JPH0145896B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a material for forming metal images, and particularly to a metal image forming material that has a high contrast image forming ability and is suitable for line work and halftone dots.

In metal image forming materials, a general drawback when using a thin metal layer (such as a vapor deposited layer or a laminated foil layer) is that it is difficult to be etched with a weak etching solution that does not soak the resist. For this reason, etching usually takes a long time, and therefore a resist with extremely high corrosion resistance must be used. Moreover, it is difficult to obtain a sharp image, and furthermore, there are disadvantages in that the edges of the image are disturbed.

On the other hand, as a means to improve this,
No. 9736 discloses a vapor deposition layer in which aluminum and a vapor-depositable organic substance are mixed. However, the organic material disclosed herein cannot be etched in a sufficiently short etching time using a weak developer that does not immerse the resist, making it impractical.

On the other hand, a technique of incorporating a chelating agent into a photosensitive resin composition is known, and is disclosed in Japanese Patent Application Laid-Open No.
95004 and 55-38510).

However, in image-forming materials in which a thin metal layer is provided between the photosensitive resin layer and the support, etching time is long even when the aluminum alcoholate described in JP-A-50-95004 is used in the photosensitive resin layer. , No. 55-38510, the etching time is longer.

In addition, there is a known technology for shortening the etching time by incorporating a metal chelating agent into the etching solution (British Patent No. 1434894 and British Patent No. 1434894).
No. 1,562,586), even a specific chelating agent has the drawback of poor resolution when it is included in the etching solution (see Comparative Example 1).

Therefore, an object of the present invention is to etch a thin metal layer in a short time without using a strong etching solution and without reducing resolution. The object of the present invention is to provide a metal image forming material that can provide sharp images.

The object of the invention is to have a thin metal layer on a support,
In a metal image forming material having a photosensitive resin layer thereon, at least one layer other than the thin metal layer on the support is coated with at least one of the following metal chelating agents.
This is achieved by a metal imaging material characterized in that it contains a species.

[Metal chelating agent] phenol derivatives anthraquinone derivative Orthoxyazo compounds The present invention will be explained in detail below.

A specific example of the layer structure of the metal image-forming material according to the present invention is one in which a thin metal layer is provided on a support and a photosensitive resin layer is provided on the thin metal layer. In embodiments with additional components, for example, between various layers provided on the support, such as between the support and a thin metal layer or a thin metal layer and a photosensitive resin layer, a subbing layer is provided as an intermediate layer. The metal image-forming material of the present invention can have a very wide variety of layer configurations, including embodiments in which a layer is provided, and embodiments in which a protective layer is further provided on the photosensitive resin layer. .

The metal of the metal thin layer used in the metal image-forming material of the present invention is a layer formed of a metal that can be etched with a conventionally known etching solution.
Aluminum-based metals described in Publication No. 139720 and Japanese Unexamined Patent Publication Nos. 48-65927 and 48-65928
Tellurium, molybdenum, boronium, cobalt, zinc, copper, nickel, iron,
Mention may be made of tin, vanadium, germanium, silver and silver emulsion. The thickness of this thin metal layer is determined by the optical density required for the resulting image, and the two are almost proportional; for example, if the image is a line drawing or halftone dot, a relatively high density is required. The optical density must be at least 2.0 or higher, especially when the material of the present invention is used as a mask for printing on PS printing plates.
Since an optical density of 3.0 is required, the thickness is determined accordingly. The relationship between the thickness of the metal thin layer and the optical density is generally the same, although it may differ somewhat depending on the method of forming the metal thin layer, for example, the vacuum deposition conditions. Although it is not particularly prohibited to make the metal thin layer thicker than necessary in order to obtain the desired optical density, it is not prohibited to make the metal thin layer thicker than necessary. This is not desirable because it takes time. Furthermore, considering that excessive etching time may deteriorate the resist, it is better to avoid making the metal thin layer thicker than necessary.

The support on which the thin metal layer used in the metal image-forming material of the present invention is provided holds the thin metal layer as an image-forming layer provided thereon directly or indirectly (via another layer). Furthermore, the metal image-forming material of the present invention can be formed into various forms in consideration of the intended use. Therefore, considering the form of ordinary image-forming materials, the metal image-forming material of the present invention is preferably in the form of a sheet, film, or plate, and depending on its use, it may be transparent or semi-transparent. It can be transparent or opaque.
The support must not be affected by the etching solution that corrodes the thin metal layer, and must not be such that the layer provided thereon is easily peeled off by the etching solution. Many conventionally known materials can be used for the support, including ceramics, amorphous glass, crystalline glass, metals, alloys, plastics, and composite materials thereof. These materials can be opaque or transparent, but if necessary, a coloring agent or an opaque agent can be added to a transparent material to make it translucent or opaque. However, many possible fields of application include imaging the imaging material of the present invention with a metal layer, allowing light to pass through to non-image areas where there is no metal layer and the support is exposed to the screen; The image area is a so-called transmission type application field in which light is blocked by a metal layer, and in the case of an image forming material used in such a field, the support thereof must be transparent. On the other hand, in applications where the formed image is recognized by reflected light, the support does not need to be transparent.

The photosensitive resin that is the material of the photosensitive resin layer of the metal image forming material according to the present invention may be a photosensitive resin that is a combination of orthoquinone diazides and a novolak resin, or a diazo resin and a water-soluble resin or an alkali-soluble resin. A rubber-azide photosensitive resin that is a combination of a photosensitive resin, an azide compound, and a natural rubber, a synthetic rubber, or a cyclized rubber thereof;
A photosensitive resin that incorporates an azide group into its molecule,
Examples include various photosensitive resins used as photoetching resists, such as cinnamic acid photosensitive resins and photopolymerizable photosensitive resins having ethylenically unsaturated double bonds.

Below, these photosensitive resins will be described in detail.

The photosensitive resin which is a combination of orthoquinone diazide and novolac resin is 2, 3, 4.
-trioxybenzophenone-bis-[naphthoquinone-1,2-diazide-5,5-sulfonic acid ester], 2-naphthoquinone-1,2-diazide-5-sulfonyloxy]-hydroxy-7-naphthalene, naphthoquinone -1,2-diazide-5
-sulfanilide, naphthoquinone-1,2-diazide-5-sulfonic acid novolak ester, and other orthoquinone diazides in combination with novolak resins. These orthoquinone diazides become alkali-soluble when exposed to light, so they are important as materials for physical work.

The photosensitive resin that is a combination of the diazo resin and a water-soluble resin or an alkali-soluble resin includes a water-soluble diazo resin obtained by condensing an aromatic diazonium salt and an active carbonyl-containing compound, especially an aldehyde such as formaldehyde, in an acidic medium;
Alternatively, the anion component of the water-soluble diazo resin
BF ₄ ^- , PF ₆ ^- , SiF ₆ ^-- , SbF ₆ ^-- , BeF ₄ ^-- , IO ₄ ^-
Or an oil-soluble diazo resin substituted with an organic sulfonate and a water-soluble resin such as gelatin, polyvinyl alcohol, partially saponified polyvinyl acetate, methylcellulose, hydroxyethylcellulose, hydroxypropylmethylcellulose, carboxymethylcellulose, polyethylene glycol, polyvinylpyrrolidone, styrene, Examples include alkali-soluble resins such as methyl methacrylate, 2-hydroxyethyl methacrylate, and copolymers of glycidyl methacrylate and acrylic acid methacrylic acid.

As the rubber-azide photosensitive resin, p
-phenylene bisazide, p-azidobenzophenone, 4,4'-diazidobenzophenone, 4,
4'-diazidophenylmethane, 4,4'-diazidostilbene, 4,4'-diazidochalcone, 2,6
-di-(4′-azidobenzal)cyclohexanone,
Examples include photosensitive resins in which an azide compound such as 2,6-di-(4'-azidobenzal)-4-methylcyclohexanone is combined with natural rubber, synthetic rubber, or a cyclized rubber thereof.

Examples of photosensitive resins incorporating an azide group into the molecule include polyazidovinyl benzoate, polyazidovinyl phthalate, polyazidostyrene, polyvinylazidobenzal acetal, polyvinylazidonaphthyl acetal, azidobenzaldehyde phenol resin, and azidophenol. Examples include azide polymers of amine-formalin condensation polymer polyvinyl alcohol, azide polymers of cellulose such as azide phthalate of partially hydrolyzed cellulose acetate, and azide polymers of gelatin and casein.

The cinnamic acid-based photosensitive resins include polyvinyl cinnamate, poly(m-vinyl nitrocinnamate), poly-α-cyanovinyl cinnamate, poly-α-vinyl nitrocinnamate, and poly-β-nitrovinyl cinnamate. vinyl,
Poly-α-vinyl chlorocinnamate, poly-β-chlorovinyl cinnamate, polycinnamylidene vinyl acetate, polyvinyloxyethyl cinnamate, polyvinylthioethyl cinnamate, poly(2-cinnamoyloxyethyl acrylate), poly( 2
-cinnamoyloxyethyl methacrylate),
Poly(cinnamoyloxyvinyl acetate), poly(p-cinnamoyloxyvinylbenzene). Vinyl polymers such as poly(p-cinnamoylstyrene); copolymers of these with other polymers; ring-opening polymers of oxirane rings such as polyglycidyl cinnamate and polycinnamylidene glycidyl acetate; Polymers in which photosensitive groups have been introduced in whole or in part by performing a polymer reaction on a polymer containing an alkyl halide with a carboxylic acid salt having a photosensitive group in an aprotic polar solvent, such as polychloroethyl vinyl ether, polychloride, etc. Polymers obtained by reacting vinyl acetate, poly(β-chloroethyl acrylic acid ester), polyepichlorohydrin, polyepibromohydrin, etc. with salts of cinnamic acid or its derivatives; cationic polymers of vinyl ethers, such as polyvinyl ethers. Examples include roxyethylcinnamate.

Among cinnamic acid-based photosensitive resins, U.S. Patent No.
A mixture of the unsaturated photosensitive polyester compound described in No. 3030208 and the photosensitive resin represented by the chemical structural formula below is very suitable. The latter photosensitive resin is [A] −CH ₂ −CR ₁ COOR ₂ CO(−CR ₃ =CH) _a ---(CH=
CH)) - _b R ₄ (wherein, R ₁ is a hydrogen atom, a halogen atom, a nitrile group, or a lower alkyl group, R ₂ is a divalent aliphatic group, R ₃ is a hydrogen atom or a nitrile group, and R ₄ is aromatic nucleus, a and b are 0 or 1, and a+b is 1 or 2) and [B] a polymer having acrylic acid or methacrylic acid as units.

Examples of photopolymerizable photosensitive resins having ethylenically unsaturated double bonds are detailed in U.S. Pat. Suitable examples of monomers include acrylic esters and methacrylic esters of polyhydric alcohols, such as acrylic acids such as ethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, trimethylolpropane, pentaerythritol, neopentyl glycol, etc. Methacrylic acid esters may be mentioned by way of example. Esters of acrylic acid and methacrylic acid modified and derived from bisphenol A, such as reaction products of bisphenol A-epichlorohydrin epoxy resin prepolymers and acrylic acid or methacrylic acid, alkylene oxide adducts of bisphenol A, or hydrogen thereof Additives such as acrylic acid and methacrylic esters may be used. Other bisacrylamide or bismethacrylamide of diamines such as methylenebisacrylamide, ethylenebisacrylamide, ethylenediamine, propylenediamine, butylenediamine, pentamethylenediamine, etc.
Reaction products of diol monoacrylates or diol monomethacrylates with diisocyanates, triacrylic formals or triallylcyanurates, etc. can also be used.

The metal chelating agent used in the image forming material of the present invention is one that can form a chelate compound with the metal of the thin metal layer provided on the support during etching.

The chelating agent used in the present invention is at least one of phenol derivatives, anthraquinone derivatives, and orthoxyazo compounds.

Examples of phenol derivatives include 8-oxyquinoline, orthoxyquinoline, 2,4-dioxyquinoline, 5-nitroquinoline, 5-nitro-2-
Examples include aminophenol, 4-nitro-2-aminophenol and salts thereof.

Anthraquinone derivatives include anthraquinone-α-sulfonic acid, anthraquinone-β-sulfonic acid, anthraquinone-1,5-disulfonic acid, anthraquinone-1,8-disulfonic acid, anthraquinone-2,6-disulfonic acid, anthraquinone-2, Examples include 7-disulfonic acid and salts thereof.

Examples of the orthoxyazo compound include eriochrome black T and eriochrome black A.

A mode in which the metal chelating agent is contained in at least one layer other than the metal thin layer is that when the metal chelating agent is mixed into the photosensitive resin layer provided on the metal thin layer, the metal chelating agent is contained in the intermediate layer (the metal thin layer and the photosensitive resin layer). There are four typical cases: when the substance is mixed in the undercoat layer (between the support and the thin metal layer), and when it is mixed in the protective layer provided on the photosensitive resin layer. As an example, there may be a combination of two or more of these, and other specific examples include a wide variety of layer configurations.

The amount of metal chelating agent added varies depending on the layer structure, but
About 0.001g/ ^m2 or more, particularly preferably about 0.01g/m2
^m2 or more.

In order to prepare the metal image forming material according to the present invention, first, various methods such as vacuum evaporation method, sputtering method, ion plating method, electrodeposition method, electrophoresis method, vapor phase deposition method, spray method, etc. are applied to the surface of the specified support. This is carried out by forming a desired metal layer by the method described above, and further forming a photosensitive resin layer (a protective layer as necessary) thereon (via an intermediate layer as necessary). When a metal chelating agent is mixed into the photosensitive resin layer, the coating liquid for forming the photosensitive resin layer includes one or more resins selected from the various photosensitive resins mentioned above and the metal chelating agent. Make a solution with water or an organic solvent. If a metal chelating agent is mixed into the undercoat layer between the support and the metal thin layer or the protective layer on the photosensitive resin layer, which is provided as necessary, the intermediate layer between the photosensitive layer and the metal thin layer, The materials used in each layer and the metal chelating agent are dissolved in water or an organic solvent. The coating solution prepared in this manner is applied onto the metal layer by a known coating method such as a roller coating method, an air knife coating method, a dipping method, a curtain coating method, or a spray coating method, and then allowed to dry. Then, a photosensitive resin layer is formed. The dry thickness of the photosensitive resin layer may be about 0.1 to 10 μm. If it is too thin, the resist layer will be weak; if it is too thick, etching will take an excessively long time, and a resist image that accurately corresponds to the exposed image may not be formed. The location where the metal chelating agent is mixed is determined depending on the type of photosensitive resin used, the etching solution, or the etching method (one bath or two baths). It is necessary that the metal chelating agent be present in the non-image areas.

For the metal image forming material prepared as described above, the photosensitive resin layer is subjected to imagewise exposure using a known technique, the photosensitive resin layer is developed with an etching treatment solution, and the photosensitive resin layer is simultaneously (one-bath method) or Next, the thin metal layer is etched (two-bath method), and if desired, the resist formed by the photosensitive resin layer is removed to obtain the desired metal image.

Since the metal image forming material according to the present invention contains a specific metal chelating agent in at least one layer other than the thin metal layer on the support, a weak alkali, acid, or oxidizing agent aqueous solution that does not immerse the resist can be used. Etching processing can be carried out in a sufficiently short time even when using a metal etching solution of 100%, and the working time is greatly shortened, while the edge sharpness of the etched portion is good and an image with high resolution can be obtained.

The present invention will be illustrated below with reference to Examples, but the embodiments of the present invention are not limited thereto.

Example 1 Approximately 400 mg of Al is placed in a vacuum evaporation device.
A polyethylene terephthalate film (support) with a thickness of 100 μ was placed in an Al ₂ O ₃ boat and placed in a vacuum evaporation apparatus so that the distance from the evaporation source was approximately 30 cm, and the degree of vacuum was 5 × 10 ^-5. Thickness under Torr
An 800 Å thick Al deposited film was obtained. The following photosensitive resin composition was coated on this vapor-deposited film so that the film thickness after drying was 2.5 μm, and the film was dried in a dryer at 100° C. for 5 minutes.

Styrene and methacrylic acid copolymer 5 g (styrene/methacrylic acid = 70/30) Pentaerythritol triacrylate 5 g 2-isopropylthioxanthone 1 g Anthraquinone-2,6-disulfonic acid 2 g Methyl cellosolve 100 ml Metallic image formed in this way A sample of the material was passed through a bright room printer Up-6 (3kW metal halide lamp, manufactured by Ueno Chemical Co., Ltd.) and the halftone original was printed.
It was pattern-exposed for 20 seconds and immersed in a 0.1N aqueous sodium hydroxide solution for 30 seconds at a temperature of 25°C. It was confirmed that the thin metal layer in the unexposed areas was completely removed, while the brightness of the thin metal layer in the exposed areas was almost completely reversed from that of the original, and the sharpness of the halftone dot edges was also good.

On the other hand, when a metal image forming material was prepared in the same manner using a photosensitive resin composition in which anthraquinone-2,6-disulfonic acid was removed from the photosensitive resin composition and treated with the above etching solution, the etching time was also reduced. It took a long time of 3 minutes, and it was confirmed that the edge sharpness of the finished halftone image was poor.

Example 2 A suitable amount of Al ₂ Fe alloy was placed in an Al ₂ O ₃ boat placed in a vacuum evaporation apparatus, and a 100μ thick polyethylene terephthalate film (support) was placed at a distance of about 30 cm from the evaporation source. An aluminum-iron alloy film with a thickness of 800 Å was obtained under a vacuum degree of 5×10 ^-5 Torr. On this vapor-deposited film, the following photosensitive resin composition was coated with a whirlpool coating to a thickness of 2.0 μm after drying.

Methyl methacrylate and methacrylic acid copolymer 5g (methyl methacrylate/methacrylic acid =
80/20) Pentaerythritol triacrylate 5g 2-isopropylthioxanthone 1g Isoamyl dimethylaminobenzoate 0.5g Methyl cellosolve 100ml Next, the following protective composition was coated thereon to a thickness of 2.0μ as a protective layer.

Polyvinyl alcohol 10g (PVA-GL-05 manufactured by Nippon Gosei) 4-nitro-2-aminophenol Na 3g Water 100ml The sample thus obtained was exposed in the same manner as in Example 1, and a 0.1N aqueous sodium hydroxide solution was used. When the liquid temperature was 25°C and the immersion time was 10 seconds, the thin metal layer in the unexposed area was completely removed, while the thin metal layer in the exposed area was almost completely reversed in brightness compared to the original, resulting in halftone dots. It was confirmed that the sharpness of the edges was good.

Example 3 On the Al vapor deposited film created in the same manner as in Example 1,
Film thickness after drying adhesive layer (intermediate layer) with the following composition
The whiter was applied to a thickness of 1μ.

Hydroxyphenyl methacrylamide, 5g acrylonitrile, methyl methacrylate,
Copolymer of methacrylic acid 5g (30/40/25/5) 5-nitro-2-aminophenol 2g Methyl cellosolve 100ml Next, the following photosensitive resin composition was applied thereon to form a dried film with a thickness of 2.0μ. I applied whirler on it.

Polyvinyl acetate/long chain acrylate copolymer 100ml emulsion (Gelva TS-100, Monsanto
Corp.) Diazo resin (Fairmount #4) 4 g The sample thus obtained was exposed as in Example 1 and developed in tap water for 10 seconds. Next, this sample was heat-treated at 100℃ for 5 minutes, and then immersed in a 0.1N aqueous sodium hydroxide solution.
At 25℃ and immersion time for 30 seconds, the thin metal layer in the unexposed area is completely removed, while the thin metal layer in the exposed area is almost completely reversed in contrast to the original, and the sharpness of the halftone dot edges is good. This was confirmed.

Example 4 On a polyethylene terephthalate film (support) having a thickness of 100 μm, a subbing layer having the following composition was coated so that the film thickness after drying was 1 μm.

Cresol novolac resin 5g (manufactured by Gunei Kagaku Co., Ltd.) Eriochrome Black T 2g Methyl cellosolve 100ml Next, an Al vapor deposited film was provided on this in the same manner as in Example 1, and a photosensitive film with the following composition was further applied on top of this in the same manner as in Example 1. The resin layer was applied so that the film thickness after drying was 2.5 μm.

Cresol novolak resin 2.5g (manufactured by Gunei Chemical Co., Ltd.) 1,2-naphthoquinonediazide-5-sulfonic acid ester of cresol novolak resin
5g (esterification rate: 25 mol%) Methyl cellosolve 100ml A sample of the photosensitive material thus obtained was exposed and developed in the same manner as in Example 1, and the solution temperature was 25%.
℃ and immersion time for 35 seconds, the thin metal layer in the exposed area is completely removed, while the thin metal layer in the unexposed area matches the original in almost perfect contrast, resulting in an image with good halftone dot edge sharpness. It was done.

Comparative Example 1 A metal image forming material was obtained by removing anthraquinone-2,6-disulfonic acid from the photosensitive resin composition in Example 1, and after exposing this material in the same manner, it was added to the following processing solution at a temperature of 25°C. Soaked for 30 seconds.

(Treatment liquid) Sodium hydroxide 2g Anthraquinone-2,6-disulfonic acid 6g Water 1 In Example 1, the image resolution was 100 lines/mm, whereas the resolution was inferior by 70 lines/mm.

Comparative Example 2 Etching treatment was carried out in the same manner as in Example 1 except that anthraquinone-2,6-disulfonic acid in the photosensitive resin composition of Example 1 was replaced with aluminum alcoholate or aluminum chelate compound described in JP-A-50-95004.

As a result, the etching time is
It took 60 seconds at 25°C.

Comparative Example 3 Etching treatment was carried out in the same manner as in Example 3 except that 5-nitro-2-aminophenol in the adhesive layer was replaced with polyaminocarboxylic acid.

As a result, the etching time was 75 seconds at 25°C.

Claims (1)

[Scope of Claims] 1. In a metal image forming material having a thin metal layer on a support and a photosensitive resin layer thereon, at least one layer other than the thin metal layer on the support is coated with the following metal chelate. A metal image-forming material characterized by containing at least one type of agent. [Metal chelating agent] Phenol derivative Anthraquinone derivative Orthooxyazo compound