JPH09274276A - Production of photographic substrate and silver halide photographic material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To form a back layer excellent in lubricity, adhesion resistance and antistatic performance and having a uniform surface by specifying the temp. of a photographic substrate and the temp. of a photographic coating soln. and coating the substrate with the coating soln. SOLUTION: When a top layer is formed by coating on the rear side of a photographic substrate, the temp. of the substrate is regulated to 30-50 deg.C, preferably 35-45 deg.C and the temp. of a coating soln. is regulated to 25-40 deg.C, preferably 25-35 deg.C. The top layer preferably contains higher fatty acid ester and a lower layer under the top layer preferably contains a conductive cationic polymer. Since the temp. of the substrate is higher than the conventional temp. (about 20 deg.C), the film forming state of the higher fatty acid ester-contg. overcoating layer is varied and the leaching of the cationic polymer as an antistatic agent in the lower layer in a processing bath, that is, the formation of scum can be suppressed. Since the temp. of the coating soln. is high, the occurrence of surface trouble due to a stringy state peculiar to a slide coater can be prevented.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a photographic support which is excellent in slipperiness, adhesion resistance and antistatic property and provides a back layer having a uniform surface, and a halogen comprising the support. The present invention relates to a silver halide photographic light-sensitive material.

[0002]

2. Description of the Related Art A photographic light-sensitive material usually has a photosensitive silver halide emulsion layer on one side of a support, and the side of the support (back side) opposite to the side coated with this silver halide emulsion layer.
Is not coated with a silver halide emulsion layer. It is known that an antistatic layer is provided on the back surface of the above photographic light-sensitive material in order to prevent uneven exposure to light due to static electricity generated during the manufacturing process or during use. On the other hand, photographic light-sensitive materials include winding, rewinding in shooting, developing, printing, projection, etc., including manufacturing processes such as coating, drying, and processing.
Also, during handling such as transportation, contact friction with various devices, machines, adhesive parts of photosensitive materials such as cameras, or with adhering substances such as dust and fiber waste often causes serious adverse effects. . In particular, since the back surface often comes into direct contact with various equipment, for example, the occurrence of scratches and abrasions, deterioration of drivability of photosensitive materials in cameras and other machines,
It is easy for film layers to occur. The occurrence of these scratches appears on the image-resistant surface at the time of printing or image, and is a serious defect in practical use. In addition, recently, due to the expansion of the use and processing methods for photosensitive materials such as high-speed coating, rapid photography, and rapid processing, and the diversification of environments during use such as in a high temperature and high humidity atmosphere, photosensitive materials have been conventionally used. As a result, they are subject to severer handling, and scratches and deterioration of driveability are more likely to occur. Therefore,
It is desired to develop a high-quality support having a slip property and an antistatic effect that can sufficiently withstand even under such severe conditions, high scratch resistance, and high surface uniformity, and a photosensitive material having the same. .

Further, generally, in a high-speed photographic film, the coating thickness of a photosensitive emulsion layer containing silver halide becomes large. Such a film having a thick coating thickness of the emulsion layer is apt to curl particularly at low temperatures, and is easily scratched on the back surface due to factors such as a pressure plate while running in the camera. In some cases, the scratches may appear on the print, which may be a quality problem. Various methods have been developed to overcome such defects and obstacles. For example, JP-A-3-23438 and JP-A-3-148650 disclose a combination of a cationic polymer having conductivity and a higher fatty acid ester as a back surface. However, when the above materials are used, the outermost layer of the coating layer (back layer) becomes non-uniform, and the slipperiness and antistatic effect are not always sufficient. In a thick system (for example, a thickness of 20 μm or more), it curls under low humidity and the above-mentioned quality defects due to scratches cannot be completely prevented.

[0004]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to provide a method for producing a photographic support which is excellent in slipperiness, adhesion resistance and antistatic property and provides a back layer having a uniform surface. That is. Further, the object of the present invention is to withstand even severe conditions such as photographing, developing treatment, printing, and projection, and is less likely to be scratched even when curled under low humidity, slipperiness, adhesion resistance, antistatic property, It is intended to provide a silver halide photographic light-sensitive material having a back layer excellent in surface uniformity and the like.

[0005]

The above-mentioned problems of the present invention have been solved by the following method for producing a photographic support and a silver halide photographic light-sensitive material. That is, in the present invention, (1) in coating the outermost layer on the back surface of a photographic support, the temperature of the photographic support is 30 ° C. or higher and 50 ° C. or lower, and the temperature of the photographic coating liquid is 25 ° C. or higher. A method for producing a photographic support, which comprises coating at 40 ° C. or lower, (2) the temperature of the support is 35 ° C. or higher and 45 ° C. or lower, and the temperature of the photographic coating liquid is 25 ° C. or higher and 35 ° C. or lower. (3) The method for producing a photographic support according to item (1), (3) The photograph according to item (1) or (2), wherein the outermost layer contains a higher fatty acid ester. For manufacturing a support for
(4) The method for producing a photographic support according to item (1), (2) or (3), characterized in that a conductive cationic polymer is contained in the lower layer of the outermost layer, (5) At least one silver halide emulsion layer is provided on one side of the support, the thickness of the emulsion layer is 20 μm or more, and the surface of the support opposite to the emulsion layer coating side has the following general formula ( I)
A surface layer containing an aliphatic group-containing ester compound represented by is attached, and the support is (1), (2) or (3).
Or a silver halide photographic light-sensitive material characterized by being obtained by the method described in (4), R ¹ COOR ^{2 of} the general formula (I) (wherein R ¹ and R ² have 12 or more carbon atoms). And (6) the thickness of the silver halide emulsion layer is 25 μm or more and 35 μm or less, the silver halide photographic light-sensitive material according to item (5). It is provided.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, the coating solution for the outermost layer on the back surface preferably contains a higher fatty acid ester.
The higher fatty acid ester is represented by the following general formula (I). General formula (I) R ¹ COOR ² (In the formula, R ¹ and R ² represent an alkyl group or an alkenyl group having 12 or more carbon atoms.) The following is represented by the general formula (I) which can be preferably used in the invention. Specific examples of the higher fatty acid ester will be shown.

[0007]

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[0008]

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In introducing the ester compound into the outermost layer, it is preferable to use it together with a binder capable of forming a film. Such polymers include cellulose esters such as cellulose triacetate, cellulose diacetate, cellulose acetate maleate, cellulose acetate phthalate, hydroxyalkylalkyl cellulose phthalates and cellulose long chain alkyl esters; formaldehyde and cresol, salicylic acid or oxyphenyl. A polycondensation polymer such as a polycondensation product with acetic acid or a polycondensation product of terephthalic acid or isophthalic acid and polyalkylene glycol; a homo-polypolymer such as acrylic acid, methacrylic acid, styrenecarboxylic acid or styrenesulfonic acid, or a polycondensation product thereof. Monomer or maleic anhydride and styrene derivative, alkyl acrylate, alkyl methacrylate,
Copolymers with vinyl chloride, vinyl acetate, alkyl vinyl ether or acrylonitrile, or ring-opening half-esters or half-amides thereof, partially hydrolyzed polyvinyl acetate; monomers having a polymerizable unsaturated bond such as polyvinyl alcohols There are synthetic polymers such as homopolymers or copolymers obtained from

Even when a binder is used, water, an organic solvent or a mixture thereof can be used as a solvent. Examples of the above-mentioned organic solvent and the organic solvent described herein include alcohols such as methanol, ethanol and butanol; ketones such as acetone and methyl ethyl ketone; methylene chloride: halogenated hydrocarbons such as carbon tetrachloride and chloroform; Examples thereof include ethers such as diethyl ether, dioxane and tetrahydrofuran, aromatic hydrocarbons such as benzene, toluene and xylene.

The binder is preferably used in an amount of 1 to 10 times the amount of the ester compound, and is preferably contained in the outermost layer in an amount of 10 mg / m ² to 10 g / m ^2. . When forming the outermost layer, it is preferable to use a matting agent together with the ester compound. Examples of the matting agent include silica, inorganic compounds such as strontium barium sulfate, and organic polymers such as polymethylmethacrylate and polystyrene. Fine particles having an average particle diameter of 0.01 to 10 μm are preferable.

The outermost layer formed as described above preferably contains the ester compound in an amount of 5 mg to 1000 mg / m ² (more preferably 10 mg to 200 mg / m ² ).

In the present invention, the cationic polymer contained in the lower layer of the outermost layer is represented by the following general formula (II).

[0014]

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(In the above formula (II), R ⁷¹ and R
⁷² each represent an alkyl group, a cycloalkyl group, an aralkyl group, an aryl group or an alkenyl group, these R ⁷¹ and R ⁷² may form an alkylene chain bonded to each other; R ⁷³ is a carbon number 10 The following alkylene group and aralkylene group are represented; M ^71- and M ^72- represent an anion; and n represents about 10 to 300. )

Typical examples of the above include the polymers shown below.

[0017]

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The above compounds are the same as those described in JP-A-53-92.
No. 125 or No. 54-18728. The above-mentioned cationic polymer content is an aqueous dispersion prepared by dissolving the above-mentioned cationic polymer in water, an organic solvent or a mixed solvent thereof, or in the presence of a suitable dispersant such as a surfactant. It can be formed by preparing the above coating solution, applying it to one side of a support, and drying. Alternatively, when various photographic constituent layers are already coated on the back surface of the support, they can be formed by utilizing an overcoating or permeating method. As the coating method, the coating method used when forming the emulsion layer can be used. The above-mentioned cationic polymer is preferably contained in the polymer-containing layer in an amount of 5 to 500 mg / m ² (more preferably 20 g to 100 mg / m ² ).

The present invention is characterized in that the temperature of the support and the temperature of the photographic coating liquid are regulated when the outermost layer on the back surface of the photographic support is coated. Usually, the temperature of the support is 30 ° C. or higher and 50 ° C. or lower, the temperature of the coating liquid is 25 ° C. or higher and 40 ° C. or lower, preferably the temperature of the support is 35 ° C. or higher and 45 ° C. or lower, and the temperature of the coating liquid is 25 ° C. or higher It shall be 35 ° C or lower. More preferably, the temperature of the support is 36 to 40 ° C, and the temperature of the coating liquid is 28 to 32 ° C. In this case, when the temperature of the support exceeds 50 ° C., the coating liquid evaporates and foams easily, and when the temperature is lower than 30 ° C., the components of the coating liquid tend to precipitate.
When the temperature of the coating liquid exceeds 40 ° C, the coating liquid also evaporates and foams easily, and when the temperature is less than 25 ° C, liquid sagging easily occurs.

The particle size of the matting agent such as SiO ₂ added to the back layer is in the range of 0.01 to 3.0 μm, and the amount is preferably 0.5 to 90 mg / m ² . The support used in the present invention includes cellulose esters such as cellulose triacetate, cellulose butyrate acetate and cellulose propionate acetate, polyesters such as polyethylene naphthalate and polyethylene terephthalate, polystyrene and polycarbonate. In the present invention, a surface treatment is preferable in order to bond the support and the light-sensitive material constituting layer. Surface activation treatments such as chemical treatment, mechanical treatment, corona discharge treatment, flame treatment, ultraviolet treatment, high frequency treatment, glow discharge treatment, active plasma treatment, laser treatment, mixed acid treatment, ozone oxidation treatment, and the like. Among the surface treatments, ultraviolet irradiation treatment, flame treatment, corona treatment, and glow treatment are preferable.

It is also preferable that the photosensitive layer also contains a matting agent. The matting agent may be on either the emulsion side or the back side, but is particularly preferably added to the outermost layer on the emulsion side. The matting agent may be soluble in the processing solution or insoluble in the processing solution, and preferably both are used in combination. For example, polymethyl methacrylate, poly (methyl methacrylate /
Methacrylic acid = 9/1 or 5/5 (molar ratio)), polystyrene particles, and the like are preferable. 0.8 to 10 as particle size
μm is preferable, and the particle size distribution is preferably narrow,
It is preferable that 90% or more of the total number of particles is contained between 0.9 and 1.1 times the average particle size. It is also preferable to add fine particles of 0.8 μm or less at the same time in order to enhance the matt property, for example, polymethylmethacrylate (0.2 μm).
m), poly (methyl methacrylate / methacrylic acid = 9
/ 1 (molar ratio), 0.3 μm)), polystyrene particles (0.25 μm), colloidal silica (0.03 μm)
Is mentioned.

In the present invention, the silver halide emulsion is usually used after physical ripening, chemical ripening and spectral sensitization. The additive used in such a process is RDNO. 1
7643, the same No. 18716 and the same No. 3071
No. 05, and the relevant parts are summarized in the table below. In the light-sensitive material of the present invention, two or more kinds of emulsions having different characteristics of at least one of the grain size, grain size distribution, halogen composition, grain shape and sensitivity of the light-sensitive silver halide emulsion are mixed in the same layer. Can be used. U
S4,082,553 grain-covered silver halide grains, US Pat. No. 4,626,498, JP-A-59
It is preferred to apply the internally fogged silver halide grains and colloidal silver described in -214852 to the photosensitive silver halide emulsion layer and / or the substantially non-photosensitive hydrophilic colloid layer. The fogged silver halide grain inside or on the surface means a silver halide grain which enables uniform (non-imagewise) development regardless of the unexposed area and exposed area of the light-sensitive material. , Its preparation method is US 4,62
6,498 and JP-A-59-214852. Inner of core / shell type silver halide grain in which the inside of the grain is fogged The silver halide forming the grain may have a different halogen composition. As the silver halide having the inside or surface of the grain fogged, any of silver chloride, silver chlorobromide, silver iodobromide and silver chloroiodobromide can be used. The average grain size of these fogged silver halide grains is 0.01 to 0.75 μm, especially 0.05 to 0.6.
μm is preferred. The grain shape may be regular grain or polydisperse emulsion, but monodispersity (at least 95% of the weight or number of silver halide grains has a grain size within ± 40% of the average grain size). It is preferable that

In the present invention, it is preferable to use non-photosensitive fine grain silver halide for the color light-sensitive material. The non-photosensitive fine grain silver halide is a fine grain of silver halide which is not exposed to light during imagewise exposure for obtaining a dye image and is not substantially developed in the developing treatment, and it is preferable that the fog is not fogged in advance. . The fine grain silver halide has a silver bromide content of 0 to 100 mol%, and may contain silver chloride and / or silver iodide as needed.
Preferably, it contains 0.5 to 10 mol% of silver iodide. The fine grain silver halide preferably has an average grain size (average diameter of circles corresponding to the projected area) of 0.01 to 0.5 μm, more preferably 0.02 to 0.2 μm. Fine grain silver halide can be prepared by the same method as that for ordinary photosensitive silver halide. The surface of the silver halide grains does not need to be optically sensitized, and no spectral sensitization is required. However, prior to adding this to the coating solution, it is preferable to add a known stabilizer such as a triazole-based, azaindene-based, benzothiazolium-based, or a mercapto-diameter compound or a zinc compound in advance. Colloidal silver can be contained in the layer containing fine silver halide grains. The amount of silver applied to the light-sensitive material of the present invention is 6.
0 g / m ² or less is preferable, and 4.5 g / m ² or less is most preferable.

In the color light-sensitive material, the photographic additives that can be used in the present invention are described in RD, and the description portions related to the following table are exemplified. Type of additive RD17643 RD18716 RD307105 1. Chemical sensitizer page 23 page 648 right column page 866 2. Sensitivity increasing agent, page 648, right column 3. Spectral sensitizers, pages 23 to 24, page 648, right column 866 to 868, super sensitizers, page 649, right column Whitening agent Page 24 Page 647 Right column Page 868 5. 5. Light absorber, page 25-26, page 649, right column, page 873, filter-page 650, left column, dye, ultraviolet absorber. 6. Binder page 26 page 651 left column pages 873 to 874 7. Plasticizer, page 27, page 650, right column, page 876, lubricant Coating aid, pages 26 to 27, page 650, right column, pages 875 to 876, surfactant 9. Static page 27, page 650, right column, pages 876-877, inhibitor 10. Matting agent 878-879

The support of the present invention can be used in a color negative or color reversal light-sensitive material, but it is particularly preferable to use it in a high speed color negative light-sensitive material.

[0026]

Next, the present invention will be described in more detail with reference to examples.

Example 1 The following undercoat liquid was applied as a subbing layer on a cellulose acetate film (support) so that the amount was 25 ml / m ² and dried at 70 ° C. for 2 minutes. <Undercoat liquid> Gelatin 4.1 g Methanol 150 ml
Formalin 0.2g Pure water 9.0ml Acetone 370ml Salicylic acid 6.2ml Methylene chloride 225m
l Then, the following antistatic coating composition was applied on the undercoat layer in an amount of 20
It was applied so as to be ml / m ² and dried at 70 ° C. for 3 minutes to form an antistatic layer. Antistatic coating composition Cationic polymer below 6.8 ml Ethylene glycol 20.6 ml Methanol 400 ml Acetone 200 ml (cationic polymer)

[0028]

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Next, the following coating composition for surface layer was applied to the above antistatic layer at a coating speed of 50 m / min so as to be 27.5 ml / m ^2, and dried at 100 ° C. for 3 minutes. (A) Surface coating composition Higher fatty acid ester compound (I) 0.84 g Methylene chloride 285 ml Methanol 83 ml Acetone 628 ml Diacetyl cellulose 7.9 g SiO ₂ fine particles 0.27 g Compound (I) (n) C ₂₁ H ₄₃ COOC ₁₈ H ₃₇ (Compound (1) above) During this coating, the temperature of the support was 38 ° C. and the temperature of the coating solution was 30.
° C. Application is a slide type keyer (application width 1.5
m). On the other hand, for comparison, coating was performed in the same manner as in Example 1 except that the support temperature and the liquid temperature were changed. These are Comparative Examples 1 and 2. The number of drips in this coating was measured and is shown in Table 1 below.

[0030]

[Table 1]

The emulsion was coated on the film base thus undercoated and back coated, and the emulsion was coated on the undercoat side. The emulsion layer is disclosed in JP-A-3-194539, 2
A photosensitive layer having a thickness of 23 μm described on pages 7 to 33 is installed, and
A color negative film having 0 sensitivity of 1600 was prepared. With respect to the color negative film thus obtained, the slip property, scratch resistance and surface specific resistance were measured by the following methods. The results are shown in Table 2 below.

Measurement of Dynamic Friction Coefficient The dynamic friction coefficient was evaluated by using a steel ball having a diameter of 5 mm manufactured by Toyo Baldwin Co., Ltd. under the conditions of a load of 10 g and a speed of 20 cm / min. Measurement of scratch resistance Scratch resistance was scratched with a diamond needle of 0.025 mmR at a continuous load of 0 to 100 g using a Haydon-18 type measuring instrument (manufactured by Shinto Kagaku Co., Ltd.), and the scratch was scratched with transmitted light. The load (g) at which it became visible was measured and evaluated. Measurement of surface specific resistance The surface specific resistance was measured by a TR-8601 type measuring instrument (manufactured by Takeda Riken Co., Ltd.) at an applied voltage of 100 v and a relative humidity of 30% based on JIS-K-6911 (197 g) and evaluated. .

[0033]

[Table 2]

As is clear from the results shown in Table 2,
The sample according to the present invention was excellent in slipperiness and scratch resistance without lowering the surface resistivity. On the other hand, the samples for comparison had a problem that the surface resistivity was remarkably increased or the scratch resistance was deteriorated due to coating unevenness. Further, when the sample of the above silver halide light-sensitive material was subjected to automatic development processing under high humidity (98%), the processed negative film was curled in both Examples and Comparative Examples, but only Comparative Example was scratched,
The present invention could not.

[0035]

EFFECTS OF THE INVENTION By raising the temperature of the support (usually around 20 ° C.), the film forming morphology of the overcoat layer containing higher fatty acid ester is changed, and the treatment bath of the lower layer cationic polymer (antistatic agent) is changed. Elution, that is, scum formation can be suppressed. Further, by raising the temperature of the coating solution for the outermost layer on the back surface (usually around 20 ° C.), it is possible to eliminate the occurrence of the dripping-like surface failure peculiar to the slide coater.

Claims (6)

[Claims] 1. When applying the outermost layer to the back surface of a photographic support, the temperature of the photographic support is 30 ° C. or more and 50 ° C.
Hereinafter, the method for producing a photographic support is characterized in that the photographic coating liquid is applied at a liquid temperature of 25 ° C. or higher and 40 ° C. or lower. 2. The photographic support according to claim 1, wherein the temperature of the support is 35 ° C. or higher and 45 ° C. or lower, and the temperature of the photographic coating liquid is 25 ° C. or higher and 35 ° C. or lower. Production method. 3. The method for producing a photographic support according to claim 1, wherein the outermost layer contains a higher fatty acid ester. 4. The cationic polymer having conductivity is contained in the lower layer of the outermost layer.
The method for producing the photographic support according to 2 or 3. 5. A support having at least one silver halide emulsion layer on one side thereof, the emulsion layer having a thickness of 20 μm or more, and the surface of the support opposite to the emulsion layer coating side. Is provided with a surface layer containing an aliphatic group-containing ester compound represented by the following general formula (I), and the support is obtained by the method according to claim 1, 2, 3 or 4. A silver halide photographic light-sensitive material characterized by the above. General formula (I) R ¹ COOR ² (wherein, R ¹ and R ² represents an alkyl or alkenyl group having at least 12 carbon atoms.) 6. The silver halide emulsion layer has a thickness of 25 μm.
It is more than m and less than 35 μm.
3. The silver halide photographic light-sensitive material described in 1. above.