JPH0348502B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a metal-based image forming method. Conventionally, image reproductions suitable for display boards or name labels generally have images printed on a support by screen printing, such as images printed on aluminum vapor-deposited films.
Furthermore, it has been manufactured by applying a protective layer such as varnish over it. In addition, as an image reproduction material suitable for masking materials and electrical wiring boards, a metal layer is placed on a support,
A metal etching protective layer is placed on the area corresponding to the image area by screen printing or exposure and development using a photosensitive resin, and after the metal layer is etched, it can be manufactured as it is or by coating with the protective layer. Ta. However, these methods have problems such as being expensive due to the complicated process, lacking resolution, making it difficult to express minute images, and lacking the durability of the resulting image reproductions. . As a result of intensive research, the present inventors have solved the problems with these image reproductions and manufacturing methods, and have developed a method for producing them on a support. After exposing an image to a metal image-forming material consisting of a thin metal layer and a photosensitive resin layer, a metal and/or metal compound layer corresponding to the image or a reverse image is etched. By doing so, they discovered a method for obtaining a metal image-formed product in which a thin metal layer forming an image is interposed between the support and a photosensitive resin layer that does not have an image, and completed the present invention. . That is, the present invention provides a metallic thin layer that can be etched with an alkaline aqueous solution containing an alkaline earth group metal and a photosensitive resin layer having a diazo group, an azide group, a cinnamoyl group, or an acryloyl group on a support. A metal image forming method for an image-forming material, which comprises exposing a metal-based image-forming material to light and then impregnating it with an alkaline aqueous solution containing an alkaline earth group metal to develop only a thin metal layer. It is. In the present invention, a latent image refers to a photosensitive resin layer that has changed due to reactions such as photopolymerization or photodecomposition upon exposure to light, but no image appears even when developed with the developer used in the present invention, and it cannot be identified with the naked eye. Say something that is in a difficult situation. However, if an appropriate developer is selected, an image can be developed. The metallic image-forming material used in the present invention is:
A support such as glass, acrylic resin board, styrene resin board, glass fiber, plastic board such as reinforced epoxy resin board, polyester film, vinyl chloride film, etc., a thin metal layer on top of it, and a photosensitive resin layer on top of it. This is an essential component layer. The metal thin layer on the support may be any metal as long as it can be etched with an alkaline aqueous solution containing an alkaline earth metal, including aluminum, polonium, iron, magnesium, silicon, titanium,
Metals such as cobalt, copper, indium, iridium, lead, manganese, molybdenum, nickel, palladium, platinum, rhodium, selenium, silver, tantalum, tin, tungsten, vanadium, zinc, zirconium, and alloys and oxides of the above metals,
It is made of metal compounds such as nitrides, borides, carbides, sulfides, and salts, and the metal is preferably aluminum or aluminum-iron alloy, and the metal compound is preferably aluminum oxide. The metal thin layer is vacuum deposited on the support,
sputtering, high frequency ion plating,
It is formed by a conventional method such as plating or laminating. Note that a thin metal layer may be provided on a support such as a film and may be provided by adhering it to a support such as glass or an acrylic resin plate.
Thickness of metal thin layer is 0.005~200μ, especially 0.01~0.1μ
A range of is preferred. The photosensitive resin formed on the metal thin layer is
It is a photosensitive resin that is insoluble in an aqueous solution containing an alkaline earth group metal and has a diazo group, an azide group, a cinnamoyl group, or an acryloyl group.
As the photosensitive resin having a diazo group, the novolak resin naphthoquinone-1,2-diazide-5
Examples include sulfonic acid esters, reaction products of sulfonated phenol resins and N,N-dimethylaminophenyl-p-diazonium salts, and examples of photosensitive resins having azide groups include partially saponified polyvinyl acetate and azidophthalic anhydride. Examples include styrene maleic acid ester of 3-(4-azidophenoxy)ethanol, and styrene maleic acid ester of 3-(4-azidophenoxy)ethanol as photosensitive resins having cinnamoyl groups.
An example is an esterified resin of a maleic anhydride copolymer and an ethylene oxide adduct of cinnamic acid. In addition, the photosensitive resin having the above acryloyl group includes a carboxyl group, a sulfonic acid group, a phosphoric acid group,
Contains a polymer substance containing one or more groups selected from phosphonic acid groups and their salts, a photopolymerizable unsaturated compound, a photopolymerization initiator, a free radical generator, a heat stabilizer, a sensitizer, etc. Examples of polymeric substances having one or more of the above groups include methyl methacrylate/methacrylic acid copolymer;
Styrene/methacrylic acid copolymer, methyl methacrylate/methacrylic acid/2-ethylhexyl acrylate copolymer, sulfonic acid group-containing polyester or polyamide, 2-methyl-2-(N,
Examples of copolymerizable unsaturated compounds include N-dimethylamino)methyl-1,3-propanediol/terephthalic acid copolymer, bis-aminopropylpiverazine/adipic acid/ε-caprolactam copolymer, etc. Monomers such as alkyl acrylates, 2-hydroxyacrylates, aminoalkyl acrylates, ether alkyl acrylates, glycidyl acrylates, halogenated alkyl acrylates, and polyfunctional acrylates, and ethylenically unsaturated groups in the side chains. Examples include partial esterification of styrene/maleic anhydride copolymer with aryl alcohol, glycidyl methacrylate adduct of methyl methacrylate/methacrylic acid copolymer, and photopolymerization initiators include benzoin alkyl ether. , benzophenone, Michler's ketone, anthraquinone and its derivatives, triallylimidazole dimer, etc., and free radical generators include p-aminophenyl ketone compounds, leukotriphenylmethane dyes, cyclic diketone compounds, thioketone compounds, and mercaptan compounds. Examples of heat stabilizers include hydroquinone monomethyl ether and phenothiazine, and examples of sensitizers include dyes such as xanthene, acridikene, dianine, pyrazoline, and coumarin. Furthermore, a colored metal image may be formed by adding actinic ray absorbers such as inorganic pigments such as carbon black, iron oxide, and titanium oxide, as well as organic pigments and dyes to the photosensitive resin. In addition, as active light absorbers, carbon black, iron oxide,
Inorganic pigments such as titanium oxide, organic pigments such as CI Pigment Black 1 (CI50440), 2,2',
benzophenone compounds such as 4,4'-tetrahydroxy-4-methoxy-benzophenone and 4-dodecyloxy-2-hydroxybenzophenone;
Luxor First Black L (CI17),
Examples include dyes such as CI Disperse Black (CI11255). Note that these photosensitive resin layers are formed on a thin metal layer.
It can be produced by coating, spraying, laminating, etc. An actinic ray absorbing layer comprising an adhesive resin, an actinic ray absorbing agent and/or a coloring agent may be provided between the metal thin layer and the photosensitive resin layer. Furthermore, the metallic image-forming material may include an adhesive layer between each layer, an adhesive layer on the photosensitive resin layer, and an adhesive layer on the photosensitive resin layer, if necessary.
A release layer, cover film, protective layer, etc. may be provided. The thickness of the photosensitive resin layer is usually 0.5 to 100 microns, particularly preferably 1 to 50 microns. The above metal image-forming materials are exposed to light from various light sources such as mercury lamps, carbon arc lamps, metal halide lamps, and xenon lamps, and then developed. The developer used in the method of the present invention is preferably an aqueous solution of hydroxides of alkaline earth metals such as magnesium, calcium, and barium; some compounds, such as barium hydroxide, have good effects when used alone, but usually It is preferable to contain an alkali metal compound in order to increase the etching rate of the thin metal layer. In this case, the atomic ratio of the alkali metal atoms to the alkaline earth group metal atoms is usually 10 times or less, preferably 5 times or less, and more preferably 1 time or less. When using the above aqueous solution as a developer, an appropriate alkaline strength is selected depending on the composition of the thin metal layer, taking into account the development speed and etching shape, but usually the pH is 8 to 14, preferably 11 to 14. In good condition. Inorganic salts exhibiting alkalinity such as sodium aluminate and calcium hypochlorite, oxidizing agents, or other metal salts such as iron, aluminum, and copper can also be added to this treatment liquid. Next, the process of forming a metallic image formed product obtained by the method of the present invention will be explained using the drawings. FIG. 1 is a sectional view of the metallic image-forming material used in the present invention, which is composed of a support 1, a metallic thin layer 2, and a negative-positive type photosensitive resin layer 3. First, when the material is exposed to light, it becomes as shown in the cross-sectional view of FIG. 2, and the photosensitive resin layer 4 in the exposed area undergoes a photoreaction.
Next, when this is developed with the developer, it becomes as shown in the cross-sectional view of FIG. In other words, the photosensitive resin layer 5 in the unexposed area does not dissolve but swells and allows the developer to pass through.
The underlying thin metal layer 6 is etched. On the other hand, since the photosensitive resin layer 4 in the exposed area does not swell and does not allow the developer to pass through, only the underlying thin metal layer 7 remains with an image formed thereon. EXAMPLES The present invention will be described in more detail with reference to Examples below. Reference Example 1 After cleaning and drying the surface of a biaxially stretched polyethylene terephthalate film with a thickness of 100μ, aluminum was vapor-deposited to a thickness of 0.05μ under a vacuum on the order of 10 ^-5 Torr using a resistance heating type vacuum evaporator.
This aluminum vapor-deposited polyester film is used as DENSITOMETER DM- manufactured by Dainippon Screen Co., Ltd.
256, the optical density was 2.4. Next, solutions of photosensitive resins having the compositions shown in Table 1 were prepared, and each solution was coated onto the aluminum-deposited polyester film to a thickness of 3 μm using a reverse coater. Further, this photosensitive resin was coated with the composition solution shown in Table 2 using a reverse coater, and the colored metallic image-forming materials of Samples 1 and 2 and the metallic image-forming materials were coated with the composition solution shown in Table 2 using a reverse coater. It was created. Sample 1 had a black surface and a metallic luster from vapor-deposited aluminum on the back surface.

【table】

【table】

[Table] Example 1 The colored metallic image-forming material of Sample 1 obtained in Reference Example 1 was heated using an ultra-high pressure mercury lamp (3K.W., 70
cm) for 8 seconds each, washed with water, and then immersed in an aqueous solution of 40 g of barium hydroxide at 38°C. After being immersed for about 1 minute and 30 seconds, it was washed with water and dried. When this colored metallic image formed product was viewed from the polyester film side, a name label with the same image as the original image was obtained. Moreover, the resolution was good and the edges were sharp. Example 2 The metallic image-forming material of Sample 2 obtained in Reference Example 1 was exposed to an ultra-high pressure mercury lamp (3K.W., 70cm) for 8 seconds each using a negative film on which a figure consisting of lines was drawn. After exposure and washing with water, immerse for about 3 minutes in a solution of 500ml of a saturated solution of calcium hydroxide, 0.8g of sodium hydroxide, 0.5g of sodium chlorite, and 0.8g of trisodium phosphate at 30°C, then wash with water and dry. did. The obtained metal-based image formed product consisted of a light-shielding layer made of vapor-deposited aluminum and a light-transmitting layer without vapor-deposited aluminum, and could be used as a second original image for copying. This metallic image-formed material had good resolution and good edge sharpness.

[Brief explanation of drawings]

Figure 1 is a cross-sectional view of the metallic image-forming material used in the present invention, Figure 2 is a cross-sectional view of the material shown in Figure 1 after exposure, and Figure 3 is the developed material shown in Figure 2. FIG. 3 shows a cross-sectional view of the metal-based image-formed product of the present invention after the treatment. 1: Support, 2: Metal-based thin layer, 3: Photosensitive resin layer, 4: Exposed area of photosensitive resin layer, 5: Unexposed area of photosensitive resin layer, 6: Unexposed area of metal-based thin layer , 7:
Exposed area of thin metal layer.

Claims (1)

[Claims] 1. A metal-based image-forming material provided on a support with a metal-based thin layer that can be etched with an alkaline aqueous solution containing an alkaline earth group metal and a photosensitive resin layer having a diazo group, an azide group, a cinnamoyl group, or an acryloyl group. In the metal image forming method of
A method for forming a metal image, which comprises exposing a metal image-forming material to light and then impregnating it in an alkaline aqueous solution containing an alkaline earth group metal to develop only a thin metal layer.