JPH0811365B2 - Photosensitive laminated film for engraving mask - Google Patents

Description

TECHNICAL FIELD The present invention relates to a photographic surface, a pattern, a pattern on the surface of a processed material such as glass, stone, ceramics, metal, plastic, wood, and leather.
The present invention relates to a photosensitive laminated film used as an engraving mask in the process of exposing an image by engraving characters etc. by sandblasting or by chemical solution etching. Due to the developability, a fine and delicate image can be easily obtained, and it has excellent resistance to sandblasting or chemicals, and its surface has strong adhesiveness, so it can be used for engraving without using an adhesive. The present invention relates to a photosensitive laminated film for an engraving mask, which can be attached to and transferred to a processed material to be used.

2. Description of the Related Art Conventionally, as a surface processing method for engraving an image on the surface of a processing material such as glass, metal or plastic, the method conventionally used is to print a resist ink directly on the surface of the processing material by printing a resist ink. The method of forming a resist film of the image or a method in which an image is similarly printed by screen printing on a non-woven fabric surface of glass fiber is called a mask, and a method of forming a resist film by adhering this to the surface of the processing material is used. In any case, the surface of the resist film is sandblasted, and the part without the resist film is polished and engraved to show an image, or if the processing material is glass, it is treated with hydrofluoric acid to remove copper. In this case, an image is exposed by corroding and engraving the part without the resist film with an aqueous solution of ferric chloride.

However, in the conventional method as described above,
In each case, the pattern image is printed by screen printing, so it is efficient and advantageous when the number of processed identical patterns is large, but when the processed number is small, such as 10 or less, print The plate-making (plate-making) process requires a lot of cost and time, which is not economically and efficiently advantageous.

Further, conventionally, various methods for producing a sandblasting mask using a liquid photosensitive resin have been proposed. For example, make a rubber frame on a processing material such as a glass plate, pour the photosensitive resin directly on it and cover it with cellophane paper, place a negative film, expose it, then peel off the cellophane paper and develop it to make an image mask. Forming method
No. 46-35681), a liquid photosensitive resin composition is sandwiched between two transparent films, and a pattern photomask is brought into close contact with the film to expose it, and the transparent film on the photomask side is peeled off. There is a method (Japanese Patent Laid-Open No. 53-99258) in which a hardened portion is removed to form a pattern, this surface is attached to the surface of the processing material, and the film on the opposite side is peeled off to form a pattern mask. Next, a liquid photosensitive resin (10% of the photocurable liquid) is placed in a mold made up of spacers on a support layer capable of sandblasting (eg, a polyester film having a thickness of 100 μm)
0% modulus 500kg / cm ² ) is injected, exposed and developed to form an image mask consisting of a photo-cured photosensitive resin layer having through-holes corresponding to the design, and rubber adhesive is applied to this support side. And applying it to the processing material (JP-A-55-96270)
No.), 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 mask pattern layer, and a mask pattern layer and a support layer positioned between the support layer and It adheres well to the mask pattern layer,
A mask transfer material for sandblasting which comprises a holding layer which is peelable from the support and has a property of being destroyed by sandblasting (JP-A-60-104938, JP-A-60-104938).
No. 104939) was proposed. However, in each case, since a liquid photosensitive resin composition is used instead of a film, an operation of injecting the resin composition using a mold or a spacer is essential, and this step is complicated and requires skill. In addition to the required operation, the exposure apparatus also required a dedicated machine, which was not economical. Further, after wash-out development of these liquid photosensitive resin compositions after exposure, organic solvents such as acetone and benzene, alkaline aqueous solutions such as caustic soda and sodium borate, calcium chloride alcohol solutions, and aqueous surfactant solutions such as neutral detergents. Must be used
This has caused various disadvantages such as safety and health problems for the operator, the collection and wastewater treatment, and the effect on the corrosive corrosion of the equipment.

In addition, it is inconvenient and time-consuming to attach an adhesive to the processing material, and the surface adhesiveness of the unsaturated polyester polymer or unsaturated polyurethane-based polymer component is used as the photosensitive resin composition. And a composition that develops sandblast resistance is disclosed, but in any case, the adhesive force is insufficient, the mask pattern of a fine pattern peels from the processing material during sandblasting, which causes the occurrence of processing defects It was.

DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention The present invention solves the above-mentioned problems, and in the production of an image mask used when engraving the surface of a processing material such as glass, metal or plastic, To easily and precisely form a sophisticated image by photographic method;
It can be handled as a film, and since only water is used for development, exposure and development are easy to handle, safe and economical, and the mask surface after development is strong by thermocompression bonding or the use of an aqueous salt solution. Exhibits excellent adhesiveness; can be attached to a processing material and transferred without an adhesive; since a mask holding layer is provided, the support can be easily peeled off during fine transfer, eliminating misalignment, and sandblasting It is an object of the present invention to provide a photosensitive laminated film for an engraving mask, which has advantages such as prevention of separation of fine parts and accurate engraving at times.

Means for Solving the Problems As a result of various studies, the inventors of the present invention have developed a photosensitive resin composition of a specific component which has photographic sensitivity capable of faithfully reproducing a fine original image and is water-developable. The above-mentioned problems have been successfully solved by applying it to a support provided with an image mask holding layer and forming a resist layer which is engraved by sandblasting or a chemical solution.

That is, the features of the present invention are (A) a support, (B) an image mask holding layer which can be peeled from the support as a film, and (C) a water-soluble polymer and a photocrosslinking agent or a molecule to be applied by coating. A photosensitive laminated film for an etching mask, comprising a layer of a water-developable photosensitive resin composition composed of a water-soluble polymer having a photocrosslinkable group.

The (A) support in the photosensitive laminated film of the present invention is necessary for the production of the laminate and the handling during use, and includes polyester (PET), polypropylene (P).
P), polyethylene (PE), polystyrene (PS), polyvinyl chloride (PVC), polycarbonate (PC) and other synthetic resin films, synthetic paper, coated paper coated with synthetic resin, etc. Therefore, the thickness is 50μ
The range of m to 500 μm is preferable.

In the photosensitive laminated film of the present invention, (B) is interposed between the (A) support and the (C) photosensitive resin composition layer.
The image mask holding layer is designed to facilitate the peeling of the support after the design image is adhered to the surface of the processing material to eliminate the positional deviation of precision and minute images, and the entire surface of the image mask during engraving such as sandblasting. The purpose of this is to prevent the fine parts from coming off and to remove it as a film after engraving. The image mask holding layer must be one that is not easily resisted by engraving or etching because the area other than the image mask portion, which is the resist layer, is easily destroyed by the chemical solution used for sandblasting or etching. The thickness of the layer is 30 μm or less, particularly preferably in the range of 1 to 10 μm. Further, although (A) is slightly adhered to the support, it does not peel off from the support during water development, and after being attached to the processing material,
When the support is forcibly peeled off, it must be something that can be easily peeled off, so rather than the adhesive force with the support,
(C) It is necessary to use a material having a larger adhesive force with the photosensitive resin composition layer that can be developed with water. That is, polyvinyl alcohol (PVA) and its derivatives, polyvinyl derivatives such as polyvinyl butyral, ethyl cellulose, cellulose acetate, cellulose nitrate, and polyvinyl chloride, polystyrene, polyamide, etc. as a developing solution in combination with a support and different materials. A polymer that is insoluble in water and capable of forming a self-supporting film is suitable.

In forming the image mask holding layer, a coating solution may be prepared by dissolving the above-mentioned film-forming polymer in a solvent, coated on one surface of the support, and dried to form a coating.

Next, as the photosensitive resin component of the (C) water-developable photocrosslinkable composition layer, a water-soluble polymer and a photocrosslinking agent such as polyvinyl alcohol and a diazo resin (paraformaldehyde condensate of 1-diazodiphenylamine). Sulfate), polyvinylpyrrolidone and sodium 4,4'-bisazidostilbene-2,2'-disulfonate, polyvinyl methyl ether and mono (di) acryloxyethyl phosphate, etc., or a water-soluble compound having a photocrosslinkable group in the molecule. Examples of the organic polymer include polyvinyl alcohol in which a stilbazolium group is introduced by acetalization, polyvinyl alcohol in which N-methylolacrylamide is added, and the like. Or a solution obtained by compatibilizing or dispersing a photopolymerizable unsaturated compound and a photopolymerization initiator in the photosensitive solution, for example, in an aqueous solution of polyvinyl alcohol and diazo resin, 2
-Hydroxyethyl acrylate and anthraquinone-2
Examples thereof include those in which sodium sulfonate is compatible, those in which bentaerythritol triacrylate and benzophenone are added to a polyvinyl alcohol aqueous solution into which a stilbazolium group is introduced, and which are emulsified and dispersed by stirring.

Furthermore, for these photosensitive components, polyvinyl acetate,
Mix various polymer emulsions such as ethylene-vinyl acetate copolymer, polystyrene and polyvinyl chloride with their plasticizers, fine powders such as silica and alumina, colorants such as dyes and pigments, and various additives such as surfactants. An aqueous dispersion of the composition thus obtained is prepared, and this is applied onto the above-mentioned support film and dried to form (C) a layer of a water-developable photosensitive resin composition. In the case of sandblasting, the thickness of this layer is selected according to the particle size of the abrasive used, the air pressure of the spray, the depth of engraving (spraying time to the same place), and in the case of etching with a chemical, the chemical Erosive,
An appropriate thickness may be selected depending on the concentration and the immersion time.
Usually its thickness is in the range of 0.05-2 mm.

Further, the formation of the photosensitive laminated film for an engraving mask of the present invention will be described in detail.

First, the original positive film is adhered to the surface of the (C) water-developable photosensitive resin composition layer of the photosensitive laminated film, and an actinic ray having a wavelength of 300 to 500 nm such as an arc lamp, a xenon lamp, a metal halide lamp, or a high pressure mercury lamp. The exposure time is set according to the thickness of the film of the photosensitive resin composition, and exposure is performed using a normal printer exposure device having a light source that generates After the exposure, it is immersed in normal temperature for a few minutes to absorb and swell the non-exposed portion, lightly rub with a brush or sponge, sprayed with water, completely washed out and dried. To adhere the image mask for engraving after water development to the processing material, place the image mask on the processing material surface and heat it with an iron, etc., or use an inorganic salt such as periodate on the processing material surface or the mask surface. Sodium, lithium chloride, lithium bromide, lithium nitrate, calcium ammonium thiocyanate, zinc chloride and other water-soluble polymers can be solubilized and applied with a dilute aqueous solution of salts that swell, and an image mask can be pressure bonded. This makes it possible to easily attach and fix the image mask on the surface of the processed material. After that, when the support on the surface is peeled off, the surface of the image mask holding layer is exposed, and engraving is performed from this surface.

As described above, the photosensitive laminated film for an engraving mask of the present invention can be exposed in the form of a film and then subjected to water development, so that it is extremely easy to handle and is a washout solution used for the development. Is water at room temperature, which is safe for the operator and economically advantageous. Furthermore, since the obtained image mask has strong adhesiveness on the surface, it can be attached to the processed material without using an adhesive, which is convenient.

Further, the size of the photosensitive film laminate of the present invention is not particularly limited, the length direction is endless, and about 2 m in the width direction is no problem, so it should be sufficiently applied to large-sized processing materials. And its practicality is extremely large.

In processing the processing material on which the engraving mask of the present invention is formed, sandblasting as a mechanical engraving,
There is chemical etching as chemical etching,
In each case, the commonly used method can be applied. That is, in sandblasting, abrasives such as gold sand having various particle sizes are jetted from a nozzle, the part without an image mask is abraded by collision friction with the abrasive, and the resist film part is impacted by the abrasive. Is not polished because it absorbs. The film thickness of the image mask depends on the depth of the engraving to be applied. In the case of deep engraving, the film thickness is made thicker to withstand jetting for a long time (for example, 0.1 to 2 mm). In the case of shallow carving for reflection, the film thickness may be thin (for example, 20 to 80 μm).

The engraving depth is adjusted by the injection pressure, the injection time, the distance between the processing material and the injection nozzle, and the particle size of the abrasive.

On the other hand, the etching process using a chemical liquid is mainly glass, using a hydrofluoric acid aqueous solution for stone materials, a ferric chloride aqueous solution for copper and copper alloy processing materials, and hydrochloric acid for other metals.
Corrosion is performed by coating and dipping with an aqueous solution of nitric acid or sulfuric acid.

 Hereinafter, the present invention will be described in detail with reference to examples.

Example 1 Average polymerization degree of 1700, saponification degree of 88 mol% Polyvinyl alcohol (PA-18 manufactured by Shin-Etsu Chemical Co., Ltd., PA-18) 15 parts by weight dissolved in 85 parts by weight of water was added to a solution of ethylene-vinyl acetate copolymer having a solid content of 50% by weight. Combined emulsion (Showa High Polymer, "EVA AD-
50 ") 120 parts by weight, diazo resin 5 parts by weight, water-dispersible blue pigment 0.2 parts by weight, and polyoxyethylene lauryl phenyl ether nonionic activator 1 part by weight are added and mixed to obtain a water-developable photosensitive resin composition. A liquid material was prepared. A 75 μm polyester film is used as the support, and when forming the image mask holding layer, ethyl cellulose (“Ethocel STD-10” manufactured by Dow Chemical Co., Ltd.) is used as a support film in a mixed solvent of ethyl alcohol and toluene 1: 1. 10% by weight of a solution dissolved in 10% by weight is dried to form an image mask holding layer of cellulose having a thickness of about 5 μm. The photosensitive resin composition is applied to this surface and dried to form a photosensitive layer having a thickness of 80 μm. A photosensitive laminated film was produced.

An original positive film having a fine pattern was brought into close contact with the photosensitive film surface of the above laminated film and exposed for 5 minutes from a distance of 1 m by a 3KW metal halide lamp. Then, after removing the original positive film, soak it in water at room temperature for about 3 minutes,
The non-exposed area was swollen with water, rubbed lightly with a sponge, developed with water, and dried with hot air at 50 ° C. to prepare an image mask with a fine pattern. No peeling occurred between the support, the image mask holding layer and the photosensitive resin composition layer during the development process.

Next, this image mask was pressure-bonded to an 8 mm-thick glass plate with an iron heated to 120 ° C., and strong adhesive attachment was obtained. Then, when the polyester film support was peeled off, the polyester film support was easily peeled off between the image mask holding layer and the polyester film support, and the image mask could be transferred without displacement.

Compress the glass plate with Alundum # 80 abrasive with compressed air.
At 4 kg / cm ^2, was subjected to polishing engraving from nozzles having a diameter of 3.6mm was injected from a distance of about 10 cm, the image mask
Even if sprayed for 30 seconds, the image mask was not peeled or damaged, and the glass plate was not polished at all.
On the other hand, in the area where there is no image mask and the glass surface is covered only with the image mask holding layer, polishing engraving proceeds at a depth of about 1 mm in about 10 seconds, and an image faithful to the original image is engraved. After finishing the engraving, wet the processing material with water and let the mask absorb water,
The film was peeled off.

Example 2 N-methyl-γ- (p-formylstyryl) -pyridinium methosulfate 1.4 mol% by acetalization reaction of 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%. 15 parts by weight of stilbazolium-added polyvinyl alcohol obtained by addition to 15 parts by weight of acrylate oligomer (“Aronix M-8030” manufactured by Toagosei Kagaku Co., Ltd.) and 15 parts by weight of pentaethathritol triacrylate in a solution prepared by dissolving 85 parts by weight of water in 85 parts by weight of water. ,
As a photopolymerization initiator, 3 parts by weight of 2-chlorothioxanthone ("Kayakyu CTX" manufactured by Nippon Kayaku) was added with stirring and dispersed. In addition, 50% by weight of this dispersion
A water-developable photosensitive composition liquid was prepared by adding and mixing 55 parts by weight of an aqueous polyvinyl acetate emulsion (“MA-6” manufactured by Hoechst Synthetic) and 0.2 parts by weight of a water-dispersible purple pigment.

This photosensitive solution was applied to the surface of the ethyl cellulose coating of the 75 μm polyester ferm used in Example 1 and dried to obtain a photosensitive resin laminated film having a photosensitive resin composition layer thickness of 100 μm.

In producing an image mask for hydrofluoric acid etching from this photosensitive resin laminated film, exposure was carried out in the same manner as in Example 1 and water development was carried out to produce an image mask having a fine pattern. No peeling occurred between the support, the image mask holding layer and the photosensitive resin composition layer during the water development step.

Next, when this image mask was attached to a glass plate having a thickness of 8 mm, a 1% aqueous solution of sodium periodate was applied to the glass plate and pressure-bonded to obtain strong adhesion. After that, when the polyester film support was peeled off, it was easily peeled off between the image mask holding layer and the polyester film, and the image mask could be transferred without displacement. When etching this glass plate, 50% by weight hydrofluoric acid aqueous solution was applied to the image mask surface, and after about 2 minutes, washed with water,
An image mask with a corrosion depth of 50 μm could be etched. At this time, the image mask holding layer made of ethyl cellulose having a thickness of 5 μm on the surface of the image mask showed almost no resistance to the hydrofluoric acid solution, while the mask film of the resist layer was not affected by hydrofluoric acid at all. After the completion of the etching, the processing material was wetted with water to absorb the mask film, and the film was peeled and removed.

Example 3 A laminated film having the same structure as the photosensitive laminated film of Example 1 was produced by the same procedure as described in Example.

Next, an image mask which was exposed and developed in the same manner as in Example 1 was prepared using an original positive film having a relatively large pattern. The image mask did not peel off from the support during the development process.

Using a copper plate with a thickness of 2 mm as a processing material, apply a 5% aqueous solution of lithium chloride on this surface, attach an image mask by pressure bonding on this, peel off the polyester film support, and transfer the image mask to the copper plate Was done. When etching this by corrosion, 1
After immersion for 5 minutes, an image with a corrosion depth of 20 μm could be etched on the part of the resist layer other than the image mask. No peeling of the image mask or attack by the ferric chloride solution was observed during the corrosion process. After the etching was completed, the mask film was peeled and removed.

Claims (1)

[Claims] 1. An image releasable as a film from a support comprising (A) a support (B) one or more components selected from the group consisting of polyvinyl alcohol and its derivatives, polyvinyl butyral, cellulose acetate and cellulose nitrate. Mask-holding layer, and (C) Water-developable photosensitive material composed of a water-soluble polymer having a photocrosslinkable group in the molecule, which is composed of polyvinyl alcohol introduced by acetalization of a stilbazolium group, which is applied by coating. A photosensitive laminated film for an engraving mask, which comprises a resin composition layer.