JP2711486B2 - Photographic support - Google Patents

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 provides an excellent image, and more particularly to a metal support having a specular reflection property or a type 2 diffuse reflection property, which enhances the brightness and whiteness of the metal surface and has a wide directivity. The present invention relates to a photographic support which gives an image with less roughness and excellent sharpness.

[0002]

2. Description of the Related Art Conventionally known as a photographic support, T
A transparent plate or film made of AC, PET, polycarbonate, or the like; or a film or plate containing paper, synthetic paper, baryta paper, or a white pigment, or a metal plate such as an aluminum plate whose surface is anodized When a photographic support having a metal-reflective or second-class diffuse-reflective surface is used, a photographic or recording medium excellent in gradation reproducibility, hue reproducibility, image sharpness, etc. (For example, JP-A-61-210346, Japanese Patent Application No. 61-168800).
Nos. 61-168801 and 61-168802
No. 61-168803, No. 61-168804
No. 61-168805, No. 61-249873
JP-A-63-24251 and JP-A-63-24247.
Nos. 63-24251 and 63-24252).

In this case, natural mica, inorganic substances such as fish scales and pearls, etc. can be used to provide specular reflectivity or second-class diffuse reflectivity.
Metals such as silver, copper, chromium, nickel and platinum or alloys thereof are used, and aluminum is generally considered to be good.

[0004]

It is preferable that the photographic support having such a mirror-reflective or second-class diffuse-reflective metal surface has a higher reflectance, but this reflectance is
Since it is determined by the type of metal or alloy used, there is a drawback that the obtained reflectivity is limited.

The inventors of the present invention have conducted intensive studies to solve the above-mentioned drawbacks. As a result, by alternately providing a low-refractive-index thin film and a high-refractive-index thin film on a metal surface, the reflectance higher than the reflectance inherent in the metal is obtained. The present inventors have found that the brightness and the whiteness of a photographic support can be improved by using this ratio, and have reached the present invention. Accordingly, an object of the present invention is to provide a photographic support having a high reflectance on a metal surface and having excellent brightness and whiteness.

[0006]

SUMMARY OF THE INVENTION The above objects of the present invention are as follows.
A photograph in which two or more layers composed of a low-refractive-index thin film and a layer composed of a high-refractive-index thin film are alternately provided in this order on a substrate having a metal surface having specular reflectivity or second-class diffuse reflectivity. Support for the low refractive index thin film and the high refractive index thin film.
A photographic support characterized in that the relationship between the folding ratio and the film thickness is represented by 1700 ≦ n _L × d _L + n _H × d _H ≦ 3000 . n _L : refractive index of low refractive index thin film d _L : thickness of low refractive index thin film / Å n _H : refractive index of high refractive index thin film d _H : thickness of high refractive index thin film / Å

In the present invention, the substrate having a metal surface is a paper or a film provided with a metal thin film on the surface thereof, and the metal can be appropriately selected from known materials. Preferred examples of the metal in this case include a metal mainly composed of aluminum described in JP-A-50-139720 and JP-A-48-65927.
No. 48-65928 and No. 50-2925, tellurium, molybdenum, polonium, cobalt, zinc, copper, nickel, iron, tin, vanadium, germanium, silver or silver emulsion, chromium, Examples thereof include metals such as titanium and alloys thereof. Among these, aluminum is particularly preferable as the metal thin film.

As a method of providing these metals as a layer made of a metal thin film on a substrate, a known thin film manufacturing method such as a vacuum evaporation method, a sputtering method, an ion plating method, and an electrodeposition method can be used. One or more layers of a metal thin film may be provided.

[0009] The thickness of the metal thin film or we become layers, 20 to 40
It is preferably in the range of 00 °, especially 50 to 200
It is preferably in the range of 0 °. The low refractive index thin film in the present invention means a thin film having a refractive index of less than 1.5, and the high refractive index thin film means a thin film having a refractive index of 1.5 or more.

In the present invention, it is necessary that the difference between the refractive indices of the low refractive index thin film and the high refractive index thin film is 0.1 or more, and the higher the difference between the refractive indices, the higher the reflectance and the wider the reflection band. Obtainable. Therefore, the difference between the two refractive indexes is preferably 0.5 or more, particularly 0.7 or more,
Most preferably, it is 0.9 or more. Examples of the low refractive index thin film in the present invention include MgF ₂ , SiO ₂ , and SrF ₂
And examples of the high refractive index thin film include Zn
S, SiO, TiO ₂ , ZrO ₂ , Al ₂ O ₃ , Ta ₂
Those using O ₅ , CeO ₂ , Cr ₂ O ₃ or the like can be given.

In order to increase the reflectivity of only light of a specific wavelength, it is necessary to alternately provide a plurality of layers composed of a low refractive index thin film and a high refractive index thin film in this order .
In order to increase the reflectivity of almost the entire visible light region, a two-layer structure in which one layer of a low-refractive-index thin film is provided on a metal surface and one layer of a high-refractive-index thin film is provided thereon. Is preferred. In this case, a low refractive index thin film (refractive index:
thickness _d L (Å) and the high refractive index thin film (refractive index of n _L): n
_H ), the film thickness d _H (Å) is 1700 ≦ n _L × d _L + n
It is necessary to satisfy _H × d _H ≦ 3000
Ri, in _{particular, 2000 ≦ n L xd L +} n H × d H ≦ 27
00 is preferably satisfied. Further, it may be an integral multiple of the film thickness determined in this way.

Since the surface reflectance of the support of the present invention produced as described above is higher than the reflectance specific to metal,
It becomes a photographic support having excellent brightness and whiteness. In addition, the directivity is widely improved by the increase in the reflectance.

The support of the present invention can be widely used as a photographic reflection support. For example, a silver halide emulsion layer for black and white photographic paper is provided, and a protective layer is provided thereon.
Further, as in the case of ordinary color photographic paper, a color photographic paper light-sensitive material can be obtained by providing two or more light-sensitive silver halide emulsion layers each containing a different color coupler.

As another method of use, a color reversal photosensitive material, a direct positive type color photographic paper, or a direct positive type color copy material using a light fogging method can be obtained.
On this support, a red-, green-, and blue-sensitive silver halide emulsion layer containing silver halide grains having different spectral densities and a dye used in a silver die breach (SDB) method is provided. It is also possible to obtain an SDB-type print photosensitive material by providing the same.

Further, the present invention can be applied to recording materials such as reflective disk plates and disk films using silver halide. More specifically, the support of the present invention is disclosed in Japanese Patent Application Nos. 61-168802 and 61-16880.
No. 3, No. 61-168804, No. 61-168805
Nos., 61-249873 and 61-259794
And the photosensitive materials described in JP-A-61-275572 and the like can be widely used.

The support of the present invention is further provided with a mordant layer thereon to diffuse and transfer the decolorizing dye to a material for forming a color image, or to provide an undercoat layer on the support with a physical development nucleus. Or a silver diffusion transfer type silver image forming material, or a development inhibitor or a desilvering inhibitor described in JP-B-59-3737 or JP-A-50-65230. An adsorption layer (ADL) of a heterocyclic compound having an iodine ion, a bromine ion, a mercapto group, or a heterocyclic compound capable of forming imino silver can also be provided.

Another method of using the photographic support of the present invention is described in US Pat. No. 4,500,626,
No. 133449, No. 59-218443, Japanese Patent Application No. 60
It can also be used as a photothermographic material and / or a dye fixing material (image receiving material) described in JP-A-79709.

[0018]

The support of the present invention has a mirror-reflective or secondary
Since it has a higher reflectance than the reflectance of the metal surface having the seed diffuse reflection, the brightness and the whiteness are increased and the directivity is improved, so that an image having less roughness and excellent sharpness can be obtained.

[0019]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto. "Parts" indicating the amount of addition indicates "parts by weight".

Embodiment 1 [Preparation of support] Preparation of vapor-deposited film 25 μm thick filled with 2% by weight of silica having an average particle diameter of 3 μm
Place the polyethylene terephthalate film m in a vacuum deposition apparatus, vacuum degree of 10 ^- perform vacuum evaporation under ⁵ torr, to form a layer having a thickness on the surface is made of an aluminum deposited film of 800Å and a substrate having a metal surface I got

Next, similarly, a layer made of a low-refractive-index thin film is formed on the layer made of the above-mentioned aluminum vapor-deposited film.
After gF ₂ (n _L = 1.38) is formed to a thickness of 900 °, ZnS ( n
_H = 2.3 ) was formed to a thickness of 300 ° to produce a vapor-deposited film. The mixture shown in the following Table 1 was applied onto the layer composed of the above-mentioned vapor-deposited film, and dried to form an adhesive layer.

[0022]

[Table 1] ビ ニ ル Vinyl chloride / vinylidene chloride / vinyl acetate / maleic anhydride Acid copolymer (66/10/20/4 by weight) 56 parts Adduct of tolylene diisocyanate and trimethylolpropane 37 parts Epoxidized fatty acid alkyl ester 7 parts (molecular weight: about 350) ───────────────────────────

On the other hand, on the back side of the above-mentioned vapor-deposited film (the side opposite to the vapor-deposited side), a polyurethane-based
After drying, the liquid type adhesive was applied so as to be 3 g / m ² and dried at 100 ° C. for 2 minutes to form an adhesive applied layer surface.

[0024]

[Table 2] 100 parts by weight of Polybond AY-651A (Sanyo Chemical Industries, Ltd. 15 parts by weight of Polybond AY-651C (product name of adhesive manufactured by Sanyo Chemical Industries, Ltd.) ──────────────

The low-density polyethylene surface of the following polyethylene-laminated paper is combined with the above-mentioned adhesive-coated layer surface by 80%.
The support was heat-pressed at 20 ° C. and a pressure of 20 kg / cm ² to obtain a support of the present invention.

Preparation of Polyethylene Laminated Paper Timber pulp composed of 20 parts of LBSP and 80 parts of LBKP was beaten to 300 ml of Canadian freeness by a disc refiner, and sodium stearate was added to a mixture of 1.0 part of sodium stearate.
Parts, anionic polyacrylamide 0.5 parts, aluminum sulfate 1.5 parts, polyamide polyamine epichlorohydrin 0.5 parts, and alkyl ketene dimer 0.5 parts, all added at an absolute dry weight ratio to wood pulp. Paper having a basis weight of 160 g / m ^{2 was formed} by the machine.

The density is 1.0 g by machine calender.
/ Cm ³ . After subjecting this base paper to corona discharge treatment, low density polyethylene (MI = 7 g / 10 min, density 0.9
23 g / ml) by extrusion coating to a thickness of 3
A polyethylene resin layer was formed to have a thickness of 0 μm. Next, after the other surface (back surface) was subjected to corona discharge treatment, high-density polyethylene (MI = 8 g / 10 min, density 0.9
50 g / ml) extrusion coating to a thickness of 30
A polyethylene resin layer having a thickness of μm was formed, and a double-sided polyethylene laminated paper was prepared.

On the above-mentioned support (on the side of the vapor deposition surface), Japanese Patent Application No.
Silver halide emulsions and the like prepared as shown in Table 3 below according to Example 4 of 1-168801 were sequentially applied and dried to obtain a photographic paper for color photography.

[0029]

Preparation of silver halide emulsion (1) (1 solution) H ₂ O 1000 ml NaCl 5.5 g gelatin 32 g (2 solutions) sulfuric acid (1N) 24 ml (3 solutions) Silver halide solvent of the following formula 1 3 ml ( 1% by weight aqueous solution)

Embedded image (4 solution) KBr 15.66g NaCl 3.30g H ₂ O were added 200 ml (5 fluid) AgNO ₃ 32g H ₂ O were added 200 ml (6 _{fluid) KBr 62.72g NaCl 13.22g H 2 IrCl} 4. 45 ml (0.001 wt% aqueous solution) H ₂ O were added 600 ml (7 solution) AgNO ₃ 128g H ₂ O were added 600 ml ──────────────────── ─────
─────────

(Liquid 1) was heated to 56 ° C., (Liquid 2) and (Liquid 3) were added, and then (Liquid 4) and (Liquid 5) were added simultaneously for 30 minutes, and 10 minutes later, (Six liquids) and (7
Solution) was added simultaneously for 20 minutes. 5 minutes after the addition, the temperature was lowered to desilver, and water and gelatin were added.
pH was adjusted to 6.2, average particle size 0.45 μm,
Coefficient of variation (standard deviation divided by average particle size: s /
d) A monodispersed cubic silver chlorobromide emulsion containing 0.08 and 70 mol% of silver bromide was obtained.

Sodium thiosulfate was added to the obtained emulsion to perform optimum chemical sensitization. Next, (4 solutions) and (6
Liquid), the amounts of KBr and NaCl, (liquid 4) and (liquid 5)
Was changed as shown in Table 4 below to prepare silver halide emulsions (2), (3) and (4) having different silver chloride contents.

[0032]

[Table 4] ─────────────────────────────────── (4 liquids) (6 liquids) (4 liquids) ) And (5 solutions) ──────────── ──────────── Emulsion KBr NaCl Addition time of KBr NaCl ──────────── ───────────────────── (2) 6.71g 7.70g 26.88g 30.84g 12 minutes (3) 3.36 9.35 13.44 37.44 10 (4) 0.22 10.89 0.90 43.61 8の The obtained silver halide emulsions (1) to (4) The average grain size, coefficient of variation, and halogen composition are shown in Table 5 below.

[0033]

Table 5 Average grain size Coefficient of variation Silver halide (% by weight) ) Emulsion μms / average dBrCl─────────────────────────────────── (1) 0.45 0.08 70 30 (2) 0.45 0.07 30 70 (3) 0.45 0.07 15 85 (4) 0.45 0.08 1 99 ──────────────────────────── ───────

A color photographic material was obtained by sequentially laminating a first layer to a seventh layer on a support with the components and amounts shown in Table 5 below in the following manner. First layer: The blue-sensitive sensitizing dye (a) of (Chemical Formula 2) is added to the silver halide emulsion (4).

Embedded image ^Was added at 7.0 × 10 ⁻⁴ mol per mol of Ag × to perform spectral sensitization. Furthermore, a yellow coupler (d) of the formula (3)

Embedded image And a color image stabilizer (e) of formula (4)

Embedded image Is dissolved and mixed with the solvent (f), dispersed and added in a predetermined amount.
The coating solution for the layer was used. The obtained coating solution is applied onto a support.
Dried to form a first layer.

Third layer : The silver halide emulsion (3) was added to the green-sensitive sensitizing dye (b) of formula (5).

Embedded image ^Was added at 4.0 × 10 ⁻⁴ mol per mol of Ag × to perform spectral sensitization. Further, the mazetan coupler of formula (6) (h)

Embedded image And (I) a color image stabilizer of formula (7)

Embedded image With the solvent (j)

Embedded image And a predetermined amount was added after mixing, dissolving and dispersing to obtain a coating solution for the third layer. The obtained coating solution was applied on a support and dried to form a third layer.

Fifth layer The silver halide emulsion (2) is added to the red-sensitive sensitizing dye (c) of the formula (9).

Embedded image ^Was added in an amount of 1.0 × 10 ⁻⁴ mol per mol of Ag ×, and spectral sensitization was performed. Further, a cyan coupler (n) of the formula (10)

Embedded image And a compound of formulas 11 to 13 in a molar ratio of 1: 3: 3.

Embedded image

Embedded image

Embedded image Was mixed and dissolved in the solvent (f) of dibutyl terephthalate, dispersed and added in a predetermined amount to obtain a coating solution for the fifth layer. The obtained coating solution was applied on a support and dried to form a fifth layer.

The second layer, the fourth layer, the sixth layer and the seventh layer were prepared in the same manner as described above, and the obtained solution was coated on a support so that the used amount was as shown in Table 6. -Dry to produce photographic paper for color photography (hereinafter referred to as sample).

[0038]

[Table 6] ─────────────────────────────────── Layer Main composition and usage ──── ７ 7-layer gelatin 1.33 g / m ² Polyvinyl alcohol acrylic modified copolymer ( 0.17 g / m ² ６ 6-layer gelatin 0 0.54 g / m ² UV absorber (k) 0.21 g / m ² (1: 5 of the compound represented by (Formula 14) to (Formula 16))
3 (molar ratio) mixture)

Embedded image

Embedded image

Embedded image 0.09 ml / m ² of solvent (m)

Embedded image ─────────────────────────────────── Five-layer silver halide emulsion (2) Silver: 0.22 g / m ² of gelatin 0.90 g / m ² (of 10) cyan couplers (n) 0.36 g / m ² (Formula 11) to (Formula 13) of the color image stabilizer (o) 0.17 g / m ² dibutyl phthalate Solvent (f) 0.22 ml / m ² (Chemical formula 9) Red-sensitive sensitizing dye (c) 1.0 × 10 ^-4 mol / Ag × 1 mol ────────────────────── Four-layer gelatin 1.60 g / m ² UV absorber (k) of (Chemical Formula 14) to (Chemical Formula 16) 0.62 g / M ² (Chemical formula 18) 0.05 g / m ²

Embedded image Solvent (m) of (Chemical Formula 17) 0.26 ml / m ² ─────────────────────────────────── Three-layer silver halide emulsion (3) Silver: 0.15 g / m ² Gelatin 1.80 g / m ² Magenta coupler (h) 0.38 g / m ² Color image stabilizer (Chemical formula 7) i) 0.16 g / m ² of the solvent (j) 0.38 ml / m ² of the green sensitizing dye (b) 4.0 × 10 ⁻⁴ mol / Ag × 1 mol防止 Prevention of color mixture of two-layer gelatin 0.99 g / m ² Agent (g) 0.08 g / m ²

Embedded image １ Single layer silver halide emulsion (A) silver: 0.26 g / m ² of gelatin 1.83 g / m ² (of 3) of yellow coupler (d) 0.91 g / m ² (of 4) of the color image stabilizer (e) 0.19 g / m ² dibutyl phthalate solvent (f) 0.36 ml / m ² of the blue-sensitive sensitizing dye (a) 7.0 × 10 ⁻⁴ mol / Ag × 1 molに お い て In Table 6 above, the first layer is a blue-sensitive layer, the second layer is an anti-mixing layer, the third layer is a green-sensitive layer, and the fourth layer is The ultraviolet absorbing layer, the fifth layer is a red sensitive layer, the sixth layer is an ultraviolet absorbing layer, and the seventh layer is a protective layer. The sample was subjected to sensitometric gradation exposure through a blue, green, and red three-color analysis filter or the like using a 2854 ° K light source, or stretched through a negative film for image exposure for printing. A photographic image was obtained through each step of development, bleach-fix and rinsing.

The development was performed at 35 ° C. for 45 seconds using the color developing solution A in the developing step (Table 7).

[Table 7] Color developer A water 800 ml Diethylenetriaminepentaacetic acid 1.0 g Sodium sulfite 0.2 g N, N-diethylhydroxylamine 4.2 g Potassium bromide 0.6 g Sodium chloride 1.5 g Triethanolamine 8.0 g Potassium carbonate 30 g N-ethyl-N- (β-methanesulfonamidoethylamino) -3-Methyl-4-aminoaniline sulfate 4.5 g 4,4′-diaminostilhen-based fluorescent image whitening agent 2.0 g (Whitex4: trade name of Sumitomo Chemical Co., Ltd.) Add water and 1000 ml with KOH pH 10.25 ──────────────────────────────────

The fixing was performed at 35 ° C. for 45 seconds with the bleaching-fixing solution A in the bleach-fixing step (Table 8).

[Table 8] ─────────────────────────────────── Bleaching treatment fixer A Ammonium thiosulfate 150 ml (54 _{wt%) Na 2 SO 3 15g HN} 4 [Fe (3) (EDTA)] 55 g EDTA · 2Na 4g glacial acetic acid 8.61g water to make a total volume to 1000ml (pH5.4) ───────── ──────────────────────────

The rinsing step (Table 9) was carried out with the rinsing liquid A at 28 to 35 ° C. for 1 minute and 30 seconds.

[Table 9] Rinse solution A EDTA ・ 2Na ・ 2H ₂ O 0 Ｇ4g Water is added and the total amount is 1000ml (pH 5.4) ───────────────────────────────────

Embodiment 2 FIG. MgF ₂ (n _L = 1.2) as a layer made of a low-refractive-index thin film provided on an aluminum-deposited film.
38) to a thickness of 800 °, and ZnS (n _H = 2.3) to a thickness of 500
A photographic paper for color photography was produced in exactly the same manner as in Example 1 except that each was formed by vacuum evaporation so that Å was obtained, and a photographic image was obtained in exactly the same manner.

Embodiment 3 FIG. Provided on aluminum deposition film
MgF as a layer composed of a low refractive index thin film_Two(N _L= 1.
38) by vacuum evaporation to a layer thickness of 700 °.
TiO 2 as a layer made of a high refractive index thin film_Two
(N_H= 2.7) is sputtered to a film thickness of 500 °.
Except for the ring, exactly the same as in Example 1 for color photography
A photographic paper was prepared and a photographic image was obtained in exactly the same manner.

Comparative Example 1 A color photographic printing paper was produced in exactly the same manner as in Example 1 except that the thickness of the aluminum vapor-deposited film layer was set to 800 °, and the layer composed of the low-refractive-index thin film and the layer composed of the high-refractive-index thin film were not provided. To obtain a photographic image.

Comparative Example 2 MgF ₂ (n _L = 1.38) having a film thickness of 500 as a layer made of a low refractive index thin film on a layer made of an aluminum vapor-deposited film
と し て, and Z as a layer made of a high refractive index thin film
A photographic paper for color photography was produced in exactly the same manner as in Example 1 except that each of nS (n _H = 2.3 ) was formed by vacuum evaporation so as to have a film thickness of 400 °. Obtained.

Comparative Example 3 As a layer made of a low refractive index thin film, a layer made of MgF ₂ (n _L =
1.38) to form a layer by vacuum evaporation to a thickness of 900 °, and then a Ti
A photographic paper for color photography was produced in exactly the same manner as in Example 1 except that O ₂ (n _H = 2.7) was sputtered to a film thickness of 800 °, and a photographic image was obtained in exactly the same manner.

The images of the photographs obtained in the examples and comparative examples were measured for specular reflectance and diffuse reflectance using a Hitachi 607 color analyzer (trade name, manufactured by Hitachi, Ltd.) (wavelength of the measured light). Are 440 nm, 550 nm and 6
50 nm), the luminance was evaluated by the regular reflectance, and the whiteness was evaluated by the diffuse reflectance. The results are as shown in Table 10. The above results demonstrate that the use of the photographic support of the present invention improves the brightness and whiteness of the obtained photographic image.

[Table 10]

Claims (1)

(57) [Claims] 1. A layer having a low refractive index thin film and a layer having a high refractive index thin film are alternately formed on a substrate having a metal surface having specular reflectivity or second-class diffuse reflectivity in this order. A photographic support comprising: a low refractive index thin film;
Refractive index and thickness of the relationship of the refractive index thin _{films, 1700 ≦ n L xd L +} n H × d H ≦ photographic support, characterized by being represented by 3000; _{n L:} refractive index of the low refractive index thin film d _L : thickness of low refractive index thin film / Å n _H : refractive index of high refractive index thin film d _H : thickness of high refractive index thin film / Å