JPH02178651A - Photographic substrate - Google Patents

Abstract

PURPOSE:To obtain a photographic substrate having improved adhesion of a polyethylene layer to a printed part by applying an ink prepd. by dispersing and dissolving at least an org. pigment and/or an org. dye and an ethylene/ acrylic acid copolymer in an alcohol and/or a fatty acid alkyl ester, to a surface (rear surface) opposite to a surface provided with a photographic emulsion layer. CONSTITUTION:An ink prepd. by dispersing and dissolving at least a colored pigment and/or dye and an ethylene/acrylic acid copolymer in an alcohol and/or a fatty acid alkyl ester is applied to a surface (rear surface) opposite to a surface where a photographic emulsion layer is to be formed. For example, in a photographic substrate 1 constituted of a base body 4 consisting of waterproof paper or plastic film, resin coated layers 2, 5 formed by coating a melt- extruded polyethylene resin compsn., and an ink layer 3. Further, an electroconductive back-coat layer 7 is usually provided to the surface of the polyethylene resin compsn. 2 of the rear surface, and a sub-coat layer 8 and a photographic emulsion layer are provided further on the polyethylene resin compsn. 5 of the front surface. Thus, the adhesion of the base paper to the printing ink and the printing ink to the resin coating layer are improved.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a photographic support, and more specifically, to printing of characters, figures, symbols, etc. using printing ink on the surface opposite to the surface on which a photographic emulsion layer is provided. The present invention relates to a photographic support coated with

[Prior Art and Problems to be Solved by the Invention] Photographic paper is basically composed of a support, a silver halide emulsion layer (photographic emulsion layer), and a protective gelatin layer. When used, both sides of the base paper are generally coated with a polyolefin resin such as polyethylene in order to impart water resistance to the base paper. In a photographic support using such polyolefin resin coated paper, the side on which the photographic emulsion layer is coated is called the "surface", and the side on which the photographic emulsion layer is not coated is called the "surface". It's called the "back side." Therefore, an image is formed on the front surface, but on the back surface of the photographic support, characters such as product names, manufacturing companies, symbol marks, etc., figures, symbols, etc. are printed using printing ink.

It is often printed with a flexographic printing material using a printing ink that uses a black dye on the surface of the base paper before it is coated with a polyolefin resin.

The printing effect on the back side has a density that allows the printed area to be clearly seen, the processing liquid does not seep into the printed area during photo processing, and the density is such that it is not detected by the machine's mark detection device when cutting after photo processing. required.

When manufacturing a photographic support coated with a polyethylene resin composition, if the adhesion between the polyethylene layer and the printed part is weak in the case where back printing is performed and the polyethylene resin composition is extruded from an extruder and coated, it may cause stress in the post-process. This causes delamination in the printing section, causing trouble. Furthermore, if the adhesion is poor, the printed area will become floating, ie, blister, and cannot be used as a product.

That is, when the material is cut from areas with weak adhesion and parts of the blister and subjected to photo processing, the processing liquid seeps into the areas with weak adhesion and parts of the blister, spoiling the appearance and causing a problem in commercial value.

Furthermore, conventionally, characters, figures, symbols, etc. are printed without taking into account the size at the time of final cutting, so when cutting, the printed parts are often separated, which not only makes no sense but also looks unsightly. was there.

[Purpose of the invention]

Therefore, it is an object of the present invention to improve the adhesion of the printed part to the substrate, and especially to improve the adhesion between the polyethylene layer and the printed part in photographic supports coated with a polyethylene resin composition after printing on a paper substrate. The object of the present invention is to provide a photographic support printed using an ink.

[Means for solving problems]

As a result of intensive research to achieve the above purpose, the present inventor has
At least organic pigments and/or dyes and ethylene-based
This was achieved by using an ink in which an acrylic acid copolymer was dispersed and dissolved in alcohol and/or fatty acid alkyl ester.

Various organic pigments and dyes are known, but the dyes and pigments related to the present invention may be any dye or pigment that does not have an adverse effect on the photographic emulsion 1 and does not change color due to chemical changes or the like during photographic processing. good. Specific examples of these include carbon black, cyanine blue, yellow, acid dyes in which C, I, and A are Ac1d Black 2, and titanium oxide (white).

The ethylene/acrylic acid copolymer used in the present invention is
As described in JP-A No. 61-230142, this primer is known as a primer for extrusion coating of a photographic support layer base paper and a polyolefin (ethylene) resin composition. The proportion of acrylic acid monomer is 5 to 30 mol, more preferably 10 to 30 mol.
25 molti is good. Further, the minimum film forming temperature of these ethylene/acrylic acid copolymers is preferably 40 to 100°C.

The solid content weight ratio of the organic pigment and/or dye and the ethylene/acrylic acid copolymer can be determined by considering the adhesion of the printed part. A range of 10 to 10,000 times would be appropriate.

The ink according to the present invention is prepared by dispersing and dissolving alcohol and/or fatty acid alkyl ester-based organic solvents. This is to speed up the drying of the solvent, and also because it is difficult to transfer the ink onto water-resistant photographic support paper substrates and polyethylene resin compositions with aqueous inks. Therefore, it is desirable that alcohols and fatty acid alkyl esters have little or no irritation to the human body and have low boiling points and high vapor pressures at low temperatures.
- Examples include propatool, ethanol, and ethyl ethanoate alone or in mixtures containing these with organic solvents. Further, the ink according to the present invention may contain a small amount of water as a dispersion/dissolution aid.

The surface to be printed using the ink according to the present invention is the surface of the photographic support opposite to the surface on which the photographic emulsion layer is provided, and if the photographic support is a resin-coated paper type, it is the paper base surface. It may also be on the coated resin surface, but for reasons such as protection of the printed area, it is preferable to print on a paper base and then coat with resin.

The printed part printed using the ink related to the present invention is
It is desirable to wind the film into a narrow roll for use in a laboratory machine, and to arrange it in advance so that it will not be divided when it is cut into sheets after color development processing.

This is because when the color development process is performed with a roll processor, the cutting detector detects the mark printed on the back side of the sheet, which may cause a malfunction or cause a series of sentences to be divided. If this happens, not only will the printing become meaningless, but it will also become unsightly.

Therefore, for example, when processing a roll of photographic paper made of a photographic support with front printing of the present invention in a roll processor, the length from the connection part of the photographic paper to the exposure start position must be determined after cutting. Programming may be done by taking into account the position of front printing on photographic paper.

Printing performed using the ink according to the present invention may be monochrome (one time) or multicolor printing (multiple times) in which characters, figures, symbols, etc. are color-coded. Particularly in multicolor (multiple printing) printing, printing may be performed on both the paper substrate surface and the polyethylene resin composition surface depending on the case. Further, for reasons such as making the photographic support more fancy, the entire surface may be colored at a density lower than the minimum optical density in the area printed with the ink according to the present invention. The basic composition and method of the colorant for coloring the entire surface may be the same as or different from the composition and method of the ink according to the present invention. Further, this entire surface coloring may be done before or after printing performed using the ink of the present invention, but in order to make characters, figures, symbols, etc. appear more vivid, coloring may be performed on the entire surface prior to printing performed using the ink of the present invention. Coloring is preferable.

Embodiments of the present invention will be described below with reference to the drawings.

FIGS. 1 and 2 are schematic cross-sectional views of a resin-coated photographic support 1. FIG. In FIG. 1, a photographic support 1 includes a substrate 4 made of water-resistant paper or a synthetic resin film, resin coatings J12 and 5 made of a melt-extrusion coating of a polyethylene resin composition, and an ink according to the present invention. ! ! It consists of 3. On the back polyethylene resin composition 2, a normally conductive barafcoat layer 17 is further provided, and on the front polyethylene resin composition 5, a subcoat layer 8 and a photographic emulsion layer are further provided. 2 is similar to FIG. 1, except that a colored layer 6 is provided on the entire surface prior to providing the ink layer.

Further, FIG. 3 is a plan view showing a state in which the characters printed on the back side of the photographic support 1 according to the present invention do not fall on the cutting line 9 (indicated by a broken line) that is to be cut into photographic printing paper. Although the cutting line is not printed, it may be printed if necessary.

The photographic support used in the practice of the present invention is a paper substrate coated on both sides with a resin capable of forming a film.

The resin for coating the base paper used in the present invention is preferably a polyolefin resin or an electron beam curable resin. Examples of the polyolefin resin include homopolymers such as low-density polyethylene, high-density polyethylene, polypropylene, polybutene, and polypentene, or ethylene and propylene. Copolymers consisting of two or more olefins such as polymers, linear low-density polyethylenes that are copolymers of ethylene and α-olefins, and mixtures thereof, with various densities and melt indexes individually. Or they can be used in combination. Particularly in the present invention, it is preferable to use low density polyethylene, medium density polyethylene, high density polyethylene, ethylene-propylene copolymer, etc. alone or in combination of two or more kinds of resins.

As an electron beam curable resin, the molecular side chain or the molecular terminal has
Examples include resins having a C═C unsaturated bond such as an acryloyl group or a methacryloyl group. Typical examples include ester acrylate, ester methacrylate, epoxy acrylate, epoxy methacrylate,
Examples include urethane acrylate, urethane methacrylate, monofunctional acrylate, monofunctional methacrylate, polyfunctional acrylate, and polyfunctional methacrylate.

In addition, in the resin for coating the base paper in the present invention, white pigments such as titanium oxide, zinc oxide, Merck, calcium carbonate, etc., fatty acid amides such as stearic acid amide, alaxin substituted amyl, zinc stearate, stearic acid amide, etc. Fatty acid metal salts such as calcium phosphate, aluminum stearate, magnesium stearate, zinc balmitate, zinc ζ listate, calcium palmitate, hindered phenol, hindered amine, various antioxidants such as phosphorus type, sulfur type, cobalt blue, ultramarine blue. , blue pigments and dyes such as Cerulean Blue 7 Talocyanine Blue, magenta pigments and dyes such as Cobalt Violet 1,7 Asto Violet, and Manganese Violet, optical brighteners, and ultraviolet absorbers. Preferably, they are added in combination.

The photographic support according to the BAK of the present invention is manufactured by a so-called extrusion coating method in which a heated and molten resin is cast onto a running base paper, and both sides of the support are coated with the resin. Further, in the case of an electron beam curable resin, the resin is applied with a commonly used coater such as a gravure coater or a blade coater, and then an electron beam is irradiated to harden the resin for coating.

Further, before coating the base paper with the resin, it is preferable to subject the base paper to a corona discharge treatment and an activation treatment such as a flame treatment.

The emulsion side surface of the photographic support has a glossy surface, a matte surface, a silky surface, etc. depending on the use, and the back surface is usually a matte surface, and the front surface or the back surface is also treated with corona discharge if necessary. Activation treatments such as the following can be performed. There is no particular limit to the thickness of the resin layer of resin-coated paper, but it is generally 5μ.
Advantageously, a coating thickness of the order of m to 50 μm is applied.

The base paper for the resin-coated paper-type photographic support used in the present invention may be any of ordinary natural pulp paper, synthetic fiber paper, or so-called synthetic paper made by bonding a synthetic resin film, but softwood pulp may be used as the base paper. Natural pulp paper whose main component is wood pulp, hardwood pulp, softwood hardwood mixed pulp, is advantageously used.

There are no particular restrictions on the thickness of the base paper, but paper with good surface smoothness is preferred, and its basis weight is 50 t/P? ~25
0r tide is preferred. Further, the base paper mainly composed of natural pulp can contain various polymer compounds and additives. For example, starch derivatives, polyacrylamides, polyvinyl alcohol derivatives, dry paper strength agents such as gelatin, sizing agents such as fatty acid salts, rosin derivatives, dialkyl ketene dimer emulsions, melamine resins, urea resins, epoxidized polyamide resins, etc. A wet paper strength enhancer, a stabilizer, a pigment, a dye, an optical brightener, a latex, an inorganic electrolyte, a pH adjuster, and the like can be contained in an appropriate combination.

The back coat 1 according to the present invention can contain various polymer compounds and additives.

Water-soluble polymers include starch derivatives such as oxidized starch and phosphate esterified starch, polyvinyl alcohol, polyacrylamide, poly-N-vinylpyrrolidone, agar, alginine soda, etc. Surfactants include alkylbenzene sulfone salts, sulfosuccinic acid, etc. 7-ionic surfactants such as ester salts, nonionic surfactants such as saponin and alkylene oxide compounds, amphoteric surfactants such as amino acids, aminosulfonic acids, and amino alcohol esters;
Fluorine-containing surfactants as exemplified in 4I Publication No. 50-99529, as fluorescent brighteners,
It is possible to prepare a resin containing compounds described or exemplified in JP-A No. 54-94318 and the like.

In carrying out the present invention, silver halide photographic configuration! tI
Apparatuses for applying the back coat coating liquid onto the hydrophobic support surface on the opposite side where J is provided include air knife coaters, roll coaters, bar coaters, blade coaters, slide hopper coaters, gravure coaters, flexogravure coaters, and their like. Examples include combinations. Prior to coating, it is desirable to activate the surface of the hydrophobic support by corona treatment, flame treatment, or the like.

Various drying devices can be used to dry the applied coating liquid, including hot air dryers such as straight tunnel dryers, arch dryers, air loop dryers, and sine curve air float dryers, infrared heating dryers, dryers that use microwaves, etc. I can give it to you.

The silver halide photographic emulsion layer according to the present invention includes six types. Examples include a photographic emulsion layer for enlargement positives, a photographic emulsion layer for contact positives, a photographic emulsion layer for negatives, a color photographic emulsion layer, a photographic emulsion layer for printing, a photographic emulsion layer for direct positives, a photographic emulsion layer for diffusion transfer method, etc. . Regarding the color photographic emulsion layer, for example, JP-A-62-172346 and JP-A-62-1
Contains the coupler disclosed in Publication No. 72350, 30°C or higher9
A silver halide color photographic emulsion that can be developed within 0 seconds may also be used.

In addition, such photographic emulsion layers contain binders such as gelatin and gelatin derivatives, chemical sensitizers such as hypo, metal sensitizers such as gold salts and platinum salts, and hexahalogenoiridium (II).
I) Complexes, high contrast agents such as hexahalogenorhodium (1) complexes, nucleic acid decomposition products, silver halide particles such as mercapto heterocyclic compounds described or exemplified in JP-A-50-147925 and JP-A-51-107129. Crystal habit modifiers, color sensitizers, stabilizers, anti-capri agents, color photographic couplers, hardeners cited or exemplified in JP-A-52-65432 and JP-A-52-88340 , dihydroxybenzene compounds, coating aids, fogging agents, additives for direct positive photographic emulsions such as dyes for direct positive photographs, dye developers, and other additives.

The silver halide photographic material according to the present invention can be exposed to light as described in "Photographic Light-sensitive Materials and Handling Methods" (Kyoritsu Shuppan, written by Gobe Miyamoto, Photographic Technology Course 2), depending on the photographic material.
Processes such as development, stopping, fixing, bleaching, and stabilization are performed.
In particular, multilayer silver halide color photographic materials that are subjected to bath bleach-fixing treatment after color development are CD-1 [, CD-mV C and above two compounds are Kodak's trade name), droxychrome (May and Baker's trade name). ) etc. It can be processed with any number of crude drug color developers. Benzyl alcohol, thallium salt, 7-edone, etc. may be added to the developing solution containing the crude drug. Further, a useful one-bath bleach-fix solution is a solution of a metal salt of an aminopolycarboxylic acid (for example, a ferric complex salt such as ethylenediaminetetraacetic acid or propylenediaminetetraacetic acid), and as a fixing agent, sodium thiosulfate, Ammonium deosulfate and the like are useful. Such a one-bath bleach-fix solution can contain various additives. For example, desilvering promoters (e.g., mercaptocarboxylic acid as described in U.S. Pat. No. 3,512.979, Belgian Percentage No. 682,
mercapto-heterocyclic compounds described in No. 426), antifouling agents, pH adjusters or buffering agents, hardening agents (e.g., magnesium sulfate, aluminum sulfate, potassium alum, etc.), surfactants, etc. can be contained in combination. Further, such one-bath bleach-fix solutions can be used at various pH values, but the useful pH range is from pH 6.0 to
It is 8.0.

Next, examples will be described in order to explain the present invention more specifically.

[Example 1] Kraft process hardwood pulp (LBKP) 50w ffi% and sulfide process hardwood pulp (LBSP) 50'ff
Paper is made with a mixed pulp consisting of LIkts, and the basis weight,
A base paper having a thickness of 150 f/wl and a thickness of 150 μm was obtained. Next, use the printing ink liquid with the composition shown in Table 1! i14 has been adjusted.

Next, the printing ink liquid was printed on the back side of the base paper using a flexo printing machine, and after drying, both sides were coated with polyethylene extrusion coating using a laminator under the conditions shown in Table 2 to obtain a photographic support. Ta.

Each sample obtained as described above was left at 50° C. for 16 hours to evaluate its adhesion to polyethylene.

The evaluation criteria are O mark (100-chip adhesion) by visual evaluation;
It was expressed as Δ (adhesion of 80J or more) and × (adhesion of 0 to 80J). The results obtained are shown in Table 2.

As is clear from Table 2, it can be seen that the use of the ink of the present invention improves the adhesion of the printed area.

[Example 2] In Ink 43, the entire back side was colored with the same ingredients except that 0.5 part by weight of the organic black pigment was changed to 0.05 part by weight of yellow dye or 0.06 part by weight of back color dye. ,j! Partial printing was done using Ink Boiled 3.

As a result, it was found that the adhesive properties were equal to or better than those without printing.

Effect: By using the specific printing ink described in claim 1 on the back side of the photographic support, the printing area of the base paper, the printing ink, the printing ink and the resin is lower than that of the photographic support using conventional ink. A photographic support with improved adhesion to the coating layer could be obtained. According to the second aspect of the present invention, the support coated with the polyethylene resin composition by the Rona discharge treatment was able to obtain stronger adhesion between the ink layer and the resin layer.

In addition, even when the photographic support described in the YT claim is cut into photographic printing paper, the characters, figures, and symbols are not separated, so the meaning to be conveyed can be understood better than before, and it has a preferable appearance. ing. The support described in claim 4 has richer information to be transmitted in the form of characters, figures, and symbols, and the adhesiveness of the printing ink is considerably high, so the quality is not inferior compared to partial printing.

[Brief explanation of the drawing]

1 and 2 are enlarged side sectional views of a photographic support according to the present invention. Figure 3 shows that when the letters, figures, symbols, etc. printed on the back of the photographic support are used as photographic printing paper, even if they are cut with a slitter, etc., the letters, figures, etc. are not printed on the broken line indicating the cutting schedule, so the letters, figures, etc. , is a plan view showing a state in which symbols and the like are not divided. l... Photographic support 2... Back polyethylene resin composition 3... Ink layer 4... Substrate 5 made of water-resistant paper or synthetic resin film... Surface polyethylene resin composition 6... Full-surface colored layer 7...Back coat layer 8...Sub;-to layer 9...Line indicating cutting schedule

Claims (1)

[Scope of Claims] 1) At least a colored pigment and/or dye and an ethylene-acrylic acid copolymer are added to one side (front side) on which the photographic emulsion layer is disposed and the opposite side (back side) to alcohol and ethylene-acrylic acid copolymer. /
Alternatively, a photographic support characterized by using an ink dispersed and dissolved in a fatty acid alkyl ester. 2) A photographic support according to claim 1, wherein said ink is corona discharge treated after being applied to a paper substrate and coated thereon with a polyethylene resin composition. 3) The photographic support according to claim 1 or 2, wherein the display of characters, figures, symbols, etc. using the ink is arranged in advance so as not to be cut during cutting after color development treatment. 4) Claims 1 and 2, wherein the back surface is entirely colored with a density lower than the lowest optical density in the ink-applied area.
, or the photographic support described in 3.