JPH0269754A - Photosensitive laminated film for etching mask - Google Patents

Abstract

PURPOSE:To easily obtain fine and elaborate images by successively laminating a water-developable photosensitive compsn. layer, a water-developable photosensitive tacky compsn. layer and a transparent releasable film on a base. CONSTITUTION:This laminated film is constituted successively of the base, the water-developable photosensitive compsn. layer, the water-developable tacky compsn, layer and the transparent releasable film. The tacky compsn. layer is formed by applying a photosensitive tacky compsn. on the release treated surface of the transparent releasable film adjacent to the above-mentioned layer and drying the coating. This tacky compsn. layer is stuck to the surface of the photosensitive compsn. layer of the laminate of the two layers; the base and the photosensitive compsn. layer or the laminate of the three layers formed by interposing an image mask holding layer consisting of a film between these two layers by taking advantage of the tackiness of the layer. The fine and elaborate images are easily and accurately formed by a photographic method in this way.

Description

[Detailed Description of the Invention] 吏朏上■Hadako Corporation The present invention is for engraving photographic images, patterns, letters, etc. on the surface of processed materials such as glass, stone, ceramics, metal, plastic, wood, and leather by sandblasting. It also relates to a photosensitive laminated film used as an etching mask in the process of developing an image by etching with a chemical solution.More specifically, it relates to a photosensitive laminated film that is used as an etching mask in the process of developing an image by etching with a chemical solution. It is easily obtained, has excellent resistance to sandblasting or chemical solutions, and has a strong adhesive surface, so it can be affixed or transferred to processed materials without using adhesives. This invention relates to a photosensitive laminated film for masks.

The conventional surface processing method for engraving an image on the surface of processed materials such as glass, metal, and plastic is to print resist ink directly onto the surface of the processed material using a screen printing method. A method of forming a resist film with the desired image, and a method of printing a similar image on a non-woven fabric made of glass fiber by screen printing, which is called a mask, and bonding it to the surface of the processing material to form a resist film. In either case, the surface of the resist film is sandblasted, and the areas where there is no cyst film are sandblasted and engraved to reveal the image, or if the processed material is glass, it is This method involves corroding and engraving the areas where there is no resist film using an acid, or in the case of copper, an aqueous solution of ferric chloride to reveal an image.

However, in the conventional method described above, the pattern image is printed by screen printing in any case, so it is efficient and advantageous when a large number of the same pattern is processed. When the quantity to be processed is small as described below, the printing plate production (plate making) process requires a lot of cost and time, which is disadvantageous both economically and in terms of efficiency.

Furthermore, various methods have been proposed for producing sandblasting masks using liquid photosensitive resins. For example, a rubber frame is made on a processing material such as a glass plate, a photosensitive resin is directly poured into it, it is covered with cellophane paper, a negative film is placed, exposed, the cellophane paper is peeled off, and the image mask is developed. A method of forming (Japanese Patent Publication No. 4635681), between two transparent films,
Sandwich the liquid photosensitive resin composition, place a patterned photomask in close contact with it, expose it to light, and remove the transparent film on the photomask side. A method of forming a pattern by removing the non-hardened portion, bonding this surface to the surface of the processed material, and peeling off the film on the other side to form a pattern mask (Japanese Patent Application Laid-Open No. 53-99258) etc.Next, in a formwork constituted by a sandblasting support layer (for example, a 100 μm thick polyester film) and spacers,
Liquid photosensitive resin (100% modulus of photocuring liquid is 500
kg/co is injected, exposed and developed to form an image mask consisting of a photocured photosensitive resin layer having through-holes corresponding to the design. Rubber paste is applied to the support side, and the processing material is processed. (Japanese Unexamined Patent Publication No. 55-96270),
In addition, a mask pattern layer made of a liquid photosensitive resin composition having a specified molecular structure and component performance, a support layer for holding the same, and a mask pattern layer located between the mask pattern layer and the support layer, A sandblasting mask transfer material (Japanese Patent Application Laid-open No. 104939/1983), which has a retaining layer that adheres well to the layer but is separable from the support and has the property of being destroyed by sandblasting, etc. Proposed. However, since a liquid photosensitive resin composition is used in either case, the resin composition must be poured into the mold using a mold or a spacer, which is a complicated and skillful operation. Furthermore, the exposure equipment also requires a dedicated machine, which increases costs. Furthermore, for washing out and developing these liquid photosensitive resin compositions after exposure,
Do you use acetone, Hensen, etc.? 3 drugs, caustic soda,
Alkaline aqueous solutions such as sodium borate, calcium chloride alcoholic solutions, and surfactant aqueous solutions such as neutral detergents must be used, which is not only economically disadvantageous, but also poses safety and health problems for the handlers, and recalls. This results in various disadvantageous problems, such as the effects on water treatment, wastewater treatment, and corrosion of equipment.

In addition, it is time-consuming and inconvenient to attach the photosensitive resin composition to the processed material, especially when adhesives must be used. Compositions have been disclosed that exhibit adhesive properties and sandblasting resistance, but in all cases, the adhesion is insufficient, and during sandblasting, a fine mask pattern is removed from the processed material. lI
This may cause machining defects.

The present invention was developed in view of the situation of ridges, and is useful in the production of masks used when engraving the surface of processed materials such as glass, metal, and plastic. , it is possible to easily and accurately form fine and delicate images using photographic methods; it can be handled in film form, exposure and development are easy to handle, and development uses only water, making it safe and economical. , The surface of the mask after development exhibits strong adhesiveness, allowing it to be attached to and transferred to processing materials without adhesive; and if necessary, a retaining layer may be provided to transfer minute designs.
It is an object of the present invention to provide a photosensitive laminated film for an engraving mask, which makes it easy to peel off a support, eliminates positional deviation, and prevents minute spots from coming off during sandblasting, allowing accurate engraving.

The present invention will be explained in detail below.

Means for Solving the Problems In order to solve all the drawbacks of the already known sandblasting masks mentioned above, the present inventors have conducted various studies on photosensitive laminated films, and as a result, they have developed a method that faithfully reproduces minute original images. A photosensitive composition that has reproducible photographic sensitivity performance and can be developed with water, and a photocrosslinkable adhesive composition that can also be developed with water are applied to a support provided with a mask image-retaining layer if necessary. The photosensitive laminated film, which is coated with a transparent mold release film and coated with a resist layer for sandblasting or chemical engraving and an adhesive layer for transfer, can be used as a mask for engraving to achieve the above-mentioned purpose. The inventors have discovered what can be achieved and have completed the present invention.

That is, the characteristics of the present invention are as follows: (^) a support, (B) a water-developable photosensitive composition layer, (C) a water-developable photosensitive adhesive composition layer, and (D) a transparent release film. It consists of a photosensitive laminated film that is constructed in sequence.

Furthermore, the present invention can optionally provide the above (A) support and (B)
) An image mask holding layer as a film that can be peeled off from the support layer can be interposed between the photosensitive composition layers.

(8) The support in the photosensitive laminated film of the present invention is
Materials that are necessary for the production and handling of laminates, such as synthetic resin films such as polyester, polypropylene, polyethylene, polystyrene, polyvinyl chloride, and polycarbonate, synthetic paper, and coated paper coated with synthetic resin. The thickness is 5 mm for ease of handling and retention.
A material having a diameter of 0 μm to 500.171) is suitable because it has a stiffness.

In the photosensitive laminated film of the present invention, the support and (B)
The image mask holding layer interposed between the photosensitive composition layer and the photosensitive composition layer is not an essential constituent material, but if the design image is precise or minute, it can be used to easily peel off the support after being adhesively attached to the surface of the processed material. The purpose is to prevent positional deviation by covering the entire surface of the image mask during sandblasting to prevent minute spots from coming off.
Not particularly necessary. This image mask holding layer must be easily destroyed by sandblasting or the chemicals used in the molding, and must have little resistance to engraving or etching, so the thickness of the film layer should be 30 μm or less, especially 1 to 10 μm.
The thickness range is preferably m. (8) A substance that is slightly adhered to the support, but does not peel off from the support during water development, and can be easily peeled off when the support is forcibly peeled off after being attached to the processing material. Therefore, it is sufficient to use a material that has a stronger adhesive force with the water-developable photosensitive composition layer (B) than with the support material.

In other words, polyvinyl alcohol and its derivatives, cellulose derivatives such as ethyl cellulose, cellulose acetate, and cellulose nitrate, and polyvinyl chloride, polystyrene, polyamide, etc., which are insoluble in water and self-possessing as a developer, are used in combinations of different materials with supports. Polymers that can form a retentive film are preferred.

In forming this image mask protective layer, a coating material may be prepared by dissolving the above film-forming polymer in a solvent, applied to one surface of the support, and dried to form a coating film.

Next, (B) the photosensitive components of the water-developable photocrosslinkable composition layer include (1) an insoluble polymer and a photocrosslinking agent, such as polyvinyl alcohol and a diazo resin (a sulfate of a formaldehyde condensate of l-diazodiphenylamine); ), polyvinylpyrrolidone and 447-pisazidostilbene-2.
Examples include sodium 2'-disulfonate, polyvinyl methyl ether and mono(di)acryloxyethyl phosphate.

■Water-soluble polymers with photocrosslinkable groups in the molecule, e.g.
Examples include polyvinyl alcohol into which a stilbazolium group is introduced by acetalization, and polyvinyl alcohol to which N-methylolacrylamide is added. ■is■
Or, a photosensitive solution prepared by dissolving or dispersing a photopolymerizable unsaturated compound and a photopolymerization initiator in the photosensitive liquid of Compatible with sodium acid, stilbazolium group
An example is one in which penquerythritol triacrylate and benzophenone are added to an aqueous solution of polyvinyl alcohol prepared by four people, and then emulsified and dispersed by stirring. Furthermore, for these photosensitive components, polymer emulsions such as polyvinyl acetate, ethylene vinyl acetate copolymer, polystyrene, polyvinyl chloride and their plasticizers,
An aqueous dispersion of the composition obtained by mixing various additives such as fine powders such as silica and alumina, colorants such as dyes and pigments, and surfactants is prepared, and this is applied to the above-mentioned support film. It is dried to form (C) a water-developable photosensitive composition layer. In the case of sandblasting, the thickness of this layer is selected depending on the grain size of the grain used, the jet air pressure, and the depth of engraving (time of spraying on the same spot). erosive properties of chemical solutions;
An appropriate thickness may be selected depending on the concentration and immersion time.

Usually its thickness is in the range of 0.05 to 21TII1).

Next, as the adhesive component of the water-developable photosensitive adhesive composition layer (C), a water-soluble adhesive described in JP-A-48-56240 is suitable. Among these, a solution polymer of 70 to 90% by weight of 2-hydroxyethyl acrylate or 2-hydroxypropyl acrylate and 30 to 10% by weight of 2-hydroxyethyl methacrylate or 2-hydroxypropyl methacrylate in an isopropyl alcohol solvent is a good solution. It is suitable as the adhesive component of the present invention because it has water compatibility, strong adhesive strength, and excellent photocrossability.

To impart photosensitivity to this adhesive component, a polyfunctional acrylate such as trimethylolpropane triacrylate, pentaerythritol triacrylate, tetrafunctional urethane acrylate, polyfunctional epoxy acrylate, etc. is used as a photocrosslinking agent in the isopropanol solution of the adhesive component. A composition solution may be prepared by adding and mixing a photopolymerization initiator such as benzophenone, benzylbenzyl dimethyl ketal, hengeine, thioxanthone, and the like.

In forming this adhesive composition layer (C), the above-mentioned photosensitive adhesive composition liquid is applied to the release-treated surface of the transparent release film (D) adjacent thereto, dried, and this adhesive composition layer is formed. Either a two-part laminate of (A) the support and (B) the photosensitive composition layer already produced by using the method or a three-part laminate with an image mask holding layer made of the above film interposed between the two. (B)
If it is laminated onto the surface of the photosensitive composition layer, the photosensitive film laminate of the present invention can be obtained.

The thickness of the photosensitive adhesive composition layer (C) used here is not particularly limited, but a thickness of 20 to 200 μm is preferably within the range, and this layer also functions as a resistance layer for sandblasting and the like. Next, (D) the transparent release film is a film made of a transparent film such as polyester, polypropylene, polystyrene, polyethylene, etc. coated with a silicone-based U-type agent, and the thickness of the film is the same as that of the film surface. Since the original image is exposed in close contact with the original image, if the layer is too thick, light will scatter within this layer and image reproducibility will deteriorate, so it is better to make it as thin as possible, but from the viewpoint of processing and handling, it should be 20 to 60 μm. is the preferred range.

In more detail, how to use the photosensitive laminated film for engraving masks of the present invention will be explained in more detail. First, the original positive film is placed in close contact with the (D) transparent release film surface of the photosensitive laminated film, and a normal light source that generates active light with a wavelength of 300 to 500 nm, such as an arc lamp, xenon lamp, metal halide lamp, or high-pressure mercury lamp, is used. Expose using a printer exposure device, setting an exposure time that corresponds to the thickness of the photosensitive film. After exposure (D) 33 Peel and remove the clear film, immerse it in water at room temperature for a few minutes to absorb water and swell the unexposed area, rub it lightly with a brush or sponge, and spray with water to completely wash it out. Wash and dry. If you want to save the etching mask after development, do you have to put it on the adhesive side of the image mask once? It is a good idea to reapply the transparent release film that you removed.

The adhesive layer on the surface of the image mask is a photo-crosslinked adhesive layer and has strong adhesive force, so that the image mask can be easily adhered and fixed to the surface of the processed material. Thereafter, when the surface support is peeled off, the image mask surface or the surface of the image mask holding layer provided as necessary is exposed, and the etching process is performed from this surface.

As mentioned above, the photosensitive laminated film for engraving masks of the present invention can be exposed and developed in film form, so it is extremely easy to handle, and the washing solution used for development can be kept at room temperature. water, which is safe for those who handle it and economically advantageous. Furthermore, the obtained image mask has a strong adhesive layer on the surface, so
It is convenient because it can be attached to processed materials without using adhesives.

In addition, regarding the size of the photosensitive film laminate, it is endless in the length direction, and there is no particular restriction of 1UTf of about 2 m in the width direction, so it can be fully applied to large processing materials. The practical value is extremely large.

In processing the material from which the etched mask of the present invention is formed, mechanical engraving is performed by sandblasting, and chemical etching is performed by chemical etching, both of which are normally performed. The method described will be applied. In other words, sandblasting involves injecting abrasive materials such as diamond sand with various particle sizes from a nozzle.
The portions without the mask are polished and engraved due to the collision friction with the abrasive material, and the resist film portions are not polished because they absorb the impact of the abrasive material. The thickness of the mask film varies depending on the depth of the engraving, and in the case of deep engraving, the film thickness is increased to withstand long-term spraying. (e.g. 0.1-2ffi1) 1) Also,
On the other hand, in the case of shallow engraving, the film thickness may be thinner.

(For example, 20 to 80 μm) The depth of engraving is adjusted by the injection pressure, injection time, distance between the processing material and the injection nozzle, and the particle size of the abrasive.

On the other hand, chemical engraving mainly uses hydrofluoric acid aqueous solution for glass and stone, ferric chloride aqueous solution for copper and copper alloy processing materials, and hydrochloric acid, nitric acid, sulfuric acid, etc. for other metals. Corrosion engraving is performed by applying and dipping using an aqueous solution.

Hereinafter, the present invention will be explained in detail with reference to Examples.

Example 1 A solution of 15 parts by weight of polyvinyl alcohol (Shin-Etsu Chemical PA-18) dissolved in 85 parts by weight of water with an average degree of polymerization of 1700 and a degree of saponification of 88 mol% was mixed with ethylene-vinyl acetate with a solid content concentration of 50% by weight. 120 parts by weight of polymer emulsion (Showa Kobunshi type EVA AD-50), 5 parts by weight of diazo resin
A photosensitive composition liquid was prepared by adding and mixing a mold part, 0.2 parts by weight of a water-dispersible blue pigment, and 1 part by weight of a polyoxyethylene lauryl phenyl ether nonionic activator. A 75μ polyester film was used as the support, and when forming the image mask holding layer, ethyl cellulose (manufactured by Dow Chemical Company, Ethocel 5TD-10) was used as the support film.
in a mixed solvent of ethyl alcohol and toluene 1:1.
A solution melted at 5% by weight was applied and dried to form an image mask holding layer of ethyl cellulose having a thickness of approximately 5 μm.A photosensitive composition solution was applied to this surface and dried to form a photosensitive layer with a thickness of 80 μm.
A laminated film (referred to as Laminate A) was produced.

Next, 80 parts by weight of 2-hydroxyethyl acrylate and 20 parts by weight of 2-hydroxyethyl methacrylate were added to 200 parts by weight of isopropyl alcohol as a solvent, 2 parts by weight of benzoyl peroxide was added as a polymerization catalyst, and the temperature was 60°C in a nitrogen stream. Solution polymerization was carried out for 2 hours to obtain a water-soluble adhesive solution. In order to impart photosensitivity to this adhesive, 50 parts by weight of pentaerythritol triacrylate as a photocrosslinking agent and 3 parts by weight of benzophenone as a photopolymerization initiator were added and mixed to prepare a photosensitive adhesive composition solution.
This solution was applied to the release surface of a separately prepared polypropylene release film with a thickness of 18 μm so that the thickness after drying would be 50 μm, and then laminated to form a laminated film (referred to as Laminate B), and then dried. Immediately, the photosensitive laminated stone film was bonded to the photosensitive layer surface of the laminated film of Laminated A, which had already been prepared, to obtain a photosensitive laminated stone film.

When producing a sandblasting engraving mask from this photosensitive laminated film, an original positive film with a fine pattern is brought into close contact with the transparent release film surface of the laminated film.
It was exposed for 5 minutes from a distance of 1 m using a W metal halide lamp. Next, peel off the transparent mold release film, immerse it in water at room temperature for about 3 minutes to absorb water and swell the non-exposed area, rub it lightly with a sponge, develop it, dry it with hot air at 50℃, and create a fine pattern. An image mask was created. During the development process,
No peeling occurred between the support, the image mask holding layer, and the photocrosslinking composition layer. In order to measure the adhesive strength of the surface of the mask part using a separately prepared sample, a medium size of 15 mm and a length of 1.
200 g of a sample of size oo+nI++ was placed on a glass plate.
Crimp with cJO force and 180' at a speed of 100n+m/min 2.1) When the separation resistance was measured, it was 1400.
g, indicating strong adhesion.

Next, this mask was pasted on a glass plate with a thickness of 8 mm, and when the polyester film support was set to ;/+1 Alt, it was easily peeled off between the image mask holding layer and the polyester film support, and the mask was transferred without positional shift. We were able to.

This glass plate was placed in a sandblast a, and abrasive engraving was performed by spraying Alundum #80 abrasive solvent at a compressed air pressure of 4 kg/cJ from a distance of approximately 10C++1 from a nozzle with a diameter of 3.61. Even after spraying for 30 seconds, the mask film did not peel or break, and the entire glass plate was not polished.

On the other hand, in the area where there was no mask and the glass surface was covered only with the image mask holding layer, polishing engraving progressed to a depth of about lIn1)1 in about 10 seconds E, and an image faithful to the original was engraved.

After the engraving was completed, the processed material was wetted with water, the mask film was absorbed, and the film was peeled off.

Example 2 N-methyl-γ-(p-formylstyryl) was added to polyvinyl alcohol (PA-18 manufactured by Shin-Etsu Chemical Co., Ltd.) with an average degree of polymerization of 1700 and a degree of saponification of 88 mol% by an acetalization reaction.
-Stilbazolium-added polyvinyl alcohol 1 obtained by adding 1.4 mol% of pyridinium methosulfate
Acrylate oligomer (70 Nixt 8030 manufactured by Toagosei Chemical Co., Ltd.) was added to a solution of 5 parts by weight dissolved in 85 parts by weight of water.
15-weight weighing section, pentaex-little triacrylate 1
5 parts by weight and 3 parts by weight of 2-chlorothioxanthone (Nippon Kayaku Kayacure CTX) as a photopolymerization initiator were added and dispersed with stirring. Further, 55 parts by weight of a 50M 1% aqueous polyvinyl acetate emulsion (MA-6 manufactured by Hoechst Synthesis) and 0.2 parts by weight of a water-dispersible purple pigment were added and mixed to this dispersion to prepare a photosensitive composition liquid. .

This photosensitive solution was applied to the ethyl cellulose coated surface of the 75 μm polyester film used in Example 1 and dried to produce a laminated film (hereinafter referred to as Laminate A') having a photosensitive layer thickness of 100 μm.

This laminate A' is laminated with the same laminate B as in Example 1,
A photosensitive laminated film was obtained.

To prepare a mask for hydrofluoric acid etching from this photosensitive laminated film, exposure and development were carried out in the same manner as in Example 1 to produce an image mask with a fine pattern. During the development process, no peeling occurred between the support, the image mask holding layer, and the photosensitive composition layer.

Next, when this mask was attached to a glass plate with a thickness of 8 mm and the polyester film support was peeled off, it was easily peeled off between the image mask holding layer and the polyester film, and the mask could be transferred without positional shift. . When etching this glass plate, a 50% by weight aqueous hydrofluoric acid solution was applied to the mask surface and washed with water after about 2 minutes, so that the corrosion depth was 50 μm.
I was able to engrave the image of m. At this time, it was found that the 5 μm thick ethyl cellulose image mask holding layer on the mask surface showed almost no resistance to the hydrofluoric acid solution, and that the entire mask was not attacked by the hydrofluoric acid at all. After etching, the processed material is wetted with water to allow the mask film to absorb water.
The film was peeled off.

Example 3 Same as Example 1 except that the ethyl cellulose image mask holding layer was omitted in the structure of the photosensitive laminated film of Example 1.
A laminated film was produced with the same configuration as the photosensitive laminated film.

Next, using an original positive film with a relatively large pattern, exposure and development were performed in the same manner as in Example I to prepare an image mask. During the development process, the image mask portion never separated from the support.

A copper plate with a thickness of 2 mm was used as a processing material, and when an image mask was pressed and pasted onto the surface of the plate and the polyester film support was peeled off, only the image mask was transferred to the copper plate. When etching this, it was immersed in an aqueous ferric chloride solution with a specific gravity of 1.3 for 15 minutes, and an image with a corrosion depth of 20 μm could be etched on the masked surface. During the corrosion process, no peeling of the mask or immersion in the ferric chloride solution was observed. After etching was completed, the mask film was peeled off and removed.

Claims (2)

[Claims] (1) (A) support, (B) water-developable photosensitive composition layer, (C) water-developable photosensitive adhesive composition layer, and (
D) A photosensitive laminated film for an engraving mask, comprising a laminate in which transparent release films are sequentially laminated. (2) According to claim (1), an image mask holding layer as a film that can be peeled from the support is interposed between the (A) support and (B) the water-developable photosensitive composition layer. Photosensitive laminated film for engraving masks.