners.

The necessary requirements for the hardener are that it exhibits effective hardenability, that it does not adversely affect the photographic characteristics, fog, and other properties of the silver halide emulsion, and that it is water-soluble. It is easy to manufacture and low in cost.

In accordance with the above-mentioned demand, vinyl sulfone-based, ethyleneimine-based, epoxy-based, N-methylol-based, cyanuric chloride-based hardeners have been studied, and Japanese Patent Publication No. 47-61.
51, JP-A-48-19220, 51-78788.
No. 52-128130, No. 52-130362
No. 60-205443 and Japanese Patent Application Laid-Open Nos. 55-736 and 60-1708.
41, an N-methylol hardener has been disclosed as almost satisfying the above-mentioned desired properties. However, it has been found that the cyanuric chloride type hardener has a major drawback. The first problem is that blocking occurs in the coated and wound product during the manufacturing process of the black-and-white light-sensitive material, which hinders production. The second problem is that defective gloss occurs. Black-and-white light-sensitive materials, especially black-and-white photographic printing papers, cause fatal problems and markedly reduce the commercial value.

Further, it was found that the N-methylol hardener has the same drawbacks as the cyanuric chloride hardener. Also in this case, as in the above, the first problem is that blocking occurs in the coated and wound product during the manufacturing process. The second problem is that, like the above-mentioned hardener, poor gloss occurs. A third problem is that the amount of water absorbed during the development process is large, the drying after the process is delayed, and the processing efficiency is remarkably deteriorated particularly in high-speed processor processing. As described above, the black-and-white light-sensitive material containing a large amount of the developing agent internally is desired to have a hardening agent free from these problems.

(Object of the Invention) An object of the present invention is to firstly provide a means for preventing the coated wound product from being blocked during production, and secondly to provide a black and white light-sensitive material having a good surface gloss. The third object is to provide a black-and-white light-sensitive material having excellent processing and drying properties.

(Structure of the Invention) The above-described objects of the present invention are achieved by the following combinations of hardening agents. That is, it is achieved by containing 0.3 mol or more of polyoxybenzene or its derivative per mol of silver as a developing agent in the silver halide photographic emulsion layer and containing the compounds represented by the following (I) and (II). it can.

General formula (I) [In the formula, R ₁ represents a chlorine atom, a hydroxy group, an alkyl group,
Alkoxy group, alkylthio group, -OM group, (here M
Is a monovalent metal atom. ), -NR'R "(where R '
And R ″ each represent a hydrogen atom, an alkyl group or an aryl group) or —NHCOR (wherein R represents a hydrogen atom, an alkyl group or an aryl group), and R
₂ represents a group having the same meaning as R ₁ except for chlorine atom. ] General formula (II) (In the formula, R is hydrogen, an alkyl group or a substituted alkyl group, a phenyl group or a substituted phenyl group, An acyl group represented by, a carbamoyl group or an alkoxycarbonyl group, Is a sulfonyl group represented by. Here, R ₃ represents an alkyl group or a substituted alkyl group, a phenyl group or a substituted phenyl group, an alkenyl group, an amino group or a substituted amino group. R ₄ represents an alkyl group or a substituted alkyl group, a phenyl group or a substituted phenyl group. ) The addition amount of polyoxybenzene or its derivative as a developing agent used in the present invention is 0.3 mol or more, preferably 0.4 to 1.4 mol per mol of silver. As these developing agents used in the present invention, hydroquinone and 2-
Methyl-hydroquinone, 2-phenylhydroquinone, 2-chloro-hydroquinone, 2-tert-butyl-hydroquinone, 2,5-di-tert-butyl-
Examples thereof include hydroquinone, trimethyl-hydroquinone, catechol, 4-tert-butyl-catechol, homocatechol, and pyrogallol.

When used as a black-and-white light-sensitive material, hydroquinone or the like is preferably a silver halide emulsion layer, but may be partly added to adjacent layers.

Further, as an auxiliary agent, a developing agent other than the above-mentioned polyoxybenzene or a derivative thereof, for example, 3-pyrazolidones, aminophenols, ascorbic acid or a derivative thereof: reductones or phenylenediamines, is used as a silver halide emulsion layer. Medium and / or other photographic layers (eg protective layers, intermediate layers, antihalation layers,
Back layer).

The compound represented by the general formula (I) will be described in detail below.

An alkyl group represented by R ₁ in the above general formula (I),
Examples of the alkoxy group and the alkylthio group include an alkyl group having 1 to 3 carbon atoms, and examples thereof include a methyl group, an ethyl group, a methoxy group, an ethoxy group, a methylthio group and an ethylthio group.

Examples of M representing a monovalent metal atom of the —OM group represented by R ₁ include sodium, potassium, ammonium and the like, and R ′ and R ″ of the —NR′R ″ group.
Examples of the alkyl group represented by include an alkyl group having 1 to 3 carbon atoms, such as a methyl group and an ethyl group, and an aryl group includes a phenyl group.

Further, the alkyl group and aryl group represented by R of —NHCOR represented by R ₁ are synonymous with the alkyl group and aryl group represented by R ′ and R ″, respectively.

R ₂ is a group having the same meaning as R ₁ described above except a chlorine atom.

Next, typical examples of the hardener according to the present invention represented by the above general formula [I] will be described.

Next, examples of the compound used in the present invention are shown by showing R, R ₃ and R ₄ represented by the general formula (II). However, the compounds used in the present invention are not limited to these.

The compounds represented by the above general formulas [I] and [II] used in the present invention are added to the silver halide emulsion layer, but in addition to the above emulsion layer, they are partially added to other non-photosensitive auxiliary layers. Good.

In the present invention, the addition amount of the compounds represented by the above general formulas [I] and [II] varies depending on the amount of the developing agent, but is in the range of 1 to 20 mg of gelatin, preferably 5 to 20 mg.
It is 50 mg.

The weight ratio of the compounds of the above general formulas (I) and (II) is in the range of 1:40 to 40: 1, preferably 1:10 to 10: 1.

Incidentally, the object of the present invention can be achieved only by using the general formulas [I] and [II] used in the present invention in combination. Can't be reached.

Gelatin to which the hardening agent of the present invention is applied, in the production process thereof, so-called alkali-treated (lime-treated) gelatin dipped in an alkali bath, acid-treated gelatin dipped in an acid bath, and both treatments are performed before gelatin extraction. Double soaked gelatin, or "Bull. Soc. Sci. Photo.
o. It may be any of the oxygen-treated gelatin as described in "Japan" No. 16, p. 30 (1966).

Gelatin to which the hardening agent of the present invention is applied, if necessary, is partially colloidal albumin, casein, carboxymethyl cellulose, cellulose derivative such as hydroxyethyl cellulose, agar, sodium alginate, sugar derivative such as starch derivative, synthetic hydrophilicity. Colloids such as polyvinyl alcohol, poly-N-vinylpyrrolidone, polyacrylic acid copolymers, polyacrylamides or their derivatives / partial hydrolysates can be replaced, and so-called gelatin derivatives, ie, functional groups contained in the molecule. Amino group, imino group, hydroxy group, and carboxyl group treated with a reagent having one group capable of reacting with them, or a graft polymer in which the molecular chains of other polymer substances are bound. You may replace and use it.

J. Polymer Sci AI 9,3199
Acrylic acid, methacrylic acid or their derivatives such as esters, amides and nitriles described in (1971), or polymers or copolymers of what are commonly called vinyl monomers such as styrene can also be used. it can.

Further, high boiling point organic solvents such as alkyl phthalate (dibutyl phthalate etc.) Phosphate (diphenyl phthalate etc.) citrate, fatty acid ester, trimetate etc. have a boiling point of 30 ° C. to 15 ° C.
Low boiling organic solvents at 0 ° C, such as ethyl acetate, lower alkyl acetates such as butyl acetate, ethyl prohionate, 2
It may be dissolved and mixed in grade butyl alcohol and methyl isobutyl ketone.

The silver halide used in the black and white photographic material of the present invention is used as a light-sensitive component of all kinds of silver halides such as silver chlorobromide, silver iodochlorobromide, silver iodobromide, silver bromide and silver chloride. It is also possible to sensitize ruthenium, palladium, platinum, and gold noble metal salts, sulfur sensitization with sulfur compounds, selenium sensitization with selenium compounds, reduction sensitization with stannous salts, polyamines, etc. Sensitization can be performed with various compounds such as those with a xylene oxide compound. Furthermore, cyanine dyes, which can be optically sensitized with merocyanine dyes, further triazole compounds, azaindene compounds, stabilizers such as benzothiazolium compounds, wetting agents such as dihydroxyalkanes, antistatic agents, UV absorber, water-dispersible fine particle polymer substance obtained by emulsion polymerization, saponin, polyethylene glycol lauryl ether, sodium dodecylbenzenesulfonate, JP-B-47-930
3, coating aids such as fluorinated surfactants such as No. 48-43130, and various other known photographic additives can be added.

As the support of the black-and-white light-sensitive material to which the curing method of the present invention is applied, for example, a film sheet of baryta paper, laminated paper, glass, cellulose acetate, cellulose night, polyester, polyamide, polystyrene or the like can be used.

(Examples) Hereinafter, the present invention will be described with reference to Examples.

Example 1 The composition has a silver bromide content of 65.5 mol%, a silver chloride content of 34.0 mol%, and a silver iodide content of 0.5 mol%, and an average grain size of 0.45 μm.
m silver iodochlorobromide gelatin emulsion was prepared by the neutral single jet method. After physical ripening, desalting was carried out by washing with water, gelatin was added, and then sodium thiosulfate was added for chemical sensitization, and then a stabilizer and a surfactant were added to complete the emulsion. The resulting gelatin-silver halide emulsion was divided into 8 parts.

Regarding the compound (I-1) and the compound (II-1) used in the present invention, the amounts shown in Table 1 are added per 100 g of gelatin. Hydroquinone is added to the divided gelatin-silver halide emulsion in an amount shown in Table 1 per mol of silver.

The resulting emulsion both sides as silver photographic base coated with polyethylene layers, 1.7g / m ^2, gelatin 5.0 g / m ²
And was dried. The obtained sample is 5 at 40 ℃
Warmed for days.

One part of each sample was immersed in a developing solution having the following composition for 20 seconds at 30 ° C., 5 seconds for a stop solution (2% acetic acid solution), and 20 seconds for 30 seconds in a fixing solution having the following composition for about 25 ° C. 2 under running water
The water absorption amount after washing with water for 0 seconds was obtained. The results obtained are shown in Table 2.

(Developer A) Water 750 ml Hydroquinone 1.0 g Sodium sulfite 4.0 g Sodium carbonate (monohydrate) 15.0 g Potassium bromide 0.7 g Water was added 1,000 (Fixer B) Water 750 ml Ammonium thiosulfate 150 g Sulfite Sodium (anhydrous) 16 g Acetic acid 20 ml Ammonium sulfate (16 hydrate) 15 g Water is added to make 1,000 ml.

Further, eight kinds of samples immediately after coating were sequentially superposed, uniformly pressed at a pressure of about 5 kg / cm ² , and heated at 40 ° C. for 5 days. After heating, the blocking (peelability) between the emulsion side and the back side of the support of each sample was evaluated. Further, the obtained eight kinds of samples were uniformly exposed, and developed with the developer at 20 ° C. for 60 seconds,
After stopping, fixing, washing with water, and drying, the black gloss value was obtained with Gloss Meter VG-1D manufactured by Nippon Denshoku Industries Co., Ltd. The above results obtained are shown in Table 2.

As is clear from Table 2, sample Nos. 7 and NO.
No. 8 has excellent water absorption blocking (peeling property) and black gloss.

Example-2 Gelatin prepared by the same method as in Example-1
Hydroquinone was added to a silver halide emulsion in an amount of 0.
Add 35 moles. Further, the emulsion was divided into 7 parts.

Compound (I-1) Compound (II-
1) For comparison, formaldehyde (III) and a compound (IV) represented by the following formula: Compound (IV) The amount shown in Table 3 is added per 100 g of gelatin.

The obtained emulsion was coated in the same manner as in Example 1 to prepare 4 coated samples.
Warm at 0 ° C. for 5 days. The water absorption of each sample was determined by the same method as in the above-mentioned example. The results obtained are shown in Table 4. Further, the blocking (peeling property) and the black gloss value of the emulsion surface of each sample were obtained by the same method as described above, and the obtained results are shown in Table 4.

As is clear from Table 4, sample Nos. 11 and NO.
12 and NO.13 are water absorption, blocking (peelability)
And shows excellent characteristics in black gloss.

Continuation of the front page (56) Reference JP 55-736 (JP, A) JP 60-170841 (JP, A) JP 56-130740 (JP, A) JP 51-78788 (JP , A)

Claims (1)

[Claims] 1. A silver halide photographic emulsion layer containing at least 0.3 mol of polyoxybenzene or its derivative per mol of silver as a developing agent, and at least one compound represented by the following general formula (I). And a silver halide black-and-white photographic light-sensitive material containing at least one compound represented by the general formula (II). General formula (I) [In the formula, R ₁ represents a chlorine atom, a hydroxy group, an alkyl group,
Alkoxy group, alkylthio group, -OM group (where M is a monovalent metal atom), -NR'R "(wherein R'and R" are a hydrogen atom, an alkyl group and an aryl group, respectively). Or -NHCOR (wherein R is a hydrogen atom, an alkyl group or an aryl group), and R ₂
Represents a group having the same meaning as R ₁ above except a chlorine atom. ] General formula (II) (In the formula, R is hydrogen, an alkyl group or a substituted alkyl group, a phenyl group or a substituted phenyl group, An acyl group represented by, a carbamoyl group or an alkoxycarbonyl group, Is a sulfonyl group represented by. Here, R ₃ represents an alkyl group or a substituted alkyl group, a phenyl group, a substituted phenyl group, an alkenyl group, an amino group or a substituted amino group. R ₄ represents an alkyl group or a substituted alkyl group, a phenyl group or a substituted phenyl group. )