JPS6137610B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to an improvement in a method for curing a gelatin film constituent layer in a silver halide photographic material using a paper substrate coated with a polyolefin resin as a support. In general, silver halide photographic materials are made of various layers such as a silver halide photographic emulsion layer, a filter layer, an intermediate layer, a protective layer, an undercoat layer, and an antihalation layer, which are supported by a suitable support such as paper, glass, or synthetic resin film. It is constructed by being laminated on the body. Further, the constituent layers other than these supports are composed of so-called gelatin membranes mainly composed of gelatin. Therefore, the physical properties of the constituent layer made of gelatin film mainly depend on the physical properties of gelatin. By the way, the properties of gelatin itself, such as a low melting point, water-swellability, and weak mechanical strength, are major drawbacks in terms of the physical properties of the constituent layers of silver halide photosensitive materials. For this reason, various hardening agents have traditionally been applied to gelatin to cause crosslinking reactions with functional groups such as amino groups, carboxyl groups, and amide groups in gelatin molecules.
Efforts have been made to improve the physical properties of gelatin. As these hardening agents, there are many conventional hardening agents such as aldehyde hardening agents, epoxy hardening agents, ethyleneimide hardening agents, acryloyl hardening agents, and vinylsulfone hardening agents. However, many of these hardening agents have adverse photographic effects and cannot be used in excess of a certain amount, making it impossible to obtain sufficient gelatin film strength. Further, when curing a gelatin film, it is necessary to reach the maximum value of the curing effect as soon as possible after drying. This is not only to increase the physical strength of the gelatin membrane to the desired level, but also to
This is to prevent deterioration of photographic performance due to so-called post-curing phenomenon during storage. As a method for achieving these effects, a method has been proposed in which a nonvolatile salt of a volatile acid, such as sodium acetate, is added to the constituent layers. (Special Publication No. 48-13709). According to this method, the pH of the gelatin coating solution is
Even if the film has a normal pH (5 to 7), only the volatile acid evaporates during drying, and after drying, the film surface pH increases and curing is accelerated. However, it has been found that the silver halide photographic material thus obtained has the problem of significant fogging during storage. Furthermore, a method has been proposed in which a polyhydric alcohol such as glycerin or ethylene glycol is added to the constituent layers. (Japanese Patent Application Laid-Open No. 49-86329). It has been found that in this method as well, if polyhydric alcohol is contained to such an extent that it can substantially accelerate curing, there is a problem in that fogging occurs during storage. The present invention has been made to solve the above-mentioned drawbacks, and is capable of rapidly hardening a gelatin film using the minimum necessary amount of hardening agent without adversely affecting photographic performance, and also eliminating the post-hardening phenomenon during storage over time. The object of the present invention is to provide a curing method that significantly reduces the As a result of intensive research to achieve the above object, the present inventors have found that the gelatin film constituent layer in a silver halide photographic light-sensitive material using a paper base coated with a polyolefin resin as a support is rate 7.5% by weight
It has been found that the object can be achieved by maintaining the above conditions and curing with one or more curing agents selected from vinyl sulfone type curing agents and halogen-substituted S-triazine type curing agents. The present invention has been completed based on this research fact. In the method of the present invention, when the paper moisture content of the support base material is kept above a certain level and the gelatin constituent layer is hardened with a hardening agent, the amount of hardening agent used is significantly reduced;
It is possible to quickly obtain the desired film strength without adversely affecting photographic performance, and since the effects of this phenomenon vary significantly depending on the type of curing agent, a specific curing agent is recommended. This goal was achieved by combining the following: The paper moisture content of the paper base coated with the polyolefin resin used in the present invention is 7.5 to 12% by weight.
It is. If the water content is less than 7.5% by weight, the desired accelerating effect cannot be obtained even with the curing agent used in the present invention. The water content is preferably 12% by weight or less, because if the water content exceeds this, the surface of the polyolefin resin will be subjected to corona discharge treatment in order to improve the adhesion between the polyolefin resin layer of photographic resin-coated paper and the gelatin constituent layer. This is because when doing so, there is a problem of drilling through holes in the resin coated paper. In order to add water to the paper so that the water content is 7.5% by weight or more, it may be carried out at any stage before the gelatin film, which is a constituent layer, is substantially hardened. Adding water using a humidifier after applying a silver halide emulsion layer to polyolefin resin-coated paper requires a relatively long time and may have a negative effect on photographic performance, so it is added before applying the emulsion. It is preferable. More preferably, the polyolefin resin is added in a paper making machine, coating machine or humidifier before coating the paper with the polyolefin resin. Further, when paper is made, a strong electrolyte compound with or without deliquescent property may be included. In order to maintain a moisture content of 7.5% by weight in the polyolefin resin-coated base paper until the desired film strength is obtained, it is not necessary to adjust the surrounding environmental conditions to a particularly constant temperature and humidity, and the emulsion coated or coated It is sufficient if it is not rolled but rolled. However, when rewinding, it is preferable to do this for as short a time as possible, preferably within one hour, to prevent moisture from escaping into the atmosphere. Moreover, various weights of base paper can be used. Generally, the weight of the paper varies depending on its intended use, with relatively thin films being used in photographic papers and relatively thick papers being used in color and black and white printing papers. Although the curing accelerating effect obtained by the present invention can be observed using paper of any thickness, the effect becomes even greater when the paper is made thinner. Therefore, thinning the paper for the purpose of reducing the weight of the roll, reducing cost, and increasing the length of each roll will further enhance the effects of the present invention. Examples of the polyolefin resin coated on the base paper include polyethylene, polypropylene, polyisobutylene, ethylene-propylene copolymers, or mixtures thereof. Coating is preferably carried out on both sides, and the polyolefin resin on one side may contain a white pigment such as titanium white, a fluorescent color enhancer, a colored pigment, or an antifoggant. The vinylsulfone curing agent used in the present invention is, for example, an aromatic compound as described in German Patent No. 1100942, Japanese Patent Publication No. 44-29622.
No. 47-25373, an alkyl compound bonded with a hetero atom,
Sulfonamides and ester compounds as described in JP-A No. 47-8736, 1,3,5-tris[β as described in JP-A-49-24435;
-(vinylsulfonyl)-propiol]-hexahydro-S-triazine or JP-A-57-
It includes alkyl compounds such as those described in Publication No. 44164, and representative examples thereof are shown below, but are not limited thereto.

【table】

[Table] In addition to the above-mentioned exemplified compounds, compounds having at least 3 vinylsulfonyl groups in the molecular structure,
For example, reaction products obtained by reacting exemplary compounds [5] to [22] with a compound having a group that reacts with a vinylsulfonyl group and a water-soluble group are also included. Specific examples of compounds having a group that reacts with the vinylsulfonyl group and a water-soluble group include the following compounds.

【table】

[Table] includes, for example, the following compounds. These compounds are disclosed in, for example, Japanese Patent Publication No. 47-6151, Japanese Patent Publication No. 53-2726, Japanese Patent Application Laid-open No. 127229-1982, West German Patent No. 2500427, and U.S. Patent No.
It can be synthesized by the method described in specifications such as No. 3288775. The amount of the curing agent used in the present invention varies depending on the type, physical properties, photographic properties, and processing conditions of the intended gelatin film, but it is generally the dry amount of gelatin relative to the gelatin in the coating solution. 0.05 to 40 weight percent of, preferably
0.1-10% by weight. In addition, if necessary, it is also possible to use the curing agent in combination with other curing agents within a range that does not impair the effects of the present invention. The curing agent may be added at any stage of preparing the coating solution for forming the gelatin film, but when it is added to the silver halide emulsion layer, it is generally added after the second ripening of the silver halide. Good. The higher the pH of the coating solution to which the curing agent used in the present invention is added, the faster the curing speed becomes. The curing accelerating effect obtained by the method of the invention alone is sufficiently satisfactory, and there is no need to unnecessarily increase the pH of the coating solution. The preferred pH range of the coating solution is 5.5 to 7.5. Generally, a certain amount of time is required for the hardening reaction of the hardening agent against gelatin to proceed and obtain the desired degree of hardening, and it is necessary to store the finished product during that period. Further, in order to shorten this storage period, the product may be stored under heating (preferably at 30 to 40°C). The method of the present invention has a remarkable effect of accelerating hardening during this storage period, and has the advantage of being able to significantly shorten this storage period. Also, if storage is not completely sealed, for example due to differences in air humidity due to seasonal differences,
Although large variations may occur in the curing speed, the method of the present invention has the advantage of being able to cure rapidly without being affected by the humidity in the air. The silver halide emulsion used in the present invention uses all types of silver halides such as silver chloride, silver iodide, silver bromide, silver iodobromide, silver chlorobromide, and silver chloroiodobromide as a light-sensitive component. This emulsion can be enriched with noble metal salts such as ruthenium, rhodium, palladium, iridium, platinum, gold, etc., such as ammonium chloroparadate, potassium chloroplatinate, potassium chloroparadite, potassium chloroaurate, etc. Various chemical sensitizations can be carried out, such as sulfur sensitization using sulfur compounds, selenium sensitization using selenium compounds, reduction sensitization using stannous salts, polyamines, etc., and sensitization using polyalkylene oxide compounds. . This emulsion can also be optically sensitized with cyanine dyes, merocyanine dyes, etc. In addition, stabilizers such as couplers, mercury compounds, triazole compounds, azaindene compounds, benzthiazolium compounds, zinc compounds, dihydroxy Wetting agents such as alkanes, antistatic agents, film property improvers made of water-dispersible particulate polymeric substances obtained by emulsion polymerization, coating aids such as saponin, polyethylene glycol lauryl ether, and other various photographic additives. agents can be added. The binder gelatin used in the constituent layers of the present invention is generally ordinary gelatin such as acid-treated gelatin or alkali-treated gelatin. Derivative gelatin such as lucarbamoyl gelatin, albumin, agar, gum arabic, alginic acid, casein, partially hydrolyzed cellulose derivatives, partially hydrolyzed cellulose derivatives,
Partially hydrolyzed polyvinyl acetate, polyacrylamide, polyvinylpyrrolidone and copolymers of these vinyl compounds can also be used. When carrying out the present invention, if necessary, curing agents other than those used in the present invention, such as aldehyde-based, epoxy-based, ethyleneimino-based,
It is also possible to use curing agents such as methanesulfonic acid type, N-methylol type, carbodiimide type, chromium salt, zirconium salt, mucochloric acid, etc. in combination. The present invention will be specifically described below with reference to Examples.
The embodiments of the present invention should not be limited thereby. Example 1 A silver iodobromide emulsion layer and a gelatin protective layer were simultaneously coated on polyethylene resin-coated paper whose paper weight was 70 g/m ² and whose moisture content was maintained at 6.0, 7.5, and 9.0 weight percent. (-19), (-22), (-
1), (-2) and Comparative Compounds 1 and 2 were added in the amounts shown in Table 1, respectively. (Amount of hardening agent added per 1g gelatin) Comparative compound 1 HCHO 2

[Formula] Each dried sample was rolled into a roll, the emulsion coating layer was brought into close contact with the polyethylene layer on the back side of resin-coated paper having the respective moisture content, and the sample was stored at 30°C and relative humidity of 55% for 3 or 7 days. , heat-treated at 50°C with a relative humidity of 80% for 3 days, then immersed for 3 minutes in a 3% aqueous solution of sodium bicarbonate kept at 30°C, and then the membrane surface of the gelatin layer was immersed in a saphire needle with a tip of 0.3 mm in diameter. The results are shown in Table 1, which was measured by the load (g) at which scratches started to appear on the membrane surface and expressed as membrane surface strength. In addition, each sample was stored for 30 days at 30°C and 55% relative humidity after coating and drying, and after wedge exposure, it was developed at 20°C for 1 minute and 30 seconds using a developer containing hydroquinone as the main ingredient, and centocytometry was performed to determine the sensitivity. Table 2 shows the results of measurement of fog. Note that the sensitivity in the table is for comparative compound 1.
The sensitivity is expressed as a relative value when the sensitivity when coated on a support with a water content of 6.0% by weight is 100.

【table】

[Table] From now on, when the exemplified compounds related to the present invention are used as curing agents, curing can be significantly accelerated without substantially adversely affecting photographic performance by keeping the moisture content of resin-coated paper at 7.5% by weight or more. I understand that. Example 2 A corona treatment was performed on a support coated with polyethylene resin on both sides, with a paper weight of 150 g/m ² and a moisture content of 6.0, 7.5, and 9.0 weight percent, to create a multilayer sample with the following layer structure. . As a curing agent, the above (-
19) and (A-21) at a molar ratio of 1:0.5 (-A19), (-1) comparative compound 3
were added in the amounts shown in Table 3. 1st layer: Blue-sensitive silver chlorobromide gelatin emulsion layer containing yellow coupler 2nd layer: Gelatin intermediate layer 3rd layer: Green-sensitive silver chlorobromide gelatin emulsion layer containing magenta coupler 4th layer: Gelatin intermediate layer 5th layer: Red-sensitive silver chlorobromide gelatin emulsion layer containing a cyan coupler 6th layer: Gelatin protective layer Each sample was stored or heat-treated under the same conditions as in Example 1 and measured using the same method as in Example 1. The film strength was measured. The results are shown in Table 4. Regarding photographic properties, 4-amino-3-methyl-N-ethyl-N
-(β-methanesulfonamidoethyl)aniline was used as the main ingredient for color development at 33°C for 3.5 minutes, followed by bleaching, fixing, and water washing in accordance with conventional methods, followed by sensitometry. These results are shown in Table 5. In the table, the sensitivity is expressed as a relative value when the sensitivity in the case of a comparison sample with a moisture content of 6.0% by weight is set as 100 in sensitometry through each color filter.
Also, B, G, and R in the table represent blue, green, and blue, respectively.
Red indicates that sensitometry was performed by measuring the color density reflected through the filter.

【table】

【table】

【table】

[Table] As is clear from Tables 4 and 5, when the curing agent according to the present invention is used and the water content of the paper support is
It can be seen that when the content is 7.5% or more, an excellent curing accelerating effect can be obtained without impairing photographic properties even when applied to multilayer color photographic paper. Example 3 The sample used in Example 2 was rolled into a roll and packaged with a polyethylene sheet, and stored at 30°C with relative humidity of 44% and 88% for 3 and 7 days. The degree of cure was measured by the method. The results are shown in Table 6.

[Table] As is clear from Table 6, the curing agent (-A-
19), (-1) to reduce the moisture content of the support paper to 7.5
% or higher, it is less affected by changes in the humidity in the air, and stable film strength can be quickly obtained.

Claims (1)

[Claims] 1. A gelatin film constituent layer in a silver halide photographic light-sensitive material using a paper base coated with a polyolefin resin as a support is prepared so that the paper moisture content of the paper base is 7.5 to 7.5.
A gelatin film constituent layer in a silver halide photographic light-sensitive material, which is maintained at 12% by weight and cured with one or more hardening agents selected from vinyl sulfone hardeners and halogen-substituted S-triazine hardeners. curing method.