JPS60238826A - Image forming material - Google Patents

Abstract

PURPOSE:To enable an image to be formed only by peeling a photosensitive film by laminating on a support a metal compd. layer, its surface treating layer, and a photosensitive layer increasable in adhesion to the surface treating layer by exposure in succession. CONSTITUTION:The layer of a metal compd., such as SnO2, In2O3, TiO2, ZnO, or CuI, is formed on a support made of ceramics or film forming polymer, by the vapor deposition or sputtering method. This layer is coated with a solvent soln. of a thermoplastic resin, such as a terpolymer of vinyl chloride.vinyl acetate.maleic anhydride, or polyvinylformal, and dried to form its surface treating layer. It is further coated with a solvent soln. of a binder polymer a polymerizable ethylenically unsatd. compd., etc., and dried to laminate the photosensitive layer and thus obtain an image forming layer.

Description

DETAILED DESCRIPTION OF THE INVENTION (11) Technical field to which the invention pertains The present invention relates to a dry image forming material, more specifically a support, a single layer consisting of a +1+ metal compound alone or a mixture of a metal compound and a metal, or (11) A laminated multilayer selected from a metal compound, a metal or a mixture of a metal compound and a metal, at least one layer of which is composed of a metal compound layer or a mixture of a metal compound and a metal. A layer characterized by being a layer (hereinafter referred to as metal [
(referred to as layer A), a metal surface treatment layer, and a photosensitive layer in this order. The adhesive force of the photosensitive layer with the metal surface treatment layer increases when exposed to light, and the photosensitive layer is peeled off after exposure. By doing so, the metal compound layer, etc. in the exposed area and the metal surface treatment layer are removed from the support, and the metal compound layer, etc. and the metal surface treatment layer in the unexposed area remain on the support.

That is, it relates to a positive-positive type peel-off image forming material.

The images produced by this eA can be used in a wide range of applications such as second original drawings, lithographic printing plates, film for plate making, printed circuit boards, original images for projection, original images for displays, electrodes for electroluminescence, tapes for labels, etc. It will be done. In particular, the metal arsenide layer of the present invention can be used as a transparent conductive metal compound thin film, and can be used in liquid crystal displays, plasma display electrodes, and ELDs.

It is used to prevent fogging and freezing of window glass, charge leakage layers in electrophotography, antistatic layers, electrodes of photoelectric conversion elements (hereinafter referred to as liquid crystal displays, etc.), etc.

(2) Prior art and its problems Conventionally, as materials or methods for forming metal images by peeling, there are
No. 20555, JP-A-54-150120, etc.

The present inventors disclosed in Japanese Patent Publication No. 56-15505 that a thin layer of a metal or metal compound and a binder polymer [from a quinone-based, diazo-based, azide-based or benzophenone-based photosensitizer] were used on a support. Negative with a photosensitive layer
Positive-type release metal imaging materials have already been proposed.

Furthermore, in the specification of Japanese Patent Publication No. 56-20535, the present inventors described a thin layer of metal or metal compound on a support and a binder cylinder molecule "composed of an arsenide, an acrylamide monomer, and a photopolymerization initiator". We have proposed a metal image forming material by peeling off a positive stamp with a photosensitive layer 2. In this material, a photosensitive layer is provided directly on a thin metal layer, the adhesive strength between the metal layer and the photosensitive layer is increased by exposure, and the photosensitive layer is exposed to light. By post-peeling, it is removed from the metal layer support in the exposed area,
A metal image is formed by leaving unexposed areas of the metal layer on the support. However, the drawback of this material is that only a limited number of compositions can be used as a photosensitive layer that increases the adhesion strength with the metal layer directly through exposure, and the sensitivity or storage stability when not exposed to light is not necessarily fully satisfied. I couldn't get any good results.

Furthermore, JP-A-54-150120 discloses an image forming layer made of a metal or a metal compound on a support, an intermediate layer made of a thermoplastic polymer having film-forming ability Z, and
In a photosensitive material having as an essential layer a photosensitive layer consisting of a photosensitive composition containing a photodegradable compound containing G atoms and a binder 2 made of a thermoplastic polymer having film-forming ability, the photosensitive layer is irradiated with actinic light. and then heated, whereby the interfacial adhesive force between the image forming layer and the support is reduced, or the interfacial adhesive force between the image forming layer and the intermediate layer is reduced. A photosensitive image forming material, and a method for using the photosensitive image forming material, which comprises heating and peeling off the material, leaving the unexposed image forming layer on the support to form an image. has been done. However, with this material and method, heat treatment is required after exposure and before peeling, and furthermore, the image quality changes depending on the temperature or time of the heat treatment, making it difficult to stably obtain a good image 2. It has the following drawbacks.

Furthermore, the image forming material of the present invention is used as a transparent conductive thin film with a pattern formed on an insulating substrate (support),
Conventional techniques for use in applications such as liquid crystal displays are as follows.

Conventionally, the following method has been adopted as a technique for forming the transparent conductive thin film pattern f of this ridge, both for metal thin films and metal compound thin films.

A photosensitive resist composition liquid is applied onto the transparent conductive thin film on the substrate, dried, and exposed to actinic light through the original while being brought into close contact with the original.

Thereafter, the photosensitive resist layer is developed to form a relief resist image.

Using this resist image, the transparent conductive thin film is etched with an acidic etching solution to form a pattern 2, and then the resist film is peeled off with a solution. Conventional patterning technology uses the methods described above, so depending on the type of transparent conductive thin film, a very strong acidic solution is used, and in some cases, the etching speed is slow, so it is necessary to further dissipate the charge. The process is dangerous, requires the use of auxiliary means 2 such as rubbing or physically scraping the membrane surface, requires wastewater treatment, and has drawbacks such as difficulty in obtaining consistent results.

For example, SnO□, In2O3, Tie, , Zn
Metal acid compounds such as O, ITO (tin oxide) have the disadvantage that they are particularly difficult to etch.

It also had drawbacks, such as the large number of work steps, which required time and equipment costs.

(3) Purpose of the Invention The present inventor has conducted extensive research in order to solve the above-mentioned problems, and has completed the present invention Z.

An object of the present invention is to provide an image forming material that can form an image by simply peeling off the photoresist film without requiring any treatment such as heating after exposure.

A further object of the present invention is to provide an image-forming material with excellent sensitivity (and sharp images) and excellent storage stability that prevents corrosion or fogging of the metal compound layer etc. when not in use. be.

A further object of the present invention is to provide an image forming material that can simultaneously pattern a transparent conductive thin film by peeling off and developing a photosensitive layer after exposure, and that can be used for applications such as liquid crystal displays.

(4) Key Points of the Invention The peelable image forming material of the present invention will be explained in more detail.

The image forming material of the present invention has a structure including, in this order, a support, a metal compound layer tube, a metal surface treatment layer, and a photosensitive layer whose adhesive strength with the metal surface treatment layer increases upon exposure to light. When this image forming material 2 is imagewise exposed, the adhesive force between the photosensitive layer and the metal surface treated layer in the exposed areas increases, but the adhesive force between the photosensitive layer and the metal surface treated layer in the unexposed areas does not change. If the photosensitive film is then peeled off, the metal surface treatment layer, metal compound layer, etc. in the exposed area will be removed from the support, but the metal compound layer, etc. in the unexposed area will be removed from the support together with the metal surface treatment layer. The image remains. To show the relationship between the support and the adhesive force between each layer from the viewpoint of the image forming mechanism of the present invention described above, the adhesive force between the photosensitive layer and the metal surface treatment layer when unexposed is the bond between the metal surface treatment layer and the metal compound. Adhesion between layers and metals (lower than that between the composite layer, etc. and the support), adhesive strength between the photosensitive layer and the metal surface treatment layer after exposure, and between the metal surface treatment layer and the metal [the composite layer, etc.] It is necessary that the adhesive strength be higher than that between the metal compound layer, etc. and the support.

As the support used in the present invention, various materials 2 having a metal compound layer or the like formed on the surface thereof can be used. Generally, polymer f-hybrid compounds, glass, ceramics, films,
Formable polymer compounds, metals, etc. are used. In particular, when used for applications such as liquid crystal displays, it is used as an insulating substrate. Polymers (Compounds include polyesters such as polyethylene terephthalate, polycarbonates, polyamides, polyolefins such as polypropylene, polyvinyl chloride, polystyrene, polymethyl methacrylate, and synthetic resins such as copolymers thereof, diacetyl cellulose, triacetyl cellulose, propyl Examples include cellulose derivatives such as cellulose and mixed cellulose esters.

These supports contain various additives, such as pigments and dyes, for coloring, opacity, imparting writability, etc.

Fillers and the like may also be added. In addition, these supports are subjected to corona discharge treatment and sandblasting treatment.

Surface treatment 7 such as chemical etching and coating with a polymer compound can also be performed.

The shape of these supports is generally a film or a sheet, but they may also be three-dimensional structures.

Examples of metal compounds that can be used for the metal compound layer etc. provided on the support include tin oxide (SnO2).
, indium oxide b (In, o3) - titanium dioxide, acid ratio zinc (ZnO), ITO, copper iodide (CuI)
.

Cd2SnO4 and the like are used, but are not limited to these.

The above-mentioned metal compound layer can be used as a single layer or a multilayer, and it is also possible to use a single layer or a multilayer metal compound layer laminated with a metal layer. Examples of metals used in this metal layer include gold, palladium, aluminum, zinc, copper, silver, nickel, chromium, cobalt, titanium, iron, lead,
Tin, platinum.

Examples include, but are not limited to, copper-zinc alloys, nickel-chromium alloys, and nickel-iron alloys. Moreover, when used in applications such as metal and metal compound liquid crystal displays used in the present invention, the metal compound layer and the like are used as a transparent conductive thin film.

Vacuum deposition, sputtering, electroless plating, and ion blating can be used to form these metal layers on the support.

The thickness of the metal compound layer etc. is generally 10mμ to 1000m
It is in the range of μ. When used for applications other than transparent conductive thin films, if the thickness of the metal compound layer etc. is too thin, the light shielding effect will be poor, making it difficult to clearly distinguish the formed image. When used as a transparent conductive thin film,
If the layer thickness becomes too thin, the surface resistance will become too thick, making it unsuitable for use. chipping and a decrease in resolution.For the above reasons, the thickness of the metal compound layer, etc. is preferably from 20 mμ to 500 mμ.
It is in the range of mμ.

The metal surface treatment layer is the most significant feature of the present invention. The metal surface treatment layer is always integral with the metal compound layer, etc., even when the metal compound layer, etc., is removed from the support by peeling off the photosensitive film, or when the metal f-hyde compound layer, etc. remains on the support. Therefore, peeling must not occur between the metal compound layer, etc. and the metal surface treatment layer. Therefore, it is an essential condition for the metal surface treatment layer to have good adhesion with the metal compound layer, etc., and a resin or a silane coupling agent that satisfies this condition can be used.

Furthermore, a mixture of this resin and a silane coupling agent can also be used as the metal surface treatment layer.

Resins that have good adhesion to metal compound layers, etc. that can be used in the metal surface treatment layer include vinyl chloride-vinyl acetate (maleic anhydride, acrylonitrile, or vinyl alcohol) terpolymer, and polysalt "vinyl". , polyvinyl acetate, polyvinyl formal, polyvinyl butyral,
Polysalts [hypinylidene, methacrylic acid-methyl methacrylate copolymer, polyester resins such as linear saturated polyester resins, thermosetting unsaturated polyester resins, polyurethane resins or acrylic tertiary resins, oligomer-containing photocurable resins, etc.] Thermoplastic resin.

Thermosetting resin or photocuring resin can be used.

Examples of silane coupling agents include vinyltrichlorosilane, vinyltrimethoxysilane, vinyltris(β-methoxyethoxy)silane/vinyltriacetoxysilane,
γ-Chlorpropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-β(aminoethyl)γ
~aminglobiltrimethoxysilane, N-β(aminoethyl)γ-aminopropylmethyldimethoxysilane,
Examples include r=-mercaptoglobiltrimethoxysila/, γ-methacryloxypropyltrimethoxysilane, and the like.

Among these resins or silane coupling agents, vinyl chloride-vinyl acetate-
Maleic anhydride terpolymer, polyvinyl formal, polyester resin, polyurethane resin, and silane coupling agents such as N-β (aminoethyl)γ-aminopropyltrimethoxysilane, vinyltris(β-methoxyethoxy)silane, and N-β (Aminoethyl)γ-aminoglopylmethyldimethoxysilane can be mentioned.

These resins or silane coupling agents can be used alone or in combination of two or more.

In addition, a resin and/or a silane coating agent and a pressure coloring agent that can be used in the metal surface treatment layer can be added as appropriate.

The general method for forming a metal surface treatment layer on a metal compound layer, etc. from these resins or silane coupling agents is to dissolve them in a solvent, apply them as a coating liquid on the metal compound layer, etc., and then dry them. That's spot on. Furthermore, if heat treatment or light irradiation for curing is necessary, these treatments are performed depending on the respective conditions.

The thickness of the metal surface treatment layer is generally from 1 mμ to 1000 μm.
It is in the range of mμ. If the thickness of the metal surface treatment layer is too thin, the effect of the treatment will not be recognized, and if it is made too thick, it will be effective as a protective layer for the surface of the metal compound layer, etc., but it will lead to a decrease in resolution. For the above reasons, the preferred thickness of the metal surface treatment layer is 10 mμ to 500 mμ.
is within the range of

The photosensitive layer provided on the metal surface treatment layer contains a binder polymer compound, an ethylenically unsaturated compound capable of dipolymerizing, and a photopolymerization initiator, and the adhesive strength with the metal surface treatment layer increases upon exposure to light. do.

Binder polymers that can be used in the photosensitive layer [Examples of polymers include polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, vinyl chloride-vinyl acetate-(maleic anhydride, acrylonitrile].

or vinyl alcohol) terpolymer polyvinyl acetate,
Polyvinyl formal, polyvinyl butyral, ethyl acrylate-acrylonitrile (vinyl chloride, vinylidene chloride, or styrene) terpolymer, linear thermoplastic polyester or copolyester, e.g. polyethylene terephthalate, or polyethylene terephthalate, inphthalate, alcohol-soluble polyamide , polyurethane, phenoxy, acetylcellulose, ayathylbutylcellulose, nitrocellulose, ethylcellulose, ethylene-vinyl acetate copolymer chlorinated rubber, cyclized rubber, and polyvinyl alcohol. These polymeric compounds can be used alone or in combination of two or more.

Examples of polymerizable ethylenically unsaturated compounds that can be contained in the photosensitive layer include acrylates.

There are many such as methacrylates and acrylamides,
Those that are liquid or solid at room temperature and have a boiling point of 100° C. or higher at normal pressure are preferred.

Examples of acrylates include n-butyl acrylate, cyclohexyl acrylate, 2-hydroxyethyl acrylate, and 2-butoxyethyl acrylate+2-phenoxyethyl acrylate.

Ethylene glycol diacrylate, diethylene glycol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, sorbitol diacrylate, sorbitol triacrylate, trimethylol ethane triacrylate, trimethylol bromine triacrylate, pentaerythritol triacrylate Examples include acrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, and dipentaerythritol pentaacrylate.

Methacrylates include n-butyl methacrylate),
1so-butyl methacrylate, cyclohexyl methacrylate, phenyl methacrylate.

2-Hydroxyethyl methacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, 1,5-butylene glycol dimethacrylate, 1,4-butylene glycol dimethacrylate, diethylene glycol diacrylate, neopentyl glycol diacrylate, 1,6-hexane diol dimethacrylate acrylate, bisphenol A dimethacrylate, sorbitol dimethacrylate, flubitol trimethacrylate, trimethylolethane trimethacrylate,
Trimethylolpropane trimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate.

etc. can be mentioned.

Acrylamide is an example of acrylamide.

Diacetone acrylamide, N,N-diethylacrylamide, N,N/-methylenebisacrylamide.

Examples include N-hydroxymethylacrylamide.

Examples of polymerizable ethylenically unsaturated compounds other than those mentioned above include methacrylamide, N,N'-methylenebismethacrylamide, and α-methylstyrene.

Allyl acetic acid, allyl acetone, allyl alcohol.

Allylbenzene, 2-vinylhyridine, N-vinyl-2
-Pyrrolidone, diethyl itaconate, diethyl itaconate, motuptil itaconate, diallyl maleate, diallyl fumarate, N-laurylmaleimide, acryloxyethyl phosphate, bis(acryloxyethyl)
Phosphate.

Examples include methacryloxyethyl phosphate and bis(methacryloxyethyl) phosphate.

These polymerizable ethylenically unsaturated compounds alone have 2
It is also possible to use a mixture of two or more species.

The amount of these polymerizable ethylenically unsaturated compounds added to the binder polymer F compound is usually 5 to 1.
00% by weight, preferably 10 to 60% by weight.

Photopolymerization initiators that can be used in the photosensitive layer of the present invention include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin 15O-propyl ether, benzophenone, Michler's ketone, 4.4'-
Bis(diethylamino)benzophenone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-chlorothioxanthone, benzyl, 9-phenylacridine,
These include 2-(010lofenyl)-4,5-cyphenylimidazole dimer, which can be used alone or as a mixture of two or more.

The amount of these photopolymerization initiators added is usually 01 to 40% by weight, preferably 6 to 20% by weight, based on the binder polymer compound.

In addition to the above, thermal polymerization inhibitors such as hydroquinone, hydroquinone monomethyl ether, p-benzoquinone, p-nitrophenol, dyes, pigments, etc. can also be added as appropriate.

Examples of preferable combinations of a metal surface treatment layer and a photosensitive layer include a metal surface treatment layer and a monolayer polymeric compound as a binder for the photosensitive layer when a salt f vinyl-vinyl acetate-maleic anhydride copolymer is used. C, phorihinyl butyral, ethyl cellulose.

Alcohol-soluble polyamides are preferable, and when the binder higher molecular weight compound of the photosensitive layer is polyvinyl butyral, polymerizable, ethylenically unsaturated [hypolymerizable compounds include neopentyl glycur diacrylate, trimethylolpropane triacrylate] , Penquerythritol triacrylate, Photomer 4061 C (radiation curing monomer manufactured by Sun Nopco), Photomer 4072 (radiation scarlet 1 H type monomer manufactured by Sun Nopco), 5A-7
<500 (Mitsubishi Oil [manufactured by Hi Co., Ltd., bipolar alicyclic ester acrylate], Aroex M-6100 (manufactured by Toagosei Co., Ltd., oligoester acrylate) is preferable, and when the binder monolayer polymeric compound is ethyl cellulose As the polymerizable ethylenically unsaturated compound, trimethylolpropane triacrylate, pentaerythritol triacrylate, Aloex M-80ROO (manufactured by Toagosei Co., Ltd., oligoester acrylate) is preferable, and the binder has a higher molecular weight ratio. When the compound is an alcohol-soluble polyamide, pentaerythritol triacrylate is preferred as the polymerizable ethylenically unsaturated compound.

When polyester resin is used as the metal surface treatment layer,
The binder molecular composition of the photosensitive layer is preferably polyvinyl butyral or ethyl cellulose. When the binder monolayer polymer composition is polyvinyl butyral, the polymerizable ethylenically unsaturated compound is neopentyl glycol diacrylate or pentyl cellulose. Erythritol triacrylate is preferred, and the binder Dejima molecule [When the compound is ethyl cellulose, examples of ethylenically unsaturated 16 compounds include trimethylolpropane triacrylate and pentaerythritol triacrylate.

Ryoroex M-8030 is preferred.

When low β (aminoethyl) γ-aminopropyl triethoxysilane is used as the metal surface treatment layer, the binder polymer compound of the photosensitive layer is polyvinyl pyral, phenoxy resin, alcohol-soluble polyamide, and chloride. Rubber is preferred, and when the binder polymer compound is polyvinyl butyral, examples of the ethylenically unsaturated compound include pentaerythritol triacrylate, dipentaerythritol pentaacrylate, and Photomer 4028 (manufactured by Sun Nopco, radiation-curing type). monomer).

Photomer 4072, 5A-4100 (manufactured by Mitsubishi Oil Corporation, main functional heterocyclic ester acrylate) is preferred,
When the polymer compound for the binder is a phenoxy resin and the material is an alcohol-soluble polyamide, the ethylenically unsaturated 16 compound is p/taerythritol triacrylate 1. Photomer 4072 is preferred, and when the binder polymer [hypolysate] is chlorinated rubber, pentaerythritol triacrylate is preferred as the ethylenically unsaturated compound.

When n-β (aminoethyl) γ-aminopropyl methyl dimethoxy 7 run is used as the metal surface treatment layer, the pot molecule for the binder of the photosensitive layer [as the arsenic compound, polyvinyl butyral, ethyl cellulose.

Alcohol soluble polyamide is preferred, binder mm
When the polymer compound is polyvinyl butyral or alcohol-soluble polyamide, the ethylenically unsaturated compound is preferably pentaerythritol triacrylate; As such, Aloex M-8050 is preferred.

As a photopolymerization initiator used in the photosensitive layer, alone,
In the case of a combination of two types of benzoin methyl ether, benzoin ethyl ether, and 2-chlorothioxanthone, 4. A combination of -4'-bis(diethylamino)benzophenone, benzophenone, and a certain ihabenzoin ethyl ether is preferred.

The method for forming the photosensitive layer on the metal surface treatment layer includes a binder, a polymeric compound, a polymerizable ethylenically unsaturated compound, a photopolymerization initiator, and if necessary, a thermal polymerization inhibitor, and a dye. , pigments, etc., to form a photosensitive solution by dissolving or dispersing it in a suitable solvent, and applying this directly onto the metal surface treatment layer and drying, or by coating the photosensitive solution onto another support,
A common method is to form a photosensitive layer by drying and then laminate this photosensitive layer on a metal surface treatment layer.

Methyl ethyl ketone and acetone are used as solvents.

Toluene, xylene, cyclohexanone, methyl alcohol, ethyl alcohol, isopropyl alcohol, methyl cellosol, ethyl cello.

Ethyl acetate, etc. are used.

When selecting a solvent, when applying the photosensitive rL directly onto the metal surface treatment layer, it is desirable to avoid using a solvent that will dissolve the metal surface treatment layer.

The thickness of the photoresist film is generally 0.5 to 100μ,
Preferably it is 2 to 20μ.

In the image forming material of the present invention, an upper support layer may be further provided on the photosensitive layer, if necessary.

Its main purpose is to increase the strength of the photosensitive layer when it is peeled off. However, it is preferable to use a film with excellent transparency so as not to inhibit the photosensitivity Z of the photosensitive film. From this point of view, films made of polyester, polypropylene, polyamide, polyvinyl chloride, cellulose ester, etc. are suitable. layer and glue.

By performing image exposure on the image forming material configured as described above, the adhesive force between the photosensitive layer and the metal surface treatment layer in the exposed area is increased. If the photosensitive layer is then peeled off, the metal compound layer, etc. and the metal surface treatment layer corresponding to the exposed areas are removed from the support together with the photosensitive layer, and the metal compound layer, etc. and the metal surface treatment layer corresponding to the unexposed areas are removed from the support. remains on the support to form an image.

The light source used in this case is preferably one that emits ultraviolet light, including sunlight, or short-wavelength visible light.
+11 For example, a high-pressure mercury lamp, a carbon arc lamp, a xenon lamp, a metal halide lamp, etc. are used.

A further object of the present invention is to provide a negative pattern-forming imaging material. The negative pattern forming type is composed of the above-mentioned support and a photoresist film having film-forming properties on the metal compound layer, etc., and whose interfacial adhesion with the metal compound layer etc. is reduced by actinic rays.

Before exposure to actinic rays, the interfacial adhesion between the photosensitive film and the metal compound layer, etc. is greater than the interfacial adhesion between the metal compound layer, etc. and the support; The interfacial adhesion force with the material layer, etc. is lower than the interfacial adhesion force of the latter, so when the photosensitive film is beer-covered, the metal compound layer, etc. remains on the support only in the exposed areas, resulting in a pattern that is reversed from the original. It is formed.

A negative photosensitive film is made of a binder polymer compound and a photosensitizer.The binder polymer compound includes polyvinyl chloride, 1-vinyl salt-vinyl acetate copolymer, and vinyl chloride-vinylidene chloride copolymer. Polymer, salt ratio vinyl-vinyl acetate-(maleic anhydride, acrylonitrile or vinyl alcohol) terpolymer, vinyl chloride-vinylidene chloride-(acrylonitrile, vinyl acetate or methyl methacrylate) terpolymer, acrylic ester- (
methyl methacrylate or styrene) copolymers, linear thermoplastic polyesters or copolyesters such as polyethylene terephthalate or polyethylene terephthalate isophthalate.

Synthetic resins such as alcohol-soluble polyamide, polyurethane, polyvinyl butyral or polyvinyl alcohol; acetyl cellulose, acetyl-butyl cellulose,
There are cellulose derivatives such as nitrocellulose or ethylcellulose. These polymer compounds can be used alone or in combination of two or more.

Depending on the properties of the polymer compound, suitable organic solvents such as methyl ethyl ketone, toluene, xylene, cyclohexanol, and methanol can be used.

Ethanol, isopropanol, methyl cellosolve, ethyl cellosolve or acetic acid cellosolve are used.

When selecting a solvent for KrIA, it is important to use a common solvent with the photosensitizer used in the photosensitive film, and the support material will dissolve or swell to improve its performance. Care must be taken to use materials that do not degrade the quality.

Of course, water can be used for water-soluble compounds such as polyvinyl alcohol.

Furthermore, the binder compounds can also be used in the form of emulsions, and polyvinyl chloride emulsions and polyurethane emulsions are particularly suitable for the purposes of this invention.

Since this photosensitive film peels off after exposure, the polymer compound for the binder must have good film-forming properties and appropriate film strength. Further, from the viewpoint of storage and handling of the image forming material, it is preferable that the binder has non-blocking properties.

The following can be used as the photosensitizer.

(at benzophenone (bl quinone photosensitizer 1,4-naphthoquinone, 2-methyl-1,4-naphthoquinone, anthraquinone, 2-methylanthrachy/7,2
-ethylanthraquinone, 2-chloroanthraquinone, 2-chloroanthraquinone, or p-toluquinone; the former two are particularly preferred.

(cl diazo photosensitizer 4-(p-) lilumercapto)-2,5-jethoxybenzenediazonium zinc chloride salt, sodium sulfate salt or tetramonoarsenoborate, 4-(p-) 1) lumercapto) −
Salt of 2,5-dimethoxybenzenediazonium [Hizinc salt, 4-(p-methylbenzoylamino)-2,5-dimethoxybenzenediazonium salt [Hizinc salt, 4-(
Zinc chloride salt of p-methoxybenzoylamino)-2,5-shedokbenzenediazonium, salt of 4-morpholino-2,5-butoxybenzenediazonium, rzinc salt or tetrafluoroborate.

4-morpholinobenzenediazonium tetrafluoroborate, 4-pyrrolidino-5-methylbenzenediazonium tetrafluoroborate, p-N, N-dimethylaminobenzenediazonium salt r hiszinc salt, p-N, Zinc chloride salt or tetrafluoroborate of N-diethylaminobenzenediazonium Tp-N-ethyl-Zinc chloride salt of N-hydroxyaminobenzenediazonium, 1,2-diazonaphthol-
5-Sodium sulfonate or a salt of a condensate of 4-diazodiphenylamine sulfate and formaldehyde; r azinc salt; (dl) Azide-based photosensitizer 2,6-(4'-azidobenzal)cyclohexanone.

In the second invention, an appropriate combination of a photosensitive agent and a binder polymer compound is selected in order to make the interfacial adhesion strength between the photosensitive film and the metal compound layer in the photosensitive area smaller than that in the non-photosensitive area when exposed to light. There is a need to.

°Benzophenone and quinone photosensitizers include polyvinyl chloride and vinyl chloride-vinyl acetate combination.

Synthetic resins of vinyl chloride-vinyl acetate-(areic anhydride, acrylonitrile or vinyl alcohol) terpolymer, 1-hibinyl salt-1 hibinylidene salt copolymer or 3-vinyl salt-vinylidene chloride-acrylonitrile terpolymer, and nitrocellulose Particularly preferred from the viewpoint of image quality, acetyl cellulose, acetyl butyl cellulose,
Ethyl cellulose, IR rubber or chlorinated rubber can also be used.

In addition to the above-mentioned polymeric arsenic metals, a particularly suitable example of the diazo and azide photosensitizers is polyvinyl butyral. Additionally, linear thermoplastic polyesters and copolyesters, alcohol-soluble polyamides,
polyvinyl alcohol.

Acrylic ester-(methyl methacrylate or styrene) copolymers, polyurethane emulsions or polyvinyl chloride emulsions can also be used.

The usage ratio of the photosensitizer is 1 to 2 Qwt% for benzophenone and quinone based on the binder polymer 1 arsenic metal.
, preferably from 5 to iQwtqb, and for diazo and azide systems, from 0.1 to 10Wl, preferably from 1 to 6wt. A large amount of photosensitizer colors the photosensitive film and causes a decrease in sensitivity. In addition, the photoresist film generally has a thickness of 0.5 to 100μ,
Preferably the thickness is in the range of 2 to 20 microns.

Next, the present invention will be explained in more detail with reference to Examples. Note that the present invention is not limited by the following examples.

(5) Examples of the invention [Example 1] One side of a 100μ polyethylene terephthalate film K ITU (In20395mo1% 8nO, 5mo
A transparent conductive thin film with a surface resistance of 400 Ω/hole was obtained by sputtering using a NOKET YC (1%) at an output of 5 Kw. Argon containing 77% oxygen was used as the sputtering gas.

On this transparent conductive thin film, n-β (aminoethyl)γ
-Aminopropylmethyldimethoxysila/YO, applied with methanol denatured alcohol containing 5 weights and heated to 120°C.
It was dried for 2 minutes to obtain a surface treated layer with a thickness of 751 nm.

Next, a photosensitive liquid having the following composition was coated on the surface treatment layer so that the film thickness after drying was 10 .mu.m, and dried at 90 DEG C. for 2 minutes to form a photosensitive film' (l-).

Place the positive original on the photoresist film surface and expose it to 100℃ using a high-pressure mercury lamp.
After irradiating ultraviolet rays of mJ/cI7t, the photoresist film is beer-filled, and IT is deposited on the polyethylene terephthalate film.
A positive pattern in which O and the surface treatment layer were layered was obtained.

Its resolution was 40 lines/tomo.

[Example 2] ITU (In2U395mo1% SnU25mo1%) was applied to one side of a 100μ polyethylene terephthalate film.
), a transparent conductive thin film with a surface resistance of 400 Ω/hole was obtained by sputtering at an output of 5 Kw. Is the sputtering gas argon containing 7% oxygen? Using.

On top of this transparent conductive thin film, a negative original with the following composition was placed in close contact with the photosensitive film surface at a drying temperature of 90°C for 1 minute, and then exposed to a high-pressure mercury lamp for 100°C.
When the photoresist film is exposed to ultraviolet rays of mJ% po, IT is deposited on the base polyethylene terephthalate film.
O's bodhibarn appeared clearly, and its resolution was 40 lines/tomo.

(6) Effects of the Invention The image forming material of the present invention does not require any treatment such as heating after exposure and can form an image by simply peeling off the photosensitive layer.
In addition, it has high sensitivity (images are sharp, and it has excellent storage stability with less corrosion of the metal compound layer or generation of capri) when not in use.

In particular, when used for applications such as liquid crystal displays, transparent conductive thin film Z patterns [to be removed, the photosensitive film can be simply peeled off after exposure (unlike conventional methods, dangerous aqueous solutions such as acids are not required). It also has the advantage of not requiring treatment of wastewater.

Further, in the conventional method, after etching, the resist film must be peeled off and dissolved with a solution, etc., but the present invention shortens the process in this respect, and has a large economic effect.

[Brief explanation of the drawing]

FIG. 1 is a cross-sectional view of the imaging material of the present invention. FIG. 2 is a cross-sectional view of the imaging material of the present invention being exposed to actinic light through a document. FIG. 5 shows a state 2 in which the photosensitive layer is peeled off after exposure. FIG. 4 shows a cross section and pattern of the dry image forming material of the present invention, and FIG. 5 shows a state in which the photoresist film is partially peeled off after exposure. １・・・・・・・・・Special holidays ２・・・・・・・・・
Metal compound layer, etc. Metal surface treatment layer
4...Photosensitive layer 5...Original (mask) 6...Active light 7...
...Substrate 8...Gold F4 compound layer, etc. 9
......Photosensitive film 10...Image forming material M...Masking material L...
・・・・・・Light ray 11.12・・・・・・Thin film pattern (external name) + 1 ++

Claims (1)

[Claims] 1. Support, a single layer consisting of only a medium metal compound or a mixture of a metal compound and a metal, or (11) a metal compound;
A multilayer layer selected from metals or mixtures of metal compounds and metals, characterized in that one layer is a layer consisting of a metal compound layer or a mixture of a metal compound and a metal. layer (A layer), a metal surface treatment layer, and a photosensitive layer, and when unexposed, the adhesive force between the photosensitive layer and the metal surface treatment layer is greater than the adhesive force between the metal surface treatment layer and the A layer and between the A layer and the support. The photosensitive layer and the gold lI4 surface treatment were applied so that upon exposure, the adhesion between the photosensitive layer and the metal surface treatment layer and between the metal surface treatment layer and the A layer was 100% higher than that between the A layer and the support. layer and select 7, this will result in
After exposure, the photosensitive layer is removed from the support together with the exposed layer A layer and the metal surface treatment layer by peeling the photosensitive layer,
An image forming material by peeling, characterized in that layer A and a metal surface treatment layer in unexposed areas remain on the support.