JPH03250034A - Formation of fluoropolymer film on plastic surface - Google Patents
Formation of fluoropolymer film on plastic surfaceInfo
- Publication number
- JPH03250034A JPH03250034A JP4827190A JP4827190A JPH03250034A JP H03250034 A JPH03250034 A JP H03250034A JP 4827190 A JP4827190 A JP 4827190A JP 4827190 A JP4827190 A JP 4827190A JP H03250034 A JPH03250034 A JP H03250034A
- Authority
- JP
- Japan
- Prior art keywords
- film
- polymer
- monomer
- plastic surface
- oligomer
- 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.)
- Pending
Links
- 239000004033 plastic Substances 0.000 title claims abstract description 30
- 229920003023 plastic Polymers 0.000 title claims abstract description 30
- 230000015572 biosynthetic process Effects 0.000 title description 15
- 229920002313 fluoropolymer Polymers 0.000 title 1
- 239000004811 fluoropolymer Substances 0.000 title 1
- 239000000178 monomer Substances 0.000 claims abstract description 36
- 229920000642 polymer Polymers 0.000 claims abstract description 29
- 238000010894 electron beam technology Methods 0.000 claims abstract description 22
- 238000000576 coating method Methods 0.000 claims abstract description 20
- 239000011248 coating agent Substances 0.000 claims abstract description 17
- 125000005010 perfluoroalkyl group Chemical group 0.000 claims abstract description 7
- PGFXOWRDDHCDTE-UHFFFAOYSA-N hexafluoropropylene oxide Chemical compound FC(F)(F)C1(F)OC1(F)F PGFXOWRDDHCDTE-UHFFFAOYSA-N 0.000 claims abstract description 6
- 230000001678 irradiating effect Effects 0.000 claims abstract description 4
- 229920006254 polymer film Polymers 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 19
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 11
- 229910052731 fluorine Inorganic materials 0.000 claims description 11
- 239000011737 fluorine Substances 0.000 claims description 11
- -1 polytetrafluoroethylene Polymers 0.000 claims description 8
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 7
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 229920001577 copolymer Polymers 0.000 claims description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-M acrylate group Chemical group C(C=C)(=O)[O-] NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 3
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims description 3
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical group FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 claims description 2
- 230000000379 polymerizing effect Effects 0.000 claims 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 abstract description 5
- QUKRIOLKOHUUBM-UHFFFAOYSA-N 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluorodecyl prop-2-enoate Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)CCOC(=O)C=C QUKRIOLKOHUUBM-UHFFFAOYSA-N 0.000 abstract description 4
- 229920005989 resin Polymers 0.000 abstract description 2
- 239000011347 resin Substances 0.000 abstract description 2
- 239000010408 film Substances 0.000 description 46
- 230000000052 comparative effect Effects 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 239000002904 solvent Substances 0.000 description 7
- 229920000298 Cellophane Polymers 0.000 description 6
- 238000004506 ultrasonic cleaning Methods 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- NZZFYRREKKOMAT-UHFFFAOYSA-N diiodomethane Chemical compound ICI NZZFYRREKKOMAT-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 238000007598 dipping method Methods 0.000 description 3
- 239000010419 fine particle Substances 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- STYXVTBFUKQEKM-UHFFFAOYSA-N 1,1,1,2,3,3,4,4,5,5,6,6,7,7,8,8,8-heptadecafluorooctan-2-yl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(F)(C(F)(F)F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F STYXVTBFUKQEKM-UHFFFAOYSA-N 0.000 description 1
- VPKQPPJQTZJZDB-UHFFFAOYSA-N 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl prop-2-enoate Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)CCOC(=O)C=C VPKQPPJQTZJZDB-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000010410 dusting Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 235000019256 formaldehyde Nutrition 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920005990 polystyrene resin Polymers 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Application Of Or Painting With Fluid Materials (AREA)
- Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
- Treatments Of Macromolecular Shaped Articles (AREA)
- Laminated Bodies (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、プラスチック表面にフロン溶媒を使用せずに
薄膜の含フッ素高分子皮膜を均一に形成できる方法に関
する。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a method for uniformly forming a thin fluorine-containing polymer film on a plastic surface without using a fluorocarbon solvent.
（従来Ｉ支術ン
プラスチックの表面を改質する方法として、７ツ索化基
を有する高分子皮膜を表面に形成して、撥水性、撥油性
、非粘着性、潤滑性などを付与する方法がある。従来、
この皮膜を形成するには、フッ素化基を有する高分子微
粒ｔのフロン分散液やフロン溶解液をスプレー法、スピ
ンコード法、浸漬法などで塗布し、乾燥させる方法で行
っていた。(Conventional methods for modifying the surface of plastics include forming a polymer film with 7-chain groups on the surface to impart water repellency, oil repellency, non-adhesiveness, lubricity, etc.) Traditionally,
In order to form this film, a fluorocarbon dispersion or a fluorocarbon solution of fine polymer particles having a fluorinated group is applied by a spray method, a spin code method, a dipping method, etc., and then dried.
例えば、ポリテトラフルオロエチレン（ＰＴＦＥ）のよ
うに、７０ンへの溶解が困難なものは、そのｍａｙ−を
７ｏン（トリクロロトリ７ルオロエタンなど）に分散さ
せてフロン分散液にし、パーフルオロアルキル基を有す
る（メタ）アクリレートの重合体などのように、フロン
に溶解可能なものは、フロンに溶解して、７０ン溶解液
として、それらを塗布していた。ここで、分散液や溶解
液の溶媒として、フロンを使用していたのは、作業性、
塗工性が他の溶媒より優れているためである。For example, for materials such as polytetrafluoroethylene (PTFE) that are difficult to dissolve in 70N, the may- may be dispersed in 70N (trichlorotri7fluoroethane, etc.) to make a Freon dispersion, and the perfluoroalkyl group Materials that can be dissolved in chlorofluorocarbons, such as (meth)acrylate polymers having 100% chlorofluorocarbons, were dissolved in chlorofluorocarbons and applied as a 70% solution. Here, CFCs were used as a solvent for dispersions and solutions because of workability and
This is because the coating properties are superior to other solvents.
（発明が解決しようとする問題点）
しかしながら、溶媒にフロンを使用すると、乾燥の際蒸
発した７ｏンがオゾン層を破壊するため、フロンの使用
には環境上問題があった。(Problems to be Solved by the Invention) However, when Freon is used as a solvent, the 7on evaporated during drying destroys the ozone layer, so the use of Freon poses an environmental problem.
また、塗布した分散液や溶解液の乾燥は、プラスチック
の変形や耐熱性の関係で常温で行っていたが、乾燥に数
分から数十分要するものであった。Further, the applied dispersion or solution was dried at room temperature due to the deformation and heat resistance of the plastic, but drying required several minutes to several tens of minutes.
乾燥時間を短くするには加熱すればよいが、加熱温度を
高くすると、プラスチックの形状や寸法が変化してしま
うため、あまり高くできないものであった。このため、
乾燥時間は、加熱してもまだ数十秒から数分と長くかか
り、生産性の低いものであった。The drying time can be shortened by heating, but if the heating temperature is raised, the shape and dimensions of the plastic will change, so it has not been possible to increase the heating temperature too much. For this reason,
Drying time was still long, ranging from several tens of seconds to several minutes even after heating, resulting in low productivity.
さらに、プラスチックには、種類により表面の不活性な
ものがあるが、このようなものの場合、高分子皮ｌ１ｆ
ｆｉ着性が劣り、すべでのプラスチックに適用できると
いうものではなかった。Furthermore, depending on the type of plastic, there are those with an inert surface, but in the case of such plastics, the polymer coating l1f
It had poor fi adhesion and could not be applied to all plastics.
本発明は、これらの問題を解決した含フッ素高分子皮膜
のプラスチック表面への形成方法を提供するものである
。The present invention provides a method for forming a fluorine-containing polymer film on a plastic surface that solves these problems.
（問題点を解決するための手段）
本発明は、多フッ素化基を有する電子線重合可能なモノ
マーに、該モノマーに溶解もしくは分散可能なオリゴマ
ーまたはポリマーを重量比で０．１〜３０％添加したモ
ノマー溶液をプラスチック表面に塗布した後、電子線を
０．５〜２０ Ｍｒａｄ照射してモノマーを重合、硬化
させる方法に上り含フッ素高分子皮膜をプラスチック表
面に形成するようにした。(Means for Solving the Problems) The present invention involves adding 0.1 to 30% by weight of an oligomer or polymer that can be dissolved or dispersed in an electron beam polymerizable monomer having a polyfluorinated group. After coating the plastic surface with the monomer solution, the monomer was polymerized and cured by irradiation with an electron beam of 0.5 to 20 Mrad to form a fluorine-containing polymer film on the plastic surface.
（作用）
七ツマ−は、液状であるため、フロンのような溶媒を使
用しなくでもプラスチックに塗布することができ、塗布
の場合の作業性、塗工性も溶媒分散液や溶解液と同等で
ある。(Function) Because Nanatsumar is in liquid form, it can be applied to plastics without using solvents such as chlorofluorocarbons, and its workability and coating properties are the same as those of solvent dispersions and solutions. It is.
しかし、モノマーは、一般に表面張力が小さいため、厚
膜に塗布する場合は問題ないが、薄く塗布すると、モノ
マー層が破れ、塗布ムラが生じる。However, since monomers generally have a low surface tension, there is no problem when coating a thick film, but when coating a thin film, the monomer layer is torn and uneven coating occurs.
このため、モノマー単独では膜厚が５μ趣以下の均一皮
膜を形成することができない。Therefore, it is not possible to form a uniform film having a thickness of 5 μm or less using the monomer alone.
塗布ムラをなくすには表面張力および／または粘度を大
きくすることが有効であるが、表面張力を大きくすると
、同時に濡れ性も改善されてしまい、目的とする表面改
質ができない、そこで、本発明では、モノマーに溶解も
しくは分散可能なオリゴマーやポリマーで多フッ素化基
を有するものを添加して粘度を大きくし、薄く塗布して
も塗布ムラが生じないようにした。オリゴマーやポリマ
ーは、多７７素化基を有するので、これらの添加により
皮膜の撥水性などの特性が損なわれることはない。Increasing the surface tension and/or viscosity is effective in eliminating coating unevenness, but increasing the surface tension also improves wettability, making it impossible to achieve the desired surface modification.Therefore, the present invention In this case, an oligomer or polymer having a polyfluorinated group that can be dissolved or dispersed in a monomer is added to increase the viscosity so that uneven coating does not occur even when applied thinly. Since oligomers and polymers have multiple groups, their addition does not impair the water repellency and other properties of the film.
このオリゴマーまたはポリマーの添加は、重量比で０．
１〜３０％にする。０．１％未満であると、粘度が大き
くならず、３０％を越えると、電子線を照射しても塗布
液が硬化しなくなる。The addition of this oligomer or polymer is carried out in a weight ratio of 0.
Set it to 1-30%. If it is less than 0.1%, the viscosity will not increase, and if it exceeds 30%, the coating liquid will not harden even when irradiated with an electron beam.
オリゴマーまたはポリマーを添加したモノマー溶液は、
プラスチックに塗布して電子線を照射すれば、常温でも
瞬時に重合、硬化する。このため、加熱や乾燥時開が不
要となり、生産性が高くなる。A monomer solution with added oligomer or polymer is
When applied to plastic and exposed to electron beams, it instantly polymerizes and hardens even at room temperature. This eliminates the need for heating or opening during drying, increasing productivity.
また、加熱により変形や寸法が変化しやすいもので＃Ｊ
問題なく高分子皮膜を形成できる。Also, please note that #J
A polymer film can be formed without any problems.
また、電子線は、七ツマー層を通過して、プラスチック
表層にも達するので、表面には活性点が生じ、モノマー
と反応する。このため、高分子皮膜の密着は強固になる
。Furthermore, since the electron beam passes through the 7-mer layer and reaches the plastic surface layer, active points are generated on the surface and react with the monomer. Therefore, the adhesion of the polymer film becomes strong.
本発明で使用する七ツマ−は、電子線で重合しなければ
ならないので、分子中にエチレン性不飽和二重結合を有
し、また、皮膜に撥水性や撥油性などを付与するため、
多７７素化基が２フッ素化以上のらのでなければならな
い、このようなモノマーの好ましいものとしては、炭素
数が３〜２０個、好ましくは６〜１４個で、末端に多フ
ッ素化基としてパーフルオロアルキル基を有するアクリ
レート、例えば、パーフルオロヘキシルエチルアクリレ
ート、パーフルオロオクチルエチルアクリレート、パー
フルオロオクチルブチルアクリレ−）、２−）リフルオ
ロメチルパーフルオロオクチルプロピルアクリレート、
２−トリプル？ロメチルバーフルオロヘプチルエチルア
クリレートなどである。モノマーは、１種だけのもので
も、２種以上のものをｉに合したものでもよい。Since the seven polymers used in the present invention must be polymerized with electron beams, they have ethylenically unsaturated double bonds in their molecules, and in order to impart water repellency and oil repellency to the film,
Preferably, such a monomer has 3 to 20 carbon atoms, preferably 6 to 14 carbon atoms, and the polyfluorinated group must be difluorinated or more. Acrylates having a perfluoroalkyl group, such as perfluorohexylethyl acrylate, perfluorooctyl ethyl acrylate, perfluorooctyl butyl acrylate), 2-)lifluoromethylperfluorooctylpropyl acrylate,
2-Triple? Examples include romethyl barfluoroheptylethyl acrylate. The monomer may be one type or a combination of two or more types for i.
オリゴマー ポリマーの多７７素化基は、モノマーの場
合と同様、２フッ素化以上のものであり、分子中にパー
フルオロアルキル基を有するものが好ましい。このよう
なものとしては、ポリテトラフルオロエチレン、ヘキサ
フルオロプロピレンエポキシドの重合物、テトラフルオ
ロエチレンとヘキサフルオロプロピレンの共重合体など
がある。Oligomer The polyfluorinated group of the polymer is difluorinated or more, as in the case of the monomer, and preferably has a perfluoroalkyl group in the molecule. Examples of such materials include polymers of polytetrafluoroethylene, hexafluoropropylene epoxide, and copolymers of tetrafluoroethylene and hexafluoropropylene.
これらのモノマーへの添加は、オイル状もしくは微粒子
にして添加し、均一に溶解もしくは分散するようにする
。These monomers are added in the form of oil or fine particles so that they are uniformly dissolved or dispersed.
モノマー溶液には、必要に応じで消泡剤、レベリング剤
、カップリング剤などの添加剤を添加したものでもよい
。Additives such as an antifoaming agent, a leveling agent, and a coupling agent may be added to the monomer solution as necessary.
本発明によりプラスチック表面に高分子皮膜を形成する
には、プラスチックに直接モノマーを塗布して、電子線
を照射するだけで形成できる。プラスチックは電子線に
より活性点が生じるものであれば種類を問わない、モノ
マーの塗布前の前処理は通常塵さなくてもよいが、皮膜
密着性を特に高めたい場合には、活性化処理（例えば、
コロナ放電外Ｆｌｙ＞を施してもよい。塗布は、スプレ
ー法、浸漬法、ロールコート法、スピンコード法など公
知方法によればよい。In order to form a polymer film on a plastic surface according to the present invention, it can be formed simply by applying a monomer directly to the plastic and irradiating it with an electron beam. Plastics can be of any type as long as active sites are generated by electron beams.Normally, dusting is not necessary in the pretreatment before coating the monomer, but if you want to particularly increase the adhesion of the film, activation treatment ( for example,
A corona discharge outside Fly> may also be applied. Coating may be performed by a known method such as a spray method, a dipping method, a roll coating method, or a spin code method.
電子線の照射は、市販の電子線加速器を用いて、０．５
〜２０ Ｍｒａｄ照射すればよい。線量が０．５８ｒａ
ｄ未満であると、モノマーの重合が不完全で、均一な皮
膜が形成できず、２０ Ｎｒａｄを越えると、生成した
高分子皮膜が逆に分解するようになる。The electron beam irradiation was carried out using a commercially available electron beam accelerator.
~20 Mrad irradiation is sufficient. Dose is 0.58ra
If it is less than d, polymerization of the monomer will be incomplete and a uniform film cannot be formed, and if it exceeds 20 Nrad, the formed polymer film will actually decompose.
なお、電子線照射の際に酸素が存在すると、モノマーが
重合障害を起こｔので、雰囲気は窒素ガスやアルゴンガ
スのような不活性雰囲気にするのが好ましい。Note that if oxygen is present during electron beam irradiation, polymerization of the monomer will be hindered, so the atmosphere is preferably an inert atmosphere such as nitrogen gas or argon gas.
（実施例）
実施例１
パーフルオロオクチルエチルアクリレートｒヘキスト社
製、ＡＥ８００１にヘキサフルオロプロピレンエポキシ
ドのポリマー（デュポン社製、Ｋｒｙｔｏｘｌ ４３
Ａ Ｙ ）を重量比で１０％添加したモノマー溶液を調
製し、これを、表面を清浄にしたポリスルホン樹脂表面
にスピンコード法で塗布した後、窒素ガス雰囲気下、加
速電圧２００ＫＶ、１１Ａ ｆｆｉ １０ Ｍｒａｄの
照射条件で電子線を照射しで硬化させたところ、厚さ１
μ−の高分子皮膜が得られ、皮膜は均一であった。(Example) Example 1 Polymer of hexafluoropropylene epoxide in perfluorooctylethyl acrylate (manufactured by Hoechst, AE8001) (manufactured by DuPont, Krytoxl 43)
A monomer solution containing 10% by weight of A When cured by electron beam irradiation under the following irradiation conditions, the thickness was 1
A μ-polymer film was obtained, and the film was uniform.
次に、この皮膜を形成したポリスルホン樹Ｉｌｒ表面お
よび水中での超音波１時間洗浄後の表面に対する水また
はヲウ化メチレンの接触角（ｄｅｇ）を静置液滴法で測
定したところ、次のように接触角は未処理皮膜より大き
がった。Next, the contact angle (deg) of water or methylene oxide on the surface of the polysulfone resin Ilr on which this film was formed and the surface after 1 hour of ultrasonic cleaning in water was measured using the standing droplet method, and the results were as follows. The contact angle was larger than that of the untreated film.
区 分 接触角（対ＩＩ ２０ ） 接触角（対
Ｃ１１２１□）皮膜形成前 ８３ １８
皮膜形成後 １１６ ９０超音波洗浄後
１１６ ９１まな、表面にセロハンテー
プを貼付けて剥離しても、皮膜の剥離は認められなかっ
た。Classification Contact angle (vs. II 20) Contact angle (vs. C1121□) Before film formation 83 18
After film formation: 116 90 After ultrasonic cleaning: 116 91 After applying cellophane tape to the surface and peeling it off, no peeling of the film was observed.
実施例２
実施例１でのへキサフルオロブロビレンエボキシドボリ
マーの添加量を２５％に、また、電子線照射の線量を７
８ｒａｄに変更して皮膜を形成したところ、厚さ２μ−
の高分子皮膜が得られた。この皮膜は、均一で、皮膜に
対する水またはヨウ化メチレンの接触角を同様に測定し
たところ、次のようになった。Example 2 The amount of hexafluorobrobylene eboxide polymer added in Example 1 was changed to 25%, and the dose of electron beam irradiation was changed to 7%.
When the film was formed by changing to 8rad, the thickness was 2μ-
A polymer film was obtained. This film was uniform, and when the contact angle of water or methylene iodide to the film was measured in the same way, it was as follows.
区 分 接触角（対Ｈ２０）接触角（対ＣＨ２１２
）皮膜形成前 ８３ １８皮膜形成後
１１５ ９１超音波洗浄後 １１４
９０また、セロハンテープ貼付けによる皮Ｉ
ＩＩ剥離も認められなかった。Classification Contact angle (vs. H20) Contact angle (vs. CH212
) Before film formation 83 18 After film formation
115 91 After ultrasonic cleaning 114
90 Also, skin I by pasting cellophane tape
II peeling was also not observed.
実施例３
パーフルオロオクチルエチルアクリレート［ヘキス）ｌ
ｔｌ１％ＡＥ８００］にポリテトラフルオロエチレンの
微粉末ポリマー［ダイキン（株）製、ルブロンし一２］
を重量比で０．５％添加したモノマー溶液をｉｉ１！！
Ｌ、これを、表面を清浄にしたポリメチルメタクリレー
ト表面にバーコーター＃４で塗布した後、窒素γス雰囲
気下、加Ｊ！！！電圧２００Ｋｖ、＃ｉ Ｊｉ ３ Ｎ
ｒａｄの照射条件で電子線を照射して硬化させたところ
、Ｐ′！、さ４μ論の高分子皮膜が得られ、皮膜は均一
であった。Example 3 Perfluorooctylethyl acrylate [hex)l
tl1%AE800] and a fine powder polymer of polytetrafluoroethylene [manufactured by Daikin Corporation, LeBron Shiichi 2]
A monomer solution containing 0.5% by weight of ii1! !
L. After applying this to the cleaned polymethyl methacrylate surface using bar coater #4, it was added under a nitrogen γ gas atmosphere. ! ! Voltage 200Kv, #i Ji 3 N
When cured by electron beam irradiation under rad irradiation conditions, P'! A polymer film having a thickness of 4 μm was obtained, and the film was uniform.
この皮膜に対する水またはヨウ化メチレンの接触角を実
施例１と同様の方法で測定したところ、次のようになっ
た。The contact angle of water or methylene iodide on this film was measured in the same manner as in Example 1, and the results were as follows.
区 分 接触角（対Ｈ２０） 接触角（対ＣＩ＋
２１２）皮膜形成前 ７６ ４２皮膜形
成後 １１４ ９３遁ａ波洗浄後 １
１３ ９２また、セロハンテープ貼付けによ
る皮膜剥離も認めＣ）れなかった。Classification Contact angle (vs. H20) Contact angle (vs. CI+
212) Before film formation 76 42 After film formation 114 93 After A-wave cleaning 1
13 92 Also, no peeling of the film was observed due to the application of cellophane tape C).
実施例４
実施例３でのポリテトラフルオロエチレン微粉末ポリマ
ーの添加量を５％に、塗布法をスピンコード法に、さら
に、電子線照射の線量を５８ｒａｄに変更して皮膜を形
成したところ、厚さ５μ−の高分子皮膜が得られた。こ
の皮膜は均一で、皮膜に対する水またはヨウ化メチレン
の接触角を同様に測定したところ、次のようになった。Example 4 A film was formed by changing the amount of polytetrafluoroethylene fine powder polymer added in Example 3 to 5%, changing the coating method to a spin code method, and changing the dose of electron beam irradiation to 58 rad. A polymer film with a thickness of 5 μm was obtained. This film was uniform, and when the contact angle of water or methylene iodide to the film was similarly measured, the results were as follows.
区 分 接触角（対ＩＩ 、 Ｏ） 接触角（対
ＣＩ（，１２）皮膜形成前 ７６ ４２
皮模形成後 １２０ ９３超音波洗浄後
１２０ ９３また、セロハンテープ貼付
けによる皮膜剥離も認められなかった。Classification Contact angle (vs. II, O) Contact angle (vs. CI (,12) before film formation 76 42
After skin imitation formation 120 93 After ultrasonic cleaning 120 93 Furthermore, no peeling of the film was observed due to the application of cellophane tape.
実施例５
パーフルオロヘキシルエチルメタクリレート（ヘキスト
社製、ＡＥ６００）にキシレン分散テトラ７ルオロエチ
レンーヘキサ７ルオロプロピレン重合体微粒子ポリマー
を固形分重量比で１％添加した後、しばらく放置してキ
シレンを蒸発させた。Example 5 After adding 1% solids weight ratio of xylene-dispersed tetra-7-fluoroethylene-hexa-7-fluoropropylene polymer fine particles to perfluorohexylethyl methacrylate (manufactured by Hoechst, AE600), the mixture was left to stand for a while to absorb xylene. was evaporated.
次に、このモノマー溶液を表面を清浄にしたポリスチレ
ン樹脂に浸漬法で塗布し、実施例１と同！ｊ！領で電子
線を線量１２Ｍｒａｄ照射し、硬化させた。Next, this monomer solution was applied to the polystyrene resin whose surface had been cleaned using the dipping method, and the same procedure as in Example 1 was applied! j! The sample was cured by irradiating it with an electron beam at a dose of 12 Mrad.
この皮膜の膜厚は５μ鋤で、均一であった．また、この
皮膜に対する水またはヨウ化メチレンの接触角を同様に
測定したところ、次のようになった。The film thickness of this film was 5μ and uniform. Furthermore, the contact angle of water or methylene iodide with respect to this film was measured in the same manner, and the results were as follows.
区 分 接触角（討１１□０） 接触角（対Ｃ１１
２１，）皮膜形成前 ８８ ３９皮膜
形成後 １１２ ９１、＠！音波洗浄
後 １１１ ９０また、セロハンテープ
貼付けによる皮膜剥離も認められなかった。Classification Contact angle (v11□0) Contact angle (vs C11
21,) Before film formation 88 39 After film formation 112 91, @! After sonic cleaning 111 90 Also, no peeling of the film due to cellophane tape attachment was observed.
実施例６
実施例５での共重合体微粒子添加量を１５％に、塗布法
をバーコーター法（井４）に、電子線照射の＃ｉ量を１
５）４ｒａｄにして皮膜を形成したところ、厚さ４μ−
の均一な皮膜を形成できた。Example 6 The amount of copolymer fine particles added in Example 5 was changed to 15%, the coating method was changed to the bar coater method (well 4), and the #i amount of electron beam irradiation was changed to 1.
5) When a film was formed at 4 rad, the thickness was 4 μ-
A uniform film was formed.
また、接触角は次の通りであった。Further, the contact angle was as follows.
区 分 接触角（対Ｉ ２０ ） 接触角（対Ｃ
Ｉ＋２１２）皮膜形成前 ８８ ３
９皮膜形成後 １１４ ９２超音波洗
浄後 １１３ ９０また、セロハンテー
プ貼付けによる皮膜剥離も認められなかった。Classification Contact angle (vs. I20) Contact angle (vs. C
I+212) Before film formation 88 3
9 After film formation 114 92 After ultrasonic cleaning 113 90 Furthermore, no peeling of the film was observed when the cellophane tape was attached.
（比較例）
比較例１
実施例１において、モノマー溶液のヘキサフルオロプロ
ピレンエポキシドボリマー添加量を重量比で０．０５％
にして、薄く塗布したところ、塗布面の大部分が被覆さ
れず、著しい塗布ムラのある皮膜しか形成できなかった
。(Comparative Example) Comparative Example 1 In Example 1, the amount of hexafluoropropylene epoxide polymer added to the monomer solution was 0.05% by weight.
When the coating was applied thinly, most of the coated surface was not coated, and only a film with significant uneven coating was formed.
比較例２
実施例２において、ヘキサフルオロプロピレンエボキシ
ドボリマーの添加量を５０％にして、皮膜を形成したと
ころ、モノマー溶液は硬化しなかった。Comparative Example 2 In Example 2, when a film was formed by adding 50% of the hexafluoropropylene epoxide polymer, the monomer solution did not harden.
比較例３
実施例３においで、ポリテトラフルオロエチレン微粉末
ポリマーの添加量を０．０１％にして皮膜形成を行った
が、比較例１と同様、著しく塗布ムラのある皮膜しか形
成で外なかった。Comparative Example 3 In Example 3, a film was formed by adding 0.01% of the polytetrafluoroethylene fine powder polymer, but as in Comparative Example 1, only a film with extremely uneven coating was formed. Ta.
比較例４
実施例４において、ポリテトラフルオロエチレンポリマ
ーの添加量を５０％にして皮膜形成を行ったが、比較例
２と同様、モノマー溶液は硬化しなかった。Comparative Example 4 In Example 4, a film was formed with the amount of polytetrafluoroethylene polymer added at 50%, but as in Comparative Example 2, the monomer solution did not harden.
比較例５
実施例３において、電子線照射の線量を５゜Ｈｒａｄに
変更したところ、硬化不十分のため、接触角は、あまり
大きくならず、超音波洗浄すると、小さくなってしまっ
た。Comparative Example 5 In Example 3, when the dose of electron beam irradiation was changed to 5° Hrad, the contact angle did not become very large due to insufficient curing, and became smaller after ultrasonic cleaning.
区 分 接触角（＃Ｈ２０） 接触角（対ＣＨ，
Ｉ２）皮膜形成前 ７６ ４２皮膜形
成後 ８６ ３５Ｈｉｎ波洗浄後
８０ ３６比較例６
実施例６において、電子線照射＃ｉ量をＯ，ＯＳＭｒａ
ｄにしたところ、モノマー溶液は硬化しなかった。Classification Contact angle (#H20) Contact angle (vs. CH,
I2) Before film formation 76 42 After film formation 86 After 35 Hin wave cleaning
80 36 Comparative Example 6 In Example 6, the amount of electron beam irradiation #i was set to O, OSMra
d, the monomer solution did not harden.
（発明の効果）
以上のように、本発明によれば、フロン溶媒を使用せず
にプラスチック表面に多フッ素化基を有する薄膜の高分
子皮膜を短時間に密着性よ（形成できる。(Effects of the Invention) As described above, according to the present invention, it is possible to form a thin polymer film having polyfluorinated groups on a plastic surface in a short period of time without using a fluorocarbon solvent.
Claims (8)
に、該モノマーに溶解もしくは分散可能なオリゴマーま
たはポリマーを重量比で０．１〜３０％添加したモノマ
ー溶液をプラスチック表面に塗布した後、電子線を０．
５〜２０Ｍｒａｄ照射してモノマーを重合、硬化させる
ことを特徴とするプラスチック表面への含フッ素高分子
皮膜の形成方法。(1) After coating a plastic surface with a monomer solution in which 0.1 to 30% by weight of an oligomer or polymer that can be dissolved or dispersed in the monomer is added to an electron beam polymerizable monomer having a polyfluorinated group, 0.
A method for forming a fluorine-containing polymer film on a plastic surface, comprising polymerizing and curing a monomer by irradiating 5 to 20 Mrad.
化基としてパーフルオロアルキル基を有するものである
ことを特徴とする特許請求の範囲第１項に記載のプラス
チック表面への含フッ素高分子皮膜の形成方法。(2) Fluorine-containing on the plastic surface according to claim 1, wherein the monomer has 3 to 20 carbon atoms and has a perfluoroalkyl group as a polyfluorinated group. Method of forming polymer film.
化基としてパーフルオロアルキル基を有するアクリレー
トであることを特徴とする特許請求の範囲第１項または
第２項に記載のプラスチック表面への含フッ素高分子皮
膜の形成方法。(3) The plastic surface according to claim 1 or 2, wherein the monomer is an acrylate having 3 to 20 carbon atoms and having a perfluoroalkyl group as a polyfluorinated group. A method for forming a fluorine-containing polymer film on.
ル基を有するものであることを特徴とする特許請求の範
囲第１項に記載のプラスチック表面への含フッ素高分子
皮膜の形成方法。(4) The method for forming a fluorine-containing polymer film on a plastic surface according to claim 1, wherein the oligomer or polymer has a perfluoroalkyl group.
エチレンであることを特徴とする特許請求の範囲第１項
に記載のプラスチック表面への含フッ素高分子皮膜の形
成方法。(5) The method for forming a fluorine-containing polymer film on a plastic surface according to claim 1, wherein the oligomer or polymer is polytetrafluoroethylene.
ピレンエポキシドの重合物であることを特徴とする特許
請求の範囲第１項に記載のプラスチック表面への含フッ
素高分子皮膜の形成方法。(6) The method for forming a fluorine-containing polymer film on a plastic surface according to claim 1, wherein the oligomer or polymer is a polymer of hexafluoropropylene epoxide.
レンと他のモノマーの共重合体であることを特徴とする
特許請求の範囲第１項に記載のプラスチック表面への含
フッ素高分子皮膜の形成方法。(7) The method for forming a fluorine-containing polymer film on a plastic surface according to claim 1, wherein the oligomer or polymer is a copolymer of tetrafluoroethylene and another monomer.
レンとヘキサフルオロプロピレンの共重合体であること
を特徴とする特許請求の範囲第７項に記載のプラスチッ
ク表面への含フッ素高分子皮膜の形成方法。(8) The method for forming a fluorine-containing polymer film on a plastic surface according to claim 7, wherein the oligomer or polymer is a copolymer of tetrafluoroethylene and hexafluoropropylene.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4827190A JPH03250034A (en) | 1990-02-28 | 1990-02-28 | Formation of fluoropolymer film on plastic surface |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4827190A JPH03250034A (en) | 1990-02-28 | 1990-02-28 | Formation of fluoropolymer film on plastic surface |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH03250034A true JPH03250034A (en) | 1991-11-07 |
Family
ID=12798781
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4827190A Pending JPH03250034A (en) | 1990-02-28 | 1990-02-28 | Formation of fluoropolymer film on plastic surface |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03250034A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AT406756B (en) * | 1998-12-21 | 2000-08-25 | Johannes Dr Heitz | FLUOROPOLYMER COATINGS WITH GOOD LIABILITY AND GOOD ABRASION RESISTANCE FOR USE IN MEDICINE AND A METHOD FOR THEIR PRODUCTION |
| WO2000053682A1 (en) * | 1999-03-09 | 2000-09-14 | Minnesota Mining And Manufacturing Company | Fluorine-containing releasing sheet and process of production of same |
| US6878440B1 (en) | 1999-07-02 | 2005-04-12 | 3M Innovative Properties Company | Pressure sensitive adhesive sheet and production method thereof |
| JP2012188514A (en) * | 2011-03-09 | 2012-10-04 | Fuji Xerox Co Ltd | Fluorine-containing resin particle dispersion, method for preparing fluorine-containing resin particle dispersion, coating liquid which contains fluorine-containing resin particles, method for preparing coating film which contains fluorine-containing resin particles, coating film which contains fluorine-containing resin particles, and molded body |
| JP2014153684A (en) * | 2013-02-13 | 2014-08-25 | Dainippon Printing Co Ltd | Manufacturing method of antireflection article |
| WO2015133532A1 (en) * | 2014-03-04 | 2015-09-11 | ダイキン工業株式会社 | Polymer base material, use thereof, and production method therefor |
-
1990
- 1990-02-28 JP JP4827190A patent/JPH03250034A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AT406756B (en) * | 1998-12-21 | 2000-08-25 | Johannes Dr Heitz | FLUOROPOLYMER COATINGS WITH GOOD LIABILITY AND GOOD ABRASION RESISTANCE FOR USE IN MEDICINE AND A METHOD FOR THEIR PRODUCTION |
| WO2000053682A1 (en) * | 1999-03-09 | 2000-09-14 | Minnesota Mining And Manufacturing Company | Fluorine-containing releasing sheet and process of production of same |
| US6878440B1 (en) | 1999-07-02 | 2005-04-12 | 3M Innovative Properties Company | Pressure sensitive adhesive sheet and production method thereof |
| JP2012188514A (en) * | 2011-03-09 | 2012-10-04 | Fuji Xerox Co Ltd | Fluorine-containing resin particle dispersion, method for preparing fluorine-containing resin particle dispersion, coating liquid which contains fluorine-containing resin particles, method for preparing coating film which contains fluorine-containing resin particles, coating film which contains fluorine-containing resin particles, and molded body |
| JP2014153684A (en) * | 2013-02-13 | 2014-08-25 | Dainippon Printing Co Ltd | Manufacturing method of antireflection article |
| WO2015133532A1 (en) * | 2014-03-04 | 2015-09-11 | ダイキン工業株式会社 | Polymer base material, use thereof, and production method therefor |
| JP2015180723A (en) * | 2014-03-04 | 2015-10-15 | ダイキン工業株式会社 | Polymer base material, use thereof and method of producing the same |
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