JPS5883847A - Processing solution used for metallic image forming material - Google Patents

Abstract

PURPOSE:To raise a speed of etching a metallic thin film, by adding a metal- chelating agent to a processing soln. to be used for developing a metallic image forming material or reducing dots. CONSTITUTION:A metal-chelating agent, e.g., sodium anthraquinone-2,6-disulfonate is added to a developing soln. for developing a metal image forming material or a reducing soln. for reducing dots or the like to give >=0.01mol agent/liter of processing soln. Said metallic image forming material has a photosensitive layer or an imagewise corrosion resistant layer on a support provided with a metallic thin layer, thus permitting no bubble to be produced during etching the metallic thin film, the processing soln. has always good contact with the metal to be etched due to high wettability, and unevenness in etching to be prevented.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a metal imaging material, Asahi Kantan, which has a thin metal layer on a support and has a photosensitive resin layer or an image-wise corrosion resistant layer thereon. %'lK Underarm development of metal pencil-shaped paint material 46111C used aSS and reduction Wlk tone used for halftone dots etc. after development II.

Special-450-139720% Tatami-11151-IsS6
Publication No. 41 discloses that an aqueous alkaline aqueous solution is used as an aqueous solution for am or halftone dot reduction of a metal image forming material in which a KAI layer is provided on a support and a photosensitive resin layer is provided thereon. ing. However, this technique has the disadvantage of slow etching speed.

Furthermore, if the alkali is made stronger in order to increase the etching speed, there is a problem in that severe bubbles are generated during etching and the image is damaged.

Further, 41 Publication No. 5O-292FI discloses an etching solution prepared by adding sodium monoperchlorate to an aqueous alkali solution used for a metal image forming material mainly composed of KTe on a support. However, although this technique 11 provides a faster etching speed than a monoalkaline aqueous solution, there is still a problem in that a sufficient etching speed cannot be obtained.

Therefore, an object of the present invention is to provide a processing solution that has a high etching rate for four thin metal layers.
It is an object of the present invention to provide a developer or halftone dot reducer suitable for the development of a metal image forming material having a thin metal layer on a support and a photosensitive resin layer on this layer.

The above-mentioned object of the present invention is to provide a metal thin layer on a support, on which a photosensitive resin layer or a 3-like corrosion-resistant film is applied. This is achieved by a processing liquid for metal image forming materials, 41111, which contains 1 part of metal chelated copper.

The present invention will be explained in detail below.

The metal image-forming material to which the processing solution according to the present invention is applied has at least one metal thin layer directly on the support (through a subbing layer), and this metal thin layer Directly or indirectly (through an intermediate layer) K at least one photosensitive resin layer (including the case where it is a corrosion-resistant film). The metal thin layer may be a sheet-like transparent or opaque material, and the metal thin layer may be a laminated metal foil, or a metal vapor-deposited layer formed by vapor-depositing metal by vacuum vapor deposition or sputtering method (without organic material). The first photosensitive resin layer is a layer coated with a photosensitive resin composition, and the first photosensitive resin layer is a layer coated with a photosensitive resin composition. The material serves as a resist having corrosion resistance with respect to the processing solution according to the present invention.

Examples of metal image forming materials that can be produced by applying the processing solution of the present invention include 41 Japanese Patent Publication No. 48-65927 and Japanese Patent Publication No. 48-65927;
As stated in newsletter No. 65928.

A photosensitive resin layer is provided on a metal thin layer mainly composed of Te, as described in 41 Japanese Patent Publication No. 50-2925,
o, B, Co, Zn%Ou, N1, Fe, 8n.

A photosensitive resin layer provided on a metal thin layer such as V, Ge%Ag, etc., I? As described in Japanese Patent Application Laid-open No. 54-65027, a photosensitive resin layer is provided on a metal thin layer mainly composed of BI, and Japanese Patent Application Laid-Open No. 51-135641 and No. 50
-139720, 51-131621? No., Ceramic 5s
As described in Japanese Patent Publication No. -zTxas, etc., it is possible to produce a metal image forming material in which a photosensitive resin layer is provided on a thin metal layer mainly composed of ν.

In the present invention, the developer (without the metal chelate of the present invention and other agents added) refers to the metal chelate of the present invention.
Indicates a corrosive liquid (etching liquid).

However, depending on the type of resin constituting the photosensitive resin layer used, there may be photosensitive resins that can be developed (dissolving or moistening the exposed or unexposed portions of the photosensitive resin layer) using Developing IIK. The developer according to the present invention can be said to be capable of forming both a photosensitive resin layer and a thin metal layer in a liquid bath.

That is, the application of the 81L solution of the present invention is as follows: - When developing a photosensitive resin layer in a liquid bath to form a corrosion-resistant pattern and simultaneously developing a metal layer, and when developing the photosensitive resin layer first. There are also two cases: developing only the photosensitive resin layer with a liquid to leave a corrosion-resistant film like a photo-resist, and then developing with a developer** for the metal layer.

In the present invention, the reducing liquid is used to correct the partial area of the resist of the metal image forming material and the thin metal layer or the halftone dots formed by the thin metal layer after development. When performing a partial IK etch, an X-ray side etch of 5% is applied.

In the present invention, the term "processing liquid" means both the reducing solution and the developing solution.

As the treatment solution used in the present invention (no addition of metal chelate or other agents of the present IAH), conventionally known treatments can be used depending on the metal used. Such processing liquids include alkali aqueous solutions, acid aqueous solutions, oxidizing agent water**, and the like. Examples of alkali 9 aqueous solutions include aqueous solutions of lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide, ammonium hydroxide, magnesium hydroxide, sodium carbonate, tribasic sodium phosphate, sodium aluminate, etc. used. As the acid aqueous solution, 5ill of water such as phosphoric acid, acetic acid, hydrochloric acid, nitric acid, sulfuric acid, etc. is used. In addition, examples of aqueous solutions of acids and other agents include chloric acid, bromic acid, chlorinated chloride, hypobromous acid, chlorinated chloride and their salts, hydrogen peroxide, dichloride, etc.
Water 5ilk such as iron is used.

The above two methods may be used together if necessary.

The treatment liquid according to the present invention contains the metal chelating agent shown below in the treatment ilK. In the present invention, it refers to a metal chelating agent that forms a KdP-F compound during etching with the metal of the metal thin layer provided on the support.

Metal chelating agents of the present invention include - for example, "metal chelating compounds" (e.g., "metal chelating compounds").

M. Calpin, co-funded edition) The compounds described can be used. Typical specific examples include carboxylic acids (salts) such as malon 11% succinic acid, succinic acid and their salts, aliphatic amines such as ethylene cyanide, diethylene triamine, and propylene diamine. 2.2'-Dipyridyl.

Aromatic amines such as phenanthroline, amino acids and peptides such as alanine, aspartic acid, glycine, glutamic acid, proline and their salts, iminodiacetic acid,
Nitrilotriacetic acid, 1,2-diaminocyclohexane-
N,N'-tetraacetic acid, ethylenecyaminetetraacetic acid,
Amino acids such as trimethylenediaminetetraacetic acid and their salts, citric acid, individual acid and their salt-rich oxyacids, condensed phosphoric acids such as birophosphoric acid and triphosphoric acid, nido p
Acetic acid, 0-nidobenbrozoic acid and their salts, nitrocarboxylic acids, I11 salicylaldehydes, such as salicylaldehyde, 5-sulfosacitylaldehyde and their salts, and their derivatives, acetylacetone, 70yla-heptone, etc. β-diketones, $-oxyquinoline, orthoxyquinoline, 2,4-dioxyquinoline, 5-nitroquinoline, 5-nitro-2-aminephenol, 4-nitro-2-aminophenol and their salts, etc. Phenol derivative% 2. a-zp hydroxy jujube melene-6
-sulfonic acid, 1-amino-2-su7talene-4-sulfonic acid, 1-nitroly-2-hydroxynaphthalene-3
, 6-disulfonic acid, 1,2-naphthoquinone-4-sulfonic acid and naphthalene derivatives such as salts thereof, alizarin, alizarin red S, alizarin blue8. Alizarin sapphire 8B, monozole fuchsin R8, alizarin Bordeaux, anthraquinone-α-sulfonic acid, anthraquinone-β-sulfonic acid, anthraquinone-β-sulfonic acid, anthraquinone-1.
Anthraquinone derivatives such as 5-disulfonic acid, anthraquinone-1,8-disulfonic acid, anthraquinone-2,6-disulfonic acid, anthraquinone-2,7-disulfonic acid and their salts, erioph tetrambu, lac T1 eriochrome black There are orthoxyazo compounds such as Such compound a is added to the treatment liquid at an S degree of at least -0,001 mol/L, preferably at least 41 to 0.005 mol/L.

In the present invention, a particularly preferred combination of a thin metal layer and a treatment liquid is a case in which a treatment liquid prepared by adding the metal chelating agent to an alkaline aqueous solution is applied to a thin metal layer mainly composed of At.

In the present invention, in addition to adding the metal chelating agent, an organic solvent, a surfactant, etc. can be added.

The processing according to the present invention is performed in order to reduce the contact between the metal part to be etched and the processing liquid during the process of etching, and also between the photosensitive resin layer and the thin metal layer during the reduction of force. An organic solvent that can promote the swelling of the photosensitive resin may be used to facilitate the infiltration of the liquid (decreasing force*). Various resins are used depending on the type of resin S used for the layer, but in particular, allyls (methyl alcohol, ethyl alcohol, pycyl alcohol, etc.),
Monoethers of alcohols with 1 to 5 carbon atoms and ethylene glycol (e.g., ethyl cellosolve, ethyl cellosolve, butyl cellosolve, etc.) are suitable for use in resins without causing excessive swelling of the resin [K may infiltrate]. Therefore, problems such as excessive side etching, such as etching to a place that should not be etched, do not occur, which is preferable. This organic solvent is added at a ratio of 11 to 15%, preferably 0.5 to 5% (volume ratio) of the pre-dispensing solution KO.

Various surfactants may be added to the processing solution according to the present invention for the purpose of promoting appropriate etching. As such surfactants, those described in % "Surfactant Handbook" (Takahashi Todoki, Kogaku Tosho) k and commercially available products can be used. 1 Such surfactants contain about 5XlO' to 0.1
mol/ls preferably 0.001 to 0.01 mol/L
may be added to the treatment liquid of the present invention in a proportion of .

The treatment liquid according to the invention can be applied to the metal imaging material in any manner. For example, the cough metal iii* forming material may be soaked in the treatment solution according to the present invention, or the ALL solution according to the present invention may be sprayed onto the armpit metal 1iii* forming material, Further, when used as a reducing solution for etching and correcting the qIK halftone dot area, the processing solution according to the present invention may be dropped onto a portion of the Ka reducing color using a dropper or the like.

When the above-mentioned metal image forming material is processed using the processing solution according to the present invention, it becomes possible to perform etching in a very continuous manner, and one working time is greatly shortened.

In addition, no bubbles are generated when etching a thin metal layer, and the processing solution can always maintain good SaW contact with the metal being etched, which prevents uneven etching. It disappears. Furthermore, the similarity of the halftone dot shapes before and after the qIK halftone blinking power is reduced is striking. Furthermore, the processing liquid according to the proposed invention does not need to contain any hazardous substances in storage or handling, and in that sense is highly safe.

The present invention will be further illustrated by an example below, but the embodiments of the present invention are not limited thereto.

EXAMPLE I About 4.0019 U is placed in a vacuum deposition apparatus.
j, 0. A polychrome ethylene terephthalate film (support) with a thickness of 100μ was placed in a vacuum evaporator at a distance of approximately 30zK from the evaporation source, and the film was heated under a vacuum degree of 5×10 Torr. An At film (thin metal layer) with a thickness of 800λ was obtained. The following photosensitive resin composition was coated on this vapor-deposited film with a whirlpool coating so that the film thickness after drying would be 1.5 μm, and then dried for 5 minutes in a 100° C. dryer.

The sample of the metal iii * forming material obtained in this way was passed through the dot manuscript using a bright room printer Up-6' (3kW metalnoride lamp, Ueno Kagaku 11) for 20 minutes.
The sample was exposed to light for 10 seconds and immersed in a developer according to the present invention having the composition shown below.

r Sodium hydroxide 4? At this time, bubbles are generated due to etching of the thin metal layer.

The metal thin layer in the unexposed area was completely suppressed to #I when the liquid temperature was 25°C and the immersion time was 30 seconds.
On the other hand, it was confirmed by measuring with a halftone dot meter Area Datsuta (manufactured by Koueroku Photo Industry) that the thin metal layer Nakahara Sei in the exposed area was completely reversed in brightness and darkness. . On the other hand, from among the above WA Rinju, anthracite'
In the case of processing with the comparative current** excluding non-sodium 6-disulfonate, a large amount of bubbles were generated and metal remained in a dew point shape in the unexposed areas. Furthermore, the development time was as long as 3 minutes.

Example 2 The processed photosensitive material sample obtained in Example 1 was immersed in the reduced force according to the present invention having the following composition.

At this time, the halftone dots were approximately 10%
The power was reduced, and the similarity of the halftone dots before and after the power reduction was excellent.

On the other hand, anthraquinone-2,
When reducing force using only sodium 6-disulfonate # or a comparative reducing liquid, the shape of the halftone dots after reducing force is poor, and there are parts within each halftone dot where the force reduction is delayed locally. A phenomenon was observed.

Example 3 A suitable amount of A4Fe aggregate was placed in Aj, 03PoF placed in a vacuum evaporation apparatus, and a 100μ thick polyethylene terephthalate film (support) was placed at a distance of about 30mm from the evaporation source. Arranged in an arc shape in a vacuum evaporation apparatus so that the
A 50% aluminum-iron alloy vapor deposited film (metal thin layer) was obtained. A photosensitive resin composition was applied onto this vapor-deposited film in the same manner as in Example 1.

The sample thus obtained after 5K was exposed to light in the same manner as in Example 1, and immersed in a processing solution having the following composition.

``At this time, 4 tons of sodium hydroxide,
The formation of bubbles due to etching of the thin metal layer was not observed and was completely suppressed.Also, since the *ri in the unexposed area is swollen by benzyl alcohol, the permeation rate of the alkaline solution becomes large and the liquid At a temperature of 25°C and an immersion time of 10 seconds, the thin metal layer in the unexposed areas is completely removed, while the thin metal layer in the exposed areas is mixed with the original. It was confirmed that the light and dark were completely reversed.

Example 4 An appropriate amount of B1 was placed in a Ta boat placed in a vacuum evaporation apparatus, and a 100μ thick polyethylene terephthalate film (support) was placed at a distance of approximately 30 mm from the evaporation source. Placed in a vacuum evaporation equipment, vacuum degree 5
A Bl vapor deposited film (metal thin layer) with a thickness of 2000λ was obtained under X 10''-' Torr.
-1350 positive tl17't register "l" (8ht
p+,.

The film was coated with a white photosensitive solution (Sharin's photosensitive liquid) so that the film thickness after drying was 1.5 μm, and dried in a 100° C. dryer for 5 minutes. A sample of the photosensitive material thus obtained was pattern-exposed for 45 seconds through a dot original using a brightroom printer Up-6, and then exposed to light for 45 seconds through a dot original. '', a resist of iii* corresponding to the original was formed on the photosensitive resin layer.

Next, this sample was immersed in a developer according to the present invention having the following composition.

At this time, the resist is removed at a liquid temperature of 25°C and an immersion time of 10 seconds, and while the exposed part of the B'N metal thin layer is completely removed, the remaining metal thin layer of the resist is almost completely different from the original. It was confirmed that there is a corresponding brightness and darkness.

In contrast, processing with a comparative developer obtained by excluding only sodium ethylenediaminetetraacetate from the above developer required a long development time of 2 minutes.

Example 5 An appropriate amount of U is placed in a vacuum evaporation apparatus, and 0.
A 100μ thick polyethylene terephthalate film (support) was placed in a vacuum evaporator at a distance of approximately 3051 mm from the evaporation source, and the vacuum was 5 x 10-' Torr. A ktlIA deposited film (thin metal layer) with a thickness of 800λ was obtained. The following photosensitive 511m composition was coated on this vapor-deposited film with a whirlpool coating so that the dried film had a thickness of 2 μm, and was dried in a dryer at 100° C. for 5 minutes.

A sample of the photosensitive material thus obtained was subjected to pattern exposure for 20 seconds through a dot original using a bright room printer UP-6, and then the sample was immersed in a developer having the composition shown below.

At this time, the thin metal layer in the unexposed area is completely removed, while the thin metal layer in the exposed area is completely removed between the original and the cicada. was confirmed to exist in reverse. On the other hand, in the case of processing with a comparative developer obtained by removing only sodium anthraquinone-2,7-disulfone monochloride from the above AM solutions, a long AM time of 10 minutes was required.

Patent applicant: Konishiroku Photo Industry Co., Ltd. Agent: Patent attorney Akira Sakaguchi (and 1 other person)

Claims (1)

[Claims] A thin metal layer is provided on the support, and a photosensitive resin layer or a metal imaging material having image-wise corrosion resistance is provided on the support.
A processing liquid for metal image forming materials, which is a processing liquid used for 11J6 communication and low-strength sensing, and is characterized by containing a metal chelating agent.