JPH0555018B2 - - 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 produced by coating both sides with polyolefin by a so-called extrusion coating method, in which heated and melted polyolefin is cast onto a running paper base material and then assimilated by a press 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. Japanese Patent Publication No. 47-18010 discloses that a gelatin subbing layer using a certain hardening agent is provided on the surface of a corona discharge-treated polyethylene-coated paper support to improve the adhesion with the silver halide emulsion layer to be coated. Techniques for improving this are disclosed. However, according to our knowledge, if a silver halide emulsion layer is applied immediately after forming this gelatin subbing layer,
Rather, the adhesion between the silver halide emulsion layer and the support tended to be better when the silver halide emulsion layer was directly coated on corona discharge treated polyethylene coated paper without a subbing layer. 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. However, the adhesion was not necessarily sufficient. Furthermore, in Japanese Patent Publication No. 49-17522, it was necessary to use an organic solvent in some cases, which caused pollution and operational problems. Also, special public service in 1977-
No. 15210 states that the adhesive strength can be improved by exposing the gelatin to high temperature and high humidity after subbing, and No. 50-4389 states that the adhesive strength can be improved by immersing it in a gelatin subbing solution subjected to ultrasonic vibration. This method requires a high-temperature, high-humidity zone and ultrasonic generation equipment, which is disadvantageous in terms of cost. Special Publication No. 57-9058,
JP-A No. 50-110323 discloses that a gelatin undercoat layer in which solid substances and liquid droplets are dispersed is set at a low temperature, and
A technique for forming by drying has been disclosed, but in order to obtain the full effect of the invention, it is necessary to
It is necessary to provide a subbing layer at the same time in the emulsion coating process, which is not sufficient to improve coating unevenness caused by corona discharge treatment. Special Public Service 1987
-53585 uses a mixture of gelatin maleic anhydride vinyl compound copolymer, JP-A-52-130625
No. 1 describes a technique for improving coating unevenness by adding a specific nonionic surfactant to an aqueous gelatin solution, but in these cases, 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 would impair the flatness and increase the degree of curl, making it unsuitable for practical use. OBJECT OF THE INVENTION The object of the present invention is to provide a gelatin subbing layer of a specific thickness 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 the coating properties and photographic properties of the silver halide emulsion layer are not affected. An object of the present invention is to provide a silver halide photographic light-sensitive material provided with a specific subbing layer that does not have a subbing layer. [Structure 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. Gelatin that is hardened with at least one hardening agent represented by the following general formula [] on the surface of the paper support, and has a film thickness of 0.02 g/m ² to 0.5 g/m ² in terms of coating amount after drying. This is achieved by using a silver halide photographic material provided with a subbing layer. General formula [] In the formula, R represents an alkyl group having 1 to 4 carbon atoms, A is an n-valent linking group, and The part that is bonded to is a carbon atom. l and m represent integers from 0 to 4, and n represents from 2 to
Represents the number 4. [Specific Structure of the Invention] The base paper used for the polyolefin resin-coated paper of the present invention includes natural pulp paper, synthetic pulp paper, and natural pulp and synthetic pulp, which are commonly used for photographic paper. Examples include mixed paper. Membrane papers are typically used in thicknesses 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 film is too thin, sufficient adhesion cannot be obtained; on the other hand, if it is too thick, although an improvement in adhesion 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. The hardener according to the present invention is represented by the above general formula [], and will be described in more detail here. R is an alkyl group having 1 to 4 carbon atoms, and this alkyl group includes those having a substituent, but preferably a methyl group or an ethyl group. A is an n-valent linking group as described above, specifically an alkylene group (this alkylene group also includes one having a substituent,
For example, −CH ₂ −, −CH ₂ CH ₂ −,

[Formula], etc.), Trivalent aliphatic hydrocarbon groups (e.g.

【formula】

[Formula], etc.),

[Formula] Phenylene group (This phenylene group is Including those with exchanges, such as

【formula】

[Formula] etc.), trivalent aromatic hydrocarbon group (e.g.

【formula】)

【formula】

【formula】

[Formula] (R ₁ and R ₂ are hydrogen atoms or carbon atoms from 1 to
The alkyl group of 4 and a ₁ represent an integer of 0 to 3. For example, −CONHCH ₂ CH ₂ NHCO−), (a ₂ represents an integer from 1 to 2. For example,

[Formula]) etc. Among these groups, preferred are divalent linking groups, particularly preferred are alkylene groups,

[Formula]. Specific examples of the compound of general formula [] include the following. However, it is not limited to this. Exemplary compound (1) CH ₂ =CHSO ₂ CH ₂ SO ₂ CH=CH ₂ (2) CH ₂ =CHSO ₂ CH ₂ CH ₂ SO ₂ CH=CH ₂ (3) CH ₂ =CHSO ₂ CH ₂ CH ₂ CH ₂ CH ₂ SO ₂ CH＝
CH ₂ (4) (Five) (6) (7) CH ₂ ＝CHSO ₂ CH ₂ CONHNHCOCH ₂ SO ₂ CH＝CH ₂ (8) CH ₂ ＝CHSO ₂ CH ₂ CONHCH ₂ NHCOCH ₂ SO ₂ CH＝CH ₂ (9) CH ₂ ＝CHSO ₂ CH ₂ CONHCH ₂ CH ₂ NHCO− ^** −CH ₂ SO ₂
CH＝CH ₂ (10) CH ₂ ＝CHSO ₂ CH ₂ CONHCH ₂ CH ₂ CH ₂ NH− ^** −COCH
₂ SO ₂ CH＝CH ₂ (11) (12) (13) (14) (15) (16) (17) (18) (19) (20) (twenty one) (22) (CH ₂ =CHSO ₂ CH ₂ ) ₄ C These hardeners may be used alone or in any combination. The amount of these hardeners added is 0.10 to the weight of gelatin.
From 5.0% by weight, preferably from 0.2% by weight
Addition in the range of 3.0% by weight provides the necessary adhesive strength. These hardeners can be dissolved in, for example, water or a water-soluble organic solvent, and then added to an aqueous gelatin solution to prepare a subbing solution. In addition, instead of the hardening agent according to the present invention, a hardening agent described in Japanese Patent Publication No. 53-47271, that is, a compound having at least three vinylsulfonyl groups in its molecular structure, may be used. A similar effect can be obtained by using a reaction product obtained by reacting a compound having a group that reacts with the compound and a water-soluble group. The reaction product obtained by reacting a compound having at least three vinylsulfonyl groups in its molecular structure with a compound having a group that reacts with vinylsulfonyl groups and a water-soluble group is highly water-soluble and is extremely useful as a hardening agent for gelatin. I found it to be excellent. As the above-mentioned compound having at least 3 kevinylsulfonyl groups in its molecular structure (hereinafter referred to as compound I), for example, the compound described in German Patent No.
Aromatic compounds as described in Japanese Patent Publication No. 1100942, alkyl compounds bonded with hetero atoms as described in Japanese Patent Publication No. 44-29622 and Japanese Patent Publication No. 47-25373, Japanese Patent Publication No. 47-8736 1,3,5-tris[β-(vinylsulfonyl) as described in JP-A-49-24435;
-propionyl]-hexahydro-S-triazine or alkyl compounds such as those described in Japanese Patent Application No. 118457/1984, various compounds having three or more vinylsulfonyl groups in their molecular structures are included. . Next, typical examples of Compound I will be given. -1 -2 -3 -4 CH ₃ C (CH ₂ OCH ₂ SO ₂ CH=CH ₂ ) ₃ -5 C (CH ₂ OCH ₂ SO ₂ CH=CH ₂ ) ₄ -6 N (CH ₂ CH ₂ OCH ₂ SO ₂ CH=CH ₂ ) _3-7 -8 −9 C ₂ H ₅ C (CH ₂ SO ₂ CH=CH ₂ ) ₃ −10 C ₈ H ₁₇ C (CH ₂ SO ₂ CH=CH ₂ ) ₃ −11 −12 (CH ₂ = CHSO ₂ CH ₂ ) ₃ CCH ₂ Br −13 (CH ₂ = CHSO ₂ CH ₂ ) ₂ CHCH(CH ₂ SO ₂
CH=CH ₂ ) ₂ −14 (CH ₂ = CHSO ₂ CH ₂ ) ₃ CCH ₂ OCH ₂ − ^** −C(CH
₂ SO ₂ CH=CH ₂ ) ₃ −15 C(CH ₂ SO ₂ CH=CH ₂ ) ₄ −16 −17 (CH ₂ = CHSO ₂ CH ₂ ) ₃ CCH ₂ SO ₂ CH ₂ CH ₂ Cl −18 The compound (hereinafter referred to as a compound) having a group that reacts with the vinylsulfonyl group and a water-soluble group to be reacted with the compound has a vinylsulfonyl group such as -SH group, =NH group, _-NH2 group, etc. in the molecular structure. It has a group that reacts with -OH group,
A compound having a water-soluble group consisting of a -COOH group, _-SO2H group, _-OSO3H group, or a salt thereof (for example, an alkali metal salt such as Na, K, or Li),
These reactive groups and water-soluble groups each include those in which two or more are present in the molecular structure. Next, typical examples of compounds will be given. −1 H ₂ NCOONa −2 H ₂ NSO ₃ K −3 HSCH ₂ COOH −4 HSCH ₂ COONa −5 HSCH ₂ COOK −6 HSCH ₂ COOLi −7 HSCH ₂ CH ₂ COOH −8 HSCH ₂ CH ₂ COOK −9 −10 −11 −12 H ₂ NCH ₂ CH ₂ OH −13 H ₂ NCH ₂ CH ₂ OSO ₃ H −14 H ₂ NCH ₂ CH ₂ OSO ₃ K −15 H ₂ NCH ₂ COOH −16 H ₂ NCH ₂ COONa −17 CH ₃ NHCH ₂ COOK −18 H ₂ NCH ₂ SO ₃ H −19 CH ₃ NHCH ₂ SO ₃ Na −20 H ₂ NCH ₂ CH 2 SO _{3 H} −21 H 2 NCH ₂ CH _{2 SO 3} K −22 CH ₃ NHCH ₂ CH ₂ SO ₃ Na −23 HN (CH ₂ CH ₂ OH) ₂ −24 HN (CH ₂ CH ₂ OSO ₃ K) ₂ −25 CH ₃ NHCH ₂ CH ₂ CH ₂ SO ₃ H −26 −27 C ₂ H ₅ NHCH ₂ CH ₂ CH ₂ CH ₂ SO ₃ H −28 C ₂ H ₅ NHCH ₂ CH ₂ CH ₂ CH ₂ SO ₃ Na −29 −30 −31 HN(CH ₂ COOH) ₂ −32 −33 HN(CH ₂ COOK) ₂ −34 −35 −36 -37 CH ₃ NHCH ₂ COONa In order to cause a compound to react with another compound, a solution of the compound may be added to a solution of the compound, and the mixture may be kept at room temperature or heated. When a free group is used as the water-soluble group of the compound in the reaction, the water-soluble group in the reaction product may be converted into a salt form by further reacting with an alkali after the reaction. The reaction molar ratio between the compounds differs depending on the number of vinylsulfonyl groups in the compound and the number of reactive groups in the compound, but generally one reactive group is added to a compound having n vinylsulfonyl groups. When reacting a compound that has a compound, it is preferable to react the compound at a ratio of 0.5 to n moles per mole of the compound, and it is particularly desirable to react the compound at a ratio of 1 to n-2 moles per mole of the compound. A curing agent with specific properties is obtained.
The desired amount of reaction also differs depending on the type of reactive group in the compound. For example, when the reactive group is a -SH group or a =NH group, the above reaction amount is desirable, but if the reactive group is - In the case of NH ₂ groups, it is desirable to react 1/2 of them. The reaction product obtained by the reaction of one compound to another may be a single compound in some cases, but it is generally not possible to obtain a product consisting only of a single compound in many cases. In other words, for example, some of the vinyl sulfonyl groups of the compound are annihilated by reaction with the reactive group of the compound, and some unreacted compounds or all the vinyl sulfonyl groups in the molecular structure are annihilated by the reaction of the compound. Reaction products are often obtained in the form of mixtures containing those annihilated by reaction with the functional groups. The effect based on the good water solubility as a curing agent of the present invention is due to the fact that some of the vinylsulfonyl groups of the compound are annihilated by reaction with the reactive groups of the compound, especially when the vinylsulfonyl groups are still present in the molecular structure. It is thought that the effect is exerted by two or more remaining reaction products, but even if a small amount of other reaction products such as those mentioned above are mixed, the operation and effect are not adversely affected. Therefore, the reaction product may be isolated by chromatography, etc., if necessary, but in actual use, it is necessary to isolate the reaction product as a mixture without daring to isolate only the main part of the reaction product. It is preferable to use things as is. In order to use the reaction product obtained by the above reaction as a hardening agent for gelatin, the reaction product can be added to gelatin as it is or diluted with water, or the residual solvent in the reaction product can be removed. It is preferable to distill it off and separate it as crystals or viscous liquid, then dissolve it in water and add it to gelatin. The amount added is 0.1 of the dry state amount of gelatin.
~10% by weight. The gelatin subbing liquid according to the present invention can contain various additives as necessary. Examples include matting agents, surfactants, antistatic agents, antihalation agents, coloring dyes, pigments, coating aids, antifoggants, and the like. The subbing liquid according to the present invention can be applied by a generally well-known coating method, such as a dip coating method, an air knife coating method, a curtain coating method, a roller coating method, a wire bar coating method, a gravure coating method, or the specification of US Pat. No. 2,681,294. It can be applied by the extrusion coating method using a hopper as described in the book. 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 material according to the present invention is applied to a color photographic material, it usually has three types of light-sensitive silver halide emulsion layers having different spectral sensitivities, and each emulsion layer has a yellow coupler, a magenta coupler, and cyan coupler. In such a case, the combination of the light-sensitive silver halide emulsion layer and the coupler is usually a cyan coupler in the red-sensitive silver halide emulsion layer, a magenta coupler in the green-sensitive silver halide emulsion layer,
Furthermore, a yellow coupler is combined with each of the blue-sensitive silver halide emulsion layers. 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 bivaloylacetanilide 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, back 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-pyrazolidone, 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 glycose 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> Shallow scratches were made on the emulsion surface of the sample in a checkerboard pattern with a razor, and cellophane adhesive tape was pressed onto the scratches, and then the tape was applied. The residual rate of the emulsion film relative to the adhesive area of the cellophane tape when it was peeled off was expressed as a percentage. <Test with treated film> The emulsion surface of the sample in the processing bath was scratched in a checkerboard pattern with a sharp end, and the surface was rubbed.
The remaining 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, exemplified compound (2) was added to a 1% aqueous gelatin solution.
Subtracting liquid with and without addition of 0.2, 1.0, and 3.0% by weight based on gelatin,
Dry coating amount is 0.08g/ ^m2 using wire bar coating method.
It was coated and dried at 80°C for 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] It is clear from this that the gelatin subbing to which exemplified compound (2) was added increases the adhesive strength 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 Exemplary compounds were applied to the emulsion-coated corona discharge treated surface of polyethylene-coated paper obtained in the same manner as in Example 1.
(4) was added to the gelatin at a concentration of 1.2% by weight, and the dry coating amounts were 0.009 and 0.04 g/m ² respectively for 0.2% aqueous gelatin solution, and 0.06 and 0.10 g/m ² for 1% aqueous gelatin solution, respectively. A 10% aqueous gelatin solution was applied at a concentration of 1.2 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] It can be seen from this that the gelatin undercoat containing exemplified compound (4) has good adhesive strength when the coating amount is 0.04 to 1.2 g/m ² . However, when the coating amount was 1.2 g/m ^{2 ,} although the adhesion was good, the degree of curling became large and it 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 hardening agent of the present invention was added to the emulsion-coated corona discharge treated surface of polyethylene-coated paper obtained in the same manner as in Example 1 in a 1% gelatin aqueous solution as shown in Table 3. Add to 1.0% by weight,
Using the wire bar coating method, the dry coating amount is 0.1g/
It was coated in an amount of ² m2 and dried at 80°C for 2 minutes. Example 1 for these subtracted polyethylene coated papers
An adhesive strength test was conducted in the same manner as above. The results thus obtained are shown in Table 3.

[Table] All exhibited good adhesive strength. Also, the emulsion coating properties and emulsion fog were both good. Example 4 In the same manner as in Example 1, Exemplified Compound (2), Exemplified Compound (14), and comparative hardener bis(2-vinylsulfonylethyl) ether were added to a 1% gelatin aqueous solution at a ratio of 0.8 to gelatin, respectively. % by weight, and the dry coating amount is determined by wire bar coating method.
It was coated at a concentration of 0.1 g/m ² and dried at 80°C for 2 minutes. These sublimated polyethylene-coated papers and polyethylene-coated papers immediately after corona discharge treatment were heated at 23°C.
The samples were left to stand for the number of days shown in the table below under conditions of 55% RH, and then an adhesive strength test was conducted in the same manner as in Example 1. The results are shown in Table 4.

[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. Example 5 Reaction products-1 to -6 were obtained by the following reactions. Reaction Product-1 A solution of 1.16 g (0.011 mol) of diethanolamine (Exemplary Compound-23) in 50 ml of acetone was added to a 50 ml solution of 1,3,5-trisvinylsulfonylbenzene (Exemplified Compound-1) 3.48 g (0.01 mol) in acetone. The aqueous solution was then refluxed for 2 hours, the insoluble portion was filtered off, and the filtrate was concentrated under reduced pressure to obtain a yellow viscous liquid. Reaction product-2 Tetrakis(vinylsulfonylmethyloxymethyl)methane (Exemplary compound-5) 5.52g (0.01
1.56 g (0.02 mol) of thioglycolic acid (Exemplary Compound-7) was added to a 50 ml solution of 1.56 g (0.02 mol) of thioglycolic acid (exemplary compound-7) in acetone, and after reacting at room temperature for 6 hours, the same amount of water as the acetone was added and 1N-Na ₂ CO ₃ After neutralizing by adding 20 ml, concentrate under reduced pressure to obtain colorless crystals. Reaction product-3 70 ml of water containing 1.33 g (0.012 mol) of sancosine sodium salt (exemplified compound-37) in 50 ml of acetone solution of 4.32 g (0.01 mol) of tetrakis(vinylsulfonylmethyl)methane (exemplified compound-15)
Add an aqueous solution of and react under reflux for 2 hours. After the reaction, acetone was distilled off under reduced pressure, and water was added to make 283 ml.
Make a 2% aqueous solution. Reaction Product-4 Taurine Na salt (Exemplary Compound-15) was added to a solution of 4.32 g (0.01 mol) of tetrakis(vinylsulfonylmethyl)methane (Exemplified Compound-15) in 50 ml of acetone.
21) Add 25ml aqueous solution of 1.1g (0.0075mol) and add 60
After reacting at °C for 3 hours, the solvent was distilled off to obtain white crystals. Reaction product-5 A solution of 1.57 g (0.015 mol) of diethanolamine (exemplified compound-23) in 50 ml of acetone was added to a solution of 4.32 g (0.01 mol) of tetrakis(vinylsulfonylmethyl)methane (exemplified compound-15) in 50 ml of acetone, and the solution was placed in a water bath. The mixture was refluxed for 2 hours, filtered, and concentrated under reduced pressure to obtain a viscous liquid. Reaction product-6 1,1,1-tris(vinylsulfonylmethyl)propane (exemplified compound-9) 3.56 g (0.01
Add 50 ml of water solution containing 0.97 g (0.01 mol) of sodium glycine salt (Exemplary Compound-16) to 50 ml of acetone solution of mol), react at 50°C for 2 hours on a hot bath, and then distill off the acetone under reduced pressure. Add 227ml,
Make a 2% solution. Next, the reaction product-1 obtained in this manner was added to a 1% gelatin aqueous solution on the emulsion-coated corona discharge treated surface of the polyethylene circularly coated paper obtained in the same manner as in Example 1.
Solid content of ~-6 is 1.5% by weight based on gelatin
⁸⁰ °C
Dry for 2 minutes. An adhesive strength test was conducted on these subbed polyethylene coated papers in the same manner as in Example 1.

[Table] From this table, all showed good adhesive strength. Also, the coating properties of the emulsion and emulsion fog were both good.

Claims (1)

[Scope of Claims] 1. A silver halide photographic material in which a silver halide emulsion layer is provided on a corona discharge-treated polyolefin-coated paper support, in which a silver halide emulsion layer is provided on the surface of the corona discharge-treated polyolefin-coated paper support. , a gelatin undercoat layer is hardened with at least one hardening agent represented by the following general formula [] and has a film thickness of 0.05 g/m ² to 0.2 g/m ² in coating amount after drying. A silver halide photographic material characterized by: General formula [] In the formula, R represents an alkyl group having 1 to 4 carbon atoms, A is an n-valent linking group, and The part that is bonded to is a carbon atom. l and m represent integers from 0 to 4, and n represents from 2 to
Represents the number 4.