JPH08262622A - Silver halide photographic material - Google Patents

Abstract

PURPOSE: To provide silver halide photographic material for printing and processing, excellent in flaw resistance and pressure fogging resistance. CONSTITUTION: Silver halide photographic material has at least one photosensitive layer containing silver halide grain on base material, and at least one hydrophilic colloid layer as a non-photosensitive layer. In such silver halide photosensitive material, the photosensitive layer or hydrophilic colloid layer on the photosensitive layer side viewing from the base material contains acid treated gelatin with an isoelectric point of 7.0 or less, and in a photosensitive material manufacturing process, the photosensitive material is dried within two minutes while controlling the surface temperature to be 35 deg.C or low after application and setting.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic light-sensitive material, and more specifically, it produces scratches and pressure fog when it is conveyed in an output machine or an automatic processor mainly used in the printing plate making industry. It relates to a difficult photosensitive material.

[0002]

2. Description of the Related Art Generally, a silver halide photographic light-sensitive material, particularly a light-sensitive material used in the printing plate making industry, is required to have a certain strength in terms of film strength in addition to photographic characteristics.
In particular, in recent years, output machines such as scanners and imagesetters that use lasers and LEDs as output light sources have appeared, and by connecting them directly or indirectly to a very clean and very dry machine. Images are being formed in the environment. The operator of such an output machine or automatic processor no longer needs to perform maintenance, inspection, maintenance, maintenance, management, etc., and the photographic light-sensitive material is accordingly contacted when passing through the output machine or automatic processor. Resistance to fogging images in non-image areas due to scratches on the roll and scratches on the film is required.

On the other hand, in the field of producing photographic light-sensitive materials in large quantities, how high speed coating and rapid drying greatly influence the production cost, which is a very important issue. Although it is the easiest method to increase the drying rate by raising the temperature of the air blown to the coated surface at the time of drying, there are problems of reticulation and adhesion, and the performance of the light-sensitive material is deteriorated. Therefore, another method is to reduce the amount of coating liquid applied.
If the water content is simply reduced, that is, just by concentrating it, the viscosity of the coating solution increases and it cannot be applied successfully. Therefore, there is a method of simultaneously reducing the amount of gelatin, but the resistance to the fog image and the scratch on the film due to the scratches described above deteriorates, and a countermeasure technique is required.

Further, as described above, in order to efficiently operate an extremely expensive output / developing system, it has been attempted to reduce the output time as well as the developing / fixing / washing processing time (rapid processing). When aiming to reduce processing time,
One of the problems is the drying property after washing with water. The easiest way to improve the drying property is to raise the drying temperature, but this measure is not preferable because the photosensitive material expands and contracts and the dimensions become unstable. In other words, no matter how short time development or fixing is possible, the binder (especially gelatin) composition as in the past is used,
It cannot be dried in a short time. Therefore, it is necessary to reduce the amount of gelatin in this case as well, but as described above, the resistance to scratches and the pressure fog resistance deteriorate, and the demand for countermeasure technology is urgent.

[0005]

SUMMARY OF THE INVENTION The first object of the present invention is to resist fog images in non-image areas due to scratches on rolls that come into contact when passing through an output machine or automatic developing machine, and scratches on the film. To provide a silver halide photographic light-sensitive material for printing plate making.

Secondly, the object of the present invention is to improve scratch resistance and pressure resistance even if the amount of the binder (particularly gelatin) is reduced in order to improve the productivity or to improve the rapid processing property by those skilled in the art. It is an object of the present invention to provide a silver halide photographic light-sensitive material for printing plate making, which does not deteriorate in fogging property.

[0007]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a silver halide photographic light-sensitive material having at least one light-sensitive layer having silver halide grains on a support and at least one hydrophilic colloid layer as a protective layer. In the material, an acid-treated gelatin having an isoelectric point of 7.0 or less is contained in the photosensitive layer or the hydrophilic colloid layer on the side of the photosensitive layer as viewed from the support, and in the manufacturing process of the photosensitive material, after coating and setting, This was achieved with a silver halide photographic light-sensitive material characterized by being dried within 2 minutes while controlling the surface temperature to be 35 ° C. or lower.

Furthermore, in a preferred embodiment for achieving the second object of the present invention, the total amount of gelatin in the photosensitive layer and the hydrophilic colloid layer on the side of the photosensitive layer as viewed from the support is 3.5 per square meter. It has been achieved with a silver halide photographic light-sensitive material characterized by being less than gram.

Furthermore, a more preferred embodiment of the present invention for achieving the second object of the present invention is that the gelatin contained in the hydrophilic colloid layer, which is the uppermost layer on the side of the photosensitive layer as viewed from the support, is isoelectric. It was achieved with the above-mentioned silver halide photographic light-sensitive material characterized by being acid-treated gelatin having a point of 7.0 or less.

Acid-processed gelatin is described by Mees in "The theo".
ry of the photographic process, 3rd edition ", The M
acmillan Co., New York (1966) and Sauer "Chemi
eund Fabrication der tierischen Leime und Gelatin
e ", Springer-Verlag, (1958) and Veis" The Macrom
olecular Chemistry of Gelatin ", Academic Press (196
As described in 4), gelatin obtained by treating collagen with an acid is different from so-called alkali-treated gelatin obtained by treating with lime or the like. The isoelectric point of acid-treated gelatin is generally around 9. on the other hand,
The acid-treated gelatin having an isoelectric point of 7.0 or less used in the present invention is a gelatin which can be produced by adjusting the acid treatment conditions (time, acid concentration, temperature, etc.) in a general method for producing acid-treated gelatin.

The present inventors have incorporated this acid-processed gelatin having an isoelectric point of 7.0 or less in the photosensitive layer on the photosensitive layer side or the hydrophilic colloid layer, and after coating and setting in the manufacturing process of the photosensitive material, By controlling the surface temperature to 35 ° C or lower and drying within 2 minutes, even if the amount of the binder (particularly gelatin) on the photosensitive layer side is reduced in order to improve productivity or rapid processing property. It has been found that a photosensitive material can be obtained in which resistance to scratches and pressure fog resistance do not deteriorate. This effect is particularly large when the gelatin contained in the hydrophilic colloid layer, which is the uppermost layer on the side of the photosensitive layer when viewed from the support, is acid-treated gelatin having an isoelectric point of 7.0 or less.

The inclusion of acid-treated gelatin in silver halide photographic light-sensitive materials is disclosed in JP-B-51-4377.
No. 7, No. 56-23139, No. 56-23140
Issue No. 56-23141, Issue No. 56-23142
No. 59-28900, 59-7724,
No. 60-17101, No. 60-49891, JP-A No. 57-642, No. 61-233737, and No. 63-157142, all of which are reticulated. Alternatively, and / or for the purpose of improving adhesion resistance, and does not disclose the constitution of the present invention. Reticulation and adhesiveness
It is apparent from the specification of the above patent that this is a problem that occurs when the drying temperature is raised in order to enable high-speed coating for improving productivity. On the other hand, the present invention is intended to conversely reduce the amount of gelatin to reduce the amount of coating liquid to be applied, improve the drying property, and overcome the problems by different means. It is a completely new technology that cannot be expected from the conventional technology.

In addition to this, JP-A-60-119551
No. 62-109039, 63-22945
No. 6, 63-229457, 63-2596
52, Dohei 1-304461, Dohei 4-32443
No. 9 and the like describe techniques using acid-treated gelatin, but none of them disclose the constitution of the present invention.

Drying in the present invention means reducing the water content to such an extent that the surface of the light-sensitive material does not have tackiness, and is preferably 15% or less, particularly 10% or less based on the dry weight of the binder. To reduce the water content so that

The actually coated emulsion is first chill set in cold air in the setting step and then hot air dried. According to the present invention, after the setting step, the surface temperature is 35 ° C. or less, particularly preferably 30 ° C. in the warm air drying step.
This process is completed within 2 minutes while controlling as follows. If the surface temperature is 35 ° C. or lower in all the drying steps, the temperature of the warm air can be changed according to the drying step. Further, after drying, the surface temperature may be increased to 35 ° C. or higher by raising the temperature of air blown for the purpose of humidity control or other purposes. The conditions of the setting process vary depending on the physical properties of the liquid to be applied, the performance of the apparatus, etc. and cannot be specified unconditionally. However, the setting process in the present invention means that the dry bulb temperature is 15 ° C or lower in low temperature air. It refers to the process of cooling and solidifying. (Of course, it is possible to dry under these conditions for a long time, but it is a condition that is practically impossible for a person skilled in the art from the viewpoint of productivity.) Has a dry-bulb temperature of 15
It refers to the step of drying in air above ° C.

The drying conditions in the manufacturing process of the silver halide photographic light-sensitive material are described in JP-A-1-296242. Here, 8% based on the binder dry weight
It takes less than 100 seconds to reach the following moisture content, and 300% or less of water content is 35 ° C or less based on the dry weight of the binder.
A technique of drying at 0% RH or less is disclosed, but this is done by drying at a relatively high temperature (30 to 50 ° C) in the early stage of drying in order to improve dimensional stability. It is intended to dry at a relatively low temperature and low humidity, and similar examples including comparative examples are described, but the description of the patent does not disclose the use of acid-treated gelatin, and the present invention is not In order to obtain different purposes and effects, it is a technique of drying under conditions that are essentially different from those of the present invention, and the drying conditions under which special effects are obtained with the acid-processed gelatin of the present invention are easily expected from the patent. Not a thing.

Further, Japanese Patent Publication No. 6-93087 describes the drying conditions in the manufacturing process of silver halide photographic light-sensitive materials. The patent is a technique in which the average surface temperature of the coating layer is contacted with air of 25 to 5% RH within 5 minutes or more and within 1 minute within 5 minutes after the temperature rises to 1 ° C lower than the temperature of the contacting air. The drying conditions disclosed in the claims, examples and the like of the patent are essentially different from the drying conditions of the present invention.

The silver halide used in the photosensitive silver halide emulsion layer of the light-sensitive material of the present invention is silver chloride or silver bromide,
Any of silver chlorobromide, silver chlorobromoiodide, silver chloroiodide, and silver bromoiodide can be used. The form and crystal habit of the silver halide grains are not particularly limited, and the method for preparing the silver halide emulsion may be any known method such as forward mixing, reverse mixing and simultaneous mixing.

The emulsion which has been physically ripened is desalted and then
It is preferable that the necessary additives are added before coating, but the desalting treatment can be omitted.

The silver halide photographic emulsion of the present invention can be chemically sensitized by a method known to those skilled in the art.
As the chemical sensitization method, known methods such as a sulfur sensitization method, a reduction sensitization method and a gold sensitization method can be used, and they can be used alone or in combination. As a sulfur sensitization method,
In addition to sulfur compounds contained in gelatin, various sulfur compounds such as thiosulfates, thioureas, thiazoles,
Rhodanine and the like can be used. Specific examples are U.S. Pat. Nos. 1,574,944, 2,278,947, 2,410,689, 2,728,668, 3,501,313, 3,656,955. No. Among the noble metal sensitizing methods, the gold sensitizing method is a typical one, which uses a gold compound, mainly a gold complex salt. Noble metals other than gold, for example, complex salts of platinum, palladium, iridium, etc. may be contained. Specific examples thereof are described in US Pat. No. 2,448,060 and British Patent 618,061.

The silver halide photographic emulsion of the present invention can be spectrally sensitized by a method known to those skilled in the art so as to have a spectral sensitivity corresponding to a desired light source.
As the sensitizing dye, cyanine dye, merocyanine dye, complex cyanine dye, complex merocyanine dye, holoholer cyanine dye, styryl dye, hemicyanine dye, oxonol dye, hemioxonol dye and the like can be used.

Useful sensitizing dyes used in the present invention are, for example, US Pat. Nos. 3,522,052 and 3,619,19.
No. 7, No. 3,713, 828, No. 3, 615, 643
Issue No. 3,615,632 Issue 3,617,293
No. 3,628,964, 3,703,377
Issue No. 3,666,480 Issue 3,667,960
Nos. 3,679,428 and 3,672,897
Issue No. 3,769,026 Issue No. 3,556,800
Issue No. 3,615,613 Issue No. 3,615,638
Nos. 3,615,635 and 3,705,809
No. 3,312,349, No. 3,677,765
Nos. 3,770,449, 3,770,440
Issue No. 3,769,025 Issue No. 3,745,014
Issue 3, Issue 3,713,828, Issue 3,567,458
Nos. 3,625,698, 2,526,632
No. 2,503,776, JP-A-48-76525.
And Belgian Patent No. 691,807. Further, supersensitization can be performed by a method known to those skilled in the art.

In the light-sensitive material of the present invention, a hydrophilic colloid layer such as an overcoat layer, an intermediate layer, a backcoat layer, an undercoat layer and the like can be provided in addition to the photosensitive emulsion layer. A matting agent may be contained in these layers.

Gelatin is preferably used as the binder which can be used in the emulsion layer, topcoat layer, backcoat layer and the like of the light-sensitive material of the present invention, but synthetic polymers such as polymer latex can also be used.
However, the acid-sensitive gelatin having an isoelectric point of 7.0 or less must be contained in the photosensitive layer or the hydrophilic colloid layer on the side of the photosensitive layer when viewed from the support. Further, as a preferred embodiment for achieving the second object of the present invention, it is preferable that the total amount of gelatin in the photosensitive layer and the hydrophilic colloid layer is 3.5 g or less per square meter. In the present invention, the total amount of gelatin, not the total amount of binder, is set to 3.5 g or less because it is mainly gelatin that has a high water absorption in the photographic light-sensitive material and affects the drying property. The type of binder on the back side is not specified, but the dry state and
It is necessary to balance the amount with the photosensitive layer surface in order to prevent deterioration of handleability due to curling in the processing solution (developing solution, fixing solution, washing water, etc.) and conveyance failure in the output machine or automatic developing machine. There is. Since it depends on the properties of gelatin, the type of hardener, the production conditions, etc., it cannot be generally stated, but preferably 0.5 g or more and 3.5 g or less per square meter, and in order to further improve the drying property. 1.0 to 3.0 grams is preferable. The acid-treated gelatin having an isoelectric point of 7.0 or less can be contained in one layer or a plurality of layers of the photosensitive layer and the hydrophilic colloid layer on the side of the photosensitive layer. The gelatin contained in the hydrophilic colloid layer, which is the uppermost layer on the layer side, is preferably acid-treated gelatin having an isoelectric point of 7.0 or less.
It may be used alone or in combination with alkali-treated gelatin in the layer. Although the content cannot be specified unconditionally, the total amount is preferably 0.5 g or more and 3.5 g or less per square meter, and more preferably 1.0 g or more and 3.0 g or less.

The photographic emulsion used in the present invention may contain various compounds for the purpose of preventing fog during the production process of the light-sensitive material, during storage or during photographic processing, or stabilizing the photographic performance. . For example, substituted or unsubstituted benzothiazolium salts, substituted or unsubstituted nitroindazoles, substituted or unsubstituted triazoles, substituted or unsubstituted benzotriazoles, substituted or unsubstituted benzimidazoles and other azoles A substituted or unsubstituted mercaptothiazole, a substituted or unsubstituted mercaptobenzothiazole, a substituted or unsubstituted mercaptobenzimidazole, a substituted or unsubstituted mercaptothiadiazole, a substituted or unsubstituted mercaptotetrazole,
Heterocyclic mercapto compounds such as substituted or unsubstituted mercaptopyridines, the above heterocyclic mercapto compounds having a water-soluble group such as a carboxyl group or a sulfone group, substituted or unsubstituted tetrazaindenes, thioketo compounds, benzene Examples thereof include thiosulfonic acids and benzenesulfinic acid.

The photographic light-sensitive material of the present invention may contain an inorganic or organic hardener in the photographic emulsion layer and other hydrophilic colloid layers. For example, chromium salts (chrome alum etc.), aldehydes (formaldehyde, glyoxal etc.), N-methylol compounds, dioxane derivatives (2,3-dihydroxydioxane etc.), active vinyl compounds, active halogen compounds (2-hydroxy 4,6). −
Dichloro-1,3,5-triazine and the like) can be used alone or in combination.

The photographic emulsion used in the present invention contains emulsion layers, overcoat layers, backing layers and the like for the purpose of suppressing irradiation, halation and the like to enhance image quality and other performance required in the printing plate making industry. The hydrophilic colloid layer can contain filter dyes known to those skilled in the art.

Further, in a photographic emulsion layer or other hydrophilic colloid layer of a light-sensitive material produced by using the present invention, a coating aid, an antistatic agent, an improvement in slipperiness, an emulsion dispersion, an adhesion prevention and an improvement in photographic characteristics (eg, , Development acceleration, contrast enhancement, and sensitization) may be included for various purposes. Nonionics such as saponins (steroids), alkylene oxide derivatives (polyethylene glycol, polyethylene glycol alkyl ethers, etc.), glycidol derivatives (alkenyl succinic acid polyglyceride, etc.), fatty acid esters of polyhydric alcohols, alkyl esters of sugars, etc. Anionic surface active agent containing an acidic group such as a carboxyl group, a sulfo group, a phospho group, a sulfuric acid ester group, a phosphoric acid ester group, such as an alkylcarboxylic acid salt, an alkyl sulfuric acid ester, an alkyl phosphoric acid ester, etc. Agents: amphoteric surfactants such as amino acids, aminoalkyl sulfonic acids, aminoalkyl sulfuric acid or phosphoric acid esters; aliphatic or aromatic quaternary ammonium salts, heterocyclic quaternary ammonium salts such as pyridinium and imidazolium What cationic surfactant can be used.

For the photographic light-sensitive material used in the present invention, any support known in the art can be used. Examples of the support include glass, cellulose acetate film, polyethylene terephthalate film, paper, baryta coated paper, polyolefin (for example, polyethylene and polypropylene) laminated paper, polystyrene film, polycarbonate film, and metal plate such as aluminum. These supports may be subjected to corona treatment by a known method, and if necessary, may be subjected to undercoating treatment by a known method.

The present invention will be specifically described below with reference to examples, but the present invention is not limited to the description.

[0031]

【Example】

Example 1 A silver chlorobromide emulsion in which silver chloride: silver bromide = 7: 3 was prepared by a control double jet method. After desalting by a flocculation method, washing with water and redissolving, sulfur + gold sensitization was applied. Acid-processed gelatin or alkali-processed gelatin having different isoelectric points were added so as to be contained in an amount shown in Table 1, and a sensitizing dye, a stabilizer, a coating aid and a hardener were added, and polyethylene was laminated. It was coated on the prepared paper support so that the coated silver amount was 1.8 g per square meter. The back side of the paper support is coated with 1.5 g of gelatin per square meter.

On top of this, a protective layer contains acid-treated gelatin or alkali-treated gelatin, a surfactant and a matting agent, and further contains 2-hydroxy 4,6-dichloro-1,3,5-triazine as a hardening agent. The coating solution was coated at the same time as the above emulsion to prepare samples having different contents in each layer of acid-treated gelatin or alkali-treated gelatin as shown in Table 1. After setting with cold air of 7 ° C, the surface temperature (maximum temperature in the drying process) was 29 ° C, 33 ° C, 37 ° C, 45 ° C in the drying process as shown in Table 1. The drying conditions were changed so that Also, while keeping the surface temperature (the highest temperature during the drying process) at 33 ° C,
As shown in Table 1, the drying time was changed by changing (concentrating or diluting) the coating liquid concentration of the photosensitive layer and the protective layer.

A needle having a diameter of 200 μm was pushed up on the surface of these samples, and when the needle was moved, the load applied to the needle was changed. After that, Mitsubishi Papermaking Developer MRA-CD
231, fixing solution MRA-CF601, using Fuji Film's automatic developing solution FG360F, developing conditions 35 ° C1
It was developed for 5 seconds, and it was examined how much weight was applied for blackening, and this was taken as pressure fog resistance. Water absorption is 20
After soaking in deionized water at ° C for 1 minute, excess water was removed, and the amount of water absorbed in the film (only on the photosensitive layer side) was measured from the weight difference before and after. The results are shown in Table 1.

[0034]

[Table 1]

From the results shown in Table 1, in the case of containing acid-treated gelatin having an isoelectric point of 7.0 or less and a surface temperature of 35 ° C. or less,
Improved pressure fog resistance (especially Comparative Example-1,
It can be seen from the comparison between Examples 2 and 7 and Invention-2). Especially when the amount of gelatin is reduced for the purpose of enhancing suitability for rapid processing, pressure fog resistance is significantly deteriorated in the conventional constitution, but acid-treated gelatin having an isoelectric point of 7.0 or less is contained and the surface temperature is 35 ° C. When the drying time is C or less and the drying time is 2 minutes or less, the required level of pressure fog resistance is maintained (especially Comparative Example-3,
It can be seen from a comparison of 4, 8, 9, 10 and Invention-3). Further, when the surface temperature is 30 ° C. or lower, a higher level of pressure fog resistance is exhibited (Invention-7). These effects are obtained only when an acid-processed gelatin having an isoelectric point of 7.0 or less is used, and it may be added to any photographic constituent layer on the side of the photosensitive layer when viewed from the support (especially for comparison. Example-
5 and 6 and the present invention-1, 3, 4, 5, and 6). In this way, the amount of liquid absorption is reduced to improve suitability for rapid processing, and more specifically, the amount of gelatin is reduced, and acid-processed gelatin is used in a light-sensitive material in which pressure fog resistance is deteriorated.
After the set, the technology of manufacturing under the condition that the surface temperature is controlled to 35 ° C or less and dried within 2 minutes is unpredictable from the conventional technology, and pursues rapid processing. This is a long-awaited technology for those skilled in the art.

[0036]

According to the present invention, in order to improve scratch resistance and pressure fog resistance, and to improve productivity,
Alternatively, it is possible to obtain a silver halide photographic light-sensitive material for printing plate making in which resistance to scratches and pressure fog resistance do not deteriorate even if the amount of binder (especially gelatin) is reduced to improve rapid processability.

Claims (3)

[Claims] 1. A silver halide photographic light-sensitive material having at least one photosensitive layer having silver halide grains on a support and at least one hydrophilic colloid layer as a protective layer, the photosensitive layer side being viewed from the support. In the photosensitive layer or the hydrophilic colloid layer of the present invention contains an acid-treated gelatin having an isoelectric point of 7.0 or less, and the surface temperature is 35 ° C or less after coating and setting in the manufacturing process of the photosensitive material. A silver halide photographic light-sensitive material characterized by being dried within 2 minutes while controlling. 2. The total amount of gelatin in the photosensitive layer and the hydrophilic colloid layer on the side of the photosensitive layer when viewed from the support is 3.5 g or less per 1 square meter.
The silver halide photographic light-sensitive material described in. 3. The gelatin contained in the hydrophilic colloid layer, which is the uppermost layer on the side of the photosensitive layer when viewed from the support, has an isoelectric point of 7.0.
The following acid-treated gelatin is used:
Alternatively, the silver halide photographic light-sensitive material according to claim 2.