JPS5941573B2 - laminated material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a laminated material, more specifically, it has a metal or metal compound layer provided with a protective layer using a base solvent,
The present invention relates to a laminated material characterized in that a photosensitive recording layer is provided on the surface of a support.

Almost all polymer supports used in photosensitive materials have a surface resistivity of 10 13 Ω or more at room temperature and humidity. However, with a support that has a surface resistivity of 10"3Ω or more at room temperature and humidity, various problems occur during the manufacturing process or when using it as a photographic film. For example, in the past, contact wear caused Accumulated static charges that occur, such as adhesion of dust, ignition of flammable materials due to spark discharge, and static marks (in photographic film, when the accumulated charges are discharged, the film surface is exposed to light, and when developed, it becomes dotted or dendritic). Various troubles such as static marks (which are called static marks) cannot be avoided.As methods for preventing static electricity on polymeric materials that cause these various permanent marks, for example, conventional methods (1) ) A kneading type in which an antistatic agent is mixed into the polymeric substance in advance (2) A coating type in which the antistatic agent is applied onto the polymeric substance, (2)
There are two ways.

However, each of these methods has some drawbacks.
For example, in the kneading method, the antistatic agent must be mixed in a large amount to be ineffective or ineffective, and in the coating method, it is essential to use an organic solvent that dissolves or swells the support. Thereafter, there were problems in that drying at high temperatures impairs the flatness of the support and caused pollution in the treatment of waste solvents, exhaust gases, and the like. In addition, when using an organic antistatic agent such as an alkyl sulfonate or a quaternary ammonium salt, the surface resistivity is highly dependent on humidity, and when the humidity is low, adsorption of water increases due to drying. The drawback was that the surface resistivity was extremely high due to the release of ions, and the antistatic function was lost.

Products using metal compounds use organic solvents during coating or kneading, so they always pose the above-mentioned pollution problem due to waste solvents. In addition, since all of these have a layer formed by dispersing metal compound particles, they have poor conductivity unless the amount of coating or kneading is increased.
The antistatic effect deteriorates. In addition, since the particles were dispersed, there were problems such as poor transparency.

Both those using the coating method and those using the kneading method have various drawbacks. By the way, methods that do not have these drawbacks have recently been developed, although in different fields, methods of forming metals and metal compounds as a thin, uniform continuous phase without using solvents, especially methods for forming metals and metal compounds such as metal oxides and alloys. There is a so-called vacuum evaporation method in which the material is deposited on a support under vacuum. As an antistatic method using a deposited layer formed by a vacuum deposition method, for example, there is a method in which a metal is deposited to prevent charging of an electron beam recording material.

(If necessary, refer to British Patent No. 1,340,403, US Pat. No. 3,336,596, etc.) Recently, attempts have been made to use such a vapor deposition method as an antistatic method for photographic recording materials. One method of using these vapor deposition methods as a photographic recording material is to provide a metal or metal compound vapor deposited layer between the photographic emulsion layer and the support. (For example, JP-A-49-51930) However, in these methods, the adhesion between the metal or metal compound vapor-deposited layer and the photographic emulsion layer is not sufficient. That is, it has the disadvantage that the emulsion layer peels off during wet processing such as development, fixing, and water washing, which are generally carried out as photographic processing. In order to overcome these drawbacks, a method has been developed in which a conductive layer with a protective layer made of an inorganic material is provided on one side of the support, and an undercoat layer and an emulsion layer are provided on the opposite side. However, the protective layer of the conductive layer used here is obtained by vacuum evaporation using a metal halide.

Therefore, the cost becomes even more expensive. In addition, before development, the conductive layer is oxidized over time and has the function of preventing an increase in surface resistivity, but after development, the conductive layer is oxidized and the surface resistance increases. It had drawbacks. Moreover, since this protective layer is a metal halide, it becomes opaque when the thickness of the deposited film is increased. Therefore, the actual film thickness is 500λ or less. However, such thin films do not have sufficient chemical and physical strength. That is, chemically, it is extremely permeable to acids, alkalis, etc. and deteriorates the deposited layer. Physically, the protective layer tends to come off due to friction, etc., and since it does not protect the deposited layer, it has the disadvantage of increasing surface resistivity. Taking into consideration the above-mentioned circumstances, the present inventor conducted research on a method of providing a protective layer on a vapor-deposited layer, particularly by coating rather than vapor deposition, and as a result, discovered a new and effective protective layer composition and developed the present invention. It was perfect for eggplant.

That is, the object of the present invention is first to provide a laminated material that is extremely inexpensive in terms of cost by providing a protective layer consisting of an organic layer by a coating method. Second aspect of the present invention
provides a method for manufacturing a laminated material that uses a coating method and can therefore be applied at a higher speed than the vapor deposition method. Third
provides a highly transparent protective layer composition. The fourth objective is to provide a protective layer composition that has excellent abrasion resistance. A fifth object is to provide a protective layer composition that prevents oxidation of a metal or metal compound layer. A sixth object is to provide a protective layer composition that only slightly reduces the conductivity of the metal or metal compound deposited layer. The seventh is chemical (
This provides a physically stable protective layer composition (with respect to acids and alkalis).

The eighth object is to provide a protective layer composition that has excellent adhesion to the vapor deposited layer. No. 9, water-based coating is possible.
There is no problem of pollution caused by solvent exhaust. The above object of the present invention is to prevent oxidation, wear resistance, and improve development, fixing, water washing, etc. of the vapor deposited layer by directly coating the acrylate latex containing a carboxyl group on the metal or metal compound layer. It has been found that photographic processing can also provide a protective layer that protects the metal-containing deposited layer and does not reduce conductivity. What is particularly important to emphasize in the present invention is that the composition has a thickness of 100λ to 1μ, preferably 1000λ to
It is to be provided within a range of 7000λ.

In addition, when the surface resistivity of the vapor deposited layer is in the range of 102 to 104 Ω, the apparent surface resistivity from above the protective layer is in the range of 103 to 106 Ω, regardless of temperature and humidity, and its value is determined by photographic processing. It does not change due to friction, air oxidation, etc. Therefore, the above-mentioned protective layer can be satisfactorily applied as a protective layer for an antistatic layer of a photographic recording material. The carboxyl group-containing acrylate copolymer used in the present invention has about 15 carboxyl group-containing units.
An acrylate copolymer containing % by weight or less.

Particularly preferred is a latex form from the viewpoint of ease of handling. For example, a monomer having a carboxyl group is a monomer copolymerized with one or more addition-polymerizable monomers such as acrylic acid, methacrylic acid, itaconic acid, acryloxypropionic acid, or maleic anhydride. It is something.

Examples of monomers used in copolymerization include acrylic esters, methacrylic esters, acrylic amide,
Methacrylic acid amide, vinyl ethers (e.g. methyl vinyl ether, vinyl butyl ether) vinyl esters (e.g. vinyl acetate, vinyl propionate) styrenes, α-β unsulfated nitrile, N-vinyl compounds (e.g. vinyl carbazole), etc. Monomers are used.

For example, acrylic esters include ethyl acrylate,
Propyl acrylate, butyl acrylate, amyl acrylate, ethylhexyl acrylate, octyl acrylate, t-octyl acrylate, 2-methoxyethyl acrylate, 2-butoxyethyl acrylate, 2-phenoxyethyl acrylate, chloroethyl acrylate , hydroxyethyl acrylate, cyanoethyl acrylate, hydroxypropyl acrylate, dimethylaminoethyl acrylate, 2,2-dimethylhydroxypropyl acrylate, 5-hydroxypentyl acrylate, diethylene glycol monoacrylate, trimethylolpropane monoacrylate, pentaerythritol monoacrylate, glycidyl acrylate, 2
-Hydroxy-3-chloropropyl acrylate, benzyl acrylate, methoxybenzyl acrylate, furfuryl acrylate, tetrahydrofurfuryl acrylate, phenyl acrylate, etc. Examples of methacrylic acid esters include methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, amyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, octyl methacrylate, sulfopropyl methacrylate, N
-ethyl-N-phenylaminoethyl methacrylate,
ethylene glycol monomethacrylate, 2-hydroxyethyl methacrylate, etc.), styrenes include styrene, methylstyrene, chlorostyrene, methoxystyrene, dimethylstyrene, etc. The α/β-unsaturated nitrile can be selected from acryloytrile, methacrylonitrile, and the like.

Among these, various combinations are selected depending on the purpose, for example, those containing 0.8 to about 15%, especially 2 to 8%, by weight of carboxyl-containing monomers, acrylic esters or methacrylates. Conveniently, the selection ranges from about 40 to 95% acid esters, from 0 to about 50% styrenes, and from O to about 50% unsaturated nitrites.

Among acrylates, those containing 70% or more of methyl acrylate have high film hardness, and as a result, have particularly excellent abrasion resistance, scratch resistance, chemical resistance (acid, alkali), and transparency. However, when it exceeds 95%, the adhesion with the vapor deposited layer decreases, and as a result, the above-mentioned resistance tends to decrease.

In addition, when forming a copolymer, up to about 10% of acrylamide, N-methylolacrylamide, glycidyl methacrylate, hydroxymethylated diacetone acrylamide, etc. can be included as a crosslinking agent. In the synthesis of these copolymers, the well-known emulsion polymerization method is particularly advantageously used. In addition, melamine-formaldehyde resin or the like may be used as a crosslinkable polymer. The amount added is preferably within 10% relative to methyl methacrylate, for example.

If it is used in excess of this amount, not only does the adhesion to the deposited film deteriorate, but also the coating drying rate tends to decrease because a long reaction time is required.

Water is used as a solvent in the present invention.

In addition, various additives can be added to the coating liquid of the present invention as desired. Such additives include plasticizers such as phosphate esters (such as tributyl phosphate), phthalates (such as dibutyl phthalate), coating aids such as small amounts of alcohols (such as methyl alcohol, ethyl alcohol, etc.), and other coating agents. The liquid may contain thickening agents such as microsilica, aluminum stearate, organic bentonite, orbentalc. It goes without saying that these additives are generally added by technical means known in the art.

In general, the method of manufacturing the coating liquid of the present invention is not particularly limited, and any manufacturing method commonly known in the art can be used. As a method for applying the coating liquid, a general coating machine, a gravure printing machine, etc. are preferable from the viewpoint of coating accuracy. Photographic light-sensitive materials used in the present invention include silver salt emulsions, diazo, photosensitive polymers, etc. For details on coating amounts, usage, processing methods, etc., please refer to Kikuchi Photo Chemistry, Kyoritsu Shuppan 1.
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It is described in detail in NewYOrk etc. Supports used in the present invention include cellulose esters such as cellulose nitrate and cellulose acetate; poly(vinyl acetal) polymers, polycarbonates, polyesters, and difunctional polyoxy organic compounds such as polyoxyalcohols. Linear polyester polymers of difunctional, saturated and unsaturated, aliphatic and aromatic dicarboxylic acids condensed with, for example alkylene glycols and/or glycerol with terephthalic acid, isophthalic acid, adipic acid, maleic acid, fumaric acid. polyesters of acids and/or azelaic acids; polyhydrocarbons, such as polyvinyl chloride; and hydrocarbon polymers, such as polystyrene and polyolefins, especially 2 carbon atoms.
Included are polymers of olefins having ~20 olefins. The above polymers may be utilized in the form of flexible films or other single insulating supports, or as coatings on glass, paper, and polymeric insulating supports. Preferred among the coated supports are:
A paper support coated with an α-olefin resin, such as a paper support coated with polyethylene, polypropylene, ethylene-butene copolymer, or the like. Hydrophilic colloid (
When the surface of the support to be coated (e.g. with a photographic emulsion) is hydrophobic, an activation treatment is usually used to improve the adhesion of the hydrophilic colloid film to the hydrophobic surface.
5 or coat with a subbing layer. Polyester film supports, such as polyethylene terephthalate supports, are typically made from terpolymers selected from acrylate lower (C4 or less) alkyl esters, vinylidene halides, acrylic acids, and acrylonitriles, such as vinylidene chloride, acrylic acids, and acrylonitriles. or a terpolymer of methyl acrylate. However, a metal-containing layer can be deposited on the undercoat layer as described above. Alternatively, it can be deposited directly onto the hydrophobic surface of the polymer film. This is because the metals and metal compounds that can be used to form the conductive layer firmly adhere to the surface of the support as described above. The layers described above may be deposited on the support using techniques well understood by those skilled in the art. Specific substances used in the vacuum-deposited layer in the present invention include, for example, aluminum, antimony, arsenic, boron, cadmium, chromium, germanium,
Iron, magnesium, silicon, titanium, cobalt, copper, gold, indium, iridium, lead, manganese, molybdenum, nickel, palladium, platinum, rhodium, selenium, silver, thallium, tellurium, tin, tungsten, vanadium, zinc, zirconium, etc. and alloys thereof, oxides, nitrides, borides, iodides, carbonides, sulfides, salts, compounds of metals, etc. Among these, particularly preferred in the present invention are gold and palladium. , titanium oxide, indium oxide, tin oxide, vanadium oxide, zirconium oxide, etc., but of course the layer is not limited to these. The thickness of the metal or metal compound layer is between 30λ and 2000λ. Furthermore, various known methods can be used as the vacuum deposition method. Since the coating composition of the present invention is water-dispersible, there is no problem of pollution caused by exhaust gas and no risk of explosion.

Moreover, the working environment is good, and the equipment is simple and inexpensive. The coating composition of the present invention causes no irritation to the human skin layer and provides sufficient adhesive strength to the vapor deposited layer without using an etching agent. Furthermore, the coating process using the coating liquid of the present invention has a wide latitude with respect to its drying temperature, which is a very great advantage in industry, especially in high-temperature coating operations. The protective layer obtained using the coating composition of the present invention has extremely high hardness, and even a thin layer of about 1000λ to 7000λ will not be damaged by mechanical friction during base transportation or during the process. It has the function of maintaining the conductivity of the deposited layer. Furthermore, the protective layer does not peel off even when subjected to oxidation prevention using air, etc., or general photographic processing such as development, washing, fixing, etc., and has excellent chemical stability and adhesion to the vapor deposited layer. The present invention provides a protective layer that does not reduce the conductivity of the deposited layer.

Furthermore, the coating composition of the present invention has excellent coexistence and stability over time.

The coating liquid composition of the present invention is generally used as follows. That is, it is applied directly onto the metal or metal compound layer provided on the back side of the support, adjusted to the required amount using a roll, squeeze roll, or air knife, dried in a drying section, and wound up. The drying temperature at this time is 80°C to 160°C, preferably 10°C to 140°C, and the drying time is 30 seconds to 10 minutes. From the viewpoint of performance and cost, it is preferably about 2 to 5 minutes. The evaluation items and evaluation methods performed in the following examples are as follows.

1. Scratch hardness test method for paint film (diamond needle) Using a Clemens type scratch hardness tester (manufactured by Toyo Seiki), a load was applied to the diamond needle (diameter 0.05~) and the sample was moved at a constant speed. The coating layer, which is the test surface, is scratched, and the point at which scratches begin to be observed is observed, and the applied load at that time is used to evaluate the scratch hardness of the coating film.

Next, a synthesis example of the copolymer of the present invention will be given.

800 CC of sodium lauryl sulfate of Synthesis Example 2.57
of water and heated to 80°C in a flask equipped with a stirrer.

Add 1.277 parts of K2S2O8 to it, add 5 parts of ethyl acrylate, 90 parts of methyl methacrylate, and 5 parts of acrylic acid for about 30 minutes and mix. At the same time, 2.57 ml of sodium lauryl sulfate diluted in 200 cc of water is added. After the addition, the mixture is further reacted at 80 to 82°C for 15 minutes. Thereafter, it is cooled to room temperature and the water sol containing only a small amount of coagulated material is passed through the mouth. At this time, the pH of the liquid is 2.9. Next, this sol was adjusted to pH 6 with diluted ammonia water. A good latex was obtained by adjusting the amount of O and further removing the coagulated material. Several examples are shown below, but all quantitative relationships in the following specific examples represent parts by weight.Example An indium oxide layer was vapor-deposited to a thickness of 600A on a 164μ polyester film.

The surface resistivity at that time was 6.0×10 2 Ω. Next, a coating solution prepared by adding 100 parts of water to 10 parts of latex (solid content 40%) consisting of methyl methacrylate/ethyl acrylate/acrylic acid (molar ratio 90/5/5) was applied using a wire bar. and dried at 120°C for 3 minutes.

Claims (1)

[Claims] 1. A laminate characterized by having a metal or metal compound layer provided with a protective layer made of an acrylate copolymer containing a carpoxyl group on the surface of the support, and a photosensitive recording layer provided on the surface of the support. material.