JP3292534B2 - Substrate coating method - Google Patents
Substrate coating methodInfo
- Publication number
- JP3292534B2 JP3292534B2 JP03124993A JP3124993A JP3292534B2 JP 3292534 B2 JP3292534 B2 JP 3292534B2 JP 03124993 A JP03124993 A JP 03124993A JP 3124993 A JP3124993 A JP 3124993A JP 3292534 B2 JP3292534 B2 JP 3292534B2
- Authority
- JP
- Japan
- Prior art keywords
- polymer
- layer
- coating
- substrate
- ring structure
- 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
Links
Description
【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION
【０００１】[0001]
【産業上の利用分野】本発明は、含フッ素脂肪族環構造
を有する重合体で基材を被覆する方法に関するものであ
る。The present invention relates to a method of coating a substrate with a polymer having a fluorinated aliphatic ring structure.
【０００２】[0002]
【従来の技術】含フッ素脂肪族環構造を有する重合体で
基材を被覆する方法として、例えば前記重合体を塗布す
る前に基材に活性エネルギー線を照射した後にシランカ
ップリング剤処理を施す方法、および基材と前記重合体
との間に重合性シランと他のラジカル共重合性単量体と
を共重合せしめたアクリル系共重合体の被膜を施す方法
が本出願人により提唱されている。As how to coat the <br/> substrate with a polymer having BACKGROUND ART Fluorine-containing aliphatic ring structure, for example, silane coupling after the irradiation with the active energy ray to the substrate prior to applying the polymer method of applying a coupling agent treatment, and a method of applying a coating of a polymerizable silane and other radically copolymerizable monomer and a copolymerizable allowed acrylic copolymer is present application between the substrate and the polymer Advocated by people.
【０００３】これらは、重合体を基材に密着させる上で
有効な方法であるが、用いられる重合体には化学的に活
性な密着基が含まれることが前提となっている。これら
密着基は、例えば紫外線を吸収するなどの性質があり、
紫外線を利用する用途においては光線透過率が減少する
などの問題があるため、特開平４−１８９８０２号公報
に見られるごとく密着基を含まない重合体が提示されて
いる。しかしながら、密着基を含まない含フッ素脂肪族
環構造を有する重合体を基材に密着せしめる方法はいま
だ提唱されていない。[0003] These are the polymer which is <br/> effective way on to adhere to the substrate, that the polymer used contains chemically active contact group is based on the premise . These contact groups, Ri nature there such absorb example ultraviolet,
In applications utilizing ultraviolet light, there is a problem such as a decrease in light transmittance. Therefore, as disclosed in JP-A-4-189802, a polymer containing no adhesive group is proposed. However, a method of causing a polymer having a fluorinated aliphatic ring structure containing no adhesive group to adhere to a substrate has not yet been proposed.
【０００４】また、重合体のフィルムを基材にラミネー
トする場合、フィルムを基材にまんべんなく接触させる
ことが技術的に困難な場合があり、部分的にフィルムが
基材に密着していない箇所が発生することがある。When a polymer film is laminated on a substrate, it may be technically difficult to bring the film into contact with the substrate evenly, and there are some places where the film is not in close contact with the substrate. May occur.
【０００５】[0005]
【発明が解決しようとする課題】本発明は、前述のよう
な欠点を解消し、密着基を有せず含フッ素脂肪族環構造
を有する重合体で基材を密着よく被覆する方法を新規に
提供することを目的とするものである。SUMMARY OF THE INVENTION The present invention
Such a drawback is eliminated, it is an object to provide a method of coating well adhered to the substrate with a polymer having a fluorinated aliphatic ring structure does not have a contact group anew.
【０００６】[0006]
【課題を解決するための手段】本発明者は、上記問題点
の認識に基づいて、鋭意検討を重ねた結果、基材に密着
しうる密着基と含フッ素脂肪族環構造を有する重合体か
らなる密着層の上に、密着基を有せず含フッ素脂肪族環
構造を有する重合体の溶液を塗布して乾燥した場合、ま
たはフィルムを熱融着した場合に、きわめて密着性が強
いことを新規に見いだすに至った。また、ひとたび基材
に密着した密着層は、密着層の重合体を溶解しうるフッ
素系溶剤で洗浄を行っても、膜厚は著しく減少するもの
の重合体は完全には除去されず、洗浄後のきわめて薄い
密着層でも、その上に塗布される被覆層の含フッ素脂肪
族環構造を有する重合体の密着性を発現させることを新
規に見いだすに至った。The present inventors SUMMARY OF THE INVENTION Based on the recognition of the above problems, intensive result of extensive investigations, the polymer having contact group and a fluorine-containing aliphatic ring structure Ru bovine close contact with the substrate Or
Ranaru on the dense adhesive layer, when dried to a solution of the polymer having a fluorinated aliphatic ring structure does not have a contact group is coated, or
Other when heat-sealed film, which resulted in finding that the very strong adhesion to the new. Also, the once adhesion layer in close contact with the substrate, even when the polymer washed in dissolved cormorants Ru fluorinated solvent of the adhesion layer, the film thickness is greatly reduced as the polymer is not completely removed, washed even very thin <br/> dense adhesive layer after, leading to finding that the expression of adhesion of a polymer having a fluorinated aliphatic ring structure of the coating layer applied thereon newly.
【０００７】本発明は、上記知見に基づいて完成された
ものであり、含フッ素脂肪族環構造を有する重合体で基
材を被覆する方法を新規に提供するものである。[0007] The present invention has been completed based on the above finding, there is provided a method of coating a substrate with a polymer having a fluorinated aliphatic ring structure in the new.
【０００８】含フッ素脂肪族環構造を有する重合体とし
ては、含フッ素脂肪族環構造を有するモノマーを重合し
て得られるものや、少なくとも２つの重合性二重結合を
有する含フッ素モノマーを環化重合して得られる主鎖に
含フッ素脂肪族環構造を有する重合体が好適である。As the polymer having a fluorinated aliphatic ring structure, a polymer obtained by polymerizing a monomer having a fluorinated aliphatic ring structure or a fluorinated monomer having at least two polymerizable double bonds is cyclized. In the main chain obtained by polymerization
A polymer having a fluorinated aliphatic ring structure is preferred.
【０００９】含フッ素脂肪族環構造を有するモノマーを
重合して得られる主鎖に含フッ素脂肪族環構造を有する
重合体は、特公昭６３−１８９６４号公報等により知ら
れている。すなわち、パーフルオロ（２，２−ジメチル
−１，３−ジオキソール）等の含フッ素脂肪族環構造を
有するモノマーを単独重合する、またはテトラフルオロ
エチレンなどのラジカル重合性モノマーと共重合するこ
とにより得られる。A polymer having a fluorinated alicyclic structure in the main chain obtained by polymerizing a monomer having a fluorinated alicyclic structure is known from JP-B-63-18964. Chi words, perfluoro (2,2-dimethyl-1,3-dioxole), or the like of the homopolymerization of a monomer having a fluorinated aliphatic ring structure, or be copolymerized with a radical polymerizable monomer such as tetrafluoroethylene Is obtained by
【００１０】また、少なくとも２つの重合性二重結合を
有する含フッ素モノマーを環化重合して得られる主鎖に
含フッ素脂肪族環構造を有する重合体は、特開昭６３−
２３８１１１号公報や特開昭６３−２３８１１５号公報
等により知られている。すなわち、パーフルオロ（アリ
ルビニルエーテル）やパーフルオロ（ブテニルビニルエ
ーテル）等のモノマーを環化重合する、またはテトラフ
ルオロエチレンなどのラジカル重合性モノマーと共重合
することにより得られる。The main chain obtained by cyclopolymerization of a fluorine-containing monomer having at least two polymerizable double bonds is added to the main chain.
Polymers having a fluorinated aliphatic ring structure are disclosed in
238111 and JP-A-63-238115. Chi words, obtained by a monomer such as perfluoro (allyl vinyl ether) or perfluoro (butenyl vinyl ether) polymerizing cyclization, or copolymerized with a radical polymerizable monomer such as tetrafluoroethylene.
【００１１】また、パーフルオロ（２，２−ジメチル−
１，３−ジオキソール）等の含フッ素脂肪族環構造を有
するモノマーとパーフルオロ（アリルビニルエーテル）
やパーフルオロ（ブテニルビニルエーテル）等の少なく
とも２つの重合性二重結合を有する含フッ素モノマーを
共重合して得られる重合体でもよい。Further, perfluoro (2,2-dimethyl-
Monomers having a fluorinated aliphatic ring structure such as 1,3-dioxole) and perfluoro (allyl vinyl ether)
And a polymer obtained by copolymerizing a fluorine-containing monomer having at least two polymerizable double bonds such as perfluoro (butenyl vinyl ether) and the like.
【００１２】含フッ素脂肪族環構造を有する重合体は、
主鎖に含フッ素脂肪族環構造を有する重合体が好適であ
るが、さらに全重合単位に対して含フッ素脂肪族環構造
を有する重合単位を２０モル％以上含有するものが透明
性、機械的特性等の面から好ましい。The polymer having a fluorinated aliphatic ring structure is
Polymers having a fluorinated alicyclic structure in the main chain are preferred, but those containing 20 mol% or more of polymerized units having a fluorinated alicyclic structure with respect to all the polymerized units are preferred for transparency and mechanical properties. It is preferable in terms of characteristics and the like.
【００１３】本発明において、密着層に用いられる含フ
ッ素脂肪族環構造を有する重合体としては、化学的に活
性な密着基を有するものであれば特に制限はないが、例
えばカルボン酸基もしくスルホン酸基またはそれらがエ
ステル化された基、アルコキシシリル基などを有する重
合体が例示されうる。また、本発明において、基材上に
密着層を形成する方法には特に制限はなく、必要な場合
は基材上にあらかじめシランカップリング剤などのプラ
イマー処理を施してもよい。例えばガラス基材を用いる
場合、重合体の密着基がアルコキシシリル基である場合
には基材にはプライマー処理は特に必要はないが、密着
基がカルボン酸基である場合には基材上にシランカップ
リング剤処理を施したほうが密着力が強く発現する。[0013] In the present invention, the polymer having a fluorinated aliphatic ring structure used in tightly sealable layer is not particularly limited as long as it has a chemically active contact groups, also for example a carboxylic acid group lay sulfonic acid group or their e <br/> esterification radicals, polymers having such a alkoxysilyl group Ru cormorants are exemplified. Further, in the present invention are not particularly limited in method for forming the <br/> tight sealable layer on the substrate, if necessary may be subjected to a primer treatment such as a silane coupling agent on the substrate . For example, when using a glass substrate, is not particularly necessary primer treatment to the substrate when contact groups of the polymer is an alkoxysilyl group, if contact group is a carboxylic acid group on the substrate The silane coupling agent treatment gives stronger adhesion.
【００１４】本発明において、被覆層に用いられる密着
基を有しない含フッ素脂肪族環構造を有する重合体とし
ては特に制限はなく、前記重合体のうち密着基を有しな
い重合体を用いる。 In the present invention, the adhesion used for the coating layer
The polymer having a fluorinated aliphatic ring structure having no group is not particularly limited, and the polymer having no adhesive group among the above polymers is preferred.
Ru using a stomach polymer.
【００１５】本発明において、重合体の密着層の上に含
フッ素脂肪族環構造を有する重合体のフィルムを熱融着
する場合、温度上昇により密着層の弾性率が低下して部
分的に流動がおこり、フィルムがまんべんなく接触する
ようになる。この場合、密着層の膜厚としては、好まし
くは１μｍ以上、さらに好ましくは３μｍ以上であるこ
とが望ましい。[0015] In the present invention, when heat sealing the polymer film having a fluorinated aliphatic ring structure on the dense adhesive layer of the polymer, partially elastic modulus of dense adhesive layer is lowered by the temperature rise And the film comes into contact evenly. In this case, the thickness of the dense adhesion layer, it is desirable that preferably 1 [mu] m or more, more preferably not less than 3.mu. m.
【００１６】本発明においては、密着層の上に被覆層を
形成するのであるが、塗布方法の選択によっては、被覆
層の塗布に用いられる重合体溶液に密着層の重合体が再
溶解して混入する可能性がある。例えば浸漬塗布法を用
いる場合には、密着層および被覆層に用いる各々の重合
体溶液に基材を一旦浸漬してから引き上げる操作を行
う。その場合、基材上に形成された密着層は被覆層に用
いられる重合体溶液に再溶解して混入する可能性があ
る。このような問題を解決するために、次のような方法
を採用することが好ましい。[0016] In the present invention, the coating layer over the dense adhesive layer
Although than is formed, depending on the choice of coating method, the polymer of the dense adhesive layer to the polymer solution used for coating the coating <br/> layer is likely to be mixed and re-dissolved. For example, in the case of using a dip coating method, once performs operations pulling after immersing the substrate in each of the polymer solution used in tight sealable layer and the coating layer. In this case, dense adhesive layer which is formed on the substrate is likely to be mixed and re-dissolved in the polymer solution used for the coating layer. In order to solve such a problem, it is preferable to employ the following method.
【００１７】すなわち基材上に、含フッ素脂肪族環構造
を有する重合体の密着層を形成したのちに、全体をパー
フルオロオクタンなどの前記重合体を溶解しうるフッ素
系溶剤に浸漬して長時間放置するか、または浸漬して超
音波で処理するなどして洗浄した場合、大部分の重合体
は除去されるが、完全には除去されない。密着層は、基
材と化学結合によって密着しているため、前記のような
フッ素系溶剤によっては除去されない、厚さが３０ｎｍ
以下である極めて薄い層が残留する。密着基を含まない
含フッ素脂肪族環構造を有する重合体は、この極めて薄
い密着層に対しても強力に密着しうる。[0017] That is on the substrate, after forming the dense adhesive layer of a polymer having a fluorinated aliphatic ring structure, Ru bovine dissolve the polymer, such as a whole perfluorooctane fluorine
Or long it is left immersed in the system solvent, or when washed, such as by treatment with immersing the ultrasound, although the majority of the polymer is removed, not completely removed. Since the adhesion layer is in close contact with the base material by a chemical bond, the adhesion layer is not removed by the fluorine-based solvent as described above, and has a thickness of 30 nm.
An extremely thin layer remains: Polymer having a <br/> fluorinated aliphatic ring structure containing no adhesion groups, Ru strongly adheres Siu against this very thin dense adhesive layer.
【００１８】本発明において、密着層の含フッ素脂肪族
環構造を有する重合体の膜厚を減じるために用いるフッ
素系溶剤として、Ｒf−Ｒh（ただし、ＲfはＣ6〜Ｃ12の
パーフルオロアルキル基、ＲhはＣ1〜Ｃ4のアルキルま
たはアルケニル基）、パーフルオロアルカン、パーフル
オロアルキルアミン、パーフルオロ（アルキルテトラヒ
ドロフラン）などが例示されうるが、密着層の重合体を
溶解しうるフッ素系溶剤であれば特に制限はない。この
ことを利用して、例えば異物の混入、または膜厚制御ミ
スなどのコーティングの失敗が起こっても、この膜を除
去して再度コーティングを行うことが可能となる。[0018] In the present invention, as a fluorine-based solvent used to reduce the thickness of the polymer having a fluorinated aliphatic ring structure in the dense adhesion layer, R f -R h (however, R f C 6 ~C 12 perfluoroalkyl group, an alkyl or alkenyl group R h is C 1 -C 4), perfluoroalkanes, perfluoroalkyl amines, the like perfluoro (alkyl tetrahydrofuran) is Ru cormorants are exemplified, a polymer of tight sealable layer it is not particularly limited as long as it is a cormorant Ru fluorine-based solvent to dissolve the. By utilizing this, for example, foreign substances, or even going on failure of a coating such as film thickness control mistake, it is possible to perform again coated by removing the membrane.
【００１９】本発明において用いる基材には特に制限は
なく、ガラス、樹脂、金属、セラミックス等任意の基材
を用いうる。[0019] base material used in the present invention is not particularly limited, glass, resin, metal, Ru cormorants using ceramics optional substrate.
【００２０】[0020]
【実施例】次に、本発明の実施例について更に具体的に
説明するが、この説明が本発明を限定するものではな
い。EXAMPLES Next, examples further specifically described the present invention, flower in which this description to limit the present invention
No.
【００２１】合成例１ パーフルオロ（ブテニルビニルエーテル）の３５ｇ、イ
オン交換水の１５０ｇ、および重合開始剤として（（Ｃ
Ｈ3）2ＣＨＯＣＯＯ）2の９０ｍｇを、内容積２００ｍ
ｌの耐圧ガラス製オートクレーブに入れた。系内を３回
窒素で置換した後、４０℃で２２時間懸濁重合を行っ
た。その結果、重合体Ａを２８ｇ得た。この重合体の固
有粘度［η］は、パーフルオロ（２−ブチルテトラヒド
ロフラン）中３０℃で０．５０であった。重合体のガラ
ス転移点は１０８℃であり、室温ではタフで透明なガラ
ス状の重合体である。また１０％熱分解温度は４６５℃
であり、光線透過率は９５％以上と高かった。重合体Ａ
の水に対する接触角は１１０度であり、撥水性がある。
重合体Ａを赤外分光光度計で分析したところ、密着基と
してカルボン酸基が確認できた。重合体Ａをパーフルオ
ロオクタンに２重量％で溶解した溶液Ａを調製した。Synthesis Example 1 35 g of perfluoro (butenyl vinyl ether), 150 g of ion-exchanged water, and ((C
H 3) 2 CHOCOO) 2 of 90 mg, the internal volume 200m
1 autoclave made of pressure-resistant glass. After purging the system with nitrogen three times, suspension polymerization was performed at 40 ° C. for 22 hours. As a result, 28 g of polymer A was obtained. The intrinsic viscosity [η] of this polymer was 0.50 at 30 ° C. in perfluoro (2-butyltetrahydrofuran). The polymer has a glass transition point of 108 ° C. and is a tough and transparent glassy polymer at room temperature. The 10% thermal decomposition temperature is 465 ° C
And the light transmittance was as high as 95% or more. Polymer A
Has a contact angle with water of 110 degrees and has water repellency.
When the polymer A was analyzed by an infrared spectrophotometer, a carboxylic acid group was confirmed as an adhesive group. Polymer A was made by adjusting the solution A was dissolved in 2 wt% to perfluorooctane.
【００２２】合成例２ 重合体Ａの１０ｇを１０００ｍｌのオートクレーブに入
れ、脱気した後、窒素ガスで２０体積％に希釈されたフ
ッ素ガスを常圧まで導入した。そのオートクレーブ全体
を２５０℃で８時間保持したのちに重合体を取り出して
純水で洗浄および熱風乾燥を行い、これを重合体Ｂとし
た。重合体Ｂを赤外分光光度計で分析したところ、密着
基は存在しなかった。重合体Ｂをパーフルオロオクタン
に２重量％で溶解した溶液Ｂを調製した。また、重合体
Ｂを２２０℃で圧縮成形し、厚さ１００μｍのフィルム
Ｃを得た。Synthesis Example 2 10 g of Polymer A was placed in a 1000 ml autoclave, degassed, and fluorine gas diluted to 20% by volume with nitrogen gas was introduced to normal pressure. After keeping the entire autoclave at 250 ° C. for 8 hours, the polymer was taken out, washed with pure water and dried with hot air, to obtain polymer B. When the polymer B was analyzed by an infrared spectrophotometer, no adhesion group was present. The polymer B was, prepare solution B was dissolved in 2 wt% to perfluorooctane. Further, the polymer B was compression molded at 220 ° C., to obtain a film C having a thickness of 100 microns m.
【００２３】実施例１ ガラス板の表面に、γ−アミノプロピルトリエトキシシ
ランを塗布し、続いて溶液Ａを塗布および熱風乾燥し
て、重合体Ａからなる密着層を形成した。この密着層に
ついて、セロテープ剥離テストを１０回実施したが、塗
膜に欠陥は発生しなかった。次に、溶液Ｂを密着層上に
塗布して１８０℃で６０分間乾燥を行った。形成された
塗膜についてセロテープ剥離テストを１０回実施した
が、塗膜に欠陥は発生しなかった。[0023] surface of Example 1 a glass plate, coated with γ- aminopropyltriethoxysilane, followed by a solution A was coated and dried in hot air to form a dense adhesion layer composed of the polymer A. For <br/> this tightly sealable layer has been carried out cellophane tape peeling test 10 times, a defect was generated in the coating film. Next, the solution B was applied on the adhesion layer and dried at 180 ° C. for 60 minutes. The formed coating film was subjected to a cellophane tape peeling test 10 times, and no defects were found in the coating film.
【００２４】実施例２ ガラスの表面に、実施例１と同様の方法で重合体Ａから
なる密着層を形成した。次にフィルムＣを熱融着により
ラミネートを行ったところ、フィルムが基材に接触して
いない部分は認められなかった。また、形成された膜に
ついてセロテープ剥離テストを１０回実施したが、膜に
欠陥は発生しなかった。[0024] surface of Example 2 glass to form a dense adhesion layer composed of the polymer A in the same manner as in Example 1. Next, when the film C was laminated by heat fusion, no portion where the film was in contact with the substrate was not recognized. The cellophane tape peel test was performed 10 times on the formed film, and no defect was found in the film.
【００２５】実施例３ ガラス板の表面に、γ−アミノプロピルトリエトキシシ
ランを塗布し、続いて溶液Ａをディップコート法により
塗布および熱風乾燥して、重合体Ａからなる塗膜を形成
した。分光光度計により塗膜の膜厚を測定したところ、
５５０ｎｍであった。次に、この塗布されたガラス板を
パーフルオロオクタンに浸漬して超音波を３分間照射し
たのちに分光光度計により膜厚を測定したところ、膜厚
は３０ｎｍ以下であった。しかし表面の水に対する接触
角は１１０度であり、重合体Ａの残留が認められた。次
にこのガラス板に溶液Ａをディップコート法により塗布
および熱風乾燥して、分光光度計により塗膜の膜厚を測
定したところ、５５０ｎｍであった。また、塗膜につい
てセロテープ剥離テストを１０回実施したが、塗膜に欠
陥は発生しなかった。Example 3 γ-Aminopropyltriethoxysilane was applied to the surface of a glass plate, and then solution A was applied by dip coating and dried with hot air to form a coating film composed of polymer A. When the film thickness of the coating film was measured with a spectrophotometer,
It was 550 nm. Next, the coated glass plate was immersed in perfluorooctane and irradiated with ultrasonic waves for 3 minutes, and the film thickness was measured with a spectrophotometer. The film thickness was 30 nm or less. However, the contact angle of the surface with water was 110 degrees, and polymer A remained. Next, the solution A was applied to this glass plate by dip coating and dried with hot air, and the thickness of the coating film was measured by a spectrophotometer. Further, the coated film was subjected to a cellophane tape peeling test 10 times, but no defects were found in the coated film.
【００２６】比較例 ガラス板の表面に、γ−アミノプロピルトリエトキシシ
ランを塗布し、続いて溶液Ｂを塗布して１８０℃で６０
分間の熱風乾燥を行った。形成された塗膜についてセロ
テープ剥離テストを１０回行ったところ、塗膜の剥離が
観察された。COMPARATIVE EXAMPLE γ-Aminopropyltriethoxysilane was applied to the surface of a glass plate, followed by application of solution B.
Min. Hot air drying. When the formed coating film was subjected to cellophane tape peeling test 10 times, peeling of the coating film was observed.
【００２７】[0027]
【発明の効果】基材と密着しうる密着基と含フッ素脂肪
族環構造を有する重合体の密着層の採用により、密着基
を含まない含フッ素脂肪族環構造を有する重合体の被覆
層を密着性よく基材と一体化できる。By adopting tight sealable layer of a polymer having a contact group and a fluorine-containing aliphatic ring structure Ru bovine close contact with the substrate according to the present invention, the adhesion based on the polymer having a free or no fluorine-containing aliphatic ring structure Coating
The layer can be integrated with the substrate with good adhesion.
フロントページの続き (58)調査した分野(Int.Cl.7，ＤＢ名) C08J 7/04 - 7/06 B05D 7/24 C09D 5/00,127/12,129/10 Continuation of the front page (58) Field surveyed (Int.Cl. 7 , DB name) C08J 7 /04-7/06 B05D 7/24 C09D 5 / 00,127 / 12,129 / 10
Claims (4)
材を被覆するにあたり、基材に密着しうる密着基と含フ
ッ素脂肪族環構造を有する重合体からなる密着層を基材
上に形成し、次いで密着基を有せず含フッ素脂肪族環構
造を有する重合体からなる被覆層を該密着層上に形成す
ることを特徴とする基材の被覆方法。1. A fluorine-per in coating a substrate with a polymer having an alicyclic structure, based on a tight sealable layer comprising a polymer having contact group and a fluorine-containing aliphatic ring structure Ru bovine close contact with the substrate Lumber
Formed above, the method of coating substrates, characterized in <br/> Rukoto to form a coating layer comprising a polymer having a fluorinated aliphatic ring structure does not have a contact group in the next physician to said seal adhesive layer .
り被覆層を形成する、請求項１に記載の方法。Wherein forming the coating layer by drying by applying a solution of the polymer, A method according to claim 1.
被覆層を形成する、請求項１に記載の方法。3. A polymer film forming a coating layer by thermal fusion method of claim 1.
るフッ素系溶剤で密着層の膜厚を減じ、次に被覆層を形
成する、請求項１、２または３に記載の方法。4. After the formation of the adhesion layer, the polymer of the adhesion layer is dissolved.
That a fluorine-based solvent reduces the thickness of the adhesion layer, and then form a coating layer
4. The method according to claim 1, 2 or 3, wherein the method comprises:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP03124993A JP3292534B2 (en) | 1993-01-27 | 1993-01-27 | Substrate coating method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP03124993A JP3292534B2 (en) | 1993-01-27 | 1993-01-27 | Substrate coating method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06220232A JPH06220232A (en) | 1994-08-09 |
| JP3292534B2 true JP3292534B2 (en) | 2002-06-17 |
Family
ID=12326099
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP03124993A Expired - Lifetime JP3292534B2 (en) | 1993-01-27 | 1993-01-27 | Substrate coating method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3292534B2 (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0745636A3 (en) * | 1995-05-08 | 1996-12-18 | E.I. Du Pont De Nemours And Company | Dynamic welding of fluoropolymers |
| JP2005060664A (en) | 2003-07-31 | 2005-03-10 | Asahi Glass Co Ltd | Fluorine containing compound, fluorine containing polymer and production process for the same, and resist composition containing the same |
| TW200517785A (en) | 2003-10-31 | 2005-06-01 | Asahi Glass Co Ltd | Fluorine compound, fluorinated polymer, and process for producing the same |
| KR101141570B1 (en) | 2003-12-03 | 2012-05-03 | 아사히 가라스 가부시키가이샤 | Pellicle and novel fluorinated polymer |
| KR20070038533A (en) | 2004-07-30 | 2007-04-10 | 아사히 가라스 가부시키가이샤 | Fluorine-containing compound, fluorine-containing polymer, resist composition and resist protective film composition |
| TW201410451A (en) * | 2012-08-09 | 2014-03-16 | Asahi Glass Co Ltd | Glass-sheet-fluorine-resin laminate |
-
1993
- 1993-01-27 JP JP03124993A patent/JP3292534B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH06220232A (en) | 1994-08-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US5356739A (en) | Stainproof protector made from fluorine-containing aliphatic cyclic polymer for preventing staining of lithographic masks | |
| JP3292534B2 (en) | Substrate coating method | |
| US9223200B2 (en) | Pellicle for lithography, pellicle-mounted photomask, and exposure treatment method | |
| WO2014123221A1 (en) | Fluorine-containing laminate | |
| US4970099A (en) | Perfluoropolymer coated pellicles | |
| JPH08258228A (en) | Agricultural fluoroplastic laminate | |
| US5502132A (en) | Process for producing a perfluoro copolymer | |
| JPH06115023A (en) | Reflection preventive film | |
| JP3053657B2 (en) | Perfluoro copolymer, its production method, its composition and its membrane | |
| JPH0219801A (en) | Reflection reducing agent | |
| JP2843672B2 (en) | Pellicle film having antireflection layer | |
| US5229229A (en) | Pellicle having reflection-preventing function | |
| JP3186844B2 (en) | Pellicle and manufacturing method thereof | |
| JPH07224242A (en) | Fluoropolymer coating composition | |
| JP3192680B2 (en) | Method of coating substrate | |
| JP3968899B2 (en) | Fluoropolymer composition and method for obtaining thin film | |
| JP2748432B2 (en) | Adhesive for optical element | |
| JPH07117188A (en) | Laminated film for agriculture | |
| JPH01123737A (en) | Agricultural clouding free coated material | |
| JPH03195757A (en) | Fluorine-containing polymer composition for coating and use thereof | |
| US5922459A (en) | Plasma-polymerized DMDAS anti-fogging film and method for manufacturing the same | |
| JPH0822929B2 (en) | Method for forming thin film of perfluoropolymer | |
| JPH08187823A (en) | Agricultural fluoroplastic film | |
| JP3400855B2 (en) | Etching method of protective film for semiconductor | |
| JPH049848A (en) | Pellicle with antireflection |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20080329 Year of fee payment: 6 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20080329 Year of fee payment: 6 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090329 Year of fee payment: 7 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20100329 Year of fee payment: 8 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20100329 Year of fee payment: 8 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20110329 Year of fee payment: 9 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120329 Year of fee payment: 10 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120329 Year of fee payment: 10 |
|
| S531 | Written request for registration of change of domicile |
Free format text: JAPANESE INTERMEDIATE CODE: R313531 |
|
| R371 | Transfer withdrawn |
Free format text: JAPANESE INTERMEDIATE CODE: R371 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120329 Year of fee payment: 10 |
|
| S531 | Written request for registration of change of domicile |
Free format text: JAPANESE INTERMEDIATE CODE: R313531 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120329 Year of fee payment: 10 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130329 Year of fee payment: 11 |
|
| EXPY | Cancellation because of completion of term |