JPH06335631A - Method and device for modifying surface of solid - Google Patents
Method and device for modifying surface of solidInfo
- Publication number
- JPH06335631A JPH06335631A JP5238349A JP23834993A JPH06335631A JP H06335631 A JPH06335631 A JP H06335631A JP 5238349 A JP5238349 A JP 5238349A JP 23834993 A JP23834993 A JP 23834993A JP H06335631 A JPH06335631 A JP H06335631A
- Authority
- JP
- Japan
- Prior art keywords
- solid
- treated
- light
- solid material
- modifying
- 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.)
- Granted
Links
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、表面処理されるべき固
体試料の表面に液体化合物または化合物溶液を毛管現象
を利用して接触させ、その状態で光を照射して固体試料
表面部分を光化学的に改質する方法および装置に関す
る。FIELD OF THE INVENTION The present invention relates to a photochemical reaction of a surface portion of a solid sample by bringing a liquid compound or a compound solution into contact with the surface of a solid sample to be surface-treated by utilizing a capillarity phenomenon and irradiating light in that state. And apparatus for mechanical reforming.
【０００２】[0002]
【従来の技術】従来、例えばフッ素樹脂の表面を改質す
ることを目的として、フッ素樹脂を金属ナトリウムを含
む液体アンモニアやナフタリンとテトラヒドロフラン等
の処理液に浸漬して表面改質を行う方法、あるいはポリ
エチレンやポリプロピレン樹脂を重クロム酸カリと濃硫
酸混液に浸漬してその表面を化学的に改質する方法が知
られている。2. Description of the Related Art Conventionally, for the purpose of modifying the surface of a fluororesin, for example, a method of immersing the fluororesin in a treatment liquid such as liquid ammonia containing sodium metal or naphthalene and tetrahydrofuran, or performing surface modification, or A method is known in which a polyethylene or polypropylene resin is immersed in a mixed solution of potassium dichromate and concentrated sulfuric acid to chemically modify the surface thereof.
【０００３】[0003]
【発明が解決しようとする課題】しかし、上記従来の化
学的改質方法では浸漬された全ての部分の改質は出来て
も、部分的改質はレジストを使わない限り不可能であ
る。また処理反応を制御することも難しく、しかも危険
な薬品を必要としていた。However, although the above-mentioned conventional chemical modification method can modify all the immersed portions, partial modification is impossible unless a resist is used. Further, it is difficult to control the treatment reaction, and a dangerous chemical is required.
【０００４】本発明は上記事情に鑑みなされたものであ
って、試料（被改質材料）表面に常温では極めて安全な
液体を、試料表面に極めて薄い層として強制的に密着さ
せ、その状態でこれに紫外光などの光を当てることによ
り、試料表面に何らの損傷をも与えることなく、しかも
選択的かつ、効果的に任意の官能基と置換させるなどし
て、試料表面を改質する方法およびその処理装置を提供
することを目的とする。The present invention has been made in view of the above circumstances, in which a liquid that is extremely safe at room temperature is forcibly adhered to the surface of the sample (material to be modified) as an extremely thin layer in the state. A method of modifying the sample surface by irradiating it with light such as ultraviolet light to selectively and effectively substitute any functional group without damaging the sample surface. And a processing device therefor.
【０００５】[0005]
【課題を解決するための手段】表面改質処理剤として液
体を用いることは、ガスに比べて被加工物との接触密度
が高いため、高密度で均質な処理ができる。また、紫外
線などの光によって露光部分のみを活性化させるため環
境的にも有利である。When a liquid is used as the surface-modifying agent, the density of contact with the object to be processed is higher than that of gas, so that high-density and uniform processing can be performed. Further, it is environmentally advantageous because only the exposed portion is activated by light such as ultraviolet rays.
【０００６】ところが、一般にこのような溶液にレーザ
ー光を入射すると、光分解により気泡が発生し、被加工
物界面の処理液が被加工物界面から離脱してしまい、効
果的な化学反応が行われないという問題がある。However, in general, when a laser beam is incident on such a solution, bubbles are generated due to photolysis, and the treatment liquid at the interface of the workpiece is separated from the interface of the workpiece, so that an effective chemical reaction takes place. There is a problem of not being forgotten.
【０００７】また被加工物表面の反応溶液との接触角が
大きいと、液面との接触面積が小さくなり、しかも前述
の気泡の発生により、その接触面積はさらに小さくな
る。そこで、紫外線等の光入射窓としてのガラス面と試
料面との間を極く薄くすると毛管現象により、反応溶液
がその間に入り込み、材料の溶液との接触角に関係な
く、試料面に薄い液膜を形成することができる。この状
態で試料面に紫外線等の光を照射すれば効果的な光改質
が可能となることが見出だされた。When the contact angle of the surface of the workpiece with the reaction solution is large, the contact area with the liquid surface is small, and the contact area is further reduced due to the above-mentioned generation of bubbles. Therefore, if the space between the glass surface as the light incident window for ultraviolet rays, etc. and the sample surface is made extremely thin, the reaction solution enters between them due to the capillary phenomenon, and a thin liquid is applied to the sample surface regardless of the contact angle of the material solution. A film can be formed. It has been found that effective light modification can be performed by irradiating the sample surface with light such as ultraviolet light in this state.
【０００８】したがって、本発明は上記課題を解決する
ため、固体試料表面に透明ガラス面を密着させ、毛細管
現象を利用して該固体試料表面と透明ガラスとの間に反
応溶液の薄膜を介在させ、その状態で光を照射して固体
試料表面部分を光化学的に改質するという手段を採用し
た。Therefore, in order to solve the above problems, the present invention makes a transparent glass surface adhere to the surface of a solid sample, and utilizes a capillary phenomenon to interpose a thin film of a reaction solution between the surface of the solid sample and the transparent glass. In this state, light was irradiated to modify the surface of the solid sample photochemically.
【０００９】すなわち、本発明は、被処理固体材料上面
に液体化合物または化合物溶液の薄層を介して透明窓材
を密着させ、該透明窓材を通して紫外線、可視光線、赤
外線を照射し、該被処理固体材料の表面をエッチング
し、該液体化合物または化合物溶液中の化学種と置換
し、あるいは化学種を堆積させることを特徴とする固体
表面の改質方法を提供するものである。That is, according to the present invention, a transparent window material is brought into close contact with the upper surface of a solid material to be treated through a thin layer of a liquid compound or a compound solution, and ultraviolet rays, visible rays, and infrared rays are irradiated through the transparent window material, Provided is a method for modifying a solid surface, which comprises etching the surface of a treated solid material, substituting with chemical species in the liquid compound or compound solution, or depositing chemical species.
【００１０】なお、透明窓材としては、板状、円筒状、
球状、ドーナツ型または鋳型のいずれであってもよい。
また被処理固体材料としては、プラスチック、金属、動
植物またはセラミックのいずれであってもよい。液体化
合物としては、水、純水、重水、アルコール、石油類、
芳香族化合物、シリコーンオイル、ファオンブリンオイ
ル、トリクロロエチレン、フロン１１３、フロン１１３
ａ、過酸化水素、ＨＣｌ、Ｈ2 ＳＯ4 、ＨＮＯ3 、ＨＣ
ＯＯＨ、（ＣＯＯＨ）2 、ＣＨ3 ＣＯＯＨ、ＮＨ3 、Ｎ
2 Ｈ4 、ＮＨ4 Ｆから選ばれるものを適宜用いることが
できる。溶媒としては、水、純水、重水、アンモニア、
硫酸、四塩化炭素、二硫化炭素、炭化水素類、ハロゲン
化合物類、アルコール類、フェノール類、有機酸および
その誘導体、ニトリル類、ニトロ化合物類、アミン類、
硫黄化合物類から選ばれるものを適宜用いることができ
る。透明窓材としては、紫外線透過ガラス、水晶、合成
石英ガラス、パイレックスガラス、光学ガラス、板ガラ
ス、サファイア、ダイアモンド、ＴｉＯ2 、ＩＲＴＲＡ
Ｎ、Ｇｅ、Ｓｉ，フッ化バリウム、フッ化マグネシウ
ム、炭酸カルシウム、フッ化リチウム、フッ化カルシウ
ム、フッ素樹脂、アクリル樹脂、スチレン樹脂、カーボ
ネート樹脂から選ばれるものを適宜用いることができ
る。紫外光としては、エキシマレーザー、Ａｒ+ レーザ
ー、Ｋｒ+ レーザー、Ｎ2 レーザー、非線形材料による
ハーモニックス紫外線レーザー、Ｄ2 ランプ、高圧水銀
ランプ、低圧水銀ランプ、Ｘｅランプ、Ｈｇ−Ｘｅラン
プ、ハロゲンランプ、エキシマランプ、あるいは空気、
窒素、または他のガス雰囲気のアーク、コロナまたは無
声放電により得られる紫外光ランプから選ばれるものを
適宜用いることができる。The transparent window material may be plate-shaped, cylindrical,
It may be spherical, doughnut-shaped or mold.
The solid material to be treated may be any of plastic, metal, animals and plants, or ceramic. Liquid compounds include water, pure water, heavy water, alcohol, petroleum,
Aromatic compounds, silicone oil, phaombin oil, trichlorethylene, CFC113, CFC113
a, hydrogen peroxide, HCl, H 2 SO 4 , HNO 3 , HC
OOH, (COOH) 2 , CH 3 COOH, NH 3 , N
A material selected from 2 H 4 and NH 4 F can be appropriately used. As the solvent, water, pure water, heavy water, ammonia,
Sulfuric acid, carbon tetrachloride, carbon disulfide, hydrocarbons, halogen compounds, alcohols, phenols, organic acids and their derivatives, nitriles, nitro compounds, amines,
Those selected from the sulfur compounds can be appropriately used. As transparent window materials, ultraviolet transparent glass, crystal, synthetic quartz glass, Pyrex glass, optical glass, plate glass, sapphire, diamond, TiO 2 , IRTRA
A material selected from N, Ge, Si, barium fluoride, magnesium fluoride, calcium carbonate, lithium fluoride, calcium fluoride, fluororesin, acrylic resin, styrene resin, and carbonate resin can be appropriately used. As the ultraviolet light, excimer laser, Ar + laser, Kr + laser, N 2 laser, Harmonics ultraviolet laser by non-linear material, D 2 lamp, high pressure mercury lamp, low pressure mercury lamp, Xe lamp, Hg-Xe lamp, halogen lamp. , Excimer lamp, or air,
What is selected from an ultraviolet light lamp obtained by arc, corona, or silent discharge in a nitrogen or other gas atmosphere can be appropriately used.
【００１１】さらに、本発明は、被処理固体材料を載置
する保持台と、該保持台に載置された被処理固体材料の
上面に載置可能に設けられた板状透明窓材と、該保持台
に載置された被処理固体材料の上面をほぼ垂直方向から
紫外線、可視光線、赤外線を照射するための投光手段と
を具備してなり、被処理固体材料と板状透明窓材との間
に毛管現象を利用して液体化合物または化合物溶液の薄
層を介在させ、その状態で投光手段から光を被処理固体
材料上面に照射して固体表面を改質するようにしたこと
を特徴とする固体表面改質装置を提供するものである。Further, according to the present invention, a holding table on which the solid material to be processed is placed, and a plate-shaped transparent window material which is provided on the upper surface of the solid material to be processed and placed on the holding table, The solid material to be treated and the plate-like transparent window material are provided with a light projecting means for irradiating the upper surface of the solid material to be treated placed on the holding table with ultraviolet rays, visible rays and infrared rays from a substantially vertical direction. A thin layer of a liquid compound or compound solution is interposed between and by using a capillary phenomenon, and in that state, the upper surface of the solid material to be treated is irradiated with light from the light projecting means to modify the solid surface. The present invention provides a solid surface modification device characterized by:
【００１２】この投光手段は紫外線、可視光線、赤外線
を被処理固体材料の上面を選択的に照射するように設け
ることができる。さらに、本発明は、回転自在に設けら
れたゴムローラと、該ゴムローラと平行に回転自在に設
けられた円筒状透明丸棒または透明パイプと、該ゴムロ
ーラと円筒状透明丸棒または透明パイプとの間にシート
状被処理固体材料を通過させるための手段と、該ゴムロ
ーラと円筒状透明丸棒または透明パイプとの対向部分に
紫外線、可視光線、赤外線を線状に照射するための投光
手段と、該ゴムローラと円筒状透明丸棒または透明パイ
プとを該シート状被処理固体材料を介して圧接する手段
とを具備してなり、該シート状被処理固体材料と円筒状
透明丸棒または透明パイプとの間に毛管現象を利用して
液体化合物または化合物溶液の薄層を介在させ、その状
態で投光手段から光を被処理固体材料上面に照射して固
体表面を連続的に改質するようにしたことを特徴とする
固体表面改質装置を提供するものである。This light projecting means can be provided so as to selectively irradiate the upper surface of the solid material to be processed with ultraviolet rays, visible rays and infrared rays. Further, the present invention provides a rotatably provided rubber roller, a cylindrical transparent round bar or transparent pipe rotatably provided in parallel with the rubber roller, and between the rubber roller and the cylindrical transparent round bar or transparent pipe. A means for passing the sheet-shaped solid material to be treated, and a projecting means for linearly irradiating ultraviolet rays, visible rays, and infrared rays to the opposing portion of the rubber roller and the cylindrical transparent round bar or transparent pipe, Means for press-contacting the rubber roller and a cylindrical transparent round bar or transparent pipe through the sheet-shaped solid material to be treated, the sheet-shaped solid material to be treated and the cylindrical transparent round bar or transparent pipe, A thin layer of liquid compound or compound solution is intervened by utilizing the capillarity, and in that state, the upper surface of the solid material to be treated is irradiated with light from the light projecting means to continuously modify the solid surface. It is intended to provide a solid surface modifying apparatus according to claim.
【００１３】この投光手段は、透明丸棒または透明パイ
プの外側に置いてもよく、また、透明パイプの内側に反
射鏡を設け、上記パイプの端側から線状ビームを投入す
る手段を設けたもの、透明パイプの内側に細長ランプを
挿入したものなど、適宜選択することができる。This light projecting means may be placed on the outside of the transparent round bar or the transparent pipe. Further, a reflecting mirror is provided on the inside of the transparent pipe, and means for introducing the linear beam from the end side of the pipe is provided. It is possible to appropriately select a lamp, a lamp having an elongated lamp inserted inside a transparent pipe, or the like.
【００１４】さらに、本発明は、凹レンズと凸レンズと
の間に表面処理されるべき被処理レンズを挟持させ、該
被処理レンズ（例えばコンタクトレンズ）と凹レンズお
よび凸レンズとの間に化合物溶液の薄層を毛管現象によ
り介在させ、その状態で光を被処理レンズの両面に照射
しその表面を改質するようにしたことを特徴とするレン
ズ表面の改質方法を提供するものである。Further, according to the present invention, a treated lens to be surface-treated is sandwiched between a concave lens and a convex lens, and a thin layer of a compound solution is provided between the treated lens (for example, a contact lens) and the concave lens and the convex lens. The present invention provides a method for modifying the surface of a lens, characterized in that both surfaces of the lens to be processed are modified by irradiating light on both surfaces of the lens to be processed in such a state that they are intervened by capillarity.
【００１５】さらに、本発明は、複雑な形状を呈する被
処理固体材料表面に、透明な液状プラスチック（例えば
シリコーンゴム、フッ素樹脂、ＰＭＭＡ）を流し込み、
鋳型を形成し、硬化剥離後、この鋳型と被処理固体材料
表面（例えば義歯）との間に化合物溶液の薄層を毛管現
象により介在させ、鋳型の側から光を被処理固体材料表
面に照射し、その表面を改質する方法を提供するもので
ある。Further, according to the present invention, a transparent liquid plastic (eg, silicone rubber, fluororesin, PMMA) is poured onto the surface of the solid material to be treated having a complicated shape,
After a mold is formed and cured and peeled off, a thin layer of the compound solution is interposed between this mold and the surface of the solid material to be treated (eg, denture) by capillary action, and the surface of the solid material to be treated is irradiated with light from the mold side. Then, the method of modifying the surface is provided.
【００１６】さらに、本発明は、窓材の形状をドーナツ
型にすることによって、その内周に対応する被処理固体
材料表面（例えば電線の被覆部、チューブの外被）とド
ーナツ型窓材の内周との間に薄液膜層を毛管現象により
介在させ、窓材の外周部から光を入射し、外周が円であ
る被処理固体材料表面に照射して、その表面を連続的に
改質することができる。また、これを複数台並べると、
さらに効果的な表面改質ができる。Further, according to the present invention, by making the shape of the window material into a donut shape, the surface of the solid material to be treated (for example, the covering portion of the wire, the outer jacket of the tube) corresponding to the inner circumference of the window material and the donut type window material. A thin liquid film layer is interposed between the inner periphery and the inner periphery by a capillary phenomenon, light is incident from the outer periphery of the window material, and the surface of the solid material to be treated having a circular outer periphery is irradiated to continuously modify the surface. Can be quality. Also, if you arrange multiple units,
Further effective surface modification is possible.
【００１７】さらに、本発明によれば、フッ素樹脂シー
トとフッ素樹脂シートまたは被接着処理材料との間に、
水、接着剤を挟み、加圧密着しながら、フッ素樹脂シー
トを通してＡｒＦエキシマレーザー光を入射すると、こ
れらフッ素樹脂シートとフッ素樹脂シートまたは被接着
処理材料とが強く化学接着されることが見出された。こ
れは水（Ｈ2 Ｏ）から光解離した２個の水素原子がフッ
素樹脂シート表面から脱フッ素を行い、弗素原子が抜け
た位置に水から解離した酸素原子が置換され、フッ素樹
脂シート表面の未結合手が同一の酸素原子を共有し強い
接着力を与えるものと考えられる。Further, according to the present invention, between the fluororesin sheet and the fluororesin sheet or the material to be adhered,
When ArF excimer laser light is made incident through the fluororesin sheet while sandwiching water and an adhesive and pressurizing and adhering, it is found that these fluororesin sheet and the fluororesin sheet or the material to be adhered are strongly chemically bonded. It was This is because two hydrogen atoms photodissociated from water (H2 O) defluoride from the surface of the fluororesin sheet, and oxygen atoms dissociated from water are replaced at the positions where the fluorine atoms are removed, and It is considered that the bonds share the same oxygen atom and give a strong adhesive force.
【００１８】接着剤の場合も同様であり、光解離した接
着剤中の水素原子が同時に励起されたフッ素樹脂シート
表面から脱フッ素を行い、弗素原子が抜けた位置に、同
様に水素原子を失った接着剤の未結合手が結合し、強い
接着力を与えるものと考えられる。The same applies to the case of the adhesive agent. Defluorination is performed from the surface of the fluororesin sheet in which the hydrogen atoms in the photodissociated adhesive agent are simultaneously excited, and the hydrogen atoms are similarly lost at the positions where the fluorine atoms are removed. It is considered that the dangling bonds of the adhesive bond to each other to give a strong adhesive force.
【００１９】さらに、本発明によれば、人工血管や臓器
などに要求される抗血栓性材料をフッ素樹脂材料を用い
て容易に形成し得ることが見出された。レーザーなどの
同一光源から放射されたコシーレント光を２光路に分
け、互いにある角度をもって再入射させれば、それらの
光が交差した部分で干渉が起こる。一般には、干渉部分
に感光剤を塗布した材料を置くが、本発明では、被処理
固体材料表面上に化合物液膜を介して透明窓材を載せ、
２方向または多方向から透明窓材を通して入射してきた
紫外線レーザー光を、被処理固体材料表面と液層との界
面で干渉させ、その部分の被処理固体材料表面のみ光化
学的に改質する。Further, according to the present invention, it was found that the antithrombogenic material required for artificial blood vessels, organs and the like can be easily formed by using a fluororesin material. If coherent light emitted from the same light source such as a laser is split into two optical paths and re-incident with each other at a certain angle, interference occurs at the intersection of these lights. In general, a material coated with a photosensitizer is placed on the interference portion, but in the present invention, a transparent window material is placed on the surface of the solid material to be treated via a compound liquid film,
Ultraviolet laser light that has entered through the transparent window material from two or more directions is interfered with at the interface between the surface of the solid material to be treated and the liquid layer, and only that surface of the solid material to be treated is photochemically modified.
【００２０】特に２方向から入射してくる２つの光束を
各々ブリュスター角を保って入射させると、ｐ偏光のみ
窓材内部に入射されるので、効率の高い回折格子状の改
質ができる。In particular, when two light fluxes coming from two directions are made incident while maintaining the Brewster angle, only p-polarized light is made incident on the inside of the window member, so that a highly efficient diffraction grating-like modification can be performed.
【００２１】また、窓材の一部の側面を平面鏡に加工し
ておき、平面鏡の反対側から窓材に紫外線レーザー光を
斜め方向から入射させ、その窓材内部を直接進む光と、
窓材内部の平面鏡部分で反射した光とを互いに干渉させ
れば、窓材と化合物薄液膜層を介した被処理固体材料表
面を回折格子状の改質ができる。特に斜め方向から入射
する紫外線レーザー光の入射角をブリュスター角に保て
ば、ｐ偏光のみで干渉を起こすため、干渉効率は高くな
る。このように材料表面を格子状に改質すれば、例えば
被処理固体材料にフッ素樹脂材料を用い、格子状に親水
基を置換すれば、親水、疎水のミクロ・ドメイン構造が
形成され、人工血管や臓器などに要求される抗血栓性材
料をフッ素樹脂材料を用いて容易に形成し得る。Further, a part of the side surface of the window material is processed into a plane mirror, and ultraviolet laser light is obliquely incident on the window material from the opposite side of the plane mirror, and light that directly advances inside the window material,
By interfering the light reflected by the plane mirror portion inside the window material with each other, the surface of the solid material to be treated through the window material and the compound thin liquid film layer can be modified in the form of a diffraction grating. In particular, if the incident angle of the ultraviolet laser light incident from an oblique direction is kept at Brewster's angle, interference occurs only with p-polarized light, so that the interference efficiency increases. If the surface of the material is modified in this way into a lattice, for example, a fluororesin material is used as the solid material to be treated, and if hydrophilic groups are substituted into the lattice, a hydrophilic or hydrophobic micro-domain structure is formed. An antithrombogenic material required for a tissue, an organ, etc. can be easily formed by using a fluororesin material.
【００２２】[0022]
【作用】前述したように改質したい物質の液体との接触
角が大きい。このため試料面との密着面積は小さくな
り、かつ、光分解により発生するバブルはさらにその密
着面積を小さくするが、本発明のように試料とガラス面
とを密着させ、そこに化合物溶液を毛管現象を利用して
浸入させれば、試料面全体に一様な薄い液膜を形成させ
ることができる。ここにガラス面側から紫外光を入射す
れば局所的に液体が光分解され、かつ、液体を透過した
一部の光によって試料表面をも励起して化学反応を行わ
せることができる。また液膜が薄いため、分解生成物は
すべて表面処理に使われ、従来バブル発生の原因になっ
た。余分の反応生成物を形成することもないため、バブ
ルも発生せず、効率が高い表面処理が可能となる。As described above, the contact angle of the substance to be modified with the liquid is large. For this reason, the contact area with the sample surface becomes small, and the bubbles generated by photolysis further reduce the contact area, but as in the present invention, the sample and the glass surface are brought into close contact with each other, and the compound solution is applied to the capillary. By infiltrating by utilizing the phenomenon, a uniform thin liquid film can be formed on the entire sample surface. When ultraviolet light is incident on the glass surface side, the liquid is locally photodecomposed, and a part of the light transmitted through the liquid also excites the sample surface to cause a chemical reaction. In addition, since the liquid film is thin, all the decomposition products were used for surface treatment, causing bubbles in the past. Since no extra reaction product is formed, no bubbles are generated and a highly efficient surface treatment is possible.
【００２３】[0023]
【実施例】以下、本発明を実施例を図示の装置を参照し
て説明する。図１は、本発明の方法を説明するための装
置の１例を示すものであって、被改質材料（試料）１に
化合物溶液２を滴下し（図ａ）、ついで合成石英ガラス
板３をこの滴下された化合物溶液２の上に被せ（図
ｂ），荷重を加えると被改質材料１とガラス板３との間
隙に毛管現象により一様な薄い液膜ができる。これに図
ｃに示すようにエキシマレーザー装置４を介して垂直方
向から紫外レーザー光を例えばマスク５を介して入射す
れば、露光部分のみ、液体が光分解し、かつ、被改質材
料１表面が励起されて両者の間で化学反応が起こる。こ
の場合、特に液膜が薄いため、液体２内でのレーザー光
線の吸収が抑えられ、被改質材料１表面に多くの紫外光
を到達させることができる。また液膜が薄いため、分解
生成物はすべて表面処理に使われため、従来の被改質材
料を化合物溶液の中に浸漬して紫外レーザー光を照射す
る場合において気泡の発生原因であった余分の反応生成
物はほとんど作られない。このため効果的な表面処理が
できる。DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below with reference to the illustrated apparatus. FIG. 1 shows an example of an apparatus for explaining the method of the present invention. A compound solution 2 is dropped on a material to be modified (sample) 1 (FIG. A), and then a synthetic quartz glass plate 3 is formed. Is coated on the dropped compound solution 2 (FIG. B), and a load is applied to form a uniform thin liquid film in the gap between the material to be modified 1 and the glass plate 3 due to the capillary phenomenon. As shown in FIG. 7C, when ultraviolet laser light is vertically incident through the excimer laser device 4 through, for example, the mask 5, the liquid is photodecomposed only in the exposed portion, and the surface of the material 1 to be modified is modified. Are excited and a chemical reaction occurs between them. In this case, since the liquid film is particularly thin, absorption of the laser beam in the liquid 2 is suppressed, and a large amount of ultraviolet light can reach the surface of the material 1 to be modified. In addition, since the liquid film is thin, all the decomposition products are used for surface treatment.Therefore, when the conventional material to be modified is immersed in the compound solution and irradiated with ultraviolet laser light, the extra bubbles that caused bubbles were generated. Almost no reaction product is produced. Therefore, effective surface treatment can be performed.
【００２４】また、図２は、本発明の方法を実施するた
めの他の装置の例を示すものであって、回転自在に設け
られたゴムローラ１１と、このゴムローラ１１と平行に
回転自在に設けられた円筒状透明丸棒または透明パイプ
１２と、円筒状透明丸棒または透明パイプ１２の上方に
設けられたシリンドリカルレンズ１３と、このシリンド
リカルレンズ１３を介してゴムローラ１１と円筒状透明
丸棒または透明パイプ１２との間の対向部分に紫外線、
可視光線、赤外線を線状に照射するための投光手段（図
示しない）と、ゴムローラ１１と円筒状透明丸棒または
透明パイプ１２との間にシート状被処理固体材料１４を
矢線方向に通過させるための手段（図示しない）と、円
筒状透明丸棒または透明パイプ１２をゴムローラ１１方
向に押圧する押圧手段とからなっている。FIG. 2 shows another example of the apparatus for carrying out the method of the present invention. The rubber roller 11 is rotatably provided, and the rubber roller 11 is rotatably provided in parallel with the rubber roller 11. The cylindrical transparent round bar or transparent pipe 12, the cylindrical lens 13 provided above the cylindrical transparent round bar or transparent pipe 12, and the rubber roller 11 and the cylindrical transparent round bar or transparent via the cylindrical lens 13. UV rays on the part facing the pipe 12,
The sheet-shaped solid material 14 to be processed passes in the direction of the arrow between the rubber roller 11 and the cylindrical transparent round bar or transparent pipe 12 and a light projecting means (not shown) for linearly irradiating visible light and infrared rays. It is composed of a means (not shown) for pressing and a pressing means for pressing the cylindrical transparent round bar or transparent pipe 12 toward the rubber roller 11.
【００２５】この装置において、反応溶液としての化合
物溶液２を上流側においてシート状被処理固体材料１４
表面に滴下すると、この化合物溶液２は円筒状透明丸棒
または透明パイプ１２の下面に達したとき毛管現象によ
り、円筒状透明丸棒または透明パイプ１２の下面に沿っ
て広がり薄層となる。したがって、その状態で投光手段
から光（例えば紫外レーザー光）を被処理固体材料１４
上面に照射することによりシート状被処理固体材料１４
表面を効率的かつ、連続的に改質することができる。In this apparatus, the compound solution 2 as the reaction solution is provided on the upstream side of the sheet-shaped solid material 14 to be treated.
When dropped onto the surface, the compound solution 2 spreads along the lower surface of the cylindrical transparent round bar or the transparent pipe 12 by a capillary phenomenon when reaching the lower surface of the cylindrical transparent round bar or the transparent pipe 12, and becomes a thin layer. Therefore, in that state, the solid material 14 to be processed is irradiated with light (eg, ultraviolet laser light) from the light projecting means.
By irradiating the upper surface, the solid material 14 to be processed in sheet form
The surface can be modified efficiently and continuously.
【００２６】図３は図２の装置の変形例を示すもので、
図２の装置と異なる点は、投光手段が、透明パイプ１２
の内側に設けられた反射鏡２１と、透明パイプ１２の内
側に細長ランプ（Ｈｇランプ）２２を挿入した点であ
る。その他の点については図２に示す装置と同様であ
り、したがって、同一符号を付すことにより、説明を省
略する。FIG. 3 shows a modification of the apparatus shown in FIG.
2 is different from the device shown in FIG.
The point is that the elongated mirror (Hg lamp) 22 is inserted inside the transparent pipe 12 and the reflecting mirror 21 provided inside. The other points are similar to those of the apparatus shown in FIG. 2, and therefore, the same reference numerals are given and the description thereof is omitted.
【００２７】この装置においても、反応溶液としての化
合物溶液２を上流側においてシート状被処理固体材料１
４表面に滴下すると、この化合物溶液２は透明パイプ１
２の下面に達したとき毛管現象により、透明パイプ１２
の下面に沿って広がり薄層となる。したがって、その状
態でランプ２２から光（例えば紫外光）を被処理固体材
料１４上面に照射することによりシート状被処理固体材
料１４表面を効率的かつ、連続的に改質することができ
る。Also in this apparatus, the compound solution 2 as the reaction solution is provided on the upstream side of the sheet-shaped solid material 1 to be treated.
4 When dropped on the surface, this compound solution 2 is transparent pipe 1
When reaching the lower surface of 2, the transparent pipe 12
Spreads along the lower surface of the to form a thin layer. Therefore, by irradiating the upper surface of the solid material 14 to be processed with light (for example, ultraviolet light) from the lamp 22 in that state, the surface of the solid material 14 to be processed can be efficiently and continuously modified.
【００２８】合成石英パイプ１１とゴムローラーで滴下
さた液体とともに、シート状被改質材料を圧縮すると、
毛細管現象により、圧縮部分に一直線状の薄い液膜がで
きる。ここにレーザー光をレンズで線状にしたビームを
照射したり、図３に示すように合成石英パイプの中に水
銀ランプを入れて線状液膜を照射すると、被改質材料が
連続的に表面改質できる。さらに、これらの表面改質装
置を複数台、シート状被改質材料上に並べると、さらに
効果的な表面改質が可能となる。When the sheet-form material to be modified is compressed together with the synthetic quartz pipe 11 and the liquid dropped by the rubber roller,
Due to the capillary phenomenon, a straight thin liquid film is formed in the compressed portion. Irradiating a linear beam of laser light here with a lens, or irradiating a linear liquid film with a mercury lamp in a synthetic quartz pipe as shown in FIG. The surface can be modified. Furthermore, by arranging a plurality of these surface modification devices on the sheet-shaped material to be modified, more effective surface modification becomes possible.
【００２９】図４は本発明の方法によりレンズ（例えば
コンタクトレンズ）の表面を改質する方法を示すもの
で、凹レンズ３１と凸レンズ３２との間に表面処理され
るべき被処理レンズ３３（曲率が凹レンズ３１および凸
レンズ３２と同一またはほぼ同一）を挟持させ、被処理
レンズ３３と凹レンズ３１および凸レンズ３２との間に
化合物溶液２を滴下し、その薄層を毛管現象により形成
させ、その状態で光（例えばエキシマレーザー光）を被
処理レンズ３３の両面に照射しその表面を改質するよう
にしたものである。これにより、被処理レンズ３３の両
面を一度に改質することができる。FIG. 4 shows a method of modifying the surface of a lens (for example, a contact lens) according to the method of the present invention. Between the concave lens 31 and the convex lens 32, the lens 33 to be treated (having a curvature of (The same or almost the same as the concave lens 31 and the convex lens 32) are sandwiched, the compound solution 2 is dropped between the lens 33 to be processed and the concave lens 31 and the convex lens 32, and a thin layer thereof is formed by a capillarity phenomenon. Both surfaces of the lens 33 to be processed are irradiated with (for example, excimer laser light) to modify the surface. Thereby, both surfaces of the lens 33 to be processed can be modified at once.
【００３０】（実施例１）図１に示す装置を用い、フッ
素樹脂（ＦＥＰ）シートの改質を行った。すなわち、化
合物溶液２として純水および水道水を用い、これを合成
石英ガラス板３で押し付け一様な薄い液膜をフッ素樹脂
（ＦＥＰ）シートとの間に形成させ、その状態で６．５
ｍＪ／ｃｍ2 のエネルギー密度でＡｒＦレーザー光を照
射したところ、純水および水道水のいずれの場合も親水
性が発現し、水との接触角３０度を得ることができた。Example 1 Using the apparatus shown in FIG. 1, a fluororesin (FEP) sheet was modified. That is, pure water and tap water were used as the compound solution 2, and this was pressed by the synthetic quartz glass plate 3 to form a uniform thin liquid film between the compound resin 2 and the fluororesin (FEP) sheet.
When irradiated with ArF laser light at an energy density of mJ / cm 2 , hydrophilicity was exhibited in both pure water and tap water, and a contact angle with water of 30 ° could be obtained.
【００３１】なお、比較のため同じフッ素樹脂（ＦＥ
Ｐ）シートを用い、同じ化合物溶液の中に浸漬して紫外
レーザー光を照射してフッ素樹脂（ＦＥＰ）シートの表
面改質を行ったところ、水との接触角３０度を得るの
に、純水の場合は、６．５ｍＪ／ｃｍ2 のエネルギー密
度のＡｒＦレーザー光の照射が必要であったが、水道水
の場合は、１５ｍＪ／ｃｍ2 のエネルギー密度のＡｒＦ
レーザー光の照射が必要であった。For comparison, the same fluororesin (FE
P) sheet was immersed in the same compound solution and irradiated with an ultraviolet laser beam to perform surface modification of the fluororesin (FEP) sheet. If water is irradiation of ArF laser beam energy density of 6.5mJ / cm 2 was required in the case of tap water, ArF energy density of 15 mJ / cm 2
Irradiation of laser light was necessary.
【００３２】（実施例２）図１に示す装置を用い、フッ
素樹脂（ＦＥＰ）シートの改質を行った。この場合、化
合物溶液２としてギ酸を用い、これを合成石英ガラス板
３で押し付け一様な薄い液膜をフッ素樹脂（ＦＥＰ）シ
ートとの間に形成させ、その状態で２５ｍＪ／ｃｍ2 の
エネルギー密度でＡｒＦレーザー光を照射したところ、
水との接触角１０度を得ることができた。Example 2 Using the apparatus shown in FIG. 1, a fluororesin (FEP) sheet was modified. In this case, formic acid was used as the compound solution 2, and this was pressed by the synthetic quartz glass plate 3 to form a uniform thin liquid film between the fluororesin (FEP) sheet and the energy density of 25 mJ / cm 2 in that state. When irradiated with ArF laser light at
A contact angle with water of 10 degrees could be obtained.
【００３３】なお、比較のため同じフッ素樹脂（ＦＥ
Ｐ）シートを用い、同じくギ酸の中に浸漬して紫外レー
ザー光を照射してフッ素樹脂（ＦＥＰ）シートの表面改
質を試みたが、気泡が発生して改質が不可能であった。For comparison, the same fluororesin (FE
An attempt was made to modify the surface of the fluororesin (FEP) sheet by immersing it in formic acid and irradiating it with an ultraviolet laser beam using the P) sheet, but it was impossible to do so because bubbles were generated.
【００３４】（実施例３）図２および３に示す装置を用
い、それぞれフッ素樹脂（ＰＴＦＥ）シートの改質を行
った。まず、フッ素樹脂（ＰＴＦＥ）シート表面にメチ
ルアルコール（ＣＨ3 ＯＨ）を１滴づつ垂らし、フッ素
樹脂（ＰＴＦＥ）シートを移動させながら連続的表面改
質を行った。このとき、２５ｍＪ／ｃｍ2 のエネルギー
密度でＡｒＦレーザー光を３０００ショット照射したと
ころ、水との接触角４５度、ベンゼンとの接触角１５度
となり、親水性、親油性を共に有する表面に改質するこ
とができた。Example 3 Using the apparatus shown in FIGS. 2 and 3, the fluororesin (PTFE) sheet was modified. First, a drop of methyl alcohol (CH 3 OH) was dropped on the surface of the fluororesin (PTFE) sheet, and continuous surface modification was performed while moving the fluororesin (PTFE) sheet. At this time, when 3000 shots of ArF laser light was irradiated at an energy density of 25 mJ / cm 2 , the contact angle with water was 45 degrees and the contact angle with benzene was 15 degrees, and the surface was modified to be both hydrophilic and lipophilic. We were able to.
【００３５】（実施例４）図４に示す装置を用い、ＰＭ
ＭＡ製コンタクトレンズ両面の表面改質を行った。ま
ず、２ｇのホウ酸アンモニア［（ＮＨ4 ）2 Ｂ4 Ｏ7 ］
を５０ｃｃの水に溶かした溶液を毛管現象によりコンタ
クトレンズ両面に液膜を形成させ、その両側から２０ｍ
Ｊ／ｃｍ2 のエネルギー密度で１０００ショットのＡｒ
Ｆレーザー光を照射したところ、水との接触角１０度が
得られ、親水性が発現された。(Embodiment 4) Using the apparatus shown in FIG.
Both surfaces of the MA contact lens were surface-modified. First, 2 g of ammonia borate [(NH 4 ) 2 B 4 O 7 ]
A solution of 50 cc of water dissolved in 50 cc of water is formed on both sides of the contact lens by capillarity, and 20 m from both sides.
1000 shots of Ar with an energy density of J / cm 2.
When irradiated with F laser light, a contact angle with water of 10 degrees was obtained and hydrophilicity was exhibited.
【００３６】（実施例５）図１に示す装置を用い、シリ
コンウエハの表面改質を行った。すなわち、シリコンウ
エハの表面に過酸化水素（Ｈ2 Ｏ2 ）を１滴垂らし、こ
れを合成石英ガラス板３で押し付け一様な薄い液膜をシ
リコンウエハとの間に形成させ、その状態で５０ｍＪ／
ｃｍ2 のエネルギー密度でＡｒＦレーザー光を１０００
ショット照射したところ、露光面にのみＳｉＯ2 が形成
され、ＥＳＣＡ分析の結果、９９ｅＶにＳｉＯ2 のピー
クが確認された。(Embodiment 5) The surface of a silicon wafer was modified using the apparatus shown in FIG. That is, one drop of hydrogen peroxide (H 2 O 2 ) is dropped on the surface of the silicon wafer, and this is pressed by the synthetic quartz glass plate 3 to form a uniform thin liquid film between the silicon wafer and the silicon wafer. /
ArF laser light 1000 at an energy density of cm 2
When shot irradiation was performed, SiO 2 was formed only on the exposed surface, and as a result of ESCA analysis, a peak of SiO 2 was confirmed at 99 eV.
【００３７】（実施例６）図１に示す装置を用い、アル
ミニウムの表面改質を行った。すなわち、アルミニウム
の表面に過酸化水素（Ｈ2 Ｏ2 ）を１滴垂らし、これを
合成石英ガラス板３で押し付け一様な薄い液膜をアルミ
ニウムとの間に形成させ、その状態で５０ｍＪ／ｃｍ2
のエネルギー密度でＡｒＦレーザー光を１０００ショッ
ト照射したところ、露光面にのみＡｌ2 Ｏ3 が形成され
た。また、この処理後の材料表面をＮａＯＨ水溶液に浸
したところ、Ａｌ2 Ｏ3 化した部分は腐食されなかっ
た。Example 6 Using the apparatus shown in FIG. 1, the surface of aluminum was modified. That is, one drop of hydrogen peroxide (H 2 O 2 ) is dropped on the surface of aluminum, and this is pressed by a synthetic quartz glass plate 3 to form a uniform thin liquid film between the aluminum and aluminum, and in that state, 50 mJ / cm 2. 2
When ArF laser light was irradiated for 1000 shots with the energy density of, Al 2 O 3 was formed only on the exposed surface. Further, when the surface of the material after this treatment was dipped in an aqueous NaOH solution, the Al 2 O 3 converted portion was not corroded.
【００３８】（実施例７）図５に示す装置を用いて、２
枚のフッ素樹脂シート（ＦＥＰ）を純水または水道水で
接着した。なお、ここで、４３はシリンドリカルレンズ
を構成する合成石英丸棒レンズ、４４はこの合成石英丸
棒レンズ４３に対し被処理部材を圧接させるためのロー
ラー、４５、４６はローラーの両端に取着された加圧用
スプリング、４１、４２は被処理部材としてのフッ素樹
脂シート、４７は矩形状ＡｒＦエキシマレーザー光であ
る。(Embodiment 7) Using the apparatus shown in FIG.
The fluororesin sheets (FEP) were adhered with pure water or tap water. Here, 43 is a synthetic quartz round bar lens forming a cylindrical lens, 44 is a roller for pressing a member to be processed against the synthetic quartz round bar lens 43, and 45 and 46 are attached to both ends of the roller. The pressing springs 41, 42 are fluororesin sheets as members to be processed, and 47 is rectangular ArF excimer laser light.
【００３９】まず、２枚のフッ素樹脂シート４１、４２
の間に純水を１滴垂らし、これらシート４１、４２を移
動させながら、シリンドリカルレンズを構成する合成石
英丸棒レンズ４３をローラー４４に密着加圧させて連続
接着処理を行った。その際、合成石英丸棒レンズ４３の
円周部から矩形状ＡｒＦエキシマレーザー光を入射する
と、この丸棒レンズ４３とフッ素樹脂シート４１が接す
る面で線状ビームが得られた。なお、このレーザー光は
エネルギー密度５０ｍＪ／ｃｍ2 、繰り返しパルス数３
０００ショットの条件で、両フッ素樹脂シート４１、４
２間の加圧強度を１０Ｋｇｆ／ｃｍ2 に保ちながら入射
した。この試料を引張り剪断試験したところ、接着強度
は３０Ｋｇｆ／ｃｍ2 であった。First, two fluororesin sheets 41, 42
One drop of pure water was dripped between them, and while the sheets 41 and 42 were moved, the synthetic quartz round bar lens 43 forming the cylindrical lens was brought into close contact with the roller 44 and pressed to carry out the continuous adhesion treatment. At that time, when rectangular ArF excimer laser light was incident from the circumferential portion of the synthetic quartz round bar lens 43, a linear beam was obtained at the surface where the round bar lens 43 and the fluororesin sheet 41 were in contact. This laser light has an energy density of 50 mJ / cm 2 and a repetition pulse number of 3
Under the condition of 000 shots, both fluororesin sheets 41, 4
Incidence was performed while maintaining the pressure intensity between the two at 10 Kgf / cm 2 . When this sample was subjected to a tensile shear test, the adhesive strength was 30 Kgf / cm 2 .
【００４０】また、純水を水道水に代えて同様の試験を
行ったところ、この場合も純水とほぼ同等の接着強度を
示した。 （実施例８）図５に示す装置を用いて、ステンレス板と
フッ素樹脂シート（ＦＥＰ）の間にエポキシ接着剤を薄
く塗布し、合成石英丸棒レンズ４３をローラー４４に密
着加圧させながら、フッ素樹脂シートとエポキシ接着剤
の境面にエネルギー密度４０ｍＪ／ｃｍ2 のレーザー光
を繰り返しパルス数６０００ショットの条件で照射し
た。その後、８０℃で１５時間接着剤を養生させたの
ち、引張り剪断試験したところ、レーザー光未照射では
１Ｋｇｆ／ｃｍ2 以下であった接着強度がレーザー光照
射後では８４Ｋｇｆ／ｃｍ2 に向上した。Further, when the same test was conducted by replacing the pure water with tap water, the adhesive strength was almost the same as that of the pure water also in this case. (Embodiment 8) Using the apparatus shown in FIG. 5, while thinly applying an epoxy adhesive between a stainless steel plate and a fluororesin sheet (FEP) and bringing the synthetic quartz round bar lens 43 into close contact with and pressing the roller 44, A laser beam having an energy density of 40 mJ / cm 2 was repeatedly irradiated on the interface between the fluororesin sheet and the epoxy adhesive under the condition of a pulse number of 6000 shots. Then, the adhesive was cured at 80 ° C. for 15 hours and then subjected to a tensile shearing test. As a result, the adhesive strength, which was 1 Kgf / cm 2 or less without laser light irradiation, was improved to 84 Kgf / cm 2 after laser light irradiation.
【００４１】（実施例９）図５に示す装置を用いて、ア
クリル板とフッ素樹脂シート（ＦＥＰ）の間にシアノー
ル系瞬間接着剤（アロンアルファー）を１滴垂らし、合
成石英丸棒レンズ４３をローラー４４に密着加圧させな
がら、フッ素樹脂シートと接着剤の境面にエネルギー密
度３０ｍＪ／ｃｍ2 のレーザー光を繰り返しパルス数７
０００ショットの条件で照射した。これを引張り剪断試
験したところ、レーザー光未照射では０．２Ｋｇｆ／ｃ
ｍ2 以下であった接着強度がレーザー光照射後では２５
Ｋｇｆ／ｃｍ2 に向上した。(Embodiment 9) Using the apparatus shown in FIG. 5, one drop of a cyanol-based instant adhesive (Aron Alpha) was dropped between an acrylic plate and a fluororesin sheet (FEP) to form a synthetic quartz round bar lens 43. While closely contacting and pressing the roller 44, a laser beam having an energy density of 30 mJ / cm 2 was repeatedly applied to the boundary surface between the fluororesin sheet and the adhesive for 7 pulses.
Irradiation was performed under the condition of 000 shots. When this was subjected to a tensile shear test, it was 0.2 Kgf / c without laser light irradiation.
The adhesive strength, which was less than m 2 , was 25 after laser irradiation.
It was improved to Kgf / cm 2 .
【００４２】なお、上記シアノール系瞬間接着剤に微量
の酢酸を混入させると、硬化時間が遅くなるため、作業
性が良くなり、長時間のレーザー繰り返しが可能にな
り、１０，０００ショット照射で引張り剪断強度は４０
Ｋｇｆ／ｃｍ2 に向上した。If a slight amount of acetic acid is mixed in the cyanol-based instant adhesive, the curing time will be delayed, the workability will be improved, and the laser can be repeatedly used for a long time. Shear strength is 40
It was improved to Kgf / cm 2 .
【００４３】（実施例１０）フッ素樹脂板上に水を１滴
垂らし、その上から石英ガラス板を密着させた後、平板
合成石英窓に対し、２光路に分けられたＡｒＦレーザー
光（エネルギー密度１０ｍＪ／ｃｍ2 、繰り返しパルス
数３０００ショット）を互いに、石英窓との入射角を３
３度に保って、被処理材料と水との界面で交差させたと
ころ、２１２３オングストローム間隔毎に親水性に改質
された部分があることが、ＳＥＭおよびＥＰＭＡの測定
から明らかになった。(Embodiment 10) One drop of water was dropped on a fluororesin plate, and a quartz glass plate was brought into close contact therewith, and then an ArF laser beam (energy density) split into two optical paths was applied to a flat synthetic quartz window. 10 mJ / cm 2 , repetitive pulse number 3000 shots), and the incident angle with the quartz window was 3
When kept at 3 degrees and crossed at the interface between the material to be treated and water, it was revealed from the measurement of SEM and EPMA that there was a hydrophilically modified portion at every 2123 angstrom interval.
【００４４】（実施例１１）円盤状合成石英窓ガラスの
側面を研削、研磨し、その面のみＡｌ蒸着を施し、内部
に平面鏡を有する窓材を作った。これをフッ素樹脂シー
ト（ＦＥＰ）表面に水を介して密着し、内部平面鏡の反
対側から窓材に対して３３度の角度で、しかも光線の半
分が平面鏡に照らされるようにしてＡｒＦレーザー光
（エネルギー密度１０ｍＪ／ｃｍ2 、繰り返しパルス数
３０００ショット）を入射させた。これによって、窓内
の平面鏡で反射した光と、窓材を直接進んだ光とが交差
する部分、すなわち、材料と水との界面で光化学的置換
が行われ、２１２３オングストローム間隔毎に親水性に
改質された部分があることが、ＳＥＭおよびＥＰＭＡの
測定から明らかになった。(Example 11) A side surface of a disk-shaped synthetic quartz window glass was ground and polished, and Al was vapor-deposited only on the side surface to form a window material having a plane mirror inside. This is adhered to the surface of the fluororesin sheet (FEP) through water, and the ArF laser beam ( An energy density of 10 mJ / cm 2 and a repetition pulse number of 3000 shots) were applied. As a result, photochemical substitution is performed at the intersection of the light reflected by the plane mirror in the window and the light directly traveling through the window material, that is, at the interface between the material and water, and hydrophilicity is obtained every 2123 angstrom intervals. It was revealed from the SEM and EPMA measurements that there was a modified portion.
【００４５】[0045]
【発明の効果】以上詳述したように、本発明によれば、
被改質材料と透明窓材とを密着させ、そこに化合物溶液
を毛管現象を利用して一様な薄い液膜を形成させ、紫外
光等を入射し局所的に液体を光分解させ、かつ、液体を
透過した一部の光によって試料表面をも励起して化学反
応を行わせるようにしたため、分解生成物はすべて表面
処理に使われ、従来気泡発生の原因になった余分の反応
生成物を形成することもないため、気泡も発生せず、高
効率で連続的に表面処理を行うことが可能となる。As described in detail above, according to the present invention,
The material to be modified and the transparent window material are brought into close contact with each other, the compound solution is formed into a uniform thin liquid film by utilizing the capillary phenomenon, and ultraviolet light or the like is incident to locally decompose the liquid, and , The decomposition product is used for surface treatment because the sample surface is also excited by a part of the light transmitted through the liquid to cause a chemical reaction. Since no bubbles are formed, bubbles are not generated and the surface treatment can be continuously performed with high efficiency.
【図１】本発明に係わる固体表面改質方法を説明するた
めの装置の一例を示す斜視図。FIG. 1 is a perspective view showing an example of an apparatus for explaining a solid surface modification method according to the present invention.
【図２】本発明に係わる固体表面改質装置の１例を示す
斜視図。FIG. 2 is a perspective view showing an example of a solid surface modifying apparatus according to the present invention.
【図３】本発明に係わる固体表面改質装置の１例を示す
斜視図。FIG. 3 is a perspective view showing an example of a solid surface modifying apparatus according to the present invention.
【図４】本発明に係わるコンタクトレンズの表面改質装
置の１例を示す側面図。FIG. 4 is a side view showing an example of a surface modification device for a contact lens according to the present invention.
【図５】本発明に係わる固体表面改質装置の１例を示す
斜視図。FIG. 5 is a perspective view showing an example of a solid surface modifying apparatus according to the present invention.
１…被改質材料、 ２…化合物溶液、 ３…合成石英ガ
ラス板、 ４…エキシマレーザー装置、 １１…ゴムロ
ーラ、 １２…円筒状透明丸棒または透明パイプ、 １
３…シリンドリカルレンズ、 １４…シート状被処理固
体材料、 ２１…反射鏡、 ２２…細長ランプ（Ｈｇラ
ンプ）。1 ... Material to be modified, 2 ... Compound solution, 3 ... Synthetic quartz glass plate, 4 ... Excimer laser device, 11 ... Rubber roller, 12 ... Cylindrical transparent round bar or transparent pipe, 1
3 ... Cylindrical lens, 14 ... Sheet-shaped solid material to be treated, 21 ... Reflecting mirror, 22 ... Elongated lamp (Hg lamp).
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.5 識別記号 庁内整理番号 ＦＩ 技術表示箇所 // Ｃ０８Ｌ 27/12 ＬＧＬ ─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. 5 Identification code Internal reference number FI technical display location // C08L 27/12 LGL
Claims (26)
化合物溶液の薄層を介して透明窓材を密着させ、該透明
窓材を通して紫外線、可視光線、赤外線を照射し、該被
処理固体材料表面と該液体化合物または化合物溶液を光
励起し、該液体化合物または化合物溶液中の化学種を置
換し、あるいは化学種を堆積させ、またはその化学種に
よってエッチングさせることを特徴とする固体表面の改
質方法。1. The surface of the solid material to be treated is brought into close contact with a transparent window material through a thin layer of a liquid compound or a compound solution on the upper surface of the solid material to be treated, and ultraviolet rays, visible rays or infrared rays are radiated through the transparent window material. And a method for modifying a solid surface, which comprises photoexciting the liquid compound or a compound solution to replace a chemical species in the liquid compound or a compound solution, or depositing a chemical species, or etching by the chemical species. .
ツ型または鋳型であることを特徴とする請求項１記載の
固体表面の改質方法。2. The method for modifying a solid surface according to claim 1, wherein the transparent window material is a plate, a cylinder, a sphere, a donut shape, or a mold.
動植物体またはセラミックであることを特徴とする請求
項１記載の固体表面の改質方法。3. The solid material to be treated is plastic, metal,
The method for modifying a solid surface according to claim 1, which is an animal or plant body or a ceramic.
ール、石油類、芳香族化合物、シリコーンオイル、ファ
オンブリンオイル、トリクロロエチレン、フロン１１
３、フロン１１３ａ、過酸化水素、ＨＣｌ、Ｈ2 ＳＯ
4 、ＨＮＯ3 、ＨＣＯＯＨ、（ＣＯＯＨ）2 、ＣＨ3 Ｃ
ＯＯＨ、ＮＨ3 、Ｎ2 Ｈ4 、ＮＨ4 Ｆから選ばれるもの
であることを特徴とする請求項１記載の固体表面の改質
方法。4. The liquid compound is water, pure water, heavy water, alcohol, petroleum, aromatic compounds, silicone oil, phaombin oil, trichlorethylene, CFC 11
3, Freon 113a, hydrogen peroxide, HCl, H 2 SO
4 , HNO 3 , HCOOH, (COOH) 2 , CH 3 C
The method for modifying a solid surface according to claim 1, which is selected from OOH, NH 3 , N 2 H 4 , and NH 4 F.
酸、四塩化炭素、二硫化炭素、炭化水素類、ハロゲン化
合物類、アルコール類、フェノール類、有機酸およびそ
の誘導体、ニトリル類、ニトロ化合物類、アミン類、硫
黄化合物類から選ばれるものであることを特徴とする請
求項１記載の固体表面の改質方法。5. The solvent is water, pure water, heavy water, ammonia, sulfuric acid, carbon tetrachloride, carbon disulfide, hydrocarbons, halogen compounds, alcohols, phenols, organic acids and their derivatives, nitriles, nitro. The method for modifying a solid surface according to claim 1, wherein the method is a compound selected from compounds, amines, and sulfur compounds.
成石英ガラス、パイレックスガラス、光学ガラス、板ガ
ラス、サファイア、ダイアモンド、ＴｉＯ2、ＩＲＴＲ
ＡＮ、Ｇｅ、Ｓｉ，フッ化バリウム、フッ化マグネシウ
ム、炭酸カルシウム、フッ化リチウム、フッ化カルシウ
ム、フッ素樹脂、アクリル樹脂、スチレン樹脂、カーボ
ネート樹脂から選ばれるものからなることを特徴とする
請求項１記載の固体表面の光改質方法。6. The transparent window material is ultraviolet transparent glass, crystal, synthetic quartz glass, Pyrex glass, optical glass, plate glass, sapphire, diamond, TiO 2 , IRTR.
2. A material selected from AN, Ge, Si, barium fluoride, magnesium fluoride, calcium carbonate, lithium fluoride, calcium fluoride, fluororesin, acrylic resin, styrene resin and carbonate resin. A method for photomodifying a solid surface according to claim 1.
ザー、Ｋｒ+ レーザー、Ｎ2 レーザー、非線形材料によ
るハーモニックス紫外線レーザー、Ｄ2 ランプ、高圧水
銀ランプ、低圧水銀ランプ、Ｘｅランプ、Ｈｇ−Ｘｅラ
ンプ、ハロゲンランプ、エキシマランプ、あるいは空
気、窒素、または他のガス雰囲気のアーク、コロナまた
は無声放電により得られる紫外光ランプから選ばれるも
のであることを特徴とする請求項１記載の固体表面の改
質方法。7. The ultraviolet light is an excimer laser, an Ar + laser, a Kr + laser, an N 2 laser, a harmonics ultraviolet laser using a non-linear material, a D 2 lamp, a high pressure mercury lamp, a low pressure mercury lamp, a Xe lamp, a Hg-Xe lamp. 2. A solid surface modification as claimed in claim 1, characterized in that it is selected from a halogen lamp, an excimer lamp, or an ultraviolet light lamp obtained by arc, corona or silent discharge in an atmosphere of air, nitrogen or other gases. Quality method.
に設けられた板状透明窓材と、 該保持台に載置された被処理固体材料の上面をほぼ垂直
方向から紫外線、可視光線、赤外線を照射するための投
光手段と、 を具備してなり、被処理固体材料と板状透明窓材との間
に毛管現象を利用して液体化合物または化合物溶液の薄
層を介在させ、その状態で投光手段から光を被処理固体
材料上面に照射して固体表面を改質するようにしたこと
を特徴とする固体表面改質装置。8. A holding table on which the solid material to be treated is placed, a plate-shaped transparent window member which is provided on the upper surface of the solid material to be treated and placed on the holding table, and the holding table. And a projection means for irradiating the upper surface of the placed solid material to be treated with ultraviolet rays, visible rays, and infrared rays from a substantially vertical direction, and between the treated solid material and the plate-shaped transparent window material. A thin layer of a liquid compound or a compound solution is intervened by utilizing a capillary phenomenon, and in that state, the upper surface of the solid material to be treated is irradiated with light from a light projecting means to modify the solid surface. Solid surface reforming device.
被処理固体材料の上面を選択的に照射する手段を備えて
いることを特徴とする請求項８記載の固体表面改質装
置。9. A solid surface reforming apparatus according to claim 8, wherein said light projecting means comprises means for selectively irradiating the upper surface of the solid material to be treated with ultraviolet rays, visible rays and infrared rays.
丸棒または透明パイプと、 該ゴムローラと円筒状透明丸棒または透明パイプとの間
にシート状被処理固体材料を通過させるための手段と、 該ゴムローラと円筒状透明丸棒または透明パイプとの対
向部分に紫外線、可視光線、赤外線を線状に照射するた
めの投光手段と、 該ゴムローラと円筒状透明丸棒または透明パイプとを該
シート状被処理固体材料を介して圧接する手段と、 を具備してなり、該シート状被処理固体材料と円筒状透
明丸棒または透明パイプとの間に毛管現象を利用して液
体化合物または化合物溶液の薄層を介在させ、その状態
で投光手段から光を被処理固体材料上面に照射して固体
表面を連続的に改質するようにしたことを特徴とする固
体表面改質装置。10. A rubber roller rotatably provided, a cylindrical transparent round bar or transparent pipe rotatably provided parallel to the rubber roller, and between the rubber roller and the cylindrical transparent round bar or transparent pipe. Means for passing the sheet-shaped solid material to be treated; light-projecting means for linearly irradiating ultraviolet rays, visible rays, and infrared rays on a portion where the rubber roller and the cylindrical transparent round bar or transparent pipe face each other, Means for press-contacting a rubber roller and a cylindrical transparent round bar or transparent pipe through the sheet-shaped solid material to be treated, and the sheet-shaped solid material to be treated and the cylindrical transparent round bar or transparent pipe. A thin layer of liquid compound or compound solution is intervened by utilizing the capillarity, and in that state, the upper surface of the solid material to be treated is irradiated with light from the light projecting means to continuously modify the solid surface. Solid surface modifying apparatus, characterized in that the.
プの外側に置かれていることを特徴とする請求項１０記
載の固体表面改質装置。11. The solid surface reforming apparatus according to claim 10, wherein the light projecting means is placed outside a transparent round bar or a transparent pipe.
けられた反射鏡と、該パイプの端側から線状ビームを投
入する手段とからなることを特徴とする請求項１０記載
の固体表面改質装置。12. The solid according to claim 10, wherein the light projecting means comprises a reflecting mirror provided inside the transparent pipe, and means for introducing a linear beam from the end side of the pipe. Surface modification device.
細長ランプを挿入したものからなることを特徴とする請
求項１０記載の固体表面改質装置。13. The solid surface reforming apparatus according to claim 10, wherein the light projecting means is formed by inserting an elongated lamp inside the transparent pipe.
されるべき被処理レンズを挟持させ、該被処理レンズと
凹レンズおよび凸レンズとの間に化合物溶液の薄層を毛
管現象により介在させ、その状態で光を被処理レンズの
両面に照射しその表面を改質するようにしたことを特徴
とするレンズ表面の改質方法。14. A lens to be treated, which is to be surface-treated, is sandwiched between a concave lens and a convex lens, and a thin layer of a compound solution is interposed between the lens to be treated and the concave lens and the convex lens by capillarity. The lens surface modification method is characterized in that both surfaces of the lens to be treated are irradiated with light to modify the surface.
求項１４記載のレンズ表面の改質方法。15. The method for modifying a lens surface according to claim 14, wherein the lens is a contact lens.
１５記載のレンズ表面の改質方法。16. The method for modifying a lens surface according to claim 15, wherein the light is an excimer laser.
とも一部対応する内面形状を有する透明プラスチックま
たはガラスからなる雌型に該被処理固体材料を液体化合
物または化合物溶液の薄層を介して密着させ、該雌型を
通して光を照射することを特徴とする固体表面の改質方
法。17. The solid material to be treated is adhered to a female mold made of transparent plastic or glass having an inner surface shape corresponding to at least part of the outer surface shape of the solid material to be processed through a thin layer of a liquid compound or compound solution. And irradiating light through the female mold, the method for modifying a solid surface.
徴とする請求項１７記載の固体表面の改質方法。18. The method for modifying a solid surface according to claim 17, wherein the solid material to be treated is a denture.
徴とする請求項１７または１８項記載の固体表面の改質
方法。19. The method for modifying a solid surface according to claim 17, wherein the light is an excimer laser.
または円筒状被処理固体材料との間に毛管現象を利用し
て、液体化合物または化合物溶液の薄層を介在させ、そ
の状態でドーナツ状透明窓材の外周部から光を入射し、
被処理固体材料面に照射して、被処理固体材料の表面を
改質することを特徴とする固体表面の改質方法。20. A thin layer of a liquid compound or a compound solution is interposed between the inner peripheral portion of a donut-shaped transparent window material and a cylindrical or cylindrical solid material to be treated by utilizing a capillary phenomenon, and in that state Light is incident from the outer periphery of the donut-shaped transparent window material,
A method for modifying a solid surface, which comprises irradiating a surface of a solid material to be processed to modify the surface of the solid material to be processed.
請求項２０記載の固体表面の改質方法。21. The method for modifying a solid surface according to claim 20, wherein the solid material to be treated is an electric wire tube.
Ｈｇ−Ｘｅランプであることを特徴とする請求項２０項
記載の固体表面の改質方法。22. The light is an excimer laser, an Hg lamp,
The method for modifying a solid surface according to claim 20, wherein the method is a Hg-Xe lamp.
は官能基に水素原子を有する接着剤の薄液層を介して、
フッ素樹脂板を加圧密着させ、該フッ素樹板を通して光
子エネルギーが１２８Ｋｃａｌ以上の紫外線を照射して
被処理固体材料とフッ素樹脂板とを直接接着することを
特徴とする請求項１または４項記載の固体表面の改質方
法。23. A thin liquid layer of an adhesive having a liquid compound or a hydrogen atom as a functional group on the upper surface of the solid material to be treated,
The fluororesin plate is brought into close contact with pressure, and ultraviolet rays having a photon energy of 128 Kcal or more are irradiated through the fluororesin plate to directly bond the solid material to be treated and the fluororesin plate. Method for modifying the solid surface of.
は官能基に水素原子を有する接着剤の薄液層を介して透
明窓材を加圧密着させ、該透明窓材を通して光子エネル
ギーが１２８Ｋｃａｌ以上の紫外線を照射してフッ素樹
脂板と該透明窓材とを直接接着することを特徴とする請
求項１、４または６記載の固体表面の改質方法。24. An ultraviolet ray having a photon energy of 128 Kcal or more is brought into pressure contact with a transparent window material through a thin liquid layer of a liquid compound or an adhesive having a hydrogen atom in a functional group on the upper surface of the fluororesin material. 7. The method for modifying a solid surface according to claim 1, 4 or 6, wherein the fluororesin plate and the transparent window material are directly adhered by irradiation with.
は溶媒の薄液層を介して、透明窓材を密着させ、該透明
窓材を通して複数方向から同一光源から放射された紫外
光を入射させ、該被処理固体材料と薄液層との界面で干
渉を生起させ、これにより該被処理固体材料表面を回折
格子状に改質することを特徴とする請求項１、４、５、
６または７記載の固体表面の改質方法。25. A transparent window material is brought into close contact with the upper surface of a solid material to be treated through a thin liquid layer of a liquid compound or a solvent, and ultraviolet light emitted from the same light source is incident from a plurality of directions through the transparent window material, The interference is generated at an interface between the solid material to be processed and the thin liquid layer, and thereby the surface of the solid material to be processed is modified into a diffraction grating shape.
6. The method for modifying a solid surface according to 6 or 7.
鏡の反対側の斜め方向から紫外線を入射し、該窓材の中
を直接進んだ光と、窓の内部平面鏡で反射した光とが、
被処理固体材料表面と薄液層との界面で干渉を生起し、
これにより該被処理固体材料表面を回折格子状に改質す
ることを特徴とする請求項６または２５記載の固体表面
の改質方法。26. A side surface of a window member is used as an internal plane mirror, and ultraviolet rays are incident from an oblique direction on the opposite side of the plane mirror, and the light directly advances in the window member and the light reflected by the internal plane mirror of the window. ,
Interference occurs at the interface between the surface of the solid material to be processed and the thin liquid layer,
26. The method for modifying a solid surface according to claim 6 or 25, characterized in that the surface of the solid material to be processed is modified into a diffraction grating.
Priority Applications (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23834993A JP3527969B2 (en) | 1993-04-02 | 1993-09-24 | Method and apparatus for modifying solid surface |
| EP94910522A EP0644227B1 (en) | 1993-03-23 | 1994-03-23 | Solid surface modifying method and apparatus |
| PCT/JP1994/000463 WO1994021715A1 (en) | 1993-03-23 | 1994-03-23 | Solid surface modifying method and apparatus |
| DE69432966T DE69432966T2 (en) | 1993-03-23 | 1994-03-23 | METHOD AND DEVICE FOR MODIFYING SOLID SURFACES |
| US08/888,862 US6117497A (en) | 1993-03-23 | 1997-07-07 | Solid surface modification method and apparatus |
| US09/639,006 US6689426B1 (en) | 1993-03-23 | 2000-08-15 | Solid surface modification method and apparatus |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5-76888 | 1993-04-02 | ||
| JP7688893 | 1993-04-02 | ||
| JP23834993A JP3527969B2 (en) | 1993-04-02 | 1993-09-24 | Method and apparatus for modifying solid surface |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06335631A true JPH06335631A (en) | 1994-12-06 |
| JP3527969B2 JP3527969B2 (en) | 2004-05-17 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP23834993A Expired - Fee Related JP3527969B2 (en) | 1993-03-23 | 1993-09-24 | Method and apparatus for modifying solid surface |
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| Country | Link |
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| JP (1) | JP3527969B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004182516A (en) * | 2002-12-02 | 2004-07-02 | Tokai Univ | Method of photochemically modifying solid material surface |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2024038871A1 (en) * | 2022-08-16 | 2024-02-22 | 株式会社エム光・エネルギー開発研究所 | Industrial machine utilizing electrical breakdown of liquid dielectric body |
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- 1993-09-24 JP JP23834993A patent/JP3527969B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004182516A (en) * | 2002-12-02 | 2004-07-02 | Tokai Univ | Method of photochemically modifying solid material surface |
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| Publication number | Publication date |
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| JP3527969B2 (en) | 2004-05-17 |
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