JPS6017030B2 - Method for processing image forming materials and method for processing metal images - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method of processing an image forming material for forming a guiding pattern or an optical image, and a method of processing a metal-based image, which has sharp, high resolution,
The present invention relates to a processing method for quickly and stably obtaining a fringe-free image.

The present invention can be used for decoration, formation of patterns effective for information transmission, and production of electrical parts. Items that can be used effectively as decorative items include arts and crafts and materials for lotus decorations. In addition, effective information transmission media include signs, display boards, advertising boards, original projection plates, optical masks,
There are printed versions. It is particularly effective for processing films for printing plates that require correction after image formation. In the field of electrical components, it can be used to produce microfabricated components such as printed circuit boards, printed coils, and electrodes. The technology of forming patterns using photosensitive resin and etching technology is widely known, and examples include optical masks using chromium as the object to be etched, printed circuit boards using copper, and shadow masks using stainless steel. Machine parts and the like are generally manufactured industrially. Many other products are being produced that use titanium, iron, nickel, zinc, silver, tellurium, selenium, bismuth, aluminum, IT0, indium oxide, and other materials to be etched. Among these, aluminum has good processability, such as high light-shielding properties, easy vapor deposition, and the ability to form foils, and also has a colorless metallic luster and high decorative effect. Particularly effective. In addition, aluminum has the advantage of being non-toxic and low cost, making it industrially useful. Images can be created using image-forming materials in which a photosensitive resin layer is laminated on a thin metal layer on a support. Methods are broadly divided into those in which the development of the photosensitive resin and the etching of the thin metal layer are carried out using the same solution, and those in which the development is carried out in different systems. In the latter case, Tokuseki Showa 50-11
As reported in No. 3972, a photosensitive resin such as polyvinyl cinnamate is used, and after pattern exposure, the photosensitive resin is first developed with a solvent such as xylene, and the exposed metal thin layer is treated with an alkali etc. A method of elution has been reported. However, the use of a solvent deteriorates the working environment and makes it difficult to dispose of waste liquid, and it also has drawbacks such as unevenness of the image if residual lines after development are not sufficiently removed. Therefore, it is preferable to use the same type of liquid, that is, a water system. That is, it is preferable to use an alkali-developed or acid-developed type photosensitive resin and to etch the aluminum metal with the alkali or acid. However, the etching speed of aluminum with a single solution of alkali or acid is not very fast, and if the solution concentration is increased to obtain a sufficient etching speed, water-based photosensitive resins are generally resistant to strong alkalis and acids. Since there is no adhesive, there is a drawback that swelling, peeling, etc. occur. In addition, a passive layer of oxide is formed on the aluminum surface, which is not dissolved by a single acid solution and is etched to widen pinholes. Undesirable. General aluminum etching agents can be roughly divided into phosphoric acid type,
Consists of three types: alkaline and fluorine. Phosphoric acid-based materials require high processing temperatures and slow etching rates. Although alkaline systems can increase the etching rate, they have a high peeling effect on the photosensitive resin and are not preferred. Fluorine-based materials have a higher etching speed and a peeling effect that is 4.5 times better than that of alkaline-based materials.However, with conventional compositions, bubbles are generated frequently, resulting in non-uniform etching due to bubble adhesion or peeling of the photosensitive resin due to bubbles. become. In No. 1999-99101, a halogen-based oxidizing agent was added to the alkaline solution to prevent the generation of bubbles and improve the etching rate, but the etching rate was insufficient. Further, in Tokoseki No. 50-13972, a metal having a lower ionization tendency than aluminum was mixed into aluminum to improve the etching rate, but the effect was not so great. Furthermore, when the image forming material having the above-mentioned structure is applied to a film for printing plate making, it is necessary to be able to correct the formed metal image by side etching, that is, reduce the force.

In reducing the force, the etching speed is particularly high to avoid peeling of the photosensitive resin, so Tokuseki Sho 53-14002, Tsubaki Kaisho 5
No. 3-49508 reports that a high etching rate can be obtained by adding bismuth or antimony to phosphoric acid or phosphorous acid. Because of the type of etching that advances in the direction, the image shape was poor and image unevenness occurred. In view of these shortcomings, the inventors have
We investigated a processing method for etching the photosensitive resin quickly and uniformly without forming arms, and found a processing method that can meet the above objectives, and completed the present invention. That is, in the present invention, an aluminum-based metal layer is provided on a support, a photosensitive resin layer is further provided, and then image exposure is performed from the photosensitive resin layer side, and the soluble portion of the photosensitive resin layer is developed. When removing the aluminum-based metal layer by dissolving it with a solution and then etching the exposed aluminum-based metal layer, a total of 0.5 to 3 ml of at least one compound of anti-hydrofluoric acid, ammonium fluoride, and ammonium hydrogen fluoride is added. W% 'I' Cupric oxide o. 2~5M% 'U' stone acid 0.01~3t%
A method for processing an image-forming material, characterized in that etching is carried out with an etching solution for aluminum-based metals containing at least three components, and a thin metal layer is present on a support to form an image of aluminum; A resin layer on the same image is placed on the aluminum metal pattern, and an etching solution for aluminum metal containing at least the three components 'A' and 'U' is brought into contact with the aluminum metal pattern, and the aluminum metal pattern layer is placed horizontally. A method of processing a metal-based image is characterized in that the size of the metal image is reduced by etching in the direction of the metal image. The present invention will be explained in detail below. The image-forming material to which the present invention can be applied consists of at least three layers: 1) support, 2) aluminum-based metal thin layer, and 31 photosensitive resin layer.

I will discuss each of them. As the support, films or plates of glass, polyethylene terephthalate, polypropylene, polyethylene, polypynychloride, polyvinylidene chloride, polycarbonate, cellulose acetate, polymethyl methacrylate, etc. can be used depending on the purpose.

The aluminum-based metal thin layer is mainly made of aluminum and contains zinc, lead, tin, tellurium, bismuth, iron, nickel, titanium, copper, chromium, etc. as an alloy, or contains nitrides, borides, etc. Examples include carbides, sulfides, and salts.

Summer vapor deposition, sputtering, ion plating, electroless plating, lamination, etc. can be applied to install such a thin layer made of aluminum-based metal on the support. If the layer thickness is too thin, Optical density decreases, metallic luster disappears, electrical conductivity decreases, and pattern quality deteriorates. Moreover, if it is too thick, etching takes time and processing time becomes longer. The applicable film thickness is 50 to 3000A, preferably 300 to 2000A. Furthermore, in order to improve the adhesion to the support, the support may be subjected to plasma treatment or flame treatment, or an adhesive layer may be provided before providing the aluminum-based metal thin layer. Next, the photosensitive resin constituting the photosensitive resin layer will be described.

As the photosensitive resin, both solvent-developed and aqueous-developed photosensitive resins can be used. Examples of solvent development include polyvinyl cinnamate systems such as TPR (manufactured by Tokyo Ohka Co., Ltd.) and azide rubber systems such as KTFR (manufactured by Kodak Corporation). However, because of problems such as processing of the developing solution, deterioration of working conditions, and insufficient removal of the developing solution after development, which may cause image unevenness, photosensitive resins for aqueous development are preferred. Among photosensitive resins for aqueous development, diazo-based, diazide-based, cinnamoyl-based, and acryloyl-based photosensitive resins are used as those of the alkali phenomenon type. Diazo-based systems include systems that combine quinone diazides and noporac resins, while diazide-based systems include polymers made by esterifying partially saponified polyvinyl acetate with azidophthalic anhydride, and polyvinyl alcohol with P-azidobenzaldehyde and phenolic hydroxyl groups. Examples include those acetalized with aldehydes. Examples of the cinnamoyl type include cinnamate dibasic acid mixed ester of polyvinyl alcohol and cinnamate ester of styrene-maleic anhydride copolymer. Acryloyl-based compounds include ethylenically unsaturated compounds that undergo chain polymerization with free radicals, such as '1' bentaerythritol triacrylate, and alkali-soluble polymeric binders, such as styrene-maleic acid copolymers. Examples include a system in which a free radical generating agent such as '31 penzophenone-Michael's ketone and dimethylaminoacetophenone is mixed. Examples of acid-developable types include acryloyl-based '1' acid-soluble polymer binders, such as 2-methyl-2-(N.N-dimethylamino/)methyl-1,3-propanediol and terephthalic acid copolymers. (2) ethylenically unsaturated compounds that chain polymerize with free radicals such as pentaerythritol triacrylate; Examples include systems mixed with free radial generators such as larzketone and dimethylaminoacetophene/sol.Also, since acryloyl systems have oxygen inhibition in both alkali development type and acid development type, they are water-soluble with oxygen blocking properties. resins, such as polyvinyl alcohol, polyvinylpyrrolidone, etc.
Alternatively, it is preferable to laminate a removable film such as polyethylene or polyester on the photosensitive resin. For lamination, a normal coating method may be used. For example, roll coating, bar coating, gravure coating, curtain coating, rotary coating lamination, etc. are applied. The thickness of the photosensitive resin layer is preferably 0.1 to 20 r. Next, a method for processing the above-mentioned image forming material will be described.

The processing method is '1} Image exposure'2) Development of photosensitive resin {3
}Etching {4) Consists of corrective etching. Each will be explained below. Image exposure includes contact, projection, scanning, optical fiber, flying spot, and CRT.
Can be used for close contact with

However, since photosensitive resins that become insolubilized or solubilized by light generally require exposure with a high energy density of 1 mJ/mJ or more, contact and scanning are most preferred. Exposure light sources include various lasers such as low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, xenon lamps, tungsten lamps, halogen lamps, argon lasers, helium-neon lasers, CRTs, flying spot tubes, etc. It can be used considering sensitivity, sensitivity and purpose. When using a general photosensitive resin, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a metal halide lamp, an argon laser, and a helium neon laser are suitable. After imagewise exposure is performed from the photosensitive resin layer side using each of the above-mentioned light sources, the soluble portion of the photosensitive resin layer is dissolved and removed by a developer (development treatment). For developing the photosensitive resin, a developer suitable for each photosensitive resin is used. Alkaline development type developers pass through aqueous solutions of potassium, sodium, cesium, rubidium hydroxides, or borates, phosphates, carbonates, etc., while acidic development types pass through hydrochloric acid, nitric acid,
Aqueous solutions of sulfuric acid, phosphoric acid, organic acids, etc. are suitable, and salts of strong acids and weak bases are also preferred. Further, it is preferable to add a surfactant to the developer. Solvent development type development, aromatic hydrocarbons such as toluene and xylene, ketones such as 2-butanone, monoalkyl ethers of ethylene glycol such as methoxyethanol, and alcohols such as inpropyl alcohol are applied. It can be selected depending on the type of photosensitive resin. Development processing of a photosensitive resin layer using such a developer can be carried out, for example, by soaking the pattern forming material after pattern exposure in the developer, rubbing it if necessary,
This is done by removing the soluble portion of the photosensitive resin. If the developer is aqueous, wash it with water; if it is a solvent-based developer, remove the remaining developer with fresh solvent. Particularly in the case of solvent development, care must be taken because insufficient rinsing will inhibit the next etching. Next, a total of 0.0% of at least one compound of hydrogen fluoride, ammonium fluoride, and ammonium hydrogen fluoride is added.
Add a photosensitive resin developer to an etching solution containing at least three components: 0.2 to 5 wt % of oxidation, 0.01 to 3 wt % of persimmon acid. The exposed portion of the aluminum-based metal thin layer is etched by contacting the image-forming material by immersion or some other method.

Hydrofluoric acid, ammonium fluoride, and ammonium hydrogen fluoride have the effect of dissolving the passive layer of oxide formed on the surface of the aluminum-based metal thin layer, and can also dissolve the aluminum-based metal. Therefore, the addition of the compound prevents uneven etching that occurs in acid-based etching and significantly speeds up etching. If the amount added is less than 0.5 wt%, there will be no effect, and if it is more than 3 skin t%, there will be no effect even if it is further added, and 0.5 to 3 mark K% is acceptable, preferably 1 to 15 wt%. Cupric oxide is
It has the effects of defoaming, promoting etching, and neutralizing pH.
Foaming caused by hydrogen gas, etc. that occurs when etching with only a solution is
This may cause non-uniform etching or peeling of the photosensitive resin layer due to bubble adhesion. Cupric oxide has an oxidizing effect and suppresses hydrogen gas generation. Further, since copper has a smaller ionization tendency than aluminum, aluminum dissolves as metal steel adheres, promoting etching. Furthermore, it has the effect of forming a local battery between the deposited steel and aluminum, further promoting etching. Further, the second oxidized steel has the effect of increasing the pH, increasing the etching rate and increasing the pH by 1 to 3. The amount added is 0. If it is less than t%, there will be little effect, and if it is too much, it will not dissolve completely. Since the effect will not be reduced even if added up to the saturation concentration, 0.2 to 5
wt% is suitable. It has a remarkable effect on re-depositing things such as aluminum, deposits such as copper, and adhesion reaction products that occur with etching using only nitric acid brushing, and it is also necessary as a parent regulator necessary for etching. be. Addition amount is 0.0
1 to 3 skin t% is suitable. Only by combining the above three components can the desired performance of high etching rate, no bubbles, and near neutrality be achieved. Further, a surfactant can be added to improve the wettability of the aluminum-based metal, which is the object to be etched, to the processing solution. Nonionic or anionic types are preferred, particularly nonionic polyoxyethylene ether types, ester polyoxyethylene ether types, glycol ester types, and anionic types such as carboxylic acid types such as aliphatic soaps and alkylbenzene sulfones. These include sulfonate types such as acid salts. Furthermore, as softeners for photosensitive resins, alcohols such as methanol, cellosolves such as methoxyethanol,
Solvents such as ketones such as 2-butan/ton can be added. The treatment method having the composition as described above is applied to the exposed aluminum-based metal thin layer and etched to form a desired image. Furthermore, the upper photosensitive resin layer may be peeled off depending on the purpose. Furthermore, the state before the photosensitive resin is peeled off, that is, an image-shaped aluminum-based metal film layer exists on the support, and the aluminum-based metal image that has the same image-like resin layer thereon is superimposed. ，
By contacting an etching solution for aluminum-based metal containing at least the three components 'A' and 'U', only the thin aluminum-based metal layer is laterally etched without affecting the resin layer. The size of metal images can be reduced. The composition of the etching solution is suitably the same as the etching solution used after development of the photosensitive resin layer, or one that is concentrated or diluted. Furthermore, before contacting with the etching solution (processing solution), a solvent may be brought into contact with the photosensitive resin layer so that the etching solution can easily penetrate the photosensitive resin layer. The solvent is preferably soluble in water, and alcohols, glycols, ketones, cellosolves, and amides are suitable. Suitable methods of contact include soaking, brushing, applying with a wipe, spraying, and wiping with a dropper. By using the method for processing image-forming materials described above, sharp, fringe-free, high-resolution, high-gradation patterns can be produced in an extremely short time and processed at low temperatures compared to conventional processing methods.

Furthermore, since the pH of the processing liquid is close to neutrality, the selectivity of the photosensitive resin is extremely high, and the processing stability is improved because the photosensitive resin does not become arms during processing. In addition, if used as a correction solution for aluminum-based metal images, the photosensitive resin layer will swell and peel, and the thin aluminum-based metal layer will be etched, resulting in correction only by side etching, which will reduce the layer thickness in the pattern area. An ideal correction process is performed in which only the area is reduced without any problems. Moreover, since the etching speed is extremely high, the processing time can also be shortened.
This invention will be explained in more detail below using examples.

Example 1 A film made of polyethylene terephthalate (100
Aluminum (purity 99.99%) was provided on the top of the base by vacuum evaporation.

The aluminum layer coated with Aoi was 830A. Furthermore, a photosensitive resin made by diluting the stock solution of photosensitive resin AZ-1350 manufactured by Shippray Co., Ltd. to 1/2 with xylene was coated with a spin coating machine for 10 minutes.
A photosensitive resin was formed on the swallow-adhesive aluminum layer. The coating amount was 1.8 mounds in terms of dry film thickness. The laminate was then dried in the open (60° C.) for 30 minutes.
The image forming material obtained in this way was used as a manuscript using a Momo W ultra-high pressure mercury lamp (Jet Light, manufactured by Oak Corporation), a halftone image made with iron salt lithium film, and a step tablet Type Pro (manufactured by Kodak Corporation). Close-contact exposure was performed at a distance of 90 meters from the light source. The exposure amount at that time was 2 hJ
/ It was me. Next, the photosensitive resin layer was developed by immersing and lightly rubbing No. 19 sand in a solution of 2 G (○) having the following composition. Next, 2 of the following composition was immersed in the solution marked with ○. The aluminum layer in the portion where the photosensitive resin had been dissolved (the aluminum layer exposed by the development process) was completely etched in about 5 seconds, and after being immersed in sand for a step, it was washed with water and dried. As a result, a positive image was obtained for an original document with no fringes and high contrast photographic characteristics.

Example 2 Aluminum with a purity of 99.99% was vapor-deposited on a film (100 μm) of polyethylene terephthalate to a film thickness of 1000 A, and the following photosensitive resin was prepared and coated using a rotary coating machine. It was coated on the aluminum adhesive layer at a ratio of 10 pm and dried in a 6 pm oven for 10 minutes.

The dry film thickness was 2.2 mounds.

On the coated photosensitive resin layer, a 5 wt % aqueous solution of polyvinyl alcohol with Keni Q unevenness and a degree of polymerization of 500 was further coated with a rotary coater to a dry film thickness of about 2 coats, and then placed in an oven for 30 minutes. Dry (60°C). The image forming material thus obtained was subjected to contact image exposure using an Oak Ice Maker W jet printer at 15 hJ/mt using a silk dot image of a silver salt lithium film as an original. Next, the image-forming material after image exposure was washed with water to remove the polyvinyl alcohol layer, and the photosensitive resin was developed by rubbing it with a sponge while soaking it in 4 wt % sodium carbonate.
Thereafter, it was immersed in a 25 oz etching solution having the following composition.
The aluminum in the non-image area was completely etched in about 5 seconds, and after being soaked in one layer of tochi sand, it was washed with water and dried.

As a result, as in Example 1, an image with no fringe and high contrast photographic characteristics was obtained. The image was negative-positive with respect to the manuscript. Example 3 A photosensitive resin TPR manufactured by Tokyo Ohka Co., Ltd. was used as the photosensitive resin, and the film thickness of the photosensitive resin was adjusted to 2.2 μm, and the same experiment as in Example 1 was conducted.

The exposure amount was set to 2 hJ/, and the film was developed with xylene, thoroughly rinsed with xylene, and then dried in an oven at 60 qo. After that, etching was performed in the same manner as in Example 1, and a sharp negative image with high gradation was obtained. Example 4 RF sputtering was performed on a glass substrate with a thickness of 2 yen using aluminum with a purity of 99.999% as a target.

The laminated aluminum was 1500A. A photosensitive resin manufactured by Shipley Co., Ltd. was applied onto the aluminum layer in the same manner as in Example 1, and the electrode pattern for a printed circuit board was closely exposed to light as an original, developed in the same manner as in Example 1, and then etched to make it sharp. I got a pattern. Thereafter, the photosensitive resin layer was peeled off using tetrahydrofuran, and the dried product was used as an electrode. As a result, it worked well without any electrical leakage or disconnection. Example 5 The halftone dot image obtained in Example 2 was immersed in the following two types of etching solutions at 22°C, and the state of the photosensitive resin layer and the decrease in the area ratio of the halftone image (amount of reduction in force) were observed. It was measured with a bag (silk spot area measuring device manufactured by Toyo Ink Manufacturing Co., Ltd.).

As a result, in Etching Solution 2, the area with a halftone dot area ratio of 50% was reduced by only 7.5% for 1 minute, but in Etching Solution 1, a reduction of 11.3% was achieved with 3 quartz sand.

In addition, in Etching Solution 1, the photosensitive resin layer did not peel off even if it was immersed for 5 minutes, but in Etching Solution 2, the photosensitive resin layer began to swell after 1 minute and 49 minutes of acid, and was completely peeled off with 2/3 minutes of sand. . Example 6 Etching solutions shown in the following table were prepared.

Each solution was made up to 23 oo. The pattern obtained in Example 2 was soaked in each solution for 1 minute.

As a result, in Etching Solution 1, the area ratio of silk dots decreased by 180% at 50%, but in Etching Solution 2, it decreased by 7.
It decreased by only 5%. In addition, in etching solution 3, 13
Although it had decreased by 5%, the image had a jittery shape that looked like it had been eaten by an insect. Furthermore, the pH' of each solution was 51, 13.2, and 0.5, respectively. From the above, Etching Solution 1 etched uniformly even though it was weakly acidic, and the etching rate was much faster than that of the alkaline etching solution. As is clear from the above examples, according to the processing method using the image forming material and the processing liquid, the etching is extremely fast and uniform compared to the conventional method.
Moreover, since it can be performed in near-neutral conditions, processing time is significantly shortened, images with high dimensional image power and no vibration can be obtained, and since there is less arming of the photosensitive resin, corrections by side etching are extremely easy. The variety of photosensitive resins that can be used has increased.

Claims (1)

[Claims] 1. An image forming material comprising an aluminum-based metal thin layer and a photosensitive resin layer sequentially provided on a support is subjected to image exposure from the photosensitive resin layer side, and the photosensitive resin layer When the soluble portion of is dissolved and removed by a developer and the exposed aluminum-based metal thin layer is then etched, (a) at least one compound of hydrofluoric acid, ammonium fluoride, and ammonium hydrogen fluoride, Total 0.5-30wt% Cupric oxide 0.2-5wt% (U) Nitric acid 0.01-30w
1. A method for processing an image-forming material, which comprises etching with an etching solution for aluminum-based metals containing at least t% of three components. 2. An aluminum-based metal image in which an image-shaped aluminum-based metal thin layer is present on a support, and an identical image-shaped resin layer is further present on the support, (a) hydrofluoric acid, ammonium fluoride, fluoride A total of 0.5 to 30 wt% of at least one compound of ammonium hydrogen (a) 0.2 to 5 wt% of cupric oxide (c) 0.01 to 30 w of nitric acid
A method for processing metal-based images, which comprises contacting an etching solution for aluminum-based metals containing at least three components of t%, etching a thin aluminum-based metal layer in the lateral direction, and reducing the size of the metal-based image. . 3. The method for processing an image forming material according to claim 1, characterized in that the etching solution for aluminum-based metals contains a nonionic or anionic surfactant. 4. The method for processing a metal-based image according to claim 2, wherein the etching solution for aluminum-based metals contains a nonionic or anionic surfactant. 5. The method for processing metal-based images according to claim 2, wherein the etching solution for aluminum-based metals contains a water-soluble organic solvent.