JPS58221840A - Photosensitive silver halide material - Google Patents

Abstract

PURPOSE:To obtain high photographic performance whether a lith type or non- lith type developer is used, by incroporating fine-grained paraffin having a specified grain size or below and at least 1 kind of compound having an alkylene oxide chain in the molecule into at least one photographic constituent layer contg. silver halide contg. a specified amount of silver chloride. CONSTITUTION:A high developing speed is necessary for silver halide used in a photosensitive emulsion to cause explosive development such as lith development, so >=50mol% silver chloride is required to be contained in the silver halide. Silver chlorobromide or silver chloroiodobromide contg. 60mol% siliver chloride, <=40mol% silver bromide and <=5mol% silver iodide is preferably used as the silver halide. The grain size of fine-grained paraffin contained in a photographic constituent layer is <=5mum, preferably <=1mum. By combining a polyalkylene oxide compound to be incorporated into the photographic constituent layer with the fine-grained paraffin, fog is not increased during non-lith development, and the photographic performance is remarkably improved whether a lith type or non- lith type processing soln. is used.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a silver halide photographic light-sensitive material, and more particularly to a silver halide photographic light-sensitive material that exhibits good photographic properties in lithium-type developers and non-lithium-type developers.

Silver halide photographic materials are used in a wide range of fields because of their ease of adjusting sensitivity, gradation, etc.

Particularly in the field of lithography, it is necessary to have extremely high contrast due to the necessity of its use, and a special technology for this purpose is the use of silver halide photographic materials containing a relatively large amount of silver chloride. This is a developer with a relatively low sulfite concentration (hereinafter referred to as a Lith type developer) that uses a dihydroxybenzene compound as a developing agent.
It has been common practice to process images to form images consisting of halftone dots and lines with very high contrast.

Furthermore, when the silver halide emulsion layer of the above-mentioned silver halide photographic light-sensitive material contains a compound having a polyalkylene oxide chain in its molecule, for example, as described in Japanese Patent Publication No. 42-25201 and Japanese Patent Application Laid-open No. 52-108130, The image becomes even more sharp and the image quality improves. In addition, photosensitive materials for graphic arts are required to have good physical properties such as dimensional stability, film formation, and processing characteristics in automatic processors. Designed to minimize the amount of gelatin.

However, the image quality improvement effect of the polyalkylene oxide compounds mentioned above is greatly influenced by the amount of gelatin, and the effect will be small if the amount of gelatin is small, so a considerably large amount is required to compensate for this effect. , sometimes reaching a large amount of several υ grams per mole of silver halide.

On the other hand, as a processing solution, although it is difficult to obtain high contrast with a Lith type developer, due to its stability, it contains a relatively large amount of sulfite and the developing agent is not limited to dihydroxybenzene compounds (non-Lith type developer) (as mentioned above). When a photographic material containing a large amount of a polyalkylene oxide compound is processed with this type of developer, the capri is increased and the contrast is significantly lowered, making it impossible to obtain good photographic properties.

Accordingly, one of the objects of the present invention is to provide a silver halide photographic material that exhibits good photographic performance whether processed with a lithium-type developer or a non-lithium-type developer.

Another object of the present invention is to provide a silver halide photographic material having excellent image contrast without affecting sensitivity or fog by using a novel combination of components.

Other details will become apparent from the description of the present specification and examples.

According to the present invention, the object of the present invention is to provide a silver halide photographic material having at least one photographic constituent layer containing silver halide containing at least 50 moles of silver chloride, in which a liquid It has been revealed that this can be achieved by using a silver halide photographic material containing at least one type of finely divided solid paraffin having a grain size of 5 μm or less and a compound having an alkylene oxide chain in its molecule.

That is, the present invention is characterized in that a polyalkylene oxide compound is contained together with liquid or solid paraffin in the photographic constituent layer of a silver halide photographic light-sensitive material for squirrels. A silver halide photographic material with excellent characteristics and high contrast could be obtained.

The present invention will be explained in more detail below.

In the present invention, the compound having a polyalkylene oxide chain in the molecule used in combination with liquid or solid paraffin is preferably represented by the following general formula (1) =
1 1 1 1 ) represents the group CH2CH2CH2-, and R4 and bird are
Hydrogen c Typical compounds represented by each of the above general formulas below: 8CHzOCzHs (m + n = 24.3 p = 12.5
)G(20C3H7 (m+n=17.5 p=6.7)(m+n
= 16.7 p = 15.3 ) α1 ) (CH2CH2O) mH (m = 67.8) ◇→ HO (CH2CH2O) mH (m = 34.6) Next, regarding the solid paran used in the present invention, The solid particle size is said to be 5 μm or less, but preferably 1 μm or less is particularly desirable. In other words, the effects of the present invention can be obtained to some extent with solid pine having a particle size of 5μ or more, but as the particle size increases, the stability over time of the paraffin dispersion or paraffin coating solution deteriorates, and the resulting coating film deteriorates. Transparency deteriorates.

The liquid paraffin or solid paraffin of the invention is contained in the dispersion and the photographic constituent layer, but in order to prepare a dispersion of solid paraffin having the above particle size, solid paraffin is dissolved in a low boiling point solvent.9. The solution is dispersed using a homogenizer, for example, into a solution containing a protective colloid such as tin or a surfactant. Even if the low boiling point solvent used above remains in the dispersion 1, it will not impede the effects of the present invention, but it is preferable to remove it by heating or reducing pressure after the dispersion is completed.

In the present invention, the amount of paraffin added to the photographic constituent layer has an effect depending on the amount added, but in reality, adding a large amount may deteriorate the physical strength of the coating film, so paraffin The amount is usually 5% to 100% by weight, based on the hydrophilic binder in the layer, and preferably 10% to 50% by weight.

On the other hand, a polyalkylene oxide compound represented by the above general formula, particularly a polyoxyethylene compound, exhibits a development accelerating effect in a non-lithium type developer, but on the contrary exhibits a development suppressing effect in a lithium type developer.

Jin's peculiar behavior is well known in the art world. This lithium development inhibitory effect gives good photographic performance when processed with a lithium type developer, but as mentioned above, when processed with a non-lithium type developer, due to its unfavorable development accelerating effect. This results in an increase in capri or a decrease in contrast, making it difficult to obtain good photographic performance. Capri inhibitors are generally added as a countermeasure, but these reduce capri and at the same time reduce the sensitivity, reduce contrast, and also suppress 1D lithium development. It is necessary to reduce the amount of the polyalkylene oxide compound, and as a result, the photographic performance in lithographic development also deteriorates.

According to the present invention, the amount of the polyalkylene oxide compound added to the photographic constituent layer is 1
0.01v to 2.0v per mole. Ofj', preferably 0.03f to 1.02. As the solvent for addition, water or an organic solvent miscible with water, such as ethanol, methanol, acetone, etc., is used.

There is no particular restriction on the timing of adding the liquid or solid paraffin and polyalkylene oxide compound used in the present invention to the photographic constituent layer, but for example, they may be added after the silver halide grain formation step or after the second ripening step. The most preferable photographic constituent layer to be added is an emulsion layer containing silver halide; Even if it is contained, the effects of the present invention can be obtained.

Further, according to the present invention, the rough in and the polyalkylene oxide compound may be contained together in a single layer, but the rough in and the polyalkylene oxide compound may be separately added to the constituent layer. It is also possible to do so.

The effects of the present invention can only be demonstrated by using liquid or solid paraffin in combination with polyalkylene oxide compounds that have the drawbacks mentioned above. It was a surprising discovery that no increase in capri was observed, and contrast was improved for both Lith type and non-Lith type processing solutions, and photographic performance was significantly improved.

The composition of silver halide (used in the photosensitive emulsion in the present invention) requires a high development speed in order to cause explosive development such as Lith type 1# (?). Silver chloride or chloriodide containing 50 moles or more of silver chloride, more preferably 60 moles of silver chloride, less than 40 moles of silver bromide, and less than 5 moles of silver iodide. Silver oxide is used. In addition, these neutral compounds are described in literature such as "The Theory of the Photographic Process" by James James, 4th edition, Macmillan Publishing (1977), pp. 88-104. method, acid method, ammonia method, forward mixing method, back mixing method, single jet method, double jet method, controlled dodagol jet method, con7 method, core shell method, etc. I can do it.

Furthermore, although there are no particular restrictions on the grain size, grain size distribution, crystal habit, morphology (normal crystal, twin crystal, etc.) of the silver halide grains used, silver halide grains with relatively uniform grain sizes of 1μ or less are preferred. preferable. Further, these silver halide grains or silver halide emulsions may contain an iridium salt and/or a rhodium salt in order to improve the closed light exposure characteristics and the like.

These silver halides generally include sulfur sensitizers such as sodium thiosulfate, thiourea ring; member metal sensitizers such as gold sensitizers, specifically chloroaurates, gold trichloride, etc.; palladium sensitizers; Specifically, palladium chloride, palladate chloride, etc., platinum compounds, iridium compounds, etc.; selenium sensitizers, such as selenite, selenourea, etc.; reduction sensitizers, such as stannous chloride, polyamines such as diethylenetriamine. can be chemically sensitized by using chemical sensitizers such as sulfite, silver nitrate, etc., alone or in combination, and still optically reach the desired wavelength by using optical sensitizers such as cyanine dyes, merocyanine dyes, etc. alone or in combination. can be sensitized to a wide range.

The present invention can also use electron-capturing compounds such as metal dopants or desensitizing dyes, and can also be applied to fogged direct positive photographic silver halide emulsions containing 50 moles or more of silver chloride.

As the silver halide vehicle having the above composition, gelatin, a gelatin conductor, a synthetic hydrophilic polymer, etc. can be used.

The silver halide photographic emulsion used in the present invention can contain various photographic additives.

For example, anti-capri agents include azaindenes, specifically 4-hydroxy-6-methyl-1,3,3a.

In addition to 7-chitrazaindene, triazoles, thiazoles, and tetrazoles, halogen-substituted acids such as calic acids and ethyleneiminated metals known in the art can be used. As the spreading agent, saponin, lauryl oleyl monoether of polyethylene glycol, etc. are used. There are no particular restrictions on the development accelerator, but
For example, compounds such as those described in JP-A-49-24427, quaternary ammonium salts, etc. can be used.

Examples of physical property improvers include homo- or 3-poly to cahyt?, such as alkyl acrylates, alkyl methacrylenides, and acrylic acids. ') w 5 pieces 2. ,,etc.
□ [Can be included. The silver halide emulsion layer or other constituent layers of the light-sensitive material according to the present invention include, for example, Japanese Patent Application No. 52-104940 and Japanese Patent Application Laid-open No. 51-562.
Antistatic agents such as those described in No. 20 and JP-A No. 49-46733 can be added.

In the present invention, the support used for coating the photosensitive emulsion may be arbitrary, such as polyethylene terephthalate film, polycarbonate film, polystyrene film, cellulose acetate film, etc. The present invention will be described below with examples. Although explained in detail, the present invention is not limited to these embodiments.

Example 1 In an aqueous binder containing gelatin, 69.8 molt of silver chloride, 30 molt of silver bromide,
Prepare a silver halide emulsion containing 0.2 mol of silver iodide,
After chemical sensitization using a combination of negative metal sensitization using chloroauric acid and sulfur sensitization using sodium thiosulfate, optical sensitization was performed by adding the merocyanine dye shown below, and further 4-hydroxy-6 as a stabilizer. -Methyl-1,3,3a, 7-
A polymer latex consisting of citrazaindene, saponin as a spreading agent, and ethyl acrylate as a physical property improver was added, and this was designated as Preparation Solution A.

(Merocyanine dye) (C), [2) 20H On the other hand, 700v of liquid dynamic barafine was added to 300c of ethyl acetate.
Dissolved in c and gelatin 200? , 260 cc of Alkanol-X C 10% manufactured by Nirasan Oil and Fat and 3.6 tons of pure water were mixed and added to the solution kept at 60°C after swelling, and then heated for 2 i50 h using a pressurized homogenizer laboratory type manufactured by Manton Gaulin Co., Ltd. in the United States. A liquid paraffin dispersion having an average particle size of 0.13 μm was obtained by dispersing at a pressure of y−.

Using the same method, the temperature was kept at 80℃ and the average particle size was 0.22μ.
A solid paraffin dispersion was obtained.

A part of the adjustment solution A was divided and nothing was added (Sample-1). 9 Exemplified Compounds (1) 500 mol of halogenated compound (Sample-2) was added. Similarly, Exemplified Compound (Sample-2) 1) was added in an amount of 1.01 to 1 mole of silver halide (sample-3) 2 exemplified compound (1) was added to 1 mole of silver halide, j71. After preparing a sample (sample-4) in which Or and the above-mentioned liquid paraffin dispersion were added in an amount of 25% by weight of paraffin based on the hydrophilic binder, mucochloric acid and glyoxal were added to each sample, and polyethylene A photosensitive material was obtained by coating silver on a terephthalate support in an amount of only 35 cm/100 ffl.

These samples were cut into small pieces and exposed to tungsten light for 2 seconds using a step wedge.

This sample was subjected to Lith development at 27° C. using Sakura Automatic Processing Machine GQ-258 and Sakuralis developer CD L-271 (both manufactured by Konishiroku Photo Industry Co., Ltd.).

On the other hand, these samples were processed using Sakura automatic processor QS-25.
Using CDM-621 (both manufactured by Konishiroku Photo Industry Co., Ltd.), a non-lithographic development process was performed at 38°C.

The results of each treatment are shown in Table 1. The contrast during evaluation expressed the slope of the leg of the characteristic curve, which is considered to be particularly important as a photographic characteristic.

(Table 1) As is clear from Table 1 above, when only a polyalkylene oxide compound is added to the paraffin-free photosensitive emulsion according to the present invention and the amount added is increased, lithium type development Although it improves the photographic properties in the case of non-lithographic development, it deteriorates the photographic properties in non-lithographic development. On the other hand, when a paraphyte is used in combination with a polyalkylene oxide compound, photographic properties can be improved in both lithium-type development and non-lithography development, and excellent contrast can be obtained without increasing fog.

Example 2 Exemplary compound (9) was added to a portion of the remaining part of the adjustment solution A at a ratio of 700 to 1 mole of silver halide, and the mixture was divided into two parts: one in which paraffin was not added (sample-5), and one in which no paraffin was added (sample-5). Sample-4 with the same amount of liquid paraffin added (sample-6) and solid paraffin added in the same manner (sample-7) were prepared, and coated and dried in the same manner as in Example-1. A non-squirrel type treatment was carried out. The results are shown in Table 2.

(Table 2) According to Table 2 above, it was found that the paraffin according to the present invention exhibits good improvement in photographic properties in both liquid paraffin and solid paraffin.

Example 3 Exemplary compound (4) was added to the remainder of the preparation solution A in an amount of 400 m9 per mol silver halide, and no paraffin was added (Sample-8) The same amount of liquid paraffin as in the sample-4 was added. (Sample-9), double the amount of liquid paraffin as Sample-9 (Sample-10), and 50 μl of 1 molar halogenated 5-nitrobenzimidazole as a capri inhibitor. Things (Sample-11)
, 5-2L-Lopenzimidazole was added in twice the amount of Sample-11 (Sample-12), and the coating and drying treatment was carried out in the same manner as in Example-1. The results are shown in Table 3.

(Table 3) According to Table 3 above, when 5-nitrobenzimidazole, a capri inhibitor, is further added to the sample used in combination according to the present invention, it has an inhibitory effect on capri, but the sensitivity and contrast decrease. Gives a bad influence to the opponent. In contrast, the combined use of paraffin and polyalkylene oxide compounds according to the present invention suppressed capri, had very little influence on sensitivity, and was found to exhibit excellent hard PA effects.

Agent Yoshimi Kuwabara Procedural Amendment Letter July 511, 1980 Special Clause 11 Commissioner Kazuo Sugi l Indication 11+'j Special Clause 11+'j Special Clause 11 No. 105047
1; 2 Name of the invention Silver halide photographic light-sensitive material, 3 Supplement 11 - Relationship with needle sweat a'1 Address of patent applicant 26-J, 1-J Nishi-Shinjuku, Shinjuku-ku, Tokyo Name (1) '27) Konishiroku Photo Industry Co., Ltd. 1 Representative IN
Director: Nobuhiko Kawamoto 4, Agent Address: 191, Address: 6, Uno ITr Sakura-cho 1, Tokyo, Column 7 of “Detailed Description of the Invention” of the specification to be amended, Contents of the amendment: Detailed Description of the Invention The explanation has been amended as follows.

(1) The entire text of pages 7 to 10 of the specification is corrected as follows.

represents an alkyl group, an aryl group, or an acyl group, and R4 and R, each have 1 hydrogen atom and 1 to 1 carbon atoms.
4 alkyl groups, cycloalkyl groups 1 carbon atoms 1 to 8
represents an alkoxy group or an aryloxy group. town,
n, and n are integers from O to 5, p++pm and pm
+ p, is an integer of O- (equity), and ml + m1,
ml + m4 and m are integers of 10 to 8o.

Typical specific examples of compounds represented by each of the above general formulas are listed below, but the present invention is not limited thereto.

(Compound example) (13HO(CHtCHtO)nl(CHtCHO)p
(CHtCHtO)nH book (2) HO(CH,CM,0)m(C%CHO)p
(CH, CH, 0)nH■ Procedural amendments Commissioner of the Patent Office Kazuo Wakasugi Indication of the case 1982 Patent Application No. 105047 2 Name of the invention Silver halide photographic light-sensitive material 3. Relationship with the Nagisa case to be amended Patent applicant address: 1-26-2 Nishi-Shinjuku, Shinjuku-ku, Tokyo) Name: (127) Konishiroku Photo Industry Co., Ltd. Representative Director -'', 4i (Embedded: Nobuhiko Kawamoto 〒 191 Residence: Hino, Tokyo 1-1 Sakuracho, Ichi (7) 10
(CH,CH,0)rIt(C horse CHO)p(OH,C
1(,0)nH1Net Show 58-221840θ0) 6. Column 7 of “Detailed Description of the Invention” of the specification to be amended Contents of the amendment The detailed description of the invention is amended as follows.

In the 1st and 2nd lines of page 22 of the specification, ``further related to the present invention'' is corrected to ``in place of the blank in''.

Konishi Roku Photo Industry Co., Ltd. Internal Procedures Amendment Document February 16, 1981 Patent Yj Director Kazuo Wakasugi 1゜ Display of Case 1989 Patent Application No. 105047 Li2! ! Name of Ming Silver Halide Photographic Light-sensitive Material 3 Relationship with the Supplementary Person Case Patent Applicant Address 1-26-2 Nishi-Shinjuku, Shinjuku-ku, Tokyo Name (+27) Konishiroku Photo Industry Co., Ltd. Representative Director Kawamoto Nobuhiko 4 Agent Address: 191 Tokyo I, 1-6, Sakura-cho, Noichi, Column L of “Detailed Description of the Invention” of the specification to be amended Contents of the amendment (1) #I9 on page 17 of the specification Insert the following between line 10 and line 10.

The present invention achieves the above object through its technical configuration. In addition, the silver halide photographic light-sensitive material according to the present invention is developed using a cerium reducing solution, a 7-Armor sterilizer, etc. When reducing force using a commonly used reducing liquid pressure such as a power liquid or an EDTA iron salt reducing liquid, the force reducing area is wide and the force reducing operation is easy to perform.

Here, the expression "wide during reduction" means that the reduction rate of the halftone dot size is larger than the reduction rate of the halftone dot density during reduction of the halftone image or the like.

6. Subject of correction The “Claims” column of the specification and “Detailed description of the invention” column 7. Contents of amendment (I) Amend the claims as shown in the attached sheet.

■ The detailed description of the invention is amended as follows.

(1) On page 4, line 13 of the specification, "liquid or paraffin" is corrected to "fine paraffin with a particle size of 5 μm or less."

(2) Page 5, line 5 Delete "liquid or solid".

(3) The entire text on page 10 of the same page is corrected as follows.

(13) HO(CHt CHt O) mW (m = 6
7.8) (14) HO(CH,CH,O)mH(m-34,6) Next, the paraffin used in the present invention is included.

The particle size of the fine paraffin contained in the photographic constituent layer is 5 μm or less as described above, and particularly preferably 1 μm or less.

In other words, the effect of the present invention can be obtained to some extent with paraffin having a particle size of 5μ or more, but as the particle size increases, the stability over time of the paraffin dispersion or the coating liquid to which the paraffin dispersion is added deteriorates, and the benefits are reduced. The transparency of the coated film deteriorates.

The paraffin used in the present invention is neutralized and contained in the photographic constituent layer as a dispersion, but in order to prepare the dispersion of paraffin having the above particle size, the paraffin is dissolved in a low boiling point solvent to form a solution, which protects gelatin, etc. It is produced by dispersing it in water containing colloids and surfactants, using a homogenizer, for example. Even if the low boiling point solvent used above remains in the dispersion, it will not impede the effects of the present invention, but after dispersion is completed, heat or reduce pressure, etc. (4), page 14, line 2 Delete the item ``Silver chloride ω mol%,''.

(5) Same page 14, page 10 [Control Double Jet] "Control double jet" I corrected.

Attached Patent Claims A silver halide photographic light-sensitive material having at least one photographic constituent layer containing silver halide containing at least (capital) mol% of silver chloride, wherein the photographic constituent layer has a shear diameter of 5μ or less. 1. A silver halide photographic light-sensitive material, characterized in that it contains fine particles of μs graphene and at least one compound having an alkylene oxide chain in the molecule.゛Procedural amendments Commissioner of the Japan Patent Office Kazuo Wakasugi 1 Indication of the case Patent Application No. 105047 of 1982 2 Name of the invention Silver halide photographic light-sensitive material 3 Relationship to the Nagisa case to be amended Patent applicant address Shinjuku-ku, Tokyo Nishi-Shinjuku 1-26-2 Name (127) Representative Director of Roku Konishi Photo Industry Co., Ltd. -
' ゛ , 4. Nobuhiko Kawamoto 191 Address 1-6 Sakura-cho, Hino-shi, Tokyo Column 7 of "Detailed Description of the Invention" of the specification subject to the amendment Contents of the amendment Detailed description of the invention The explanation has been amended as follows.

In the 1st and 2nd lines of page 22 of the specification, ``further related to the present invention'' is corrected to ``as an alternative to rough-in''.

Procedural amendment February 16, 1980 Mr. Kazuo Wakasugi, Commissioner of the Japan Patent Office l Indication of fact A1 Patent application No. 105047 of 1982 2! ! Name of Ming Silver Halide Photographic Light-sensitive Material 3 Relationship with the Supplementary IE Case Patent Applicant Address 1-26-2 Nishi-Shinjuku, Shinjuku-ku, Tokyo Name (+27) Roku Konishi! 5' Shin Kogyo Co., Ltd. Representative Director Nobuhiko Kawamoto 4 Agent 191 Address 1-5 Nogawa Sakura-cho, Tokyo 1 Date of the amendment order "Explanation" column 7, Contents of amendment (1) The following is inserted between line 9 and line 10 on page 17 of the specification.

The present invention achieves the above object through its technical structure. In addition, the silver halide photographic light-sensitive material of the present invention has a cerium-reduced form in the form button on which a silver image has been formed through development processing.
When reducing force using a commonly used force reducing liquid such as a force reducing liquid, a Far 1 force reducing liquid, or an EDTA iron salt reducing liquid, the force reducing area is wide and the force reducing operation is easy to perform.

Here, the expression "wide during reduction" means that the rate of decrease in the size of the halftone dots is greater than the rate of decrease in the density of the halftone dots in the reduction of the halftone dot image or the like.

Claims (1)

[Claims] In a silver halide photographic light-sensitive material having at least one photographic constituent layer containing silver halide containing at least 50 moles of silver chloride, the photographic constituent layer contains liquid or finely particulate solid halafine with a particle size of 5 μm or less; 1. A silver halide photographic material containing at least one compound having an alkylene oxide chain in its molecule.