JPH0297935A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To facilitate peeling from base paper and to obviate damaging at the time of peeling and sticking of the base paper by specifying the tensile strength of a photographic product consisting of resin layers and photograph constituting layer and the peeling strength to the base paper. CONSTITUTION:The photograph constituting layer 1 contg. a silver halide emulsion layer is formed on the layer 2 of polyethylene-coated paper consisting of the base paper 3 and the resin layers 2, 4. The tensile strength of the photographic product consisting of the layers 2, 1 is specified to >=700g/1.5cm and the peeling strength between the layer 2 and the base paper 3 is specified to 10 to 200g/inch. The peeling of the photographic product by winding the product around a peeling roller, etc., is then possible without damaging and elongating the image and the sticking of the product to a prepaid telephone card, canvas, etc. is possible as well.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a silver halide photographic material, and more particularly to a peelable silver halide photographic material.

[Background of the invention]

In recent years, as a new way to enjoy silver halide photographic materials, there has been an increase in the use of printed silver halide photographic materials by pasting them on telephone cards, canvases, and the like.

Usually, as a method of peeling, the resin layer and the photographic constituent layers are often wound around a roller or the like and peeled off from the support of the printed silver halide photographic light-sensitive material. that time,
It is preferable that the resin layer be easily peeled off, but if the peeling strength between the resin layer and the support is too weak, it may cause inadvertent peeling due to friction from rollers, etc. during the manufacturing process, processing, or development, which is inconvenient. be.

Therefore, it is preferable for the peel strength to be strong to some extent, but if the peel strength is too strong, the resin layer may not peel easily (or the base paper may remain on the base paper side of the resin layer when it is peeled off). Furthermore, since peel-off type silver halide photographic materials require a peeling process compared to ordinary silver halide photographic materials, tensile force is applied to the resin layer and the photographic constituent layers during peeling, making them more likely to be damaged.

On the other hand, photographic paper with specified peel strength was published in 1983-
125823, etc. However, there is no description of a technique for improving damage to resin layers and photographic constituent layers.
It was still unusable as a peelable silver halide photographic material.

[Purpose of the invention]

In order to solve the above-mentioned problems, the first object of the present invention is to provide a silver halide photographic material from which the resin layer and the photographic constituent layers can be easily peeled off from the support without damaging the image. be. Furthermore, the second objective is to create a silver halide photographic light-sensitive material in which no base paper remains on the surface of the resin layer on the base paper side when the resin layer and photographic constituent layers are peeled off from the support, and no post-processing is required. It is to provide.

[Structure of the invention]

The above object of the present invention is to provide a silver halide photographic light-sensitive material having a photographic constituent layer including a silver halide emulsion layer on a resin layer of a support provided with a resin layer. Achieved by a silver halide photographic material having a peel strength of lO to 200 g/1 nch, and a tensile strength of a photographic product consisting of the resin layer and the photographic constituent layer of 7009/1.5 cm or more. be done.

The present invention will be explained in detail below.

The peel strength of the resin layer according to the present invention is lO~200g/1
There is no particular restriction as long as it is lch, but preferably 50-1
The range is 50g/1nch. More preferably 60
~100g/1nch. Peel strength is 10
If it is less than 9/inch, peeling may occur inadvertently due to friction from rollers, etc. during the manufacturing process, processing, or development, which is inconvenient.

Also, the peel strength is 2001? / If it is stronger than 1 nch, problems such as damage to the resin layer and the photo layer may occur, or the base paper may adhere to the surface of the resin layer on the base paper side. The peel strength in the present invention was measured using a universal testing machine manufactured by Tester Sangyo Co., Ltd.
Before coating the emulsion layer, the sample was horizontally heated at 20 ctrl/m.
This is a value measured by pulling up at in.

The tensile strength of the photographic product comprising the resin layer and the photographic constituent layer according to the present invention is not particularly limited as long as it is 700 g/1.5 cm or more, but preferably 700 to 800 g/l, 5
The range is cm. Tensile strength is 7009/1.5
If it is less than cm, the resin layer and the photographic constituent layer may stretch,
I don't like it because it gets destroyed.

The tensile strength of the present invention was measured using a C-type Schopper high tensile strength tester manufactured by Toyo Seiki Seisakusho.
This is a value measured according to ISP-8113.

The resin layer used in the present invention can be made of polyethylene, which is commonly used in photographic paper.

The degree of tension is adjusted depending on the thickness of the polyethylene layer, and is preferably in the range of 15 to 30 μm.

In the silver halide photographic light-sensitive material of the present invention, the outermost layer located farthest from the support (hereinafter referred to as a protective layer) is preferably a non-photosensitive layer, although there is no particular restriction. The fact that the fine particle powder with a particle size of 11-1 Op is contained prevents the resin layer of the present invention and the photographic constituent layer from sticking to the surface of the photographic constituent layer when the resin layer and the photographic constituent layer are peeled from the support. This is preferable since there are no such malfunctions.

In the silver halide photographic light-sensitive material of the present invention, the silver halide emulsion layer having any color sensitivity may be a single monochrome layer, or it may be a commonly used multicolor color light-sensitive material.

When the silver halide photographic light-sensitive material according to the present invention is a multicolor light-sensitive material, the layer structure of the silver halide emulsion layer,
That is, the layer order of the blue-sensitive silver halide emulsion layer, the green-sensitive silver halide emulsion layer, and the red-sensitive emulsion layer is arbitrary, and the layer order of the blue-sensitive silver halide emulsion layer, the green-sensitive silver halide emulsion layer, and the red-sensitive emulsion layer is arbitrary. (layers, etc.) may be provided as desired, but a preferred specific layer structure includes, in order from the support side, a yellow dye image forming layer, a first intermediate layer, a magenta dye image forming layer, a second intermediate layer, A cyan dye imaging layer, a third intermediate layer, and a protective layer of the present invention containing a finely divided powder having an average particle size of 1-1 (] .mu.m are arranged.

Hydrophilic colloids are used in the protective layer of the present invention, and examples of hydrophilic colloids that can be used include gelatin, gelatin derivatives (such as acetylated gelatin and phthalated gelatin), albumin, and collodion. preferable.

In addition, the average particle size contained in the protective layer of the present invention is 1-10
The micron particle powder is generally referred to as a matting agent in the art, and will be referred to hereinafter as a matting agent unless otherwise specified.

Examples of the mantle agent according to the present invention include crystalline or amorphous silica, titanium dioxide, magnesium oxide, calcium carbonate, barium sulfate, alumina silicate,
Acrylic acid-ethyl acrylate copolymer, acrylic acid-methyl methacrylate copolymer, itaconic acid-styrene copolymer, maleic acid-methyl methacrylate copolymer, maleic acid-styrene copolymer, acrylic acid-
Examples include methacrylic acid-ethyl methacrylate copolymer, acrylic acid-phenylacrylate copolymer, polymethyl methacrylate-1-, polystyrene, starch, cellulose acetate propionate, and other U.S. Patent No. 1,221,980. No. 2,992゜I Old No.
It is possible to use a combination of more than one species.

The particle size of the cape agent may be an average particle size of 1 to 10 μm, preferably 2 to 7 μm.

The average particle size here refers to the diameter in the case of spherical particles, and the average value of the diameter when the projected image is converted to a circular image of the same area in the case of particles with shapes other than cubes and spheres. When the individual grain size is r, and the number is 01, it is defined by the following formula.

As a specific measuring method, the method described in JP-A-59-29243 can be used.

The matting agent according to the present invention is dispersed and contained in the outermost layer of the non-photosensitive layer. Other additives are added and dispersed using a high-speed rotating mixer homogenizer, ultrasonic dispersion, ball mill, etc., using an emulsification dispersion method using shear placement, and coated as the outermost layer of the photosensitive layer by any method used in the photographic field. It can be formed by

The coating amount of the matting agent according to the present invention is preferably 0.5 to b per ml in the outermost non-photosensitive layer. More preferably 1 to 20 m per l m2
9 Contain something.

In addition, the amount of the mantle agent is 0 to the hydrophilic colloid.
．． 1 to 2% by weight is preferred.

The support used in the silver halide photographic light-sensitive material of the present invention is a support made of ordinary paper or synthetic paper laminated with a resin.

The resin is not particularly limited, but an α-olefin polymer to which a white pigment is added is preferred, and polyethylene is particularly preferred. The thickness of the resin layer is not particularly limited, but is preferably in the range of 15 to 30 μm.

As the white pigment, inorganic and/or organic white pigments can be used, preferably inorganic white pigments, such as sulfates of alkaline earth metals such as barium sulfate, barium carbonate, etc. Examples include carbonates of alkaline earth metals such as titanium oxide, zinc oxide, etc. Among these, titanium oxide is preferred.

The silver halide emulsion used in the light-sensitive material according to the present invention includes:
Any silver halide used in ordinary silver halide emulsions, such as silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide, and silver chloride, can be used as the silver halide. Further, these silver halide emulsions can be optically sensitized using various sensitizers in order to impart photosensitivity in a desired wavelength range.

The silver halide photographic material of the present invention may contain various other photographic additives.

For example, antifoggants, stabilizers, ultraviolet absorbers, color stain inhibitors, color image fading inhibitors, antistatic agents, hardeners, etc. described in Research Disclosure No. 17643,
Surfactants, plasticizers, wetting agents, etc. can be used.

In the light-sensitive material of the present invention, hydrophilic colloids used to prepare the emulsion include gelatin, derivative gelatin, graft polymers of gelatin and other polymers, albumin, proteins such as casein, hydroxyethyl cellulose derivatives, carboxymethyl cellulose, etc. Examples include derivatives of starch, starch derivatives, and single or copolymer synthetic polymers such as polyvinyl alcohol, polyvinylimidazole, and polyacrylamide.

When the silver halide photographic light-sensitive material according to the present invention is a color photographic light-sensitive material, yellow couplers, magenta couplers, and cyan couplers can be used as couplers without any particular restrictions, and these couplers are of the two-equivalent type. It may be a 4-equivalent type coupler.

Yellow couplers include open chain ketomethylene compounds,
Magenta couplers include pyrazolone, pyrazolotriazole, pyrazolinobenzimidazole, and indacylon compounds, and cyan couplers include:
Examples include phenol couplers and naphthol couplers.

As a processing method when the photographic material of the present invention is a color photographic material, for example, a color developing bath containing a color developing agent can be used.

In addition to bath processing, there are various other methods, such as a spray method in which the processing solution is atomized, a web method in which contact is made with a carrier impregnated with the processing solution, and a development method using a viscous processing solution. The following processing methods can be used.

There are no particular limitations on the method of processing the photographic material of the present invention, and any processing method can be applied.

For example, typical methods include a method in which bleach-fixing is performed after color development, followed by further washing and/or stabilization treatment if necessary; bleaching and fixing are performed separately after color development; A method of washing with water and/or stabilizing; or pre-hardening, neutralization, color development, stop-fixing,
Washing with water, bleaching, fixing, washing with water, post hardening, washing with water in this order, color development, washing with water, supplementary color development, stopping, bleaching, fixing,
Any method may be used for processing, such as a method in which the developed silver produced by color development is bleached and then color development is performed again to increase the amount of dye produced.

pH of the color developer used in processing the photosensitive material of the present invention
preferably has a pH of 8 or more, more preferably a pH of 9 to 12.
It is an alkaline aqueous solution of The aromatic primary amine developing agent as the color developing agent is a compound having a primary amino group on an aromatic ring and having the ability to develop exposed silver halide. Precursors that form chemical compounds may also be added.

The color developing agent mentioned above is typically p-7 22-diamine type.

The color developer used in the present invention further contains various components that are normally added, such as alkaline agents such as sodium hydroxide and sodium carbonate, alkali metal sulfites, alkali metal bisulfites, alkali metal thiocyanates, and alkali metals. Halides, benzyl alcohol, water softeners, thickeners, development accelerators, and the like may optionally be included.

Examples of additives other than the above added to the color developing solution include bromides such as potassium bromide and ammonium bromide;
In addition to compounds for rapid processing solutions such as alkali iodide, nitrobenzimidazole, mercaptobenzimidazole-benzotriazoleptotetrazole, anti-stain agents, anti-sludge agents, preservatives, interlayer effect promoters, chelating agents, etc. .

Bleaching agents used in bleaching solutions or bleach-fixing solutions in the bleaching process are generally known to be those in which metal ions such as iron, cobalt, and copper are coordinated with aminopolycarboxylic acids or organic acids such as oxalic acid and citric acid. There is.

Representative examples of the above aminopolycarboxylic acids include the following.

Ethylenediaminetetraacetic aciddiethylenetriaminepentaacetic acidpropylenediaminetetraacetic acidnitrilotriacetic acidiminodiacetic acidethyl ether diaminetetraacetic acidtethylenediaminetetrabropionic acidethylenediaminetetraacetic acid disodium saltdiethylenetriaminepentaacetic acidpentanasodium saltnitrilotriacetic acid sodium saltThe bleaching solutions are as above. may contain various additives along with the bleaching agent. When a bleach-fixing solution is used in the bleaching step, a solution containing a silver halide fixing agent in addition to the bleaching agent is used. Further, the bleach-fix solution may further contain a halogen compound such as potassium bromide. And as in the case of the bleaching solution mentioned above, various other additives,
For example, pH buffering agents, antifoaming agents, surfactants, preservatives, chelating agents, stabilizers, organic solvents, etc. may be added or contained.

In addition, silver halide fixing agents such as sodium thiosulfate, ammonium thiosulfate, potassium thiocyanate, sodium thio/anate, thiourea, thioether, etc., which react with silver halide and are water-soluble, such as those used in conventional fixing processes, can be used. Compounds that form silver salts can be mentioned.

〔Example〕

Next, the present invention will be explained in detail with reference to Examples, but the present invention is not limited by these Examples.

Example 1 On a support made of polyethylene-coated paper having different peel strengths and tensile strengths as shown in Table 1, the following layers were sequentially coated from the support side to prepare a multicolor silver halide color photographic light-sensitive material.

1st layer...Blue-sensitive emulsion layer Yellow coupler (Y-1) is 0.8 g/m", blue-sensitive silver chlorobromide emulsion (silver bromide composition 70 mol%) is 0.8 g/m" in terms of silver. 30g/m'', high boiling point organic solvent (DNP) 0.
3g/m”, anti-fading agent (HP-1) 0.6g/m2
, hydroquinone derivative (HQ-1) [), 01g/
m” and coated with gelatin.

2nd layer...middle layer hydroquinone derivative (HQ-1) at 0.045g/m
' and coated with gelatin.

Third layer: Green-sensitive emulsion layer Magenta cobra (M-1) was 0.4 g/m', green-sensitive silver chlorobromide emulsion (silver bromide composition 75 mol%) was converted into silver, 041g/m2, high boiling point organic solvent (DOP) 0.
4g7m2, anti-irradiation dye (A I-1
) at 0.01 g/m" and color image stabilizer 5TB-1 at 0.01 g/m".
2g/m”, 5TB2 0.05g/m” and HQ-
1 was coated with 0.01 g/m and gelatin.

4th layer...intermediate layer ultraviolet absorber (UV-1) 0.3g/m'', (UV-1)
2) at 0.3 g/m2, and high boiling point organic solvent (DNP) at 0.
．． 4g/ln", 0.045g/+o" of HQ-1, 0.015g/m of anti-irradiation dye (AI-2)
”, and coated with gelatin.

5th layer... Red-sensitive emulsion layer Cyan coupler (C-1) is 0.4 g/m'', red-sensitive silver chlorobromide emulsion (silver bromide composition 75 mol%) is converted to silver, .2g/m2, high boiling point organic solvent (DOP) 0.2
g/+'', 0.02 g/m2 of HQ-1 and gelatin were applied.

6th layer: Intermediate layer Ul/-1: 0.3 g/m2, UV-2: 0.3 g/m
2. High boiling point organic solvent (DNP) at 0.4 g/m”, HQ
-1 at 0.045g/m", Al-2 at 0.015g#
Coated with n2 and gelatin.

Seventh layer: Protective layer 2.09 g/m'' of 4-dichloro-6-hydroxy V-s-triazine and gelatin were coated.

To the photosensitive material prepared as above, 0.003 g/m'' of a matting agent MATI was added as shown in Table 1D.

(Compound used) DOP Nidioctyl Phthalate DNP Nidinyl phthalate Q AI ■ S 1” B-2 Y-1 CH3 CH.

Q P-1 V V-2 AT 1 Nlica (average particle size: 3.0 μm) These samples were exposed to white light or red light using a sensitometer, and then subjected to the following processing steps.

[Processing step 1 Color development 33°C 3 minutes 30 seconds Bleach fixing 33°0 90 seconds Water
Washing 30~34°c 3 revolutions Drying 60~80″0
2 minutes [Color developer] Pure water
800m12 diethylene glycol
10m12 benzyl alcohol
15m (1 hydroxylamine sulfate
2g potassium bromide 1.
4g Sodium chloride 2.0g Potassium sulfite 2.0g N-methyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate 4.5g Diaminostilbene water-soluble optical brightener 2.0g Pure water Add 1Q and adjust the pH to -10.1.

[Bleach-fix solution] Pure water
600mQ ethylenediaminetetraacetic acid ferric ammonium dihydrate 60g ethylenediaminetetraacetic acid 3g ammonium thiosulfate (70% solution) 100a+Q ammonium sulfite (40% solution) 27.5mff Add pure water to make 1Q and adjust the pH to -7.1 .

As described above, the peelable silver halide photographic materials shown in FIG. 1 (Samples Nos. 1 to 20) were prepared, and the following evaluations were performed.

(1) Peeling performance x: Peels off during manufacturing, processing, or development.

Further, when the resin layer is peeled off, the base paper remains on the resin layer.

Δ: Slight peeling occurs during manufacturing, processing, or development.

○...Is it ok to use a peeling roller? It is peeled off and does not peel off during manufacturing, processing, or development.◎... It is peeled off particularly well with a peeling roller, and it does not peel off during manufacturing, processing, or development.

(2) Damage to resin layer and photographic constituent layers x: Breakage or elongation occurs in the resin layer and photographic constituent layers.

○: There is no damage to the resin layer or photographic constituent layer, but some elongation occurs.

◎...No damage to the resin layer and photographic constituent layers, no elongation G/0 (3) Sticking △...When peeled off with a peeling roller, the emulsion layer and the surface of the resin layer on the base paper side stick together a little. .

O: When peeled off with a peeling roller, there was no sticking of the emulsion layer to the surface of the resin layer on the base paper side.

(4) Overall performance ×: Not suitable for use as a peel-off type silver halide photographic light-sensitive material ○: Good as a peel-off type silver halide photographic light-sensitive material.

◎...Preferable U performance as a release silver halide photographic light-sensitive material. In particular, samples No. 15, 7.18.20 in which Mano I/Yakun was added to the 7th layer were good because there was no adhesion between the emulsion layer and the surface of the resin layer on the base paper side.

〔Effect of the invention〕

According to the present invention, the resin layer and the photographic constituent layer can be easily peeled off from the support without damaging the image, and at the same time, there is no base paper remaining on the surface of the resin layer on the base paper side, and after It was possible to provide a peelable silver halide photographic material that does not require processing.

[Brief explanation of the drawing]

FIG. 1 is a sectional view showing one example of the photographic constituent layer of the present invention. 1. Emulsion layer 2. Resin layer 3. Support 4. Resin layer As is clear from the results in Table 1, sample No. of the present invention.

Claims (1)

[Claims] In a silver halide photographic material having a photographic constituent layer including a silver halide emulsion layer on the resin layer of a support provided with a resin layer, the peel strength between the resin layer and the support is 10 to 200 g. /inch, and the tensile strength of the photographic product consisting of the resin layer and the photographic constituent layer is 7.
1. A silver halide photographic material having a weight of 00 g/1.5 cm or more.