JPH0555017B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to a silver halide photographic material in which a silver halide emulsion layer is provided on the surface of a corona discharge-treated polyolefin-coated paper support. The present invention relates to a silver halide photographic material having a gelatin subbing layer provided on the surface of a polyolefin-coated paper support. [Background of the Invention] Speeding up the development process is a recent trend in all photographic materials, and as part of this trend, so-called water-resistant photographic paper using polyolefin-coated paper as a support has been developed in photographic paper. It has been put into practical use. Water-resistant photographic paper whose support is polyolefin-coated paper, in which both sides of the paper are coated with polyolefin, significantly reduces the time required for washing and drying after development because the support does not absorb development processing solutions. It has the advantage of being water resistant,
The strength and dimensional stability of photographic paper have been significantly improved, greatly contributing to the increase in the commercial value of photographic paper. Polyolefin-coated paper is usually manufactured by coating both sides with polyolefin by a so-called extrusion coating method, in which heated and melted polyolefin is cast onto a paper base material that is running, and then assimilated with a pressure roll. . The polyolefin on the emulsion-side surface of the polyolefin-coated paper usually contains a white inorganic pigment such as titanium oxide, and its surface shape is processed into a glossy surface, matte surface, silky surface, etc. depending on the use. Next, a photographic emulsion such as gelatin-silver halide is coated on the polyolefin layer containing a white inorganic pigment such as titanium oxide to complete a waterproof photographic paper. However, since the polyolefin surface is hydrophobic, even if a hydrophilic silver halide emulsion layer is applied directly to the surface, the support and the silver halide emulsion layer do not adhere at all. Therefore, conventionally, in order to provide a silver halide emulsion layer on a support having a polyolefin surface, a method has been known in which the polyolefin surface is first subjected to an activation treatment such as corona discharge treatment or flame treatment, and then bonded. Among these methods, a method of applying a silver halide emulsion layer to the corona discharge treatment has been widely practiced. However, it has been found that the effect of this activation treatment deteriorates over time, and not only does the adhesion condition become extremely poor, but also that the polyolefin surface activated by corona discharge causes fog on the color silver halide emulsion layer. Also, uneven electrostatic charge on the polyolefin surface often results in uneven coating of the emulsion. In addition, before coating the photographic emulsion, in order to prevent the deterioration of the activation treatment effect over time, or to improve coating unevenness and photographic properties such as emulsion fog, a hydrophilic resin is applied to the polyolefin surface immediately after the activation treatment. Coating or subbing has been performed. In Japanese Patent Publication No. 47-18010, a gelatin subbing layer using a certain kind of hardening agent was provided on the surface of a corona discharge-treated polyethylene-coated paper support.
Techniques have been disclosed to improve adhesion to silver halide emulsion layers to be coated. However, according to our findings, if the silver halide emulsion layer is applied immediately after the gelatin subbing layer is formed, the adhesion between the silver halide emulsion layer and the support is rather similar to that of corona without the subbing layer. A silver halide emulsion layer coated directly on discharge-treated polyethylene-coated paper tended to be superior. On the other hand, Japanese Patent Publications No. 48-14185 and No. 49-17522 disclose techniques for maintaining the gelatin-subbed surface at a high pH level by using graft-modified gelatin or by adding basic substances; Adhesion was not always sufficient. In addition, the Japanese Patent Publication No. 49-17522 sometimes required the use of organic solvents, which caused pollution and operational problems. In addition, in Tokuko Sho 49-15210, after subtracting gelatin, by exposing it to high temperature and high humidity,
50-4389 claims that the adhesive strength can be improved by immersing the gelatin in an ultrasonically vibrated gelatin solution, but this requires a special high-temperature, high-humidity zone and ultrasonic generation equipment, which increases the cost. It was a disadvantage. Special Publication No. 57-9058, No. 50-110323,
A technique has been disclosed in which a gelatin subbing layer in which solid substances or liquid droplets are dispersed is formed by setting gelatin at low temperature and drying it. Therefore, it was not sufficient to improve coating unevenness caused by corona discharge treatment. Japanese Patent Publication No. 57-53585 uses a mixture of gelatin and maleic anhydride-vinyl compound copolymer, and Japanese Patent Publication No. 52-130625 improves coating unevenness by adding a specific nonionic surfactant to an aqueous gelatin solution. However, in these cases, the adhesion was not sufficient. In addition, JP-A-58-184144 has a technique for processing the back surface of polyolefin-coated paper, which has a similar structure but is based on a completely different technical concept. It could not be used as an undercoat because it impairs the elasticity and increases the degree of curl, making it unsuitable for practical use. OBJECTS OF THE INVENTION The objects of the present invention are to provide a gelatin subbing layer of a specific concentration containing a specific hardening agent on a corona discharge treated polyolefin coated paper support. The adhesive strength between the photographic polyolefin-coated paper support and the silver halide emulsion layer is good even immediately after the formation of the subbing layer, and it does not affect the coatability and photographic properties of the silver halide emulsion layer. An object of the present invention is to provide a silver halide photographic material provided with a specific subbing layer. [Effects of the Invention] The above object of the present invention is to provide a silver halide photographic material in which a silver halide emulsion layer is provided on a corona discharge treated polyolefin coated paper support. On the surface of the paper support, an active halogen compound,
The film is hardened with at least one hardening agent selected from epoxy compounds, ethyleneimino compounds, methanesulfonic acid ester compounds, carbodiimide compounds, isoxazole compounds, and acrylamide compounds, and the film thickness is the same after drying. This is achieved by using a silver halide photographic material provided with a gelatin subbing layer with a coating amount of 0.02 g/m ² to 0.5 g/m ² . Examples of the base paper used for the polyolefin resin-coated paper of the present invention include natural pulp paper, synthetic pulp paper, mixed paper of natural pulp and synthetic pulp, etc., which are commonly used for photographic paper. I can do it. The base paper is usually used at a thickness of 50 to 300 microns. Examples of the polyolefin forming the polyolefin resin coating layer include polyethylene, polypropylene, copolymers thereof, and mixtures of these various polymers. Particularly preferred are high density polyethylene, low density polyethylene and mixtures thereof. The thickness of the polyolefin resin coating layer is not particularly limited, but is preferably selected from a range of 15 to 50 microns. Polyolefin resin, white pigment, colored pigment,
Alternatively, it is common to use various additives such as fluorescent brighteners and antioxidants. Various methods are known for performing corona discharge treatment on polyolefin-coated paper, and these techniques may be applied to the present invention. For example, these technologies include
No. 17682, No. 37-17485, No. 45-40438, No. 48
-5043, 50-19300, 47-51905, 49
-10687, JP-A-48-28067, JP-A-58-4157,
No. 58-222118, No. 48-89731, No. 59-4437,
BP971058 etc. The subbing layer used in the present invention is formed by applying an aqueous gelatin solution containing the hardening agent according to the present invention to the surface of a polyolefin layer such as polyethylene that has been activated by corona discharge treatment. As the gelatin, any gelatin commonly used in the art, such as so-called lime-treated gelatin, acid-treated gelatin, enzyme-treated gelatin, etc., can be used. If the thickness of the undercoat layer is too thin, sufficient adhesion force cannot be obtained, and on the other hand, if it is too thick, although an improvement in adhesion force is observed, curling occurs and is not practical. Therefore, the thickness of the undercoat layer of the present invention is 0.02 g/m ² to 0.5 g/m ² after drying, preferably 0.05 g/m ² to 0.2 g/m ² . The present invention improves the adhesion between a polyolefin-coated paper support and a photographic emulsion layer by adding a hardening agent according to the present invention to a gelatin subbing solution. Hardeners that can be used in the present invention include:
2,4-dichloro-6-hydroxy-S-triazine sodium salt, 2,4-dichloro-6-methoxy-S-triazine, 2,4-dichloro-6
-(4-sulfoaniline)-S-triazine sodium salt, 2,4-dichloro-6-(2-sulfoethylamino)-S-triazine, N,N'-bis(2-chloroethylcarbamyl)piperazine Active halogen compounds such as. bis(2,3-epoxypropyl)methylpropylammonium p-toluenesulfonate,
1,4-bis(2',3'-epoxypropyloxy)butane, 1,3,5-triglycidyl isocyanurate, 1,3-diglycidyl-5-(γ-
Epoxy compounds such as acetoxy-β-oxypropyl) isocyanurate. 2,4,6-trimethylene-S-triazine,
Ethyleneimino compounds such as 1,6-hexamethylene-N,N'-bisethyleneurea and bis-β-ethyleneiminoethylthioether. 1,2-di(methanesulfonoxy)ethane,
1,4-di(methanesulfonoxy)butane,
Methanesulfonic acid ester compounds such as 1,5-di(methanesulfonoxy)pentane. Dicyclohexylcarbodiimide, 1-cyclohexyl-3-(3-trimethylaminopropyl)
Carbodiimide-p-toluenesulfonate, 1
-ethyl-3-(3-dimethylaminopropyl)
Carbodiimide compounds such as carbodiimide hydrochloride, 2,5-dimethylisoxazole perchlorate, 2-ethyl-5-phenylisoxazole-3'-sulfonate, 5,5'-(paraphenylene)hisisoxazole isoxazole compounds such as diacrylamide, 5-acetyl-1,3-diacryloyl-hexahydro-S-triazine,
1,3,5-Triacryloyl-hexahydro-
Examples include acrylamide compounds such as S-triazine. Particularly preferred hardening agents are active halogen compounds, epoxy compounds, ethyleneimino compounds, and methanesulfonic acid ester compounds. These hardeners may be used alone or in any combination. The amount of these hardeners added is 0.10 to the weight of gelatin.
It can be added in an amount ranging from 5.0% by weight, preferably 0.2% to 3.0% by weight. These hardeners can be dissolved in water or a water-soluble organic solvent, and then added to an aqueous gelatin solution to prepare a subbing solution. The gelatin subbing liquid according to the present invention can contain various additives as necessary. For example, matting agents, surfactants, antistatic agents, antihalation agents, coloring dyes, pigments, coating aids,
Antifoggants, etc. The subbing liquid according to the present invention can be applied using generally well-known coating methods, such as dip coating, air knife coating, curtain coating, roller coating, wire bar coating, and clavier coating.
Alternatively, it can be applied by an extrusion coating method using a hopper as described in US Pat. No. 2,681,294. The thus applied subbing liquid is then dried in a drying process, the conditions of which are arbitrary;
Generally, it is carried out at 60°C to 120°C for several seconds to 10 minutes. The undercoat layer may be provided at any time as long as the polyolefin coated paper has been subjected to corona discharge treatment. For example, when applying the undercoat layer according to the present invention after corona discharge treatment, or when corona discharge treated material is temporarily stored, and then the undercoat layer according to the present invention is applied and stored again. Alternatively, an undercoat layer may be provided in a step before the step of coating a silver halide emulsion. Note that the silver halide emulsion layer provided on such a subbing layer and the layer structure of the photographic light-sensitive material may be arbitrarily selected. As the silver halide emulsion layer, monochrome and color emulsion layers can be provided. When the photographic light-sensitive material according to the present invention is applied to a color photographic light-sensitive material, there are usually three
Each emulsion layer can contain one of the following three couplers: a yellow coupler, a magenta coupler, and a cyan coupler. In such cases, the combination of light-sensitive silver halide emulsion layer and coupler is usually a cyan coupler in the red-sensitive silver halide emulsion layer, a mazeta coupler in the green-sensitive silver halide emulsion layer, and a blue-sensitive silver halide emulsion layer. A yellow coupler is associated with each silver halide emulsion layer. There are no particular restrictions on the order in which the emulsion layers are stacked. Any yellow, magenta and cyan couplers may be used as desired. Preferred yellow couplers include benzoylacetanilide couplers and pivaloylacetanilide couplers. Preferred magenta couplers include 1-phenyl-3-anilino-5-pyrazolone couplers and pyrazolotriazole couplers. Preferred cyan couplers include phenolic couplers. Each of these couplers is present in the silver halide emulsion layer in an amount of 0.05 per mole of silver halide.
The content is preferably about 1 mol. In addition to the above-mentioned silver halide emulsion layer, the color photographic light-sensitive material used in the present invention may be provided with non-photosensitive layers such as a protective layer, an intermediate layer, a filter layer, and a scavenger layer in an appropriate layer order and number. I can do it. The silver halide contained in the silver halide emulsion layer used may be any of silver iodobromide, silver chlorobromide, silver bromide, silver chloroiodobromide, silver chloride, and silver chloroiodide. It may be present or a mixture thereof may be used. These silver halides can be prepared using the ammonia method,
It may be manufactured by any of the neutral method, acidic method, etc., and it may be manufactured by any of the simultaneous mixing method, forward mixing method, reverse mixing method, convergence method, etc. Furthermore, silver halide grains with or without boundaries with different halogen compositions can be effectively used. The binder that can be used in the constituent layers of the color photographic light-sensitive material used in the present invention is most commonly gelatin such as alkali-treated gelatin or acid-treated gelatin. In combination with derivatives such as gelatin, albumin, agar, gum arabic, alginic acid, partially hydrolyzed cellulose derivatives, partially hydrolyzed polyvinyl acetate, polyacrylamide, polyvinyl alcohol, polyvinylpyrrolidone, and copolymers of these vinyl compounds. It can also be used. The silver halide emulsion used is ruthenium,
Noble metal sensitization with salts of noble metals such as rhodium, palladium, iridium, platinum, and gold, activated gelatin,
Chemical sensitization can be performed, such as sulfur sensitization with unstable sulfur compounds, selenium sensitization with selenium compounds, or reduction sensitization with stannous salts, polyamines, etc. and under low pAg conditions. Further, these silver halide emulsions can be optically sensitized using various sensitizing dyes in order to impart photosensitivity in a desired wavelength range. These various optical sensitizers are used for purposes other than their original purpose, such as preventing fogging, preventing deterioration of photographic performance during storage of color photographic materials, and adjusting development (for example, gradation control, etc.). It is also possible to use it for this purpose. Furthermore, the constituent layers of the color photographic light-sensitive material used in the present invention may contain various photographic additives, such as ultraviolet absorbers, dye image stabilizers, stain inhibitors, surfactants, water-soluble anti-irradiation dyes, hardeners, A film property improver can be added. To coat each constituent layer of the color photographic light-sensitive material onto the support of the light-sensitive material of the present invention, commonly known coating methods are used, such as dip coating, roller coating, bead coating, curtain flow coating, etc. It is applied and then dried. In order to obtain a dye image using a color photographic light-sensitive material, after imagewise exposure, a color development process is performed if necessary. The processing steps basically include color development and bleach-fixing steps. In this case, each process may be independent, or two or more of the processes may use processing liquids that have those functions, so that only one process is required. Further, each step can be divided into two or more times as necessary. In addition, during the treatment process, in addition to the above, a pre-hardening bath, a neutralization bath, a first development (black and white development),
Various steps such as an image stabilizing bath and water washing are combined. The processing temperature is set within a preferable range depending on the photosensitive material and processing prescription. Generally, the temperature is 20°C to 60°C, but the color photographic material described above is particularly suitable for processing at 30°C or higher. Color developing agents used for color development include:
A variety of those widely used in various color photographic processes are included. Various additives can be added to the color developing solution as necessary. For example, alkali metal hydroxides and carbonates, alkaline agents such as tertiary phosphates, buffers such as boric acid and acetic acid, thioethers,
1-aryl-3-prazolidone, N-methyl-
Development accelerators such as p-aminophenol and polyalkylene glycol, organic solvents such as benzyl alcohol, ethylene glycol, diethylene glycol, methanol and acetone, development inhibitors such as potassium bromide and nitrobenzimidazoles, sulfites, hydroxylamine, There are preservatives such as glucose and alkanol aminos, and water softeners such as polyphosphoric acid compounds and nitrilotriacetic acid. [Specific Examples of the Invention] (1) Adhesive Strength Test <Dry Film Test> Make shallow scratches in a grid pattern with a razor on the emulsion surface of the sample, press cellophane adhesive tape on top of the scratches, and then press the tape. The residual ratio of the emulsion film to the adhesive area of the cellophane tape when the tape was peeled off was expressed as a percentage. <Test with processed film> In a processing bath, the emulsion surface of the sample was scratched in a checkerboard pattern with a sharp end, and the surface was rubbed, and the residual rate of the emulsion film was expressed as a percentage. In practice, there is no problem if this percentage is 80% or more. Example 1 Density 0.92g/ on both sides of 150μm thick photographic paper
A ^corona discharge device (HFS
−202, manufactured by Kasuga Denki Co., Ltd.) at 30W/m ² min
Corona discharge treatment was performed under the following conditions. On this corona discharge treated surface, 2,4-dichloro-6-hydroxy-S-triazine sodium salt (hardener No. 1) was added to a 1% gelatin aqueous solution at a ratio of 0.2 to gelatin.
The subbing liquid added at 1.0 and 3.0% by weight and the subbing liquid not added were coated using the wire bar coating method so that the dry coating amount was 0.1 g/m ² at 80°C.
Dried in 2 minutes. A conventional silver halide emulsion for photographic paper was coated on the polyethylene-coated paper that had been subbed and on the polyethylene-coated paper that had just been subjected to the corona discharge treatment. Table 1 shows the results of the adhesive strength test of the samples thus obtained.

[Table] This clearly shows that the gelatin subbing layer with hardener No. 1 increases the adhesion between the polyethylene coated paper and the emulsion layer. Regarding emulsion coating properties and emulsion fog,
Samples using gelatin subbing with added hardener performed well. Example 2 A polyethylene-coated paper obtained in the same manner as in Example 1 was coated with 1, 2, -
Di(methanesulfoneoxy)ethane (hardener No.
2) was added to the gelatin so that the amount was 1.2% by weight, and the dry coating amount of the 0.2% gelatin aqueous solution was 0.009, 0.03 g/m ² , respectively, and the 1% gelatin aqueous solution was 0.06, 0.09 g/m ² , and 10, respectively. % aqueous gelatin solution was coated at 1.3 g/m ² using a wire bar coating method and dried at 80° C. for 2 minutes. An adhesive strength test was conducted on these subbed polyethylene coated papers in the same manner as in Example 1. The results thus obtained are shown in Table 2.

[Table] From this table, it can be seen that the adhesive strength is good when the coating amount of the gelatin undercoat containing hardener No. 2 is 0.03 to 1.3 g/m ² . However, at a coating amount of 1.3 g/m ^{2 ,} although the adhesion was good, the degree of curling increased and was not suitable for practical use.
Further, at 0.009 g/m ² , the polyethylene surface could not be completely coated, repellency occurred, and the coating properties of the emulsion were also insufficient. Example 3 The emulsion-coated corona discharge-treated surface of polyethylene-coated paper obtained in the same manner as in Example 1 was coated with a 1% aqueous gelatin solution, and the hardened film shown in Table 3 was added to the gelatin in an amount of 1.0% by weight. It was applied using a wire bar coating method so that the dry coating amount was 0.1 g/m ² , and dried at 80° C. for 2 minutes. Table 4 shows the results of an adhesion level test conducted on these underdrawn polyethylene coated papers in the same manner as in Example 1.

【table】

[Table] It is clear from this that the gelatin subbing layer to which hardeners Nos. 3 to 6 of the present invention are added increases the adhesion between the polyethylene coated paper and the emulsion layer.
Furthermore, the coating properties of the emulsion and emulsion fog were also good. In addition, comparative hardener No. 7 caused emulsion fog and
In No. 8, the coating properties of the emulsion were insufficient. Example 4 In the same manner as in Example 1, hardener No. 1, hardener No. 2, and comparative hardener Bis(2) were added to a 1% aqueous gelatin solution.
- Vinylsulfonyl ethyl) ether was added to gelatin at a concentration of 0.8% by weight, and the dry coating amount was 0.1% by wire bar coating.
It was coated at a concentration of g/m ² and dried at 80°C for 2 minutes. These subbing layer polyethylene-coated papers and the polyethylene-coated paper immediately after corona discharge treatment were heated at 23℃ and 55℃.
% RH for the number of days shown in the table below, and then an adhesive strength test was conducted in the same manner as in Example 1. The results are shown in Table 5.

[Table] It is clear from this that the adhesive strength between the polyethylene-coated paper and the emulsion layer can be maintained over a long period of time if a gelatin subbing layer containing the hardening agent of the present invention is provided. As a comparison, when bis(2-vinylsulfonyl ethyl) ether was used, not only was the required initial adhesive strength not obtained, but it was worse than that obtained using only corona discharge. Furthermore, when a gelatin subbing containing the hardener of the present invention was provided, the coating properties of the emulsion and the effect on emulsion fog were maintained.

Claims (1)

[Claims] 1. In a silver halide photographic material in which a silver halide emulsion layer is provided on a corona discharge-treated polyolefin-coated paper support, an active halogen compound, epoxy compounds,
The film is hardened with at least one hardening agent selected from ethyleneimino compounds, methanesulfonic acid ester compounds, carbodiimide compounds, isoxazole compounds, and acrylamide compounds, and the film thickness is 0.05 based on the coating amount after drying. g/m ² ~
A silver halide photographic material comprising a gelatin subbing layer of 0.2 g/m ² .