JP2618709B2 - Photographic support - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a photographic support which gives excellent images, and in particular, a long-term storage property of a metal surface having a specular reflectivity or a second-class diffuse reflectivity. Excellent heat resistance, weather resistance, and excellent sharpness with good reproducibility of hue, gradation, etc. without peeling of the silver halide photosensitive layer during development processing, fog and spots do not occur. A photographic support to be provided.

(Prior art) Transparent plates and films of TAC, PET, polycarbonate, etc., which are conventionally known as photographic supports, paper, synthetic paper, baryta paper or films containing white pigments,
A metal reflective or second metal plate, such as a plate or a metal plate such as an aluminum plate having a surface anodized.
When a photographic support having a seed diffuse reflection surface is used, a photograph or recording medium having excellent reproducibility of gradation, hue reproducibility and sharpness of an image in the case of a color photograph can be obtained. For example, JP-A-61-210346, Japanese Patent Application Nos. 61-168800 and 61-16
No. 8801, No. 61-16802, No. 61-168803, No. 61
JP-A-168804, JP-A-61-168805, JP-A-61-249873, JP-A-63-118154, JP-A-63-24247, JP-A-63-242
No. 51, JP-A-63-24252 and the like.

Natural mica, inorganic substances such as fish scales and pearls, etc. can be used to provide specular reflectivity or second-class diffuse reflectivity, but most of them are metals such as aluminum, silver, gold, copper, chromium, nickel, platinum and the like. Generally, aluminum is preferably used as the alloy. However, when a metal base less than silver is used for a support for a photographic or recording photosensitive material using a silver halide photographic emulsion, fogging and spots tend to occur during the development process. For this reason, it is known to provide an adhesive layer of a thermoplastic resin. However, film peeling or the like is likely to occur during the development processing or during drying after the development, and there is a difficulty in providing a thin layer of, for example, 0.1 to 5 μm using a thermoplastic resin.

In addition, due to long-term aging after the development processing, the mirror surface or the second
There is a risk that the seed diffuse reflectivity may deteriorate or reflectivity unevenness may occur.

(Object of the Invention) An object of the present invention is to provide a mirror surface or a metal surface having a second type diffuse reflectivity over a long period of time after development processing,
The object of the present invention is to provide a photographic support excellent in storability which does not cause a decrease in reflectivity or unevenness in reflectivity, and gives disadvantages such as peeling of a photosensitive material layer during a developing process or before and after the developing process. There is no need to provide a photographic support.

(Constitution of the Invention) An object of the present invention is to provide a photographic support having an adhesive layer provided on a metal surface having specular reflectivity or second-class diffuse reflectivity, wherein the adhesive layer has vinyl chloride and / or A copolymer containing vinylidene chloride and 0.1 to 50 with respect to the copolymer.
Achieved by providing an adhesive layer containing weight percent epoxy compound.

The copolymer containing vinyl chloride and / or vinylidene chloride according to the present invention refers to a resin obtained by copolymerizing vinyl chloride and / or vinylidene chloride as a copolymer component with other copolymer components.

Other copolymer components include, for example, vinyl acetate, maleic anhydride, maleic acid, styrene, acrylonitrile, methyl acrylate, diethyl fumarate, 2-chloroallyl acetate, diethyl maleate, isobutyl bilyl ether, aryl acetate, isobutylene , Isopropenyl acetate and the like, and a multi-component copolymer resin with these. Among these, a copolymer of vinyl chloride and vinylidene chloride, a copolymer of vinyl chloride and vinylidene chloride and maleic anhydride, a copolymer of vinyl chloride and vinylidene chloride and vinyl acetate, and a copolymer of vinyl chloride and vinylidene chloride and maleic anhydride A copolymer of vinyl acetate, a copolymer of vinyl chloride, vinylidene chloride, maleic acid, and vinyl acetate, a copolymer of vinyl chloride and vinyl acetate, a copolymer of vinylidene chloride and acrylonitrile, and the like are preferable.

The epoxy compound according to the present invention is contained in the copolymer resin in an amount of 0.1 to 50% by weight, preferably 0.5 to 40% by weight.
%, More preferably 1 to 30% by weight, most preferably 3 to 30% by weight.

The epoxy compound according to the present invention is a compound having at least one epoxy group (oxirane ring) in a molecule, and is also called an epoxide. As the epoxy compound, either a monomer or a polymer can be used. Preferably epoxidized animal and vegetable oils, such as epoxidized soybean oil, epoxidized linseed oil and the like, and epoxidized fatty acid alkyl esters represented by the following general formula: n, m; 1 to 40 R; H and an alkyl group (C _{1 to} C ₂₀ ), an epoxidized alicyclic compound, an epoxy stearic acid ester, and an epoxyhexahydrophthalate dityl.

As the adhesive, other polymers and compounds can be used in combination with the above-mentioned copolymer and epoxy compound. For example, polyurethane resin, polyurea resin, phenol resin, melamine resin, polyester resin, silicon resin, cellulose resin, acrylic resin, polyamide resin, fluororesin, styrene resin, vinyl acetate resin, polyolefin resin, etc. .

As the polymer used in combination, a polyurethane urea resin is preferable.

Polyurethane urea resin has urethane bond And urea bonds Is a polymer having a large amount in the molecular chain, and refers to a resin obtained by reacting a polyvalent isocyanate or a prepolymer thereof with a polyvalent hydroxy compound or a polar liquid forming a continuous phase.

The adhesive layer of the present invention needs to be applied in a very thin and uniform thickness of 0.1 to 20 μm in contact with the metal reflection layer on the surface of the support substrate. When the thickness is 0.1 μm or less, poor adhesion between the metal reflection layer and the silver halide photosensitive layer occurs. When the thickness is 20 μm or more, it is disadvantageous in terms of cost, and reproducibility such as hue and gradation deteriorates. The coating amount of the adhesive layer is 0.1 to 20 g / m ² , preferably 0.3 to 15 g / m ² , more preferably 0.5 to 10.8 g / m ² on a dry basis.

Further, as the diluting solvent for the adhesive layer of the present invention, any of ketones such as MEK / acetone, chlorides such as tricrene, esters such as ethyl acetate / butyl acetate, and aromatic organic solvents such as triol can be used. Is particularly preferably ethyl acetate.

The adhesive layer of the present invention is greatly different in that it is provided on the upper surface of a thin metal layer having a metal reflectivity or a second-class diffuse reflectivity. −111
It can be applied using the method described in No. 18. Specifically, for example, dip coating, air knife coating, curtain coating, roller coating, doctor coating, wire bar coating, slide coating,
It can be applied by a gravure coating method, a reverse coating method, or the like.

In order to further strengthen the adhesion between the support according to the present invention and the silver halide emulsion, it is effective to carry out pretreatment such as corona discharge, glow discharge and fire treatment. Further, an undercoat layer of gelatin may be provided before coating of the silver halide emulsion,
It is also effective to add a surfactant or an alcohol to improve the wettability at the time of applying the undercoat layer.

A support having a specular or second-class diffusely reflective surface according to the present invention is obtained by providing a thin layer of a material which provides a specular reflector when the surface is sufficiently smooth on a support substrate. . For example, JP-A-61-210346, Japanese Patent Application No. 61-168800
And the methods described in JP-A Nos. 61-168801 and 61-249872.

The substrate of the support is conventionally used as a support,
For example, plastic films, paper, PC-paper, synthetic paper, metal plates, etc., and plates of polymers and copolymers such as polycarbonate, polystyrene, polyacrylate, polymethacrylate, and PET having excellent dimensional stability.

In the present invention, the metal used for forming the metal thin film layer is preferably a metal mainly composed of aluminum described in JP-A-50-139720 or JP-A-48-139720.
Tellurium, molybdenum, polynium, cobalt, zinc, copper, nickel, iron, tin, vanadium, germanium, silver and silver as described in -65927, 48-65928 and 50-2925. Emulsion, chrome,
Examples thereof include metals such as titanium and alloys. Among these, a particularly preferred metal thin film layer for the purpose of the present invention is an aluminum metal thin film layer.

As a method for providing the metal thin film layer, a known method for forming a thin film such as a vacuum evaporation method, a sputtering method, an ion plating method, and an electrodeposition method can be used. The metal thin film layer may be a single layer or a multilayer of two or more layers.

The thickness of the metal thin film layer is preferably in the range of 20 to 4000 angstroms, and particularly preferably in the range of 50 to 2000 angstroms.

The support of the present invention can be widely used as a photographic reflection support, and can be provided with a silver halide emulsion layer for black-and-white printing paper and a protective layer thereon. Similarly, a color photographic paper light-sensitive material can be prepared by providing two or more light-sensitive silver halide emulsion layers having different spectral sensitivities for normal color photographic paper and containing different color couplers. In addition, a color reversal photosensitive material, a direct positive color photographic paper, or a direct positive color copy material using a light fogging method can be produced. A red, green, and blue-sensitive silver halide emulsion layer containing silver halide grains having different spectral sensitivities and a dye used in a silver die breach (SDB) method is provided on the support. Provided
We can also make SDB type print photosensitive materials. or,
The present invention can also be applied to reflective disk plates, disk films and recording materials using silver halide.
For further details, see Japanese Patent Application Nos. 61-168802 and 61-168803.
No. 61-168804 and No. 61-168805, Japanese Patent Application No. 61-168804
It can be widely applied to the photosensitive materials described in JP-A-249873, JP-A-61-259794, JP-A-61-275572 and the like.

A mordant layer may be provided on the support according to the present invention to diffuse and transfer a color-developing dye to form a color image. A material for forming a silver image of a silver diffusion transfer type by providing a physical development nucleus in an undercoat layer on the support of the present invention can also be used. Further, a development inhibitor such as JP-B-59-3737 or JP-A-50-65230, or a substance having a desilvering effect, such as a heterocyclic compound having an iodobromide ion, a bromide ion, or a mercapto group, or an imino silver compound. An adsorption layer ALD of a possible heterocyclic compound can also be provided.

Further, the photographic support of the present invention is disclosed in U.S. Pat.
No. 6, JP-A-60-133449, JP-A-59-218443, Japanese Patent Application No. 60
It can be applied to a photothermographic material and / or a dye-fixing material (image receiving material) described in -79709.

(Effects of the Invention) By providing the adhesive layer of the present invention on a metal surface having a specular reflection property or a second kind diffuse reflection property, it can be stored for a long period of time after the development processing even under high heat and high humidity storage. There is no decrease in reflectivity or uneven reflection, no peeling of the silver halide photosensitive layer during development processing, and an image with excellent reproducibility of hue and gradation and excellent sharpness can be obtained. .

(Examples of the Invention) Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited thereto.

Examples 1 to 6 Comparative Examples 1 to 4 As a substrate, 2% of silica having an average particle size of 3 μm was filled.
A 25 μm polyethylene terephthalate film was placed in a vacuum evaporation apparatus, and vacuum evaporation was performed at a degree of vacuum of 10 ⁻⁵ torr to form an aluminum evaporation film having a thickness of 600 Å on the surface of the substrate.

An adhesive layer having the composition shown in Table 1 was diluted with ethyl acetate, dried, and applied to the surface of the deposited film to a concentration of 5 g / m ² after drying.
Oven dried at 00 ° C. for 2 minutes.

Next, the timber pulp consisting of 20 parts of LBSP and 80 parts of LBKP is used for discard refiner 300 d
Beat it to c, add 1.0 part of sodium stearate, 0.5 part of anionic polyacrylamide, 1.5 parts of aluminum sulfate, 0.5 part of polyamide polyamine epichlorohydrin, and 0.5 part of alkyl ketene dimer, all in an absolute dry weight ratio with respect to the wood pulp. 160 g / m ² weighed by paper machine
Paper was made.

The density was adjusted to 1.0 g / cm ³ by an asyn calender. After corona discharge treatment of this base paper, low density polyethylene (MI
= 7 g / 10 min, density 0.923 g / cc), and a polyethylene resin layer was formed by extrusion coating so as to have a thickness of 30 µm. Next, after the other surface (back surface) of the substrate was subjected to corona discharge treatment, a high-density polyethylene (MI = 8 g / 10
Min, density 0.950g / cc) extrusion coating, thickness 3
A polyethylene resin layer having a thickness of 0 μm was formed to prepare a double-sided polyethylene laminated paper.

Next, a polyurethane-based two-part adhesive having the following composition was applied to the back side of the above-described aluminum vapor-deposited film (the surface opposite to the vapor-deposited surface) so as to be 3 g / m ² after drying.
Dry for 2 minutes at ℃ The coated surface and the low-density polyethylene surface of the double-sided polyethylene laminated paper were combined and heated and pressed at 80 ° C. and a pressure of 20 kg / cm.

The above support was coated with a silver halide emulsion according to Example 4 of Japanese Patent Application No. 61-168801 to obtain a photographic paper for color photography.

The silver halide emulsion (1) used in the present invention was prepared as follows.

(1 liquid) (2 liquids) Sulfuric acid (1N) 24cc (3 liquids) (4 liquids) (5 liquids) (6 liquids) (7 liquids) (Liquid 1) was heated to 56 ° C., and (Liquid 2) and (Liquid 3) were added. Thereafter, (liquid 4) and (liquid 5) were added simultaneously for 30 minutes. After a further 10 minutes, (Sixth solution) and (Sixth solution) were simultaneously added for 20 minutes. Five minutes after the addition, the temperature was lowered and desilvering was performed. Add water and dispersed gelatin, adjust the pH to 6.2, average particle size 0.45 μm, coefficient of variation (standard deviation divided by average particle size: s / d) 0.08, monodispersion of silver bromide 70 mol% A cubic silver chlorobromide emulsion was obtained. Sodium thiosulfate was added to this emulsion to sensitize it to optimal chemistry.

Next, silver halide emulsions having different silver chloride contents (2)
(3) (4) was similarly prepared by changing KBr and NaCl amounts of the above-mentioned solutions 4 and 6, and the addition times of the solutions 4 and 5 as shown in Table 2.

Table 3 shows the average grain size, coefficient of variation, and halogen composition of the silver halide emulsions (1) to (4).

On each support, the first to seventh layers shown in Table 4 were overlaid to obtain a color photographic material.

First layer: The silver halide emulsion (4) was spectrally sensitized by adding a blue-sensitive sensitizing dye (a) at 7.0 × 10 ⁻⁴ mol per mol of Ag × 1 mol. Further, the yellow coupler (b) and the color image stabilizer (e) were mixed and dissolved in the solvent (f), dispersed and added in predetermined amounts. This was applied to form a first layer.

Third layer: The silver halide emulsion (3) was spectrally sensitized by adding 4.0 × 10 ^-4 mol of a green-sensitizing dye (b) per 1 mol of Ag × 1 mol. Further, the magenta coupler (h) and the color image stabilizer (i) were mixed and dissolved in the solvent (j), dispersed and added in predetermined amounts. This was applied to form a third layer.

Fifth layer: The silver-sensitive emulsion (2) was spectrally sensitized by adding a red-sensitive sensitizing dye (c) in an amount of 1.0 × 10 ^-4 mol per mol of Ag × 1. Further, the cyan coupler (n) and the color image stabilizer (o) were mixed and dissolved in the solvent (f), dispersed and added in a predetermined amount. This was applied to form a fifth layer.

A coating liquid was obtained in the same manner for the second, fourth, sixth, and seventh layers.

The first layer, the second layer, the third layer, and the fourth layer are formed on the undercoat layer of the support in a usual manner so as to have a predetermined amount shown in Table 4.
, 5th, 6th and 7th layers were applied and Sample Nos. 1 to 6
And a comparative sample were obtained. (See Table 5.) The above sample was subjected to gradation exposure for sensitometry or image exposure for printing by passing through a negative film through a three-color analysis filter of blue, green, and red using a 2854 ° K light source.

Thereafter, a photographic image was obtained through the steps of color development, bleach-fixing and rinsing.

Color developer A Water 800cc Diethylenetriaminepentaacetic acid 1.0g Sodium sulfite 0.2g N, N-diethylhydroxylamine 4.2g Potassium bromide 0.6g Sodium chloride 1.5g Triethanolamine 8.0g Potassium carbonate 30g N-ethyl-N- (β- Methanesulfonamidoethylamino) -3-methyl-4-aminoaniline sulfate 4.5 g 4,4'-diaminostilhen-based fluorescent brightener (Sumitomo Chemical Co., Ltd. Whitex4) 2.0 g Add water to 1000 cc KOH PH 10.25 Bleach treatment Fixing solution Formulation A Ammonium thiosulfate (54 wt%) 150 ml Na ₂ SO ₃ 15 g HN ₄ [Fe (III) (EDTA)] 55 g EDTA · 2Na 4 g Glacial acetic acid 8.61 g 5.4) Rinse solution formulation A EDTA ・ 2Na ・ 2H ₂ O 0.4g Add water and add 1000ml (pH5.4) (M) Solvent (isoC ₉ H ₁₈ O ₃ P = 0 The photographic printing paper thus obtained was evaluated by the following adhesion test method and storage stability test method. The results are shown in Table 5.

A. Adhesion test method 1) Adhesion test before drying before treatment A polyester pressure-sensitive adhesive tape (knit-Mylar tape No. 31) is attached to the emulsion surface after drying the photographic emulsion, and instantaneously peeled off.

2) Adhesion test in wet processing In a wet state, the emulsion surface of the sample after development, fixing, and washing is scratched in an eye-like manner with an iron brush, and rubbed 10 times with rubber under a load of 3 kg.

3) Adhesion test after processing and drying After developing, fixing, washing and drying, scratch the emulsion surface of the sample with an iron brush in an eye-like manner.
After 24 hours at 25 ° C. and 55% RH, the tape is instantaneously peeled off.

In the above tests 1) to 3), those in which the emulsion layer did not peel at all were classified into Class A, those which slightly peeled were classified as Class B, those which were slightly peeled were classified as Class C when the emulsion layer was practically lower limit, and those which were practically problematic. Class D.

B. Method for evaluating storage stability Samples after emulsion coating, development, fixing, washing and drying
The sample was placed in a wet thermo oven at 80 ° C. and 70% RH, and after 30 days, the state of the sample surface was visually observed.

X indicates that a decrease in reflectivity and occurrence of reflection unevenness were observed, and ○ indicates that no decrease was observed.

As is clear from the results in Table 5, by providing the adhesive layer of the present invention on the metal surface, after development, even if stored at high heat and high humidity, there is no decrease in reflectivity or occurrence of reflection unevenness, It is also apparent that the silver halide emulsion layer does not peel off.

Claims (1)

(57) [Claims] 1. A copolymer containing vinyl chloride and / or vinylidene chloride on a metal surface having specular reflectivity or diffuse reflectivity of the second kind, and an epoxy of 0.1 to 50% by weight based on the copolymer. A photographic support comprising an adhesive layer containing a compound.