JPH07311439A - Photographic base and photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain a photographic base and a photographic sensitive material having superior mechanical strength and dimensional stability and excellent. also in curl straightening property after development. CONSTITUTION:This photographic base is made of an arom. polyamide film having 1,000-2,000kg/mm<2> modulus of elasticity in both the longitudinal and transverse directions and 20-90mum thickness. A photographic emulsion layer is formed on at least one side of this photographic base to obtain the objective photographic sensitive material.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photographic support which is particularly useful for a photographic light-sensitive material used in the form of a roll film, has a small curling curl after development and is excellent in mechanical strength and dimensional stability. It relates to a photographic light-sensitive material.

[0002]

2. Description of the Related Art In recent years, the use of photographic light-sensitive materials has been diversified, and the speed of film unwinding at the time of photographing, the increase of photographing magnification, and the downsizing of photographing apparatus have been remarkably advanced. Therefore, a support for a photographic light-sensitive material has been required to have properties such as excellent mechanical strength and dimensional stability.

The biaxially stretched polyethylene terephthalate film (hereinafter also referred to as PET film) has excellent transparency, mechanical strength and dimensional stability, and it is necessary to reduce the thickness of the microfilm and dimensional stability. PET film is used in place of the triacetyl cellulose film (hereinafter also referred to as TAC film) that has been used in the past, for printing sensitive materials that are required to have high properties, and for X-ray films that require transparency and elasticity. It is used. However, in a photographic light-sensitive material that is used in a roll film like a general negative film, if a PET film that does not have curl recovery after development processing as seen in a TAC film is used, curl after development processing will not occur. In addition to being too strong and inferior in handleability, there is a problem in that, for example, in the step of printing an image on photographic printing paper after development processing, problems such as scratches, defocusing, and jamming during transportation occur.

As a method for improving the curl-up recovery property of such a PET film, there are disclosed in JP-A 1-244446 and JP-A 4-44446.
220329 and the like are PET films obtained by copolymerizing a water-absorbing component, and further, those disclosed in JP-A-4-93937, JP-A-5-69524, JP-A-5-235036, and JP-A-5-313302 are those that absorb water. A laminated film of a PET film obtained by copolymerizing a volatile component and a polyester film having a high glass transition temperature (hereinafter also referred to as Tg) has been proposed.

There is also a proposal for a photographic support made of a material other than a PET film or a TAC film. JP 50
-81325 is a photographic support made of polyethylene 2-6 naphthalate film (hereinafter also referred to as PEN film), and JP-A-3-54551 is a photographic support made of a polymer film having a flexural modulus of 550 kg / mm ² or more. Supports have been proposed.

However, PET obtained by copolymerizing a water absorbing component
The water absorption of the film is certainly improved, but it is necessary to copolymerize a large amount of water absorption component in order to obtain sufficient curl recovery after development processing.
Is considerably low and the crystallinity is also low. Therefore, there is a problem that only a film having very poor heat resistance and mechanical strength can be obtained. A laminated film of a PET film copolymerized with a water-absorbing component and a polyester film having a high Tg is aimed at solving these problems, but a polyester film having a high Tg does not have curl recovery. Therefore, the wound-up recovery property of the laminated film is lowered, which is a practical problem.

A photographic support made of a PEN film and a photographic support made of a polymer film having a flexural modulus of 550 kg / mm ² or more are simply developed for the purpose of increasing the rigidity of the support. No consideration is given to the recovery of curl after treatment. In fact, the exemplified PEN film and aromatic polyimide film are not practically problematic because they do not have curl recovery after development processing.

[0008]

In view of the above problems, an object of the present invention is to provide a photographic support having excellent mechanical strength and dimensional stability, and also excellent curl recovery after development processing. And to provide a photographic light-sensitive material.

[0009]

The above object of the present invention can be achieved by the following constitution.

1. A photographic support comprising an aromatic polyamide film, characterized in that the longitudinal and transverse elastic moduli of the aromatic polyamide film are 1000 kg / mm ² or more and 2000 kg / mm ² or less, and the thickness is 20 μm or more and 90 μm or less. The photographic support 2. The longitudinal and transverse elastic moduli of the aromatic polyamide film are 1300 kg / mm ² or more and 1700 kg / mm ² or less, and the thickness is 20 μ.
2. The photographic support according to the above 1, which is not less than m and not more than 90 μm. 3. The photographic support according to 1 or 2 above, wherein the aromatic polyamide film is made of a para-aromatic polyamide. 1, wherein the aromatic polyamide film is made of polyparaphenylene terephthalamide
4. The photographic support according to any one of 2 and 3. 5. A photographic light-sensitive material characterized in that a photographic emulsion layer is provided on at least one side of the photographic support described in any one of 1 to 4 above. Photographic photosensitive material characterized in that the photographic photosensitive material is in the form of a roll film The present invention will be described in detail below.

The aromatic polyamide film used as the support of the present invention is also called an aramid film, and is a film made of para-aramid represented by a compound synthesized from p-phenylenediamine and terephthalic acid or m-phenylenediamine. It is a film composed of a meta-aramid represented by a compound synthesized from isophthalic acid. Among them, a film made of para-aramid is preferable from the viewpoint of heat resistance and mechanical properties, and a film made of polyparaphenylene terephthalamide having a structure represented by the following chemical formula in an amount of 80% by weight or more based on the polymer is particularly preferable.

[0012] _{- (NH-C 6 H 4} -NH-CO-C 6 H 4 -CO-) n aromatic polyamide film is generally molded by a solution casting method using a strong acid such as concentrated sulfuric acid. However, since this solution exhibits liquid crystallinity, the resulting film has remarkably large anisotropy of physical properties and has high mechanical properties in one direction, but is extremely easy to tear in the direction orthogonal to it.
Therefore, it could not be used as a photographic support until now. However, the subsequent research led to the development of a molding method with little anisotropy in physical properties, and the possibility of application as a photographic support has emerged.

That is, a photographic film for color negative, which is widely used as a roll film type photographic light-sensitive material, is usually slit in a width of 16 to 35 mm and wound in a spool and housed in a cartridge. The mainstream method of connecting the photographic film and the spool is to hook the holes made in the film on the protrusions of the spool. In addition, the edge portion of the photographic film is perforated so that it can be used for frame feeding when loaded in a camera. In these cases, the photographic film is required to have strength when pulled in the longitudinal direction.

Further, the cine type automatic developing machine capable of processing a large amount of photographic film is mainly used. Since this automatic developing machine adopts a spiral conveying system with a large number of rolls, the edge of the photographic film is easily loaded.
Further, in order to convey the photographic film without slipping with a large number of roll groups, a corresponding conveying tension is required. In this case, strength in both the longitudinal direction and the width direction of the photographic support is required.

Therefore, a polymer film applicable to a photographic support is required to have not only excellent strength in only one of the longitudinal direction and the width direction, but also excellent in both the longitudinal direction and the width direction. It will be.

From such a viewpoint, the longitudinal and transverse elastic moduli of the aromatic polyamide film used in the support of the present invention are in the range of 1000 kg / mm ² or more and 2000 kg / mm ² or less.
It is preferably in the range of 1300 kg / mm ² or more and 1700 kg / mm ² or less.

When both the longitudinal and transverse elastic moduli are within this range, excellent suitability can be obtained in various cases as described above.

The thickness of the aromatic polyamide film used as the support of the present invention is such that it can be carried by a camera or various processing devices, has a rigidity that is easy to handle, and is sufficient for expansion and contraction of the photographic photosensitive layer. It is sufficient if it has sufficient rigidity, and from this point, it is 20 μm or more and 90 μm or less.

In the case of a film formed by a solution casting method such as an aromatic polyamide film, the solvent concentration in the film may be changed in the thickness direction by, for example, making the front and back different depending on the drying conditions at the time of molding. Thus, the film can be easily curled, so that the film can be previously curled so as to offset the expansion and contraction of the photographic photosensitive layer. The degree of curl imparted for such a purpose depends on the thickness of the photographic photosensitive layer and the coefficient of hygroscopic expansion, but the reciprocal of the radius of curvature is 5 to 50 m ^-1 under conditions of 23 ° C and 10% to 90% RH. Preferably there is.

The aromatic polyamide film used for the support of the present invention is colored slightly yellow due to its molecular structure. Therefore, the transmittance of the film is usually 60% or more and 85% or less, and the problem of the light piping phenomenon is small. However, there are cases where the light piping phenomenon must be highly prevented, as in the case of a photographic light-sensitive material having higher sensitivity. For such a purpose or for the purpose of adjusting the color density, a dye can be contained. The dye to be blended for such a purpose is not particularly limited in its type, but has excellent compatibility with a polymer, and from the viewpoint of film production, has excellent chemical resistance and heat resistance. is necessary. As these dyes, Bayer M
ACROLEX series, SUMIPLAST series manufactured by Sumitomo Chemical Co., Ltd., Diaresin series manufactured by Mitsubishi Kasei Co., Ltd., etc., and these may be used alone or as a mixture of two or more kinds of dyes so as to have a necessary color tone. You can As the color tone, gray dyeing is preferred as seen in general photographic light-sensitive materials. The spectral transmittance of the film is 400
By adjusting the addition amount of the dye so as to be 60% or more and 85% or less in the wavelength range of to 700 nm, the light piping phenomenon can be prevented and a good photographic print can be obtained.

The aromatic polyamide film used for the support of the present invention includes a heat stabilizer, a coloring inhibitor, an antioxidant, a crystal nucleating agent, a slip agent, an antiblocking agent, an ultraviolet absorber,
UV stabilizer, viscosity modifier, defoamer, antistatic agent, pH
Various additives such as regulators, dyes and pigments may be contained.

The aromatic polyamide film used for the support of the present invention is intended from the group of aromatic polyamide films sold under the trade name of Aramica (manufactured by Asahi Kasei) and Miktron (manufactured by Toray) from each material manufacturer. It can be obtained by appropriately selecting one having a quality suitable for.

When a hydrophobic polymer film is used as a photographic support, even if a hydrophilic photographic emulsion layer is directly coated on the polymer film, the required adhesive strength cannot be obtained. Therefore, the polymer film usually requires surface treatment.
Surface treatments for such purposes include corona discharge treatment, ultraviolet treatment, glow discharge treatment, plasma treatment, flame treatment and other surface activation treatment, resorcin treatment, phenol treatment, alkali treatment, amine treatment, trichloroacetic acid treatment. And the like, and a method of laminating one or more adhesive layers.
These methods may be used alone or in combination.

The material which can be used in the method of laminating the adhesive layer is not particularly limited, but for example, a copolyester using vinyl chloride, vinylidene chloride, butadiene, methacrylic acid, acrylic acid, itaconic acid, maleic anhydride as a starting material. Starting with coalescence, polyethyleneimine, polyester, polystyrene, polyurethane, epoxy resin,
Examples thereof include grafted gelatin, nitrocellulose and the like, and mixtures thereof. In these adhesive layers, surfactants, antistatic agents, antihalation agents, crossover cut agents, coloring dyes, pigments, thickeners, coating aids, antifoggants, antioxidants, UV absorbers, UV stabilizers. One or more kinds of various additives such as an agent and an etching treatment agent may be contained.

Further, an antistatic layer, a slipping layer, a barrier layer, an antihalation layer, a crossover cut layer,
An ultraviolet absorbing layer or the like may be laminated. The method of laminating these adhesive layers is not particularly limited, and various conventionally known methods can be used. For example, air knife coater, dip coater, curtain coater,
Examples thereof include a coating method using a wire bar coater, a gravure coater, an extrusion coater, and the like, and a method in which multi-layer extrusion is performed at the time of forming a solution of a polymer film.

The photographic light-sensitive material of the present invention is provided with a photographic emulsion layer on at least one side of the photographic support of the present invention, and the photographic emulsion layer is formed by coating a silver halide emulsion. You can

The photographic emulsion layer can be provided on one side or both sides of the photographic support. The photographic emulsion layer can be provided in one layer or two or more layers on each surface.

The silver halide emulsion can be coated on the photographic support directly or through another layer, for example, a hydrophilic colloid layer containing no silver halide emulsion. Further, the silver halide emulsion layer may be separately coated on each of the silver halide emulsion layers having different sensitivities, for example, high sensitivity and low sensitivity. In this case, an intermediate layer may be provided between each silver halide emulsion layer. Further, a hydrophilic colloid layer, a protective layer, an antihalation layer, a backing layer, a masking layer, or the like may be provided on the silver halide emulsion layer or in an intermediate layer, or anywhere between the silver halide emulsion layer and the photographic support. A non-photosensitive layer may be provided.

The silver halide emulsion used in the present invention is
For example, Research Disclosure (hereinafter abbreviated as RD) No. 17643, pages 22 to 23 (December 1979), “1. Emulsion preparation and types”, and R
D No.18716, p. 648, "The Physics and Chemistry of Photography" by Grafkeide, published by P.Glkides, Chemie et Phyziq.
ue Photographique, Paul Montel, 1967), "Photoemulsion Chemistry" by Duffin, published by Focal Press (GFDaffi)
n, Photographic Emulsion Chemistry Focal Press196
6), "Production and coating of photographic emulsions" by Zelikmann et al., Published by Focal Press (VLZelikman et al, Making and coa
Ting Photographic Emulsion, Focal Press 1964) and the like.

The silver halide emulsion used in the present invention is
U.S. Patents 3,574,628 and 3,665,394 and British Patent 1,
Monodisperse emulsions described in 413,748 and the like are also preferable.

The silver halide emulsion used in the present invention can be subjected to physical ripening, chemical ripening and spectral sensitization. The additive used in such a process is RD No.17.
643, RD No. 18716 and RD No. 308119 (hereinafter abbreviated as RD 17643, RD 18716 and RD 308119, respectively). Table 1 shows the location of the description.

[0032]

[Table 1]

When the photographic light-sensitive material of the present invention is a color photographic light-sensitive material, photographic additives that can be used are described in the above RD. Table 2 shows the relevant locations.

[0034]

[Table 2]

When the photographic light-sensitive material of the present invention is a color photographic light-sensitive material, various couplers can be used, specific examples of which are described in RD 17643 and RD 308119 below. Table 3 shows the related description.

[0036]

[Table 3]

Further, these additives are RD 308119 1007
It can be added to the photographic light-sensitive layer by the dispersion method described in page XIV.

When the photographic light-sensitive material of the present invention is a color photographic light-sensitive material, auxiliary layers such as the filter layer and the intermediate layer described in the above-mentioned RD 308119 VII-K can be provided.

When the above color photographic light-sensitive material is constructed,
Various layer configurations such as the forward layer, the reverse layer, and the unit configuration described in the above-mentioned RD 308119 VII-K can be adopted.

To develop the photographic light-sensitive material of the present invention, for example, TH James, Theory of the Photographic Process, 4th Edition.
e Photografic Process Forth Edition) Pages 291 ~ 3
Page 34 and the Journal of the American Chemical Soc
iety) 73, 3,100 (1951),
Developers known per se can be used. Further, the color photographic light-sensitive material has the above-mentioned RD 17643, pages 28 to 29,
The development can be carried out by a usual method described in RD 18716 page 615 and RD 308119 XIX.

[0041]

EXAMPLES The present invention will be described in more detail below with reference to examples.

In the following examples, the elastic modulus, the breaking strength, the heat shrinkage rate, the curl recovery property, and the suitability for processing equipment are determined as follows.

(1) Elastic Modulus and Breaking Strength The film was cut into a size of 10 mm in width and 200 mm in length, and 23
After conditioning the humidity for 12 hours under conditions of ℃ and 55% RH, Tensilon (RTA-100) manufactured by Orientec Co., Ltd. was used to perform a tensile test at a chuck speed of 100 mm / min and a modulus of elasticity of 100 mm / min. And the breaking strength.

(2) Heat shrinkage rate A sample of 150 mm x 150 mm was cut out from the film, and the temperature was 23 ° C.
After conditioning the humidity for 1 day under the condition of 55% RH, put a scoring line at 100 mm intervals. Then, heat treatment is carried out at 130 ° C. for 30 minutes, and humidity of one day is controlled under the conditions of 23 ° C. and 55% RH. The difference between the intervals of the scoring lines before and after the heat treatment is calculated and expressed as a percentage of the interval before the heat treatment. In addition,
The direction of contraction was +, and the direction of expansion was −, before the heat treatment.

(3) Curling curl recovery One side of the film is subjected to a corona discharge treatment of 8 W / (m ² · min), and then the undercoating coating solution A-1 below is applied at room temperature and normal humidity. Is applied at a speed of 50 m / min using a roll-fit coating pan and air knife, and the drying temperature
It was dried at 90 ° C. for 30 seconds to form an undercoat layer A-1 having a dry film thickness of 0.8 μm. The undercoating coating solution B-1 shown below was applied to the other surface of this film by the same method and dried to form an undercoating layer B-1 having a dry film thickness of 0.8 μm.

<Undercoating Liquid A-1> Copolymer latex liquid (solid content 30%, 30% by weight butyl acrylate, 20% by weight t-butyl acrylate, 25% by weight styrene, and 25% by weight 2-hydroxyethyl acrylate) %) 270g Compound (UL-1) 0.6g Hexamethylene-1,6-bis (ethyleneurea) 0.8g Finish with water 1000ml <Undercoating liquid B-1> 40 wt% butyl acrylate, 20 wt% styrene and glycidyl Acrylate 40% by weight copolymer latex liquid (solid content 30%) 270 g Compound (UL-1) 0.6 g Hexamethylene-1,6-bis (ethyleneurea) 0.8 g Finish with water 1000 ml Further undercoat layer A-1 And 8 W / (m ² on the undercoat layer B-1
-Min) corona discharge treatment, and undercoat layer A similarly
-1 is coated with the following subbing coating solution A-2 and dried to form a subbing layer A-2 having a dry film thickness of 0.1 μm.
The undercoating coating solution B-2 shown below was applied onto 1 and dried to form an undercoating layer B-2 having a dry film thickness of 0.8 μm.

<Undercoating Coating Liquid A-2> Gelatin 10 g Compound (UL-1) 0.2 g Compound (UL-2) 0.2 g Compound (UL-3) 0.1 g Silica particles (average particle size: 3 μm) 0.1 g Water Finish with 1000 ml <Undercoating coating liquid B-2> Water-soluble conductive polymer (UL-4) 60 g Latex liquid containing compound (UL-5) as a component (solid content 20%) 80 g Ammonium sulfate 0.5 g Curing agent (UL- 6) 12g Polyethylene glycol (weight average molecular weight 600) 6g Finish with water 1000ml Using the film coated with the above undercoat layer, the undercoat layer B-2
A corona discharge of 8 W / (m ² · min) was applied on the above, and the following coating liquid MC-1 was applied so as to have a dry film thickness of 1 μm.

(MC-1) The following components were mixed together with a dissolver and then dispersed with a sand mill to obtain a dispersion liquid.

Nitrocellulose 70 parts by weight Lauric acid 1 part by weight Oleic acid 1 part by weight Butyl stearate 1 part by weight Cyclohexanone 75 parts by weight Methyl ethyl ketone 150 parts by weight Toluene 150 parts by weight Co Deposition γ-Fe ₂ O ₃ (long axis 0.2 μm , Minor axis 0.2 μm, Hc = 650 oersted) 5 parts by weight Furthermore, the following coating solution OC-1 was applied on the coating layer of MC-1.
It was applied at 10 ml / m ² .

<OC-1> Carnauba wax 1 g Toluene 700 ml Methyl ethyl ketone 300 ml Further, corona discharge of 25 W / (m ² / min) was applied on the undercoat layer A-2 to sequentially form the following photographic constituent layers. A multilayer color photographic light-sensitive material was prepared.

In the following, the quantities shown in the photographic constituent layers are shown in quantities per 1 m ² unless otherwise specified.

Further, silver halide and colloidal silver are shown in terms of silver.

<Photographic Constituent Layer> First Layer: Antihalation Layer (HC) Black Colloidal Silver 0.15 g UV Absorber (UV-1) 0.20 g Colored Cyan Coupler (CC-1) 0.02 g High Boiling Solvent (Oil-1) ) 0.20 g High boiling point solvent (Oil-2) 0.20 g Gelatin 1.6 g Second layer; Intermediate layer (IL-1) Gelatin 1.3 g Third layer; Low sensitivity red-sensitive emulsion layer (RL) Silver iodobromide emulsion (Average particle size 0.3 μm, average iodine content 2.0 mol%) 0.4 g Silver iodobromide emulsion (Average particle size 0.4 μm, average iodine content 8.0 mol%) 0.3 g Sensitizing dye (S-1) 3.2 × 10 ^-4 (mol / silver 1 mol) Sensitizing dye (S-2) 3.2 × 10 ^-4 (mol / silver 1 mol) Sensitizing dye (S-3) 0.2 × 10 ^-4 (mol / silver 1 mol) Cyan Coupler (C-1) 0.50g Cyan coupler (C-2) 0.13g Colored cyan coupler (CC-1) 0.07g DIR compound (D-1) 0.006 g DIR compound (D-2) 0.01 g High boiling point solvent (Oil-1) 0.55 g Gelatin 1.0 g Fourth layer; high-sensitivity red-sensitive emulsion layer (RH) Silver iodobromide emulsion ( Average particle size 0.7 μm, average iodine content 7.5 mol%) 0.9 g Sensitizing dye (S-1) 1.7 × 10 ⁻⁴ (mol / silver 1 mol) Sensitizing dye (S-2) 1.6 × 10 ⁻⁴ ( Sensitizing dye (S-3) 0.1 × 10 ⁻⁴ (mol / silver 1 mol) Cyan coupler (C-2) 0.23 g Colored cyan coupler (CC-1) 0.03 g DIR compound (D- 2) 0.02 g High boiling point solvent (Oil-1) 0.25 g Gelatin 1.0 g Fifth layer; Intermediate layer (IL-2) Gelatin 0.8 g Sixth layer; Low sensitivity green sensitive emulsion layer (GL) Silver iodobromide Emulsion (average particle size 0.4 μm, average iodine content 8.0 mol%) 0.6 g Silver iodobromide emulsion (average particle size 0.3 μm, average iodine content 2.0 mol%) 0.2 g Sensitizing dye ^{S-4) 6.7 × 10 -4} ( mol / mole of silver) Sensitizing dye (S-5) 0.8 × 10 -4 ( mol / mole of silver) Magenta coupler (M-1) 0.17 g Magenta coupler (M- 2) 0.43 g Colored magenta coupler (CM-1) 0.10 g DIR compound (D-3) 0.02 g High boiling point solvent (Oil-2) 0.7 g Gelatin 1.0 g Seventh layer; High sensitivity green-sensitive emulsion layer (GH) ) Silver iodobromide emulsion (average grain size 0.7 μm, average iodine content 7.5 mol%) 0.9 g Sensitizing dye (S-6) 1.1 × 10 ⁻⁴ (mol / silver 1 mol) Sensitizing dye (S-7 ) 2.0 × 10 ^-4 (mol / silver 1 mol) Sensitizing dye (S-8) 0.3 × 10 ^-4 (mol / silver 1 mol) Magenta coupler (M-1) 0.30 g Magenta coupler (M-2) 0.13 g Colored magenta coupler (CM-1) 0.04g DIR compound (D-3) 0.004g High boiling point solvent (Oil-2) 0.35g Gelatin 1.0g 8 layers; Yellow filter layer (YC) Yellow colloidal silver 0.1 g Additive (HS-1) 0.07 g Additive (HS-2) 0.07 g Additive (SC-1) 0.12 g High boiling point solvent (Oil-2) 0.15 g Gelatin 1.0 g 9th layer; low-sensitivity blue-sensitive emulsion layer (BL) Silver iodobromide emulsion (average grain size 0.3 μm, average iodine content 2.0 mol%) 0.25 g Silver iodobromide emulsion (average grain size 0.4 μm, average iodine content 8.0 mol%) 0.25 g Sensitizing dye (S-9) 5.8 × 10 ⁻⁴ (mol / silver 1 mol) Yellow coupler (Y-1) 0.6 g Yellow coupler (Y-2) 0.32 g DIR compound (D-1) 0.003 g DIR compound (D-2) 0.006 g High boiling point solvent (Oil-2) 0.18 g Gelatin 1.3 g 10th layer; High-sensitivity blue-sensitive emulsion layer (BH) Iodobromide Silver emulsion (average grain size 0.8 μm, average iodine content 8.5 mol%) 0.5 g Sensitizing dye (S-10) 3 × 10 ^-4 (mol / silver) Sensitizing dye (S-11) 1.2 × 10 ⁻⁴ (mol / silver 1 mol) Yellow coupler (Y-1) 0.18 g Yellow coupler (Y-2) 0.10 g High boiling point solvent (Oil-2) 0.05 g Gelatin 1.0 g 11th layer; 1st protective layer (PRO-1) Silver iodobromide (average particle size 0.08 μm) 0.3 g UV absorber (UV-1) 0.07 g UV absorber (UV-2) 0.10 g Additive (HS-1) 0.2g Additive (HS-2) 0.1g High boiling point solvent (Oil-1) 0.07g High boiling point solvent (Oil-3) 0.07g Gelatin 0.8g 12th layer; 2nd protective layer ( PRO-2) Compound A 0.04 g Compound B 0.004 g Polymethylmethacrylate (average particle size: 3 μm) 0.02 g Gelatin 0.7 g-Preparation of silver iodobromide emulsion-The silver iodobromide emulsion used for the 10th layer is as follows. Prepared by the method.

A silver iodobromide emulsion was prepared by the double jet method using monodispersed silver iodobromide grains having an average grain size of 0.33 μm (silver iodide content: 2 mol%) as seed crystals.

A solution <G-1> having the following composition was treated at a temperature of 70 ° C. and pA.
While maintaining g7.8 and pH 7.0, a seed emulsion corresponding to 0.34 mol was added while stirring well.

(Formation of Internal High Iodity Phase-Core Phase)
Solution <H-1> having the following composition and solution <S-1> having the following composition
While maintaining a flow ratio of 1: 1, and were added at an accelerated flow rate (the flow rate at the end was 3.6 times the initial flow rate) over 86 minutes.

(Formation of External Low Iodity Phase-Shell Phase) Subsequently, <H-2> and <S> while maintaining pAg10.1 and pH6.0.
-2> was added at a flow rate accelerated by a flow rate ratio of 1: 1 (the flow rate at the end was 5.2 times the initial flow rate) over 65 minutes.

The pAg and pH during grain formation were controlled using an aqueous potassium bromide solution and a 56% aqueous acetic acid solution. After the particles are formed, they are washed with water by a conventional flocculation method, and then gelatin is added to redisperse them, and the pH is adjusted to 40 ° C.
And pAg were adjusted to 5.8 and 8.0, respectively.

The resulting emulsion was a monodisperse emulsion containing octahedral silver iodobromide grains having an average grain size of 0.80 μm, a broad distribution of 12.4% and a silver iodide content of 8.5 mol%.

<G-1> Ocein gelatin 100.0 g 10 wt% ethanol solution of the following compound-1 25.0 ml 28% aqueous ammonia solution 440.0 ml 56% acetic acid aqueous solution 660.0 ml Finish with water 5000.0 ml (Compound-I: polyisopropylene) Oxy-polyethylene oxy-di sodium succinate) <H-1> Ocein gelatin 82.4g Potassium bromide 151.6g Potassium iodide 90.6g Finish with water 1030.5ml <S-1> Silver nitrate 309.2g 28% aqueous ammonia solution Equivalent water Finish with 1030.5 ml <H-2> Oscein gelatin 302.1 g Potassium bromide 770.0 g Potassium iodide 33.2 g Finish with water 3776.8 ml <S-2> Silver nitrate 1133.0 g 28% ammonia solution equivalent Finish with water 3776.8 ml 10th layer For silver iodobromide emulsions used in the other emulsion layers, the average grain size of seed crystal, temperature, pAg, p
The above emulsions having different average grain sizes and silver iodide contents were prepared by changing H, flow rate, addition time and halide composition.

All were core / shell type monodisperse emulsions having a distribution of 20% or less. Each emulsion was subjected to optimum chemical ripening in the presence of sodium thiosulfate, chloroauric acid and ammonium thiocyanate, and a sensitizing dye, 4-hydroxy-6
-Methyl-1,3,3a, 7-tetrazaindene, 1-phenyl-5-mercaptotetrazole was added.

The above-mentioned light-sensitive material further comprises the compound S
U-1, SU-2, viscosity modifier, hardener H-1, H-
2, stabilizer ST-1, antifoggant AF-1, AF-2
(Weight average molecular weight of 10,000 and 1,100,000), dyes AI-1, AI-2 and compound DI-1
(9.4 mg / m ² ) is contained.

The structure of each compound used for forming the above-mentioned multilayer color photographic light-sensitive material is shown below.

[0064]

[Chemical 1]

[0065]

[Chemical 2]

[0066]

[Chemical 3]

[0067]

[Chemical 4]

[0068]

[Chemical 5]

[0069]

[Chemical 6]

[0070]

[Chemical 7]

[0071]

[Chemical 8]

[0072]

[Chemical 9]

[0073]

[Chemical 10]

[0074]

[Chemical 11]

The photographic light-sensitive material obtained as described above was subjected to perforation processing as described in JIS K7519-1982.

A film having a sample size of 12 cm × 35 mm is wound around a core having a diameter of 10 mm so that the inner side of the photographic component layer is 55,
Treat for 3 days under the conditions of ℃ and 20% RH, and add curl.
Then release from the core and soak in pure water at 38 ℃ for 15 minutes,
It is dried with a hot air dryer at 55 ° C. for 3 minutes under a load of g.
The load was removed, the sample was suspended vertically, the distance between both ends of the sample was determined, and it was evaluated how much the original distance was restored to 12 cm. The evaluation was performed according to the following criteria.

⊚: 70% or more ◯: 50% or more and less than 70% x: less than 50% If the level is ◯ or more, there is no practical problem.

(4) Suitability for processing equipment The multilayer color photographic light-sensitive material prepared as described above was processed by a cine type automatic developing machine (NCV36 type made by Noritsu Koki Co., Ltd.) and the degree of breakage of the edge of the light-sensitive material and The workability of the subsequent sorting work was evaluated according to the following criteria. In addition, ○
Above the level, there is no practical problem.

<Break of edge> Rank Content ◎: No break of edge ○: Break of a weak edge that does not affect the screen portion ×: Break of a strong edge that affects the screen portion <Workability> Rank Content ◎: No problem ○: Slightly difficult ×: Very difficult Example Commercially available aromatic polyamide film (manufactured by Asahi Kasei) No. 1
5, PEN film (made by Teijin) No.6,7, PET film (made by Teijin) No.8,9, modified PET film No.10,
11 and TAC film (made in-house) No. 12 were used for evaluation. The modified PET film was evaluated as follows.

To 100 parts by weight of dimethyl terephthalate and 64 parts by weight of ethylene glycol, 0.1 part by weight of calcium acetate hydrate as an ester exchange catalyst was added, and transesterification reaction was carried out according to a conventional method. 30 parts by weight of an ethylene glycol solution of 5-sodium sulfodi (β-hydroxyethyl) isophthalic acid (concentration: 35% by weight), and 8 parts by weight of polyethylene glycol (number average molecular weight: 3000), trioxide 0.05 parts by weight of antimony, 0.03 parts by weight of phosphoric acid trimethyl ester, 0.2 parts by weight of Irganox 1010 (manufactured by Ciba Geigy) and 0.04 parts by weight of sodium acetate were added. Then, gradually raise the temperature and reduce the pressure to 280 ° C.
Polymerization was carried out at 0.5 mmHg to obtain a copolyester having an intrinsic viscosity of 0.60.

The resulting copolymerized polyester ter was vacuum dried at 150 ° C. for 8 hours, and then melt-extruded in layers at 280 ° C. using an extruder and a T-die, while electrostatically applying on a cooling drum. They were brought into close contact with each other and solidified by cooling to obtain an unstretched sheet. Using a roll type longitudinal stretching machine this unstretched sheet,
It was stretched 3.5 times in the machine direction at 90 ° C. The obtained uniaxially stretched film was stretched using a tenter type transverse stretching machine at 100 ° C. so that the transverse stretching ratio was 3.6 times. Then, it was heat-set at 210 ° C. for 15 seconds. Then, while being relaxed in the transverse direction by 5%, it was gradually cooled to room temperature over 30 seconds to obtain a biaxially stretched film.
At this time, the line speed was adjusted so that a biaxially stretched film having a thickness of 50 μm and a thickness of 75 μm was obtained.

The thickness and mechanical properties of the film and the evaluation results obtained are shown below.

No. Fill thickness Elastic modulus Fracture heat absorption Curling process Suitability of equipment Remarks Material Material Strength Reduction ratio Recoverability Width direction Width direction Width direction Edge sorting / longitudinal / longitudinal / longitudinal workability Directional direction μm kg / mm ² kg / mm ² % 1 A 25 1500/1500 40/40 0.0 / 0.0 ◎ ○ ◎ Invention 2 A 38 1500/1500 40/40 0.0 / 0.0 ◎ ◎ ◎ Invention 3 A 50 1500/1500 40/40 0.0 /0.0 ◎ ◎ ◎ ◎ Invention 4 A 50 1000/1900 30/50 0.0 / 0.0 ○ ○ ○ Invention 5 A 50 1900/1000 30/50 0.0 / 0.0 ○ ○ ○ Invention 6 B 50 750/700 30/28 0.2 / 0.2 × × × Comparative Example 7 B 75 750/700 30/28 0.2 / 0.2 × ○ × Comparative Example 8 C 50 550/500 24/22 0.0 / 0.5 × × × Comparative Example 9 C 75 550/500 24 / 22 0.0 / 0.5 × × × Comparative Example 10 D 50 450/420 17/15 0.0 / 1.5 ○ × ○ Comparative Example 11 D 75 450/420 17/15 0.0 / 1.5 ○ × ○ Comparative Example 12 E 95 350/380 9 / 9 0.5 / 0.5 ○ × × Comparative example A: Aromatic polyamide B: Polyethylene 2-6 naphth Rate C: Polyethylene terephthalate D: Modified polyethylene terephthalate E: Triacetyl cellulose As is apparent from the above, Sample Nos. 1 to 5 of the present invention comprising an aromatic polyamide film are wound in spite of the thin film thickness. It can be seen that it is excellent in squeeze recovery and suitability for processing equipment, and in particular, when the difference in elastic modulus between the width direction and the longitudinal direction of the film is small, more excellent performance is obtained. Further, it can be seen that the comparative sample made of PEN film or PET film has no curl recovery property and is poor in suitability for processing equipment.

[0084]

The photographic support and photographic light-sensitive material according to the present invention have excellent mechanical strength and dimensional stability, and also have excellent curl recovery after development.

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Claims (6)

[Claims] 1. A photographic support comprising an aromatic polyamide film, wherein the aromatic polyamide film has an elastic modulus in the longitudinal and transverse directions of 1000 kg / mm ² or more and 2000 kg / mm ² or less,
A photographic support having a thickness of 20 μm or more and 90 μm or less. 2. The longitudinal and transverse elastic moduli of the aromatic polyamide film are 1300 kg / mm ² or more and 1700 kg / mm ² or less,
The photographic support according to claim 1, having a thickness of 20 μm or more and 90 μm or less. 3. The photographic support according to claim 1, wherein the aromatic polyamide film is made of a para aromatic polyamide. 4. The photographic support according to claim 1, wherein the aromatic polyamide film is made of polyparaphenylene terephthalamide. 5. A photographic light-sensitive material characterized in that a photographic emulsion layer is provided on at least one side of the photographic support according to any one of claims 1 to 4. 6. A photographic light-sensitive material, wherein the photographic light-sensitive material is in the form of a roll film.