JP2914449B2 - Photographic support - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a photographic support having a gelatin subbing layer provided on the surface of a resin-coated paper support which has been subjected to corona discharge treatment. [Prior Art] Conventionally, as a photographic support, a so-called baryta paper in which barium sulfate is applied to one side of a strongly sized paper has been used. Resin-coated paper coated with a resin has come to be used. However, since the surface of these water-resistant photographic supports is hydrophobic, it is difficult to firmly adhere a photographic emulsion layer using gelatin as a binder.
Therefore, a method of applying a photographic emulsion after activating the hydrophobic resin surface by corona discharge treatment, fire treatment, chemical treatment or the like has been performed. However, these methods have been found not only to deteriorate the activity of the activated resin surface with time, but also to deteriorate the adhesion to the photographic emulsion layer, and to cause uneven electrostatic charge on the polyolefin surface. In many cases, the coating state of the emulsion is not uniform. Therefore, conventionally, a gelatin film, that is, an undercoat, has been applied to the resin surface immediately after the activation treatment in order to prevent deterioration of the effect of the activation treatment over time and to improve photographic properties such as improvement of coating unevenness. JP-B-47-18010,
JP-B-48-14185, JP-B-49-17522, JP-B-49-15
No. 210, Japanese Patent Publication No. 50-4389, Japanese Patent Publication No. 57-9058, Japanese Patent Application Laid-Open No. 5
0-110323, JP-B-57-53585, JP-A-52-130625
And JP-A-58-184144 disclose techniques for improving the coating and adhesion between an undercoat layer and an emulsion layer, respectively.
In recent years, there has been a remarkable increase in the speed of emulsion coating and thinning of the emulsion in order to increase productivity, and the coating properties and adhesiveness have not always been satisfactory with these techniques. [Object of the Invention] An object of the present invention is to provide a photographic support provided with an undercoat layer having excellent adhesion to an emulsion layer. [Means for Solving the Problems] An object of the present invention is to provide a corona discharge-treated polyolefin resin-coated paper support formed by melt extrusion coating on gelatin and the following general formulas [I] and [I].
I] at least one compound selected from the compounds represented by the following formula, and the film thickness is 0.01 g / m2 to
This was achieved by a photographic support characterized in that it had a gelatin subbing layer of 0.2 g / m2. General formula [I] General formula [II] [In the formula, R ₁ , R ₂ , R ₃ , R ₅ , R ₇ , and R ₈ represent a hydrogen atom or an alkyl group, and R ₄ and R ₆ represent an alkylene group. The present invention has improved the coating properties of the photographic emulsion layer by adding the compound according to the present invention to the undercoat solution.
Anionic, cationic, or nonionic surfactants that are similar in surface chemistry to these compounds do not form a uniform solution with gelatin and have a large surface tension lowering effect, but are coated uniformly. Most of them were not suitable for practical use, for example, they could not be used or had an adverse effect on photographic performance. The compound according to the present invention that can be used in the present invention is a compound represented by the aforementioned general formulas [I] and [II]. Next, each group of the compound according to the present invention represented by the general formulas [I] and [II] will be described. R ₁ represents an alkyl group having 1 to 18 carbon atoms. R ₂ ,
R ₃ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. R ₄ represents an alkylene group having 1 to 8 carbon atoms. R ₅ represents an alkyl group having 1 to 18 carbon atoms. R ₆
Represents an alkylene group having 1 to 8 carbon atoms. Next, typical specific examples of the compound according to the present invention will be shown. These are merely examples in the above general formula, and the compounds of the present invention are not limited thereto. The ratio of the amount of the compound represented by the general formulas [I] and [II] according to the present invention to the undercoat liquid is determined by the coating conditions,
Although it depends on the coating speed, coating amount, drying conditions, etc., according to the experiments of the present inventors, the solid content is preferably in the range of 0.1 to 10% by weight, particularly 0.2 to 4% by weight, based on gelatin. If it is more than this, the photographic performance is adversely affected or the effect on the emulsion characteristics is reduced. On the other hand, if the amount is less than this, the effect of improving coating unevenness is insufficient. Some of these compounds according to the invention are commercially available and readily available. These compounds according to the present invention may be used alone or in combination of two or more. The gelatin subbing aqueous solution according to the present invention may contain various additives as necessary in addition to the compound according to the present invention. Examples include matting agents, antistatic agents, antihalation agents, coloring dyes, pigments, antifoggants, hardeners for gelatin, preservatives, fluorescent whitening agents and the like. Examples of the base paper used for the resin-coated paper of the present invention include natural pulp paper, synthetic pulp paper, and mixed paper of natural pulp and synthetic pulp. Base paper is usually used in a thickness of 50 to 300 microns. A polyolefin resin can be used as the resin forming the resin-coated paper. Examples of the polyolefin resin include polyethylene, polypropylene, a copolymer thereof, and a mixture of these various polymers. In the case of a polyolefin resin on a running base paper, the photographic support produced by the present invention is produced by a so-called extrusion coating method in which a resin melted by heating is cast, and both surfaces thereof are coated with the resin. The thickness of the resin layer is not particularly limited, but is preferably selected from the range of 10 to 50 microns. In the resin, white pigments such as titanium oxide, zinc oxide, talc, calcium carbonate, fatty acid amides such as stearamide, arachidic amide, zinc stearate, calcium stearate, aluminum stearate, magnesium stearate, etc. Fatty acid metal salts, hindered phenols, hindered amines, sulfur-based, phosphorus-based antioxidants, pigments and dyes such as cobalt blue, ultramarine blue, cecilian blue, cobalt violet, phthalocyanine blue, fluorescent brighteners, ultraviolet absorbers, and electrification It is preferable to add various additives such as an inhibitor and a surfactant in appropriate combination. Various methods of performing corona discharge treatment on resin-coated paper are known, and these techniques may be applied to the present invention. For example, Japanese Patent Publication No. 37-17682
No., JP-B-37-17485, JP-B-45-40438, JP-B-48
No. 5043, JP-B-50-19300, JP-B-47-5190, JP-B-49-10687, JP-A-48-28067, JP-A-58-4157
No., JP-A-58-222118, JP-A-48-89731, JP-A-Showa-5
No. 9-4437, BP971058 and the like. The undercoat layer used in the present invention is formed by applying an aqueous gelatin solution containing the compound according to the present invention to the surface of the resin layer activated by corona discharge treatment. As the gelatin, not only so-called lime-treated gelatin, acid-treated gelatin, enzyme-treated gelatin and the like, but also modified gelatin generally used in the art can be used. If the thickness of the undercoat layer is too small, sufficient adhesive strength cannot be obtained. On the other hand, if the thickness is too large, the adhesive strength is improved, but curling occurs and blocking occurs on the back surface, which is not preferable. Therefore, the film thickness of the undercoat layer of the present invention, the amount of coating after drying
In ^{0.01g / m 2 ~0.2g / m 2} , preferably 3.00.05g / m ² ~0.2g / m
² The undercoat liquid according to the present invention can be applied by a generally well-known coating method, for example, a dip coating method, an air knife method, a curtain coating method, a roller coating method, a wire bar coating method, a gravure coating method, or the like. The undercoat liquid thus applied is subsequently dried in a drying step, under any conditions, but generally at 60 ° C.
Performed at 150 ° C. in seconds to 10 minutes. The market value for providing the undercoat layer may be any time as long as the resin-coated paper has been subjected to corona discharge treatment. For example, when the undercoat layer according to the present invention is subsequently provided after corona discharge treatment, when the corona discharge treatment is temporarily stored, and then the undercoat layer according to the present invention is provided and stored again Or a case where an undercoat layer is provided in a step before the step of coating a silver halide emulsion. The silver halide emulsion layer and the layer structure of the photographic material provided on the undercoat layer may be of any type. These can be used for various purposes such as color photographic printing paper, black-and-white photographic printing paper, typesetting photographic printing paper, copy photographic printing paper, reversal photographic material, silver salt diffusion transfer, and printing material. For example, silver chloride, silver bromide, silver chlorobromide,
A silver iodobromide or silver chloroiodobromide emulsion layer can be provided. The silver halide photographic emulsion layer may contain a color coupler to provide a multilayer silver halide constituting layer. Further, a silver diffusion transfer image receiving layer can be provided by incorporating a physical development nucleus. As a binder for these photographic constituent layers, in addition to ordinary gelatin, hydrophilic high-molecular substances such as polyvinylpyrrolidone, polyvinyl alcohol and polysaccharide sulfate compounds can be used. Further, the above-mentioned photographic constituent layer can contain various additives. For example, as a sensitizing dye, a cyanine dye, a merocyanine dye, etc., as a chemical sensitizer, a water-soluble gold compound,
Sulfur compounds, antifoggants or stabilizers such as hydroxy-triazopyrimidine compounds and mercapto-heterocyclic compounds, etc .; hardening agents such as formalin, vinylsulfone compounds and aziridine compounds; benzenesulfonates and sulfosuccinates as coating aids Acid stains, such as dialkyl hydroquinone compounds, etc .; other fluorescent brighteners, sharpness improving dyes, antistatic agents, pH regulators, fogging agents, and water-soluble iridium during the formation and dispersion of silver halide. , A water-soluble rhodium compound or the like can be incorporated in an appropriate combination. The silver halide photographic material according to the present invention may be exposed, developed, and stopped in accordance with the photographic material, as described in "Photosensitive Materials and Handling Methods" (Kyoritsu Shuppan, Goro Miyamoto, Photographic Technology Course 2). , Fixing, bleaching, stabilization, etc. are performed. In particular, multi-layer silver halide color photographic materials which are subjected to one-bath bleach-fixing after color development are CD-III and CD-IV (the above two compounds are obtained from Kodak Co., Ltd.). Can be processed with a color developing solution of any principal agent such as (trade name) and droxychrome (trade name of May and Baker Co., Ltd.). A developer containing such a base may contain a development accelerator such as benzyl alcohol, thallium salt, or phenidone. A useful one-bath bleach-fixing solution is a solution of a metal salt of aminopolycarboxylic acid (for example, a ferric complex salt such as ethylenediaminetetraacetic acid or propylenediaminetetraacetic acid). Ammonium sulfate and the like are useful.
Various additives can be contained in such a one-bath bleach-fix solution. For example, various compounds such as a desilvering accelerator, a stain inhibitor, a pH adjusting or pH buffering agent, a hardening agent, and a surfactant can be contained in combination. Further, such a single-bath bleach-fix solution is used at various pHs,
The range is pH 6.0-8.0. EXAMPLES Hereinafter, the present invention will be described in detail with reference to examples, but the contents of the present invention are not limited to the examples. Example-1 Both surfaces of a photographic base paper having a basis weight of 170 g / m ² were subjected to corona treatment, and then the back surface was coated with high-density polyethylene (density 0.96
g / cm ³ , MI = 5) and low density polyethylene (density 0.92g / c)
A 1: 1 mixture of m ³ and MI = 5) was coated at a resin temperature of 330 ° C. to a thickness of 30 μm using a melt extrusion coater. Next, a resin composition comprising 7: 3 of low-density polyethylene and high-density polyethylene containing 10% of anatase type titanium oxide was coated on the surface at a resin temperature of 330 ° C. to a thickness of 30 μm. Next, a corona discharge treatment was performed on the surface of the polyethylene containing titanium oxide by a corona discharge treatment device. The surface of the corona discharge treated surface was coated with 0.1% aqueous solution of Exemplified Compound A in an aqueous solution of 1% gelatin at a concentration of 3.0, 0.6, or 2.0% by weight of gelatin. g / m ² and dried at 120 ° C. for 30 seconds. An ordinary silver halide emulsion for photographic paper was applied to these subbed polyethylene coated papers and the polyethylene coated paper immediately after corona discharge treatment. The material thus obtained was developed and observed with the naked eye to determine the presence or absence of coating unevenness. The effect on emulsion performance (mainly fog and sensitivity) was also examined by photographic sensitometry. The results are shown in Table 1. This indicates that the addition of the compound according to the present invention improves the unevenness of cloth coating without adversely affecting the emulsion performance. Example-2 Exemplified compound D was added to the corona discharge treated surface on the emulsion coating side of the polyethylene-coated paper obtained in the same manner as in Example-1 so that the solid content of gelatin was 0.8% by weight based on gelatin. % 0.009 g / m ² respectively coated amount in weight after drying an aqueous gelatin solution, 0.04g / m ^2, 1% aqueous gelatin solution each coated amount after drying weight ^{0.06g / m 2, 0.08g / m} 2 ,
The coating amount after drying a 10% aqueous gelatin solution is 1.4 g / m ^{2 by} weight.
Apply by wire bar coater method, 120 ℃, 30
Dried for seconds. With respect to the results of evaluation of these undercoated polyethylene-coated papers in the same manner as in Example 1,
It is shown in the table. As a result, when the coating amount of the gelatin subbing layer to which the compound according to the present invention was added was 0.04 g / m ² , 0.06 g / m ² , and 0.08 g / m ² , the coating properties and the emulsion properties were good. However, when the coating amount was 1.4 g / m ² , the curl degree was large, and the blocking with the back surface when superimposed was poor, which was not suitable for practical use. Also,
Can not completely cover the polyethylene surface the 0.009 g / m ^2,
Repelling occurred, and the coatability of the emulsion became insufficient. Example-3 Comparative compounds (1), (B), (C), (E), and (F) in a 1% aqueous gelatin solution were applied to the corona discharge-treated surface of the polyethylene-coated paper obtained on the emulsion-coated side in the same manner as in Example-1. 2) was added to gelatin at a solid content of 1.0% by weight,
The coating amount after drying by the wire bar coating method is 0.12 by weight
g / m ² and dried at 120 ° C. for 30 seconds. Table 3 shows the results of evaluation of these undercoated polyethylene-coated papers in the same manner as in Example 1. Comparative Example Compound (1) Comparative Example Compound (2) C ₁₂ H ₂₅ —O—SO ₃ Na [Effect of the Invention] From this, it can be seen that the gelatin underlayer to which the compound according to the present invention is added has no coating unevenness and good emulsion properties. .

Claims (1)

(57) [Claims] Corona discharge treated, on a polyolefin resin coated paper support formed by melt extrusion coating, containing gelatin and at least one compound selected from compounds represented by the following general formulas [I] and [II],
A photographic support comprising a gelatin subbing layer having a thickness of 0.01 g / m2 to 0.2 g / m2 in a coating amount after drying. General formula [I] General formula [II] [In the formula, R1, R2, R3, R5, R7, and R8 represent a hydrogen atom or an alkyl group, and R4 and R6 represent an alkylene group. ]