JPH0811365B2 - Photosensitive laminated film for engraving mask - Google Patents

Photosensitive laminated film for engraving mask

Info

Publication number
JPH0811365B2
JPH0811365B2 JP1211957A JP21195789A JPH0811365B2 JP H0811365 B2 JPH0811365 B2 JP H0811365B2 JP 1211957 A JP1211957 A JP 1211957A JP 21195789 A JP21195789 A JP 21195789A JP H0811365 B2 JPH0811365 B2 JP H0811365B2
Authority
JP
Japan
Prior art keywords
film
mask
water
support
image
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
JP1211957A
Other languages
Japanese (ja)
Other versions
JPH0379270A (en
Inventor
▲つとむ▼ 鈴木
郁夫 鈴木
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Aicello Chemical Co Ltd
Original Assignee
Aicello Chemical Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Aicello Chemical Co Ltd filed Critical Aicello Chemical Co Ltd
Priority to JP1211957A priority Critical patent/JPH0811365B2/en
Publication of JPH0379270A publication Critical patent/JPH0379270A/en
Publication of JPH0811365B2 publication Critical patent/JPH0811365B2/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Description

【発明の詳細な説明】 産業上の利用分野 本発明は、ガラス、石材、陶磁器、金属、プラスチッ
ク、木質材、皮革等の加工材料の表面に写真面、模様、
文字などをサンドブラストによる彫食刻、または薬液に
よる食刻によって画像を現出させる工程において、彫食
刻マスクとして用いられる感光性積層フィルムに関する
もので、さらに詳しく述べれば、良好な写真感光性と水
現像性により、微細で精巧な画像が容易に得られ、サン
ドブラストまたは薬液に対する耐性に優れ、かつその表
面は強力な接着性を有しているので、接着剤を用いるこ
となく、彫食刻の対象となる加工材料へ貼着、転写する
ことができる彫食刻マスク用感光性積層フィルムに関す
る。
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.

従来の技術 ガラス、金属、プラスチック等の加工材料表面に画像
を彫食刻させる表面加工法として従来から行われている
方法は、加工材料表面に直接スクリーン印刷方式によっ
て、レジストインキを印刷して目的の画像のレジスト膜
を形成する方法やガラス繊維による不織布面に、スクリ
ーン印刷によって同様に画像を印刷したものをマスクと
呼称して、これを加工材料表面に接着してレジスト膜を
形成する方法があり、いずれの場合にも、そのレジスト
膜面にサンドブラスト加工を施し、レジスト膜のない部
分を研磨、彫刻して画像を現出させるか、または加工材
料がガラスの場合はフッ酸により、銅の場合は塩化第二
鉄の水溶液によって、レジスト膜のない部分を腐食、彫
刻して画像を現出さる方法である。
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.

しかしながら、以上述べたような従来法においては、
いづれの場合にもスクリーン印刷によって図柄画像を印
刷するため、同一図柄の加工数量が多い場合には、能率
的で有利であるが、例えば10個以下のように加工数量が
少ない場合には、印刷版の作製(製版)工程に多くの費
用と時間を要し、経済的にも効率的にも有利とは言えな
かった。
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.

また、従来から液状感光性樹脂を用いて、サンドブラ
スト用マスクを作製する方法が種々提案されている。例
えば、ガラス板などの加工材料上にゴム枠を作り、そこ
に直接感光性樹脂を流し込んでセロファン紙で覆い、ネ
ガフィルムを置き、露光し、次いでセロファン紙をはぎ
とり、現像を行って画像マスクを形成する方法(特公昭
46−35681号)、透明な二枚のフィルムの間に、液状感
光性樹脂組成物をはさみ込み、これに図柄フォトマスク
を密着させて露光し、フォトマスク側の透明フィルムを
剥離して、非硬化部を除去して図柄を形成し、この面を
加工材料面に貼り合わせ、反対側のフィルムを剥離して
図柄マスクを形成する方法(特開昭53−99258号)等が
ある。次に、サンドブラスト可能な支持体層(例えば厚
さ100μmのポリエステルフィルム)にスペーサーによ
って構成された型枠に、液状感光性樹脂(光硬化液の10
0%モジラスが500kg/cm2)を注入して露光、現像し、図
柄に対応した貫通透孔を有する光硬化した感光性樹脂層
とより成る画像マスクを形成して、この支持体側にゴム
糊を塗り、加工材料に接着する方法(特開昭55−96270
号)、また、分子構造と成分性能の特定された液状感光
性樹脂組成物から成るマスクパターン層、これを保持す
るための支持体層、及びマスクパターン層と支持体層の
間に位置し、該マスクパターン層とはよく接着するが、
該支持体とは剥離可能であり、かつサンドブラストによ
り、破壊される性質を有する保持層から成るサンドブラ
スト用マスク転写材(特開昭60−104938号、特開昭60−
104939号)等が提案された。しかし、いづれの場合にも
フィルム状ではなく、液状の感光性樹脂組成物を用いる
ため、型枠やスペーサーを用いて樹脂組成物を注入する
操作が必須であって、この工程が複雑かつ熟練を要する
操作である上に、露光装置も専用機を必要とするため経
済性を欠いていた。さらにこれらの液状感光性樹脂組成
物の露光後の洗い出し現像には、アセトン、ベンゼンな
どの有機溶剤、カセイソーダ、ホウ酸ナトリウムなどの
アルカリ水溶液、塩化カルシウムアルコール溶液、中性
洗剤などの界面活性剤水溶液を使用しなければならず、
取扱い者の安全衛生上の問題、回収や排水処理、装置の
腐蝕食に及ぼす影響等、種々の不利な問題を発生させ
た。
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.

また、加工材料への貼り付けも、接着剤を用いなけれ
ばならないものは、手間がかかって不便であり、感光性
樹脂組成物として、不飽和ポリエステルポリマーや不飽
和ポリウレタン系ポリマー成分の表面粘着性とサンドブ
ラスト耐性を発現させる組成物が開示されているが、い
づれの場合にも粘着力が不充分で、サンドブラスト中に
細かな図柄のマスクパターンが加工材料から剥離し、加
工不良の発生を招く原因となっていた。
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.

発明が解決しようとする課題 本発明は、上記問題点を解決したものであって、ガラ
ス、金属、プラスチック等の加工材料の表面に彫食刻を
施す際に用いられる画像マスクの製作において、微細で
精巧な画像を写真法で容易に精度よく形成できること;
フィルム状で取扱うことができ、現像は水のみを用いて
いるので、露光、現像の取扱いが簡便であり、安全で経
済的であり、現像後のマスク面は熱圧着または塩類水溶
液の使用によって強力な接着性を示すこと;接着剤なし
で加工材料に貼着、転写ができること;マスク保持層を
設けているため、微細な転写の際、支持体の剥離を容易
にし位置ズレをなくし、サンドブラスト加工時に微細ヶ
所の離脱を防止して正確に彫刻できることなどの利点を
有する彫食刻マスク用感光性積層フィルムを提供するこ
とを課題とする。
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.

課題を解決するための手段 本発明者らは、種々研究を重ねた結果、微細な原画像
を忠実に再現できる写真感光性能を有し、水現像の可能
な特定成分の感光性樹脂組成物を画像マスク保持層を設
けた支持体に塗布して、サンドブラストまたは薬液によ
り彫食刻するレジスト層を形成することにより、上記課
題を解決することに成功した。
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.

すなわち、本発明の特徴は、(A)支持体、(B)該
支持体からフィルムとして剥離可能な画像マスク保持層
及び(C)塗布によって適用する水溶性高分子と光架
橋剤又は分子内に光架橋性基を有する水溶性高分子よ
り構成された、水現像の可能な感光性樹脂組成物の層か
ら成る彫食刻マスク用感光性積層フィルムにある。
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.

本発明の感光性積層フィルムにおける(A)支持体
は、積層体の製造上及び使用時の取扱い上必要なもので
あって、ポリエステル(PET)、ポリプロピレン(P
P)、ポリエチレン(PE)、ポリスチレン(PS)、ポリ
塩化ビニル(PVC)、ポリカーボネート(PC)などの合
成樹脂フィルムや合成紙、合成樹脂をコートしたコート
紙などが挙げられ、取扱い保持性の上から、厚さは50μ
m〜500μmの範囲のものが好適である。
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.

本発明の感光性積層フィルムにおいて、(A)支持体
と(C)感光性樹脂組成物層との間に介在させる(B)
画像マスク保持層は、図柄画像を加工材料面に接着貼り
付した後、支持体の剥離を容易にして精密、微細な画像
の位置ズレをなくし、サンドブラスト加工などの彫食刻
時には、画像マスク全面を覆って微細ヶ所の離脱を防止
し、しかも彫食刻後は皮膜として剥離する目的のもので
ある。この画像マスク保持層は、サンドブラストや食刻
に用いる薬液によってレジスト層である画像マスク部以
外の域は容易に破壊され、殆んど彫刻、食刻の抵抗にな
らないものでなければならないため、フィルム層の厚さ
は30μm以下で、特に1〜10μm厚みの範囲が好まし
い。また、(A)支持体と軽度に接着しているが、水現
像時には支持体から剥離せず、加工材料に貼り付け後、
支持体を強制的に剥離する場合には容易に剥離できるも
のでなければならないため、支持体との接着力よりも、
(C)水現像のできる感光性樹脂組成物層との接着力の
方が大きい材料を用いる必要がある。すなわち、ポリビ
ニルアルコール(PVA)とその誘導体、ポリビニルプチ
ラール、エチルセルロース、酢酸セルロース、硝酸セル
ロースなどのセルロース誘導体、支持体との異種材料の
組合わせでポリ塩化ビニル、ポリスチレン、ポリアミド
などの現像液としての水に不溶性で、自己保持性のフィ
ルムを造膜できるポリマーが好適である。
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.

この画像マスク保持層の形成にあたっては、前述の造
膜性ポリマーを溶媒に溶かした塗膜溶液を調製し、支持
体の一面に塗布、乾燥して塗膜を形成すればよい。
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.

次に、(C)水現像のできる光架橋性組成物層の感光
性樹脂成分としては、水溶性高分子と光架橋剤、例え
ばポリビニルアルコールとジアゾ樹脂(1−ジアゾジフ
ェニルアミンのパラホルムアルデヒド縮合物の硫酸
塩)、ポリビニルピロリドンと4,4′−ビスアジドスチ
ルベン−2,2′−ジスルホン酸ナトリウム、ポリビニル
メチルエーテルとモノ(ジ)アクリロキシエチルホスフ
ェートなど、又は分子内に光架橋性基を有する水溶性
高分子、例えば、スチルバゾリウム基をアセタール化に
より導入したポリビニルアルコール、N−メチロールア
クリルアミドを付加したポリビニルアルコールなどが挙
げられる。またはの感光液に光重合性の不飽和化合
物と光重合開始剤を相溶もしくは分散させたもの、例え
ば、ポリビニルアルコールとジアゾ樹脂の水溶液に、2
−ヒドロキシエチルアクリレートとアンスラキノン−2
−スルホン酸ナトリウムを相溶させたもの、スチルバゾ
リウム基を導入したポリビニルアルコール水溶液にベン
タエリスリトールトリアクリレートとベンゾフェノンを
添加し、攪拌によりエマルジョン化して分散させたもの
などが挙げられる。
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.

さらに、これらの感光成分に対し、ポリ酢酸ビニル、
エチレン−酢酸ビニル共重合体、ポリスチレン、ポリ塩
化ビニルなどの高分子エマルジョンとその可塑剤、シリ
カ、アルミナなどの微粉末、染料、顔料などの着色剤や
界面活性剤等各種の添加剤を混合することによって得ら
れる組成物の水性分散液を調製し、これを前述の支持フ
ィルムに塗布、乾燥して(C)水現像のできる感光性樹
脂組成物の層を形成する。この層の厚さは、サンドブラ
スト加工の場合は、使用する研磨剤の粒度、噴射空気
圧、彫刻の深さ(同一ヶ所への噴射時間)によって選択
され、また薬液による食刻の場合には、薬液の侵食性、
濃度、浸漬時間に応じて適正な厚みを選択すればよい。
通常その厚みは0.05〜2mmの範囲である。
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.

さらに、詳しく本発明の彫食刻マスク用感光性積層フ
ィルムの形成を説明する。
Further, the formation of the photosensitive laminated film for an engraving mask of the present invention will be described in detail.

まず、原画ポジフィルムを感光性積層フィルムの
(C)水現像の可能な感光性樹脂組成物層の面に密着
し、アーク灯、キセノン灯、メタルハライド灯、高圧水
銀灯など波長300〜500nmの活性光線を発生する光源を有
する通常のプリンター露光器により、感光性樹脂組成物
のフィルムの厚みに応じた露光時間を設定して露光す
る。露光後、常温に数分間浸漬して非露光部を吸水膨潤
させ、ブラシやスポンジを用いて軽くこすり、水をスプ
レーして、洗い出しを完全に行って乾燥する。水現像後
の彫食刻用画像マスクを加工材料に接着するには、画像
マスクを加工材料面に載せ、アイロンなどで熱着するか
もしくは加工材料面またはマスク表面に無機塩類、例え
ば過沃素酸ソーダ、塩化リチウム、臭化リチウム、硝酸
リチウム、塩化カルシウムチオシアン酸アンモンニウ
ム、塩化亜鉛などの水溶性高分子を可溶化、膨潤する塩
類の稀釈水溶液を塗布し、画像マスクを圧着すればよ
く、これらによって加工材料面に画像マスクを容易に貼
着固定することが可能となる。その後に、表面の支持体
を剥離すれば、画像マスク保持層の面が露出して、この
面から彫食刻の加工を行う。
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.

以上述べたように、本発明の彫食刻マスク用感光性積
層フィルムは、フィルム状で露光し、次いで水現像を行
うことができるので、取扱いがきわめて容易であり、か
つ現像に使用する洗い出し液は常温の水であって、取扱
い者にとって安全であり、経済的にも有利である。さら
に、得られた画像マスクは表面に強力な接着性を有する
ので、接着剤を使用することなく、加工材料に貼着でき
るため便利である。
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.

また、本発明の感光性フィルム積層体の大きさは、特
に制約はなく、長さ方向はエンドレスで、幅方向につい
ても2m程度は問題がないので、大形の加工材料にも十分
適用することができ、その実用性はきわめて大きい。
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.

本発明の彫食刻マスクを形成した加工材料を加工する
に当っては、機械的な彫刻としてサンドブラスト加工、
化学的な食刻として薬液によるエッチング加工があり、
いづれも通常行われている方法が適用できる。すなわ
ち、サンドブラスト加工は、種々の粒度をもった金剛砂
のような研磨剤をノズルから噴射し、画像マスクのない
部分は研磨剤との衝突摩擦によって研磨彫刻され、レジ
スト膜の部分は研磨剤の衝撃を吸収するため研磨されな
い。画像マスクの膜厚は施す彫食刻の深さによって異な
り、深彫りの場合は長時間の噴射に耐えられるよう膜厚
を厚くする(例えば0.1〜2mm)。また、反射に浅彫りの
場合は膜厚は薄くすればよい(例えば20〜80μm)。
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).

彫刻の深さの調整は噴射圧、噴射時間、加工材料と噴
射ノズルの距離、研磨剤の粒度によって行われる。
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.

一方、薬液による食刻加工は、主としてガラス、石材
の場合はフッ酸水溶液を用い、銅及び銅合金の加工材料
の場合は塩化第二鉄水溶液、その他の金属類では塩酸、
硝酸、硫酸などの水溶液を用い塗布、浸漬して腐食を行
う。
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.

以下、実施例を示して本発明を詳しく説明する。 Hereinafter, the present invention will be described in detail with reference to examples.

実施例1 平均重合度1700、けん化度88モル%ポリビニルアルコ
ール(信越化学工業製PA−18)15重量部を水85重量部に
溶解した溶液に固形分濃度50重量%のエチレン−酢酸ビ
ニル共重合体エマルジョン(昭和高分子製、「EVA AD−
50」)120重量部、ジアゾ樹脂5重量部、水分散性青色
顔料0.2重量部、ポリオキシエチレンラウリルフェニル
エーテル非イオン活性剤1重量部を添加混合して、水現
像の可能な感光性樹脂組成物液を調製した。支持体とし
ては75μmのポリエステルフィルムとし、画像マスク保
持層の形成に当っては、支持体フィルムにエチルセルロ
ース(ダウケミカル社製、「エトセルSTD−10」)をエ
チルアルコールとトルエン1:1の混合溶媒に10重量%で
溶かした溶液を塗布乾燥して、約5μmのセルロースの
画像マスク保持層を形成し、この面に上記感光性樹脂組
成物を塗布、乾燥して感光層の厚さが80μmの感光性積
層フィルムを作製した。
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.

上記積層フィルムの感光性フィルム面に微細な図柄の
原画ポジフィルムを密着させ3KWメタルハライドランプ
により1mの距離から5分間露光した。次いで、原画ポジ
フィルムを除去した後、常温の水に約3分間浸漬して、
非露光部を吸水膨潤させ、スポンジで軽くこすり洗い出
し水現像して、50℃の熱風で乾燥し、微細な図柄の画像
マスクを作製した。現像工程中、支持体と画像マスク保
持層及び感光性樹脂組成物層の間で全く剥離は起こらな
かった。
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.

次に、この画像マスクを8mm厚さのガラス板に120℃に
加熱したアイロンで圧着したところ、強力な接着貼付け
が得られた。その後、ポリエステルフィルム支持体を剥
離したところ、画像マスク保持層とポリエステルフィル
ム支持体の間で容易に剥離し、位置ズレなく画像マスク
を転写することができた。
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.

このガラス板にアランダム#80の研磨剤を圧縮空気圧
4kg/cm2にて、口径3.6mmのノズルから約10cmの距離より
噴射して研磨彫刻を行ったところ、画像マスクに対して
30秒間噴射しても、画像マスクが剥離または破損するこ
とがなく、ガラス板は全く研磨されることがなかった。
反対に画像マスクがなくガラス面が画像マスク保持層の
みで覆われている部分は約10秒間で約1mmの深さで研磨
彫刻が進行し、原画に忠実な画像が彫刻された。彫刻終
了後に加工材料を水で濡らして、マスクを吸水させて、
膜を剥離除去した。
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.

実施例2 平均重合度1700、けん化度88モル%ポリビニルアルコ
ール(信越化学工業製PA−18)にアセタール化反応によ
り、N−メチル−γ−(p−ホルミルスチリル)−ピリ
ジニウムメトサルフェートを1.4モル%付加させて得た
スチルバゾリウム付加ポリビニルアルコール15重量部を
水85重量部に溶かした溶液にアクリレートオリゴマー
(東亜合成化学製、「アロニックスM−8030」)15重量
部、ペンタエタスリトールトリアクリレート15重量部、
光重合開始剤として、2−クロロチオキサンソン(日本
化薬製、「カヤキュアーCTX」)3重量部を攪拌しなが
ら添加して分散させた。さらに、この分散液に50重量%
濃度のポリ酢酸ビニル水性エマルジョン(ヘキスト合成
製、「MA−6」)55重量部と水分散性紫色顔料0.2重量
部を添加混合して水現像の可能な感光性組成物液を調製
した。
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.

この感光液を実施例1で使用した75μmのポリエステ
ルフェルムのエチルセルロース塗膜面に塗布、乾燥し
て、感光性樹脂組成物の層の厚さが100μmの感光性樹
脂積層フィルムを得た。
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.

この感光性樹脂積層フィルムより、フッ酸食刻のため
の画像マスクを作製するに当り、実施例1と同様な操作
により露光し、水現像を行い、微細な図柄の画像マスク
を作製した。水現像工程中、支持体と画像マスク保持層
及び感光性樹脂組成物層間で全く剥離は起こらなかっ
た。
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.

次に、この画像マスクを8mm厚さのガラス板に貼り付
けるに当り、過沃素酸ソーダの1%水溶液をガラス板に
塗布して、圧着したところ強固な接着が得られた。その
後、ポリエステルフィルム支持体を剥離したところ、画
像マスク保持層とポリエステルフィルムの間で容易に剥
離し、位置ズレなく画像マスクを転写することができ
た。このガラス板を食刻するに当り、50重量%のフッ酸
水溶液を画像マスク面に塗布して約2分経過後水洗し、
腐食深度が50μmの画像マスクを食刻することができ
た。この際、画像マスク表面の5μm厚さのエチルセル
ロースから成る画像マスク保持層はフッ酸液に対し、殆
ど抵抗性を示さず、一方、レジスト層のマスク膜は全く
フッ酸に侵されなかった。食刻終了後には、加工材料を
水で濡らして、マスク膜を吸水させて、膜を剥離除去し
た。
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.

実施例3 実施例に記載したと同様の手順により、実施例1の感
光性積層フィルムと同一構成の積層フィルムを作製し
た。
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.

次に、比較的大きな図柄の原画ポジフィルムを用いて
実施例1と同様な操作により露光、現像を行った画像マ
スクを作製した。現像工程中、支持体から画像マスクが
剥離することはなかった。
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.

加工材料として厚さ2mmの銅板を用い、この表面に塩
化リチウムの5%水溶液を塗布し、この上に画像マスク
を圧着して貼り付け、ポリエステルフィルム支持体を剥
離し、画像マスクが銅板に転写された。これを腐食によ
って食刻するに当り、比重1.3の塩化第二鉄水溶液中に1
5分間浸漬したところ、レジスト層の画像マスク以外の
部分には、腐食深度が20μmの画像を食刻することがで
きた。腐食工程中、画像マスクが剥離したり、塩化第二
鉄溶液に侵されることは認められなかった。食刻終了後
はマスク膜を剥離除去した。
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)

【特許請求の範囲】[Claims] 【請求項1】(A) 支持体 (B) ポリビニルアルコールとその誘導体、ポリビニ
ルブチラール、酢酸セルロース、硝酸セルロースの群か
ら選ばれる1種以上の成分から成る、該支持体からフイ
ルムとして剥離可能な画像マスク保持層、及び (C) 塗布によって適用する、スチルバゾリウム基を
アセタール化により導入したポリビニルアルコールより
成る、分子内に光架橋性基を持つ水溶性高分子より構成
された、水現像可能な感光性樹脂組成物の層、 から成ることを特徴とする彫食刻マスク用感光性積層フ
イルム。
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.
JP1211957A 1989-08-17 1989-08-17 Photosensitive laminated film for engraving mask Expired - Lifetime JPH0811365B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP1211957A JPH0811365B2 (en) 1989-08-17 1989-08-17 Photosensitive laminated film for engraving mask

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP1211957A JPH0811365B2 (en) 1989-08-17 1989-08-17 Photosensitive laminated film for engraving mask

Publications (2)

Publication Number Publication Date
JPH0379270A JPH0379270A (en) 1991-04-04
JPH0811365B2 true JPH0811365B2 (en) 1996-02-07

Family

ID=16614503

Family Applications (1)

Application Number Title Priority Date Filing Date
JP1211957A Expired - Lifetime JPH0811365B2 (en) 1989-08-17 1989-08-17 Photosensitive laminated film for engraving mask

Country Status (1)

Country Link
JP (1) JPH0811365B2 (en)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6140006A (en) * 1998-06-15 2000-10-31 The Chromaline Corporation Integral membrane layer formed from a photosensitive layer in an imageable photoresist laminate
JP2001177136A (en) * 1999-10-05 2001-06-29 Fuji Electric Co Ltd Method of manufacturing thin-film solar battery, and equipment of processing through hole and equipment of patterning the same by powder jetting method for thin-film substrate
JP6146891B2 (en) * 2012-10-19 2017-06-14 株式会社ミマキエンジニアリング Sandblasting method
JP5928728B2 (en) * 2013-03-27 2016-06-01 山田 雄司 Transfer method that low relief images on metal surface by sandblasting and etching
JP6742711B2 (en) * 2015-10-09 2020-08-19 株式会社アイセロ Method for transferring fine pattern to surface uneven surface treated object using film for attaching uneven surface

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5589555U (en) * 1978-12-16 1980-06-20
JPS56150512A (en) * 1980-04-23 1981-11-21 Teijin Ltd Mat pattern forming method
JPS578074A (en) * 1980-06-09 1982-01-16 Hisao Yaginuma Formation of three-dimensional carved design on surface of polygonal cylindrical member
JPS60104938A (en) * 1982-05-13 1985-06-10 Asahi Chem Ind Co Ltd Mask transferring material for working surface of solid

Also Published As

Publication number Publication date
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