JPH0542660B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a photosensitive image forming material, and particularly to a photosensitive image forming material preferably used for decorative purposes.

The present inventor filed a patent application in 1983 for a method for producing a mask plate for plate making by subjecting a photosensitive material, which is formed by sequentially providing a metal thin film layer and a photosensitive layer on a support, to photo-processing.
It has been filed as No. 49341. Briefly, this method involves printing a negative or positive original onto a photosensitive material, and then forming a mask layer (photosensitive layer) on the photosensitive material.
When development or development and etching are performed according to the requirements, a relief image corresponding to the original is formed on the metal thin film layer of the photosensitive material.

Then, when the relief image is peeled off from the support with a needle, knife, etc., the metal thin film layer is also peeled off along with the photosensitive layer, and a transparent portion is revealed.

For partial correction, the metal thin film layer can be removed as desired by lightly rubbing the developed metal thin film surface with a solution that selectively dissolves the subbing layer provided between the support and the metal thin film layer. It can be removed to obtain a transparent part.

Although this plate-making material has such noteworthy characteristics, when used as a decorative material, it has the drawback that the decorativeness is extremely poor because the color of the photosensitive layer is monochromatic.

The present invention has been developed in view of these difficulties, and is characterized by the following: sequentially forming a subbing layer on a support;
A metal thin film layer and a photosensitive layer are formed, and the photosensitive layer has a stronger adhesive force with the metal thin film layer than at least one of the adhesive force between the support and the subbing layer and the adhesive force between the subbing layer and the metal thin film. It is colored and has peelable film properties, and when the relief image is peeled off, the underlying metal thin film layer is peeled off in the same shape to form the necessary image, and the metal corresponds to the lines on which letters, etc. are drawn. The thin film layer always remains on the support, and the photosensitive layer can be colored in a desired color, thereby making it possible to obtain a richly decorative image.

Furthermore, by adding a desired color to the transparent part where the photosensitive layer is peeled off and the transparent part where the metal thin film layer is removed, a polychromatic decorative photosensitive material that utilizes the metal thin film in one image is created. I was able to get

The present invention will be explained in detail below.

In the decorative photosensitive material of the present invention, as shown in FIG. 1, a subbing layer 19 and a metal thin film layer 10 are sequentially formed on a support 9, and a strong film is formed on the thin film layer 10, which firmly adheres thereto. The photosensitive layer 11 is formed by forming a photosensitive layer 11 that has a specific color and is colored in a desired color.

As the support 9 used in the present invention, a film or plate of a thermoplastic polymer compound having a smooth surface and on which a thin metal film can be provided is used. Examples include polyester, polycarbonate, polyamide, polypropylene, polyvinyl chloride, polystyrene, polymethyl methacrylate and copolymers thereof, diacetyl cellulose, triacetyl cellulose, propyl cellulose and mixed cellulose esters.

The subbing layer 19 is preferably a substance that is dissolved in a solution that can penetrate the metal thin film layer 10, and is preferably a substance that firmly adheres to the support 9 and forms a smooth (transparent) coating film. The thickness of the undercoat layer 19 is 2μ
The following are preferred. If it exceeds this range, side etching will be formed when it is melted, resulting in a decrease in resolution. Various organic and inorganic substances can be used.

Examples of the subbing layer 19 include polyvinyl acetate, polyvinyl butyral, polyvinyl formal, polyvinyl alcohol, polyvinyl chloride, polyvinyline chloride, polyvinyl fluoride, vinyl chloride-vinyl acetate copolymer, vinyl chloride-vinylidene chloride copolymer, Vinyl chloride-vinylacetate-(maleic anhydride, acrylonitrile or vinyl alcohol) terpolymer, vinyl chloride-vinylidene chloride-(acrylonitrile, vinyl acetate or methyl methacrylate) copolymer, acrylic ester-(methyl methacrylate) or styrene)
Copolymers, linear thermoplastic polyesters or copolyesters such as polyethylene terephthalate or polyethylene terephthalate isophthalate, alcohol-soluble polyamides, polyurethanes, acetylcellulose, acetylbutylcellulose, nitrocellulose, ethylcellulose, acetylpropylcellulose, chlorinated polyolefins, fluorine There are rubber, silicone surfactants, fluorine surfactants, and silane coupling agents.

These substances adhere to either the support or the metal thin film when the photosensitive layer 11 is peeled off due to the combination of the adjacent support and the metal thin film.

The solution that can penetrate the thin film layer 10 and dissolve the subbing layer 19 is one that does not dissolve the photosensitive layer 11, the metal thin film layer 10, and the support 9, such as water, a dilute acidic or dilute alkali aqueous solution, or alcohol. The solvent is selected from one or more organic solvents including organic solvents, ketone-based, ester-based, hydrocarbon-based, halogenated hydrocarbon-based, and derivatives thereof.

Any metal can be used to form the metal thin film layer 10 as long as it can form a thin film by various film forming means. The thickness of the metal thin film layer is at least 20m
It is desirable that there be μ. Below this range, the reflective effect is poor for decorative purposes. Regarding the upper limit of film thickness,
It is preferably 1000 mμ or less. If it exceeds this range, the resolution of the image will decrease and the finish of the image will be poor if it is partially peeled off according to the present invention.

As a film forming method, a vacuum evaporation method, an ion plating method, a sputtering method, an electroless plating method, an electrolytic plating method, or a combination of these methods are employed. Aluminum, zinc, gold, silver, nickel, copper, indium,
Titanium, cobalt, etc. can be obtained, and various alloys and various compounds such as TcN, CuZn, ITO, Ni-Cr, and AlN can be formed into films by sputtering, ion plating, etc.

In the electroless plating method, copper, nickel, cobalt, gold, palladium, silver, nickel-cobalt alloy, etc. can be used by any known method.

Since the photosensitive layer 11 colored in a desired color is peeled off after being formed into a relief image through photographic processing, it is necessary to have good film forming properties and appropriate film strength. Furthermore, since the underlying metal thin film is simultaneously removed from the support by peeling, it is necessary to have a stronger adhesive force with the metal thin film than the adhesive force at the interface with other layers.

The photosensitive layer may be formed of a single layer of a photosensitive composition consisting of a polymer compound for a binder, a photosensitizer, and a colorant, with a layer of a polymer compound containing a colorant and having film properties as a lower layer, and a layer of the photosensitive composition. It is also possible to have a two-type structure in which the above layer is laminated on the upper layer. In addition, in the case of a two-layer structure,
A coloring agent may be added to the photosensitive composition layer.

Both negative type and positive type photosensitive compositions can be used.

Examples of photosensitizers used in negative photosensitive compositions include condensates of 4-diazodiphenylamine sulfate and formaldehyde, condensates of 4-diazodiphenylamine zinc chloride and formaldehyde, and 4-diazodiphenylamine sulfate and formaldehyde. There are condensates of enylamine tetrafluoroborate and formaldehyde, and formaldehyde condensates of 4-diazodiphenylamine dodecylbenzenesulfonate. When the photosensitive layer is formed of a single layer of the photosensitive composition, the content of the photosensitizer to the binder polymer compound is 3 to 50%,
It is preferably 3 to 30%.

Examples of binder polymer compounds used in negative photosensitive compositions include polyvinyl alcohol, polyacrylamide, polyvinylpyrrolidone, polyvinyl methacrylate and maleic acid copolymers, alcohol-soluble polyamides, acrylamide and diacetone acrylamide copolymers,
There is partially saponified vinyl acetate. These polymer compounds can be used alone or in combination of two or more.

Examples of photosensitizers for positive photosensitive compositions include orthoquinone diazide compounds. In this case, when the photosensitive layer is formed of a single layer of the photosensitive composition, the content of the photosensitizer to the polymer compound for the binder is 5 to 5.
50%, preferably 10-30%.

Examples of polymeric compounds for use as a binder for photosensitive compositions include alkali-soluble acrylic copolymers, polyvinyl-3-methoxy-4-hydroxybenzal, polyvinyl formal, polyvinyl butyral, and polyvinyl acetate. The molecular compounds can be used alone or in combination of two or more.

In addition to the above-mentioned binder polymer compound used for forming the photosensitive composition layer, tough polymer compounds that cannot be used therein can also be used for the two-layer structure film layer. Examples include caprolactam,
Alcohol-soluble polyamides include copolymers of hexamethylene diamine adipate and 4,4'diaminodicyclohexylmethane adipate, and N-methylol derivatives of various polyamides.

Examples of dyes added to the photosensitive layer include CI 11020 for yellow, CI 18736A for orange,
CI 26110 as Red, CI as Violet
61100, CI as Blue 61525, as Green
CI 61565, CI 12020 for brown, CI 50415 for black.

Next, the production of decorative materials using such photosensitive materials will be described.

A decorative photosensitive material 12 (see FIG. 1) in which a subbing layer 19, a metal thin film layer 10, and a colored photosensitive layer 11 are sequentially formed on a support 9 is coated with a negative or positive coating as shown in FIG. 2a. When the originals 13 are overlapped and exposed to actinic rays and developed, the exposed portion or the least exposed portion is eluted depending on the type of the photosensitive layer 11.
For example, as shown in the figure, a negatively colored relief image 16 is formed in which grooves 15 correspond to lines 14 on original 13. In this case, photosensitive layer 1
1 is a film layer of a polymer compound and 2 is a photosensitive composition layer.
When it consists of layers, in addition to the development of the photosensitive composition layer, the film layer of the polymer compound requires etching treatment.

Then, as shown in FIG. 2b, another photosensitive layer portion 16' is formed.
When the relief image 16 is peeled off leaving behind, the underlying metal thin film layer 10 is also peeled off in the same shape as the relief image, and the necessary image is obtained as the recess 17 in the area without the metal thin film layer.

Here, the portion 15' of the metal thin film layer corresponding to the line 14 of the original 13 is not peeled off and remains on the subbing layer 19 and thus on the support 9, since there is no relief image 16 thereon.

In addition, as shown in FIG.
If the area is rubbed, the metal thin film is penetrated and the subbing layer is dissolved, so the metal thin film layer 10 is removed and a transparent groove 20 is obtained.

According to the present invention, the metal thin film layer provides decorative and light-shielding properties, and at the same time, dyes or pigments are added to the photosensitive composition to form a color relief image, thereby further improving the decorative effect. I can do it.

A light-colored photosensitive layer is laminated on top of the metal thin film layer to create a metallic color effect, and as described above, the areas where the metal thin film layer has been removed and the relief image area of the photosensitive layer have been peeled off are further coated. You can also add any desired color.

Examples in which the photosensitive material of the present invention is used for decorative purposes will be described below.

Example 1 10 g of fully saponified polyvinyl alcohol with an average degree of polymerization of 1700, 0.06 g of methylene blue, and 0.5 g of a condensate of 4-diazodiphenylamine sulfate and formaldehyde were dissolved in 89.5 ml of water to reduce the solid content.
A 10.5% photosensitive composition solution was prepared.

In addition, a toluene solution of chlorinated polyethylene (trade name: Elasrene, manufactured by Showa Denko) was coated on one side of a 100μ thick polyethylene terephthalate film and dried to obtain a subbing layer with a thickness of 0.1μ, and then aluminum was vacuum evaporated to obtain a film thickness of 0.1μ. A 100 mμ aluminum thin film layer was formed.

Next, apply the above photosensitive composition solution on the aluminum thin film layer in an amount such that the film thickness after drying is 10μ.
After coating using a wire bar, it was dried at 90° C. for 3 minutes to form a photosensitive layer to obtain a blue image forming material.

A positive manuscript with lines was placed in close contact with the blue photosensitive layer and irradiated with light for 50 seconds from a 2kw high-pressure mercury lamp located 1m away. When this film was developed under running water, a negative blue relief image faithful to the original was obtained on the aluminum thin film layer.

By selectively peeling off the blue relief image with a needle or the like, the aluminum thin film layer is peeled off in the same shape as the peeled blue relief image, resulting in three parts: the blue relief image part, the aluminum thin film layer part, and the transparent part. A decorative material consisting of two parts was obtained. Furthermore, when a wire rod soaked in toluene solution was used to scratch the desired part of the aluminum thin film layer, this part could be easily and quickly removed and the desired color could be added.

Example 2 Acrylamide-diacetone acrylamide copolymer with an average degree of polymerization of 700 (copolymerization ratio 6:4) 10
g, methylred 0.05g, 4-diazodiphenylamine zinc chloride salt and formaldehyde condensate
0.7 g was dissolved in 89.3 ml of water to prepare a red photosensitive composition solution with a solid content of 10.7%.

In addition, a methyl ethyl ketone solution of fluorocarbon rubber (trade name: Perflon, manufactured by Kinyosha Co., Ltd.) was applied and dried on one side of a polyethylene terephthalate film with a thickness of 100 μm to obtain an undercoat layer with a thickness of 0.2 μm. Coating was carried out at a pressure of 5 x 10 Torr to form a copper thin film layer with a thickness of 100 mμ.

The red photosensitive composition solution was applied onto the copper thin film using a wire bar in an amount such that the film thickness after drying would be 10 μm, and then dried at 90° C. for 3 minutes to obtain a red image forming material. .

When this image forming material was exposed and developed according to Example 1, a negative red relief image faithful to the original was obtained on the copper thin film. When the red relief image was partially peeled off, a transparent part was obtained, which could be partially corrected using methyl ethyl ketone in the same manner as in Example 1, and could be used as a desired decorative material.

Example 3 10 g of polyvinyl formal resin with a formal content of 8%, acetate content of 9 to 13%, and alcohol content of 5 to 6.5%, Neozapon Black RE 0.1 g and 1,
3 g of novolaque ester of 2-naphthoquinone diazide (2)-4-sulfonic acid was dissolved in 20 g of ethylene glycol monoethyl ether, 10 g of methanol, and 57 g of toluene to prepare a black photosensitive composition solution with a solid content of 13%. did.

In addition, a methyl ethyl ketone solution of linear polyester resin (product name: Vylon 200 manufactured by Toyobo Co., Ltd.) was coated on one side of a polyethylene terephthalate film with a thickness of 100 μm and dried to obtain a subbing layer with a thickness of 0.1 μm. After that, aluminum was vacuum evaporated to form a film. An aluminum thin film layer with a thickness of 100 mμ was formed.

Apply the above black photosensitive composition solution on the aluminum thin film layer in an amount such that the film thickness after drying is 5μ,
After coating using a wire bar, the coating was dried at 90° C. for 3 minutes to obtain a black image forming material.

A negative original was brought into close contact with the black photosensitive layer and exposed to light using the light source of Example 1 for 50 seconds.

Next, a developing solution was prepared by dissolving 300 g of sodium salicylate and 10 g of sodium hydroxide in 700 ml of water, and the exposed film was immersed and developed for about 5 minutes.

The film obtained by washing with water and drying has a black negative image faithful to the original formed on the aluminum thin film, and can be selectively peeled off as in Examples 1 and 2. The aluminum thin film could be easily partially modified and used as a desired decorative material.

As is clear from the above examples, the photosensitive material of the present invention is produced by coating a subbing layer on a support, then forming a metal thin film layer on top of the subbing layer, and firmly bonding the thin film layer with the subbing layer. The color relief image formed by applying a colored photosensitive layer that adheres to the surface and has film properties and is peeled off by selectively peeling off the color relief image of the photosensitive layer formed by photographic processing. The metal thin film layer can be peeled off in the same shape, allowing this area to be replaced with another color. In addition, parts of the metal thin film layer corresponding to the lines of the original are left on the support to have decorative properties, and this metal thin film layer can be removed using an appropriate solution to create images of other colors. An excellent decorative material has been obtained in which it is possible to incorporate a variety of materials, and partial corrections can be made extremely easily and quickly.

[Brief explanation of the drawing]

FIG. 1 is a cross-sectional view showing the photosensitive image forming material of the present invention, and FIGS. 2 a, b, and 3 illustrate the creation of a decorative relief image using the photosensitive image forming material of the present invention. FIG. 9...Support, 10...Metal thin film layer, 11...
Photosensitive layer, 19... subbing layer.

Claims (1)

[Scope of Claims] 1 A subbing layer, a metal thin film layer, and a photosensitive layer are sequentially formed on a support, and the photosensitive layer has an adhesive force with the metal thin film layer that is equal to or greater than the support and the subbing layer. 1. A photosensitive image forming material, characterized in that it is colored and has peelable film properties that are stronger than at least one of the adhesive force between the undercoat layer and the metal thin film layer. 2. The photosensitive image forming material according to claim 1, wherein the undercoat layer mainly contains a resin that is dissolved by a solution that can penetrate the metal thin film layer.