JPH05302077A - Agent and method for treating plastic surface - Google Patents
Agent and method for treating plastic surfaceInfo
- Publication number
- JPH05302077A JPH05302077A JP3337577A JP33757791A JPH05302077A JP H05302077 A JPH05302077 A JP H05302077A JP 3337577 A JP3337577 A JP 3337577A JP 33757791 A JP33757791 A JP 33757791A JP H05302077 A JPH05302077 A JP H05302077A
- Authority
- JP
- Japan
- Prior art keywords
- agent
- antistatic
- plastic
- treatment
- antistatic agent
- 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
- 239000004033 plastic Substances 0.000 title claims abstract description 36
- 229920003023 plastic Polymers 0.000 title claims abstract description 36
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 28
- 238000000034 method Methods 0.000 title claims description 13
- 239000002216 antistatic agent Substances 0.000 claims abstract description 37
- 239000010419 fine particle Substances 0.000 claims abstract description 24
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims abstract description 13
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000002736 nonionic surfactant Substances 0.000 claims abstract description 7
- 238000007865 diluting Methods 0.000 claims abstract description 5
- 229940051841 polyoxyethylene ether Drugs 0.000 claims abstract description 5
- 229920000056 polyoxyethylene ether Polymers 0.000 claims abstract description 5
- 239000003085 diluting agent Substances 0.000 claims description 11
- 125000005010 perfluoroalkyl group Chemical group 0.000 claims description 8
- 229910020366 ClO 4 Inorganic materials 0.000 claims description 2
- 239000012188 paraffin wax Substances 0.000 abstract description 6
- 229910001914 chlorine tetroxide Inorganic materials 0.000 abstract 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Chemical compound [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 abstract 1
- 230000000694 effects Effects 0.000 description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- -1 polytetrafluoroethylene Polymers 0.000 description 14
- 238000011109 contamination Methods 0.000 description 12
- 238000012360 testing method Methods 0.000 description 10
- 238000004140 cleaning Methods 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 6
- 239000004810 polytetrafluoroethylene Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 239000012298 atmosphere Substances 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 230000003068 static effect Effects 0.000 description 5
- 239000012756 surface treatment agent Substances 0.000 description 5
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000000428 dust Substances 0.000 description 4
- 230000005611 electricity Effects 0.000 description 4
- 230000001965 increasing effect Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000011882 ultra-fine particle Substances 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 238000010790 dilution Methods 0.000 description 3
- 239000012895 dilution Substances 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 238000004381 surface treatment Methods 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- 238000004506 ultrasonic cleaning Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
- 150000005215 alkyl ethers Chemical class 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 230000003749 cleanliness Effects 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 230000008014 freezing Effects 0.000 description 2
- 238000007710 freezing Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 230000002285 radioactive effect Effects 0.000 description 2
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000001143 conditioned effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Landscapes
- Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、静電気を帯びやすいプ
ラスチック表面の処理剤及び処理方法に関し、特に被処
理面に付着した微粒子の除去を容易に行うことが可能で
あり、且つ被処理面に表面汚染性の少ない帯電防止塗布
膜を形成することができるプラスチック表面の処理剤及
び処理方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a treating agent and a treating method for a plastic surface which is likely to be charged with static electricity, and in particular, it is possible to easily remove fine particles adhering to the treated surface and to treat the treated surface. The present invention relates to a treatment agent and a treatment method for a plastic surface capable of forming an antistatic coating film having a low surface contamination property.
【０００２】[0002]
【従来の技術】電子工業において半導体やＬＣＤのよう
な高清浄度の必要な製造工程では耐薬品性・耐高温性の
フッ素樹脂を使用することが多い。例えば、ウェットプ
ロセス用のウェーハキャリアとしてＰＦＡ（テトラフル
オロエチレン・パーフルオロアルキルビニルエーテル共
重合体）が使われ、また、洗浄槽や搬送用器具等として
ＰＴＦＥ（ポリテトラフルオロエチレン）が使われてい
る。これらはプラスチックの中ではもっとも帯電しやす
いものである。電子工業で広く使われるプラスチックと
してはさらにポリプロピレン、ポリエチレン、アクリル
等があり、これらはフッ素樹脂ほどではないが、いずれ
も非常に帯電しやすい。一方デバイスの集積度が上がる
につれて、粒経 0.1〜0.3 μm 程度の超微粒子の汚染が
その製造工程での歩留まりを大きく左右するようになっ
た。その汚染モードはクーロン力が支配的なため、この
ようなプラスチックは極めて微粒子汚染を受けやすく、
これが工程での大きな微粒子汚染源となっている。2. Description of the Related Art In the electronic industry, chemical-resistant and high-temperature-resistant fluororesins are often used in manufacturing processes such as semiconductors and LCDs which require high cleanliness. For example, PFA (tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer) is used as a wafer carrier for a wet process, and PTFE (polytetrafluoroethylene) is used as a cleaning tank, a transportation tool, and the like. These are the most easily charged of all plastics. Plastics that are widely used in the electronics industry include polypropylene, polyethylene, acrylic, and the like, which are not as much as fluororesins, but are all very easily charged. On the other hand, as the degree of integration of devices has increased, the contamination of ultra-fine particles with a grain size of 0.1 to 0.3 μm has come to greatly influence the yield in the manufacturing process. The Coulomb force is dominant in the contamination mode, so such plastics are extremely susceptible to particulate contamination,
This is a major source of particulate contamination in the process.
【０００３】このような静電気による付着超微粒子は極
めて除去が難しく、勿論フッ素樹脂に付着した超微粒子
の除去がもっとも困難である。このような汚染に対する
除去法としては、静電気を考慮したアルコール−純水−
炭酸ガスによる抵抗率制御洗浄液等が提案されている
（特開平２−53899 号公報）。しかしこの洗浄法を受け
た被洗浄面は帯電防止されてはいないので乾燥後は容易
に再帯電する。It is extremely difficult to remove such adhered ultrafine particles due to static electricity, and it is most difficult to remove the ultrafine particles adhered to the fluororesin. As a method for removing such contamination, alcohol that takes static electricity into consideration-pure water-
A cleaning solution for controlling the resistivity using carbon dioxide gas has been proposed (JP-A-2-53899). However, since the surface to be cleaned that has been subjected to this cleaning method is not antistatic, it is easily recharged after drying.
【０００４】一方フッ素樹脂の帯電防止のためには、フ
ッ素樹脂面に対しての付着力が要求されることに関連し
て、例えばパーフルオロアルキル基とヒドロキシエチル
基とを併せもつ第４級アンモニウム化合物のようなフッ
素系界面活性剤（特開平３−192186号公報）が配合され
た塗布型帯電防止剤が使用される。この帯電防止剤は、
確かにフッ素樹脂に対して十分な帯電防止性を与える
が、後述する比較例からも明らかな通り、好適とされる
濃度の本剤の水溶液でフッ素樹脂製品を処理しても、本
剤による脱微粒子効果はまったく観察されない。一般
に、フッ素樹脂のような帯電性の強い材料の表面にクー
ロン力で付着した超微粒子に対して、クーロン力を緩和
するような導電性の洗浄剤が除微粒子効果に特に有効と
考えることができるのであるが、これに反して、上記の
ようなカチオン系帯電防止剤は、除微粒子効果がまった
くないのである。さらにこの帯電防止剤に使用されるフ
ッ素系界面活性剤は通常かなり高価であるという欠点も
ある。On the other hand, in order to prevent the static charge of the fluororesin, it is required to have an adhesive force to the fluororesin surface. For example, a quaternary ammonium having both a perfluoroalkyl group and a hydroxyethyl group. A coating type antistatic agent containing a fluorine-containing surfactant such as a compound (JP-A-3-192186) is used. This antistatic agent
It does give sufficient antistatic properties to fluororesins, but as is clear from the comparative examples described below, even if a fluororesin product is treated with an aqueous solution of this product at a suitable concentration, it will not be removed by this product. No particulate effect is observed. In general, it can be considered that a conductive cleaning agent that alleviates Coulomb's force is particularly effective for removing fine particles from ultrafine particles adhered to the surface of a highly chargeable material such as fluororesin by Coulomb's force. However, on the contrary, the above-mentioned cationic antistatic agent has no effect of removing fine particles. Further, the fluorosurfactant used for this antistatic agent has a drawback that it is usually quite expensive.
【０００５】またプラスチック表面の処理が終わって乾
燥による仕上げをおこなった時、表面処理剤の有効成分
である帯電防止剤の表面濃度が高いとべとつきがおこ
り、その為に塵埃類の吸収汚染が帯電防止による微粒子
付着抑制力を上回るおそれがある。従って帯電防止剤は
微量で十分な効力を示す高性能のものでなければならな
い。また帯電防止効果と十分な微粒子除去効果を有する
表面処理剤は、フッ素樹脂表面に対しても、有効成分で
ある帯電防止剤の確実な付着を可能にするものでなけれ
ばならない。When the surface of the plastic is finished and finished by drying, if the surface concentration of the antistatic agent, which is the active ingredient of the surface treatment agent, is high, stickiness occurs, which causes absorption and contamination of dusts. There is a possibility that the particle adhesion suppression force due to prevention will be exceeded. Therefore, the antistatic agent must be a high-performance one that exhibits sufficient effect even in a trace amount. Further, the surface treating agent having an antistatic effect and a sufficient fine particle removing effect must be capable of reliably adhering the antistatic agent which is an active ingredient to the surface of the fluororesin.
【０００６】[0006]
【発明が解決しようとする課題】従って本発明の目的
は、高価なフッ素系帯電防止剤を必ずしも使用すること
なく、帯電防止効果に加えて除微粒子効果を有するよう
な表面処理剤及びプラスチック表面の表面処理方法を提
供することにある。SUMMARY OF THE INVENTION Therefore, an object of the present invention is to provide a surface treatment agent and a plastic surface which have an antistatic effect and a fine particle removing effect without necessarily using an expensive fluorine type antistatic agent. It is to provide a surface treatment method.
【０００７】[0007]
【課題を解決するための手段】本発明者はまずプラスチ
ック類の表面の微粒子は親油性と親水性を併せもつアル
コール類中での洗浄、例えば超音波洗浄により有効に除
去できることを見いだした。The inventor first found that the fine particles on the surface of plastics can be effectively removed by cleaning in alcohols having both lipophilicity and hydrophilicity, for example, ultrasonic cleaning.
【０００８】即ち、本発明によれば、帯電防止剤として
の第４級アンモニウム塩を、濃度80重量％以上の２−メ
チル−２−プロパノールで希釈したプラスチック表面処
理剤が提供される。That is, according to the present invention, there is provided a plastic surface treating agent obtained by diluting a quaternary ammonium salt as an antistatic agent with 2-methyl-2-propanol having a concentration of 80% by weight or more.
【０００９】本発明によれば、また、上記の処理剤液中
にプラスチックを浸漬して該プラスチック表面に付着し
た微粒子を除去した後、該処理剤の乾燥を行い、プラス
チック表面上に帯電防止膜を形成することを特徴とする
プラスチック表面の処理方法が提供される。According to the present invention, a plastic is dipped in the above treatment liquid to remove fine particles adhering to the surface of the plastic, and then the treatment is dried to form an antistatic film on the plastic surface. A method for treating a plastic surface is provided, which comprises forming
【００１０】本発明の表面処理剤に用いる帯電防止剤
は、洗浄処理後の乾燥で表面残存量ができるだけ少ない
ことが望まれ、このためには物質自体の帯電防止性能が
高いことのほかに、プラスチック表面へ付着力が強いこ
とが必要である。従来においては、ＰＦＡやＰＴＦＥの
ようなフッ素樹脂に対してはパーフルオロアルキル基を
もつ帯電防止剤以外はほとんど付着が起こらず、塗布型
の帯電防止が出来なかった。ところが、本発明にしたが
って２−メチル−２−プロパノールを希釈剤として使用
することにより、パラフィン鎖だけのフッ素のない帯電
防止剤であっても、これを上記希釈剤で希釈して得た表
面処理剤は、ＰＦＡにもＰＴＦＥにも十分な付着力を生
じ、付着量を減らすために希釈度を増しても十分に帯電
防止させることが可能になったのであり、これは、真に
意外なことである。The antistatic agent used in the surface treatment agent of the present invention is desired to have a surface residual amount as small as possible after drying after washing treatment. For this purpose, in addition to the high antistatic performance of the substance itself, Strong adhesion to the plastic surface is required. In the past, coating type antistatic could not be performed on fluororesins such as PFA and PTFE, except for the antistatic agent having a perfluoroalkyl group, which hardly adhered. However, by using 2-methyl-2-propanol as a diluent according to the present invention, even a fluorine-free antistatic agent having only paraffin chains is diluted with the above-mentioned diluent to obtain a surface treatment. The agent produced sufficient adhesion to both PFA and PTFE, and it became possible to sufficiently prevent static electricity even with increasing dilution so as to reduce the amount of adhesion, which is truly unexpected. Is.
【００１１】本発明において、この希釈剤として用いる
２−メチル−２−プロパノールは、勿論それ単独でも使
用できるが、その融点が25.5℃であるため、凍結防止の
ために、若干量の水を含有しているものが好適に使用さ
れる。例えば、水分含量が５重量％以上となると４℃で
も液の状態を保持することができる。但し、２−メチル
−２−プロパノールの含量が80重量％よりも低くなる
と、フッ素樹脂に対する帯電防止剤の付着力が低下する
ので好ましくない。The 2-methyl-2-propanol used as the diluent in the present invention can of course be used alone, but since it has a melting point of 25.5 ° C., it contains a small amount of water to prevent freezing. What is done is used suitably. For example, when the water content is 5% by weight or more, the liquid state can be maintained even at 4 ° C. However, when the content of 2-methyl-2-propanol is lower than 80% by weight, the adhesion of the antistatic agent to the fluororesin is lowered, which is not preferable.
【００１２】本発明において使用される帯電防止剤は、
勿論帯電防止性能の良い物質である必要があり、少なく
とも電離度の大きい第４級アンモニウム塩型でなければ
ならない。具体的には、下記一般式(1): Ｒ−Ａ−（CH2 ）3 −Ｎ+ （CH3 ）2 （Ｃ2 Ｈ4 OH）・Ｘ- (1) 〔式中、Ｒはパラフィン鎖またはパーフルオロアルキル
基、Ａは−CONH−または−SO2 NH−で表される２価の
基、ＸはNO3 , 1/2SO4 , I, Br, Cl, ClO4 または1/3P
O4 をそれぞれ示す〕で表される第４級アンモニウム塩
が好適に使用される。パラフィン鎖としての前記Ｒとし
ては、炭素数が12〜18のものが好適であり、パーフルオ
ロアルキル基としての前記Ｒとしては、炭素数が４〜12
のものが好適である。本発明においては、このＲはパー
フルオロアルキル基であることが最も好ましい。しか
し、Ｒがパラフィン鎖であっても若干は劣るものの、Ｒ
がパーフルオロアルキル基である場合とほぼ同等の帯電
防止性能が得られる。The antistatic agent used in the present invention is
Of course, it must be a substance with good antistatic performance, and it must be of a quaternary ammonium salt type having at least a large ionization degree. Specifically, the following general formula (1): R-A- ( CH 2) 3 -N + (CH 3) 2 (C 2 H 4 OH) · X - (1) [wherein, R paraffinic chains Or a perfluoroalkyl group, A is a divalent group represented by -CONH- or -SO 2 NH-, X is NO 3 , 1 / 2SO 4 , I, Br, Cl, ClO 4 or 1 / 3P
The quaternary ammonium salt represented by each of O 4 ] is preferably used. The R as a paraffin chain preferably has 12 to 18 carbon atoms, and the R as a perfluoroalkyl group has 4 to 12 carbon atoms.
Are preferred. In the present invention, this R is most preferably a perfluoroalkyl group. However, even if R is a paraffin chain
Is almost the same as the case where is a perfluoroalkyl group.
【００１３】また、下記一般式(2): Ｒ1 −Ｎ+ （CH3 ）2 （Ｃ2 Ｈ4 OH）・Ｘ- (2) 〔式中、Ｒ1 はパラフィン鎖であり、Ｘは前記と同様で
ある〕で表される第４級アンモニウム塩もかなり近い性
能がえられる。さらに下記一般式(3): Ｒ1 −Ｎ+ （CH3 ）3 ・Ｘ- (3) 〔式中、Ｒ1 及びＸは前記と同様である〕で表される第
４級アンモニウム塩は、ヒドロキシエチル基を有してお
らず、やや帯電防止性能が落ちるが、フッ素樹脂の種類
によっては、十分に使用が可能である。以上のような帯
電防止剤の処理剤中の必要濃度は0.01重量％以上で、べ
とつき対策上約 0.3重量％以下の濃度で使用した方がよ
い。Further, the following general formula (2): R 1 -N + (CH 3) 2 (C 2 H 4 OH) · X - (2) wherein, R 1 is paraffin chain, X is the The same effect can be obtained with a quaternary ammonium salt represented by Furthermore, the quaternary ammonium salt represented by the following general formula (3): R 1 -N + (CH 3 ) 3 · X − (3) [wherein R 1 and X are the same as defined above] is Since it does not have a hydroxyethyl group, the antistatic performance is slightly lowered, but it can be sufficiently used depending on the type of fluororesin. The required concentration of the antistatic agent in the treating agent is 0.01% by weight or more, and it is better to use it at a concentration of about 0.3% by weight or less in order to prevent stickiness.
【００１４】上述した帯電防止剤を２−メチル−２−プ
ロパノールで希釈して成る本発明の表面処理剤において
は、ポリオキシエチレンエーテル型非イオン界面活性剤
を添加することにより、プラスチック表面に付着した微
粒子の除去能力が著しく強化される。その添加量は、純
分で 0.005重量％以上であればよい。微粒子除去能力
は、その添加量を増す程強化されるが、必要以上に多く
すると、プラスチック表面でのべとつきを生じ、処理後
の再汚染の危険性が増大するので、一般には、固形分で
0.01〜0.05重量％程度が望ましい。このポリオキシエチ
レンエーテル型非イオン界面活性剤としては、具体的に
は、ポリオキシエチレンアルキルフェニルエーテルやポ
リオキシエチレンアルキルエーテル類が好適である。In the surface treating agent of the present invention prepared by diluting the above-mentioned antistatic agent with 2-methyl-2-propanol, a polyoxyethylene ether type nonionic surfactant is added to adhere to the plastic surface. The ability to remove fine particles is significantly enhanced. The amount added may be 0.005% by weight or more in pure content. The fine particle removal capability is enhanced by increasing the addition amount, but if it is added more than necessary, it causes stickiness on the plastic surface and increases the risk of recontamination after the treatment.
About 0.01 to 0.05% by weight is desirable. As the polyoxyethylene ether type nonionic surfactant, specifically, polyoxyethylene alkylphenyl ether and polyoxyethylene alkyl ethers are suitable.
【００１５】本発明の表面処理剤を用いてのプラスチッ
クの表面処理では、この処理液中に、ＰＦＡやＰＴＦ
Ｅ、あるいはポリプロピレン等のプラスチックを浸漬し
て、必要により、超音波洗浄等の処理を行う。これによ
り、例えば純水超音波洗浄よりはるかに良好な微粒子除
去効果が得られる。かかる洗浄に際して、さらに微粒子
除去効果を高めるにはこの表面処理剤に導電性をもたせ
ることが合理的に見える。即ち水を加え、かつ電離度の
大きい上記第４級アンモニウム塩帯電防止剤が溶解する
と、微粒子除去効果が増大するはずである。しかし上述
のようにこのような特別の効果はほとんど見いだされな
い。水の添加や第４級アンモニウム塩の存在はむしろ若
干除去効果を妨げる傾向がある。洗浄後は、処理後のプ
ラスチック表面を常法により乾燥することにより、その
表面に、べとつきのない帯電防止膜が形成され、微粒子
の付着が有効に防止される。In the surface treatment of plastics using the surface treatment agent of the present invention, PFA or PTF is added to the treatment liquid.
E or a plastic such as polypropylene is dipped and, if necessary, a treatment such as ultrasonic cleaning is performed. As a result, a much better effect of removing fine particles can be obtained than, for example, pure water ultrasonic cleaning. In order to further enhance the effect of removing fine particles during such cleaning, it seems rational to make the surface treatment agent conductive. That is, when water is added and the quaternary ammonium salt antistatic agent having a high degree of ionization is dissolved, the effect of removing fine particles should be increased. However, as mentioned above, such a special effect is hardly found. The addition of water and the presence of quaternary ammonium salts tend to rather hinder the removal effect. After washing, the treated plastic surface is dried by a conventional method to form a non-sticky antistatic film on the surface and effectively prevent adhesion of fine particles.
【００１６】本発明による処理剤並びに処理方法の適用
は特にフッ素樹脂に効果的であるが、他のプラスチック
に対してはすべてにおいてフッ素樹脂に対するより強い
帯電防止剤の付着力を示し、より微量で良好な帯電防止
特性を示し、かつ付着微粒子除去にも有効である。即ち
電子工業で一般に使用されるポリプロピレン、ポリエチ
レン、アクリル、スチレン、塩化ビニル等のいずれに対
しても適用できる。The application of the treating agent and the treating method according to the present invention is particularly effective for the fluororesin, but it shows stronger antistatic agent adhesion to the fluororesin for all other plastics, and a smaller amount. It exhibits good antistatic properties and is also effective in removing adhered fine particles. That is, it can be applied to any of polypropylene, polyethylene, acryl, styrene, vinyl chloride and the like which are generally used in the electronic industry.
【００１７】[0017]
【実施例】次に本発明を実施例によって説明するが、本
発明はその要旨を越えない限り以下の実施例に限定され
るものではない。本発明の実施例に使われた第４級アン
モニウム塩帯電防止剤は以下の４種である。 帯電防止剤Ａ： Ｃ17Ｈ35−CONH−（CH2 ）3 −Ｎ+ （CH3 ）2 （Ｃ2 Ｈ4 OH）・NO3 - 帯電防止剤Ｂ： Ｃ16Ｈ33−Ｎ+ （CH3 ）2 （Ｃ2 Ｈ4 OH）・NO3 - 帯電防止剤Ｃ： Ｃ8 Ｆ17−SO2 NH−（CH2 ）3 −Ｎ+ （CH3 ）2 （Ｃ2 Ｈ4 OH）・ 1/2SO4 帯電防止剤Ｄ： Ｃ18Ｈ37−Ｎ+ （CH3 ）3 ・Cl- EXAMPLES The present invention will now be described by way of examples, but the present invention is not limited to the following examples unless it exceeds the gist. The quaternary ammonium salt antistatic agents used in the examples of the present invention are the following four types. Antistatic agent A: C 17 H 35 -CONH- ( CH 2) 3 -N + (CH 3) 2 (C 2 H 4 OH) · NO 3 - Antistatic agent B: C 16 H 33 -N + (CH 3) 2 (C 2 H 4 OH) · NO 3 - antistatic agent C: C 8 F 17 -SO 2 NH- (CH 2) 3 -N + (CH 3) 2 (C 2 H 4 OH) · 1 / 2SO 4 antistatic agent D: C 18 H 37 -N + (CH 3) 3 · Cl -
【００１８】以下の実施例において示される試験片によ
る帯電防止効果の評価は次のように行われた。プラスチ
ック試験片はすべて５cm角２mm厚のものを用い、中性洗
剤で超音波洗浄した後水洗乾燥したものである。本発明
に係る浸漬処理を行った後、帯電防止効果を調べる場合
は過剰付着によるべとつきの発生あるいは次工程への持
込汚染等を減らすためにスピンナによる遠心脱液乾燥を
行った（この方法は自然乾燥より付着量が少いので帯電
防止性能に関しては若干悪くなる）。尚浸漬は特に記載
しない限りは室温で３分とした。試験片は約20℃、湿度
約50％の恒温恒湿室で１夜コンディショニングし、除電
バーで除電してから測定した。尚本実施例では、処理剤
中の帯電防止剤や非イオン系界面活性剤の濃度（％）は
すべて純分の重量％で示した。The evaluation of the antistatic effect by the test pieces shown in the following examples was carried out as follows. All the plastic test pieces were 5 cm square and 2 mm thick, and were ultrasonically washed with a neutral detergent and then washed with water and dried. After the immersion treatment according to the present invention, when examining the antistatic effect, centrifugal dehydration drying was performed with a spinner in order to reduce the occurrence of stickiness due to excessive adhesion, contamination brought into the next step, etc. Since the amount of adhesion is less than that of natural drying, the antistatic performance will be slightly worse). The dipping was performed at room temperature for 3 minutes unless otherwise specified. The test piece was conditioned overnight in a constant temperature and constant humidity chamber at about 20 ° C. and a humidity of about 50%, and then discharged with a charge removing bar to measure. In this example, the concentrations (%) of the antistatic agent and the nonionic surfactant in the treating agent are all shown by weight% of the pure content.
【００１９】実験例１ 塗布型帯電防止剤の帯電防止機構はその物質としての吸
湿性が大きいことが本質的であるが、さらに被塗布表面
に対する付着性が優れていることが重要な条件である。
従って界面活性が支配的要因となるので、界面活性剤が
使われているが、この付着性が水溶液で十分に得られな
い場合は有機溶剤で稀釈されている。しかしＰＦＡやＰ
ＴＦＥに対しては、パラフィン鎖を疎水基としてもつ界
面活性剤では従来塗布型電防止剤に使われてきたメタノ
ールやイソプロピルアルコールで稀釈しても必要とする
付着性が得られない。水や多くの有機溶剤による稀釈を
比較例として、帯電防止剤Ａに対する本発明の稀釈剤に
よった場合のＰＴＦＥ試験片における摩擦帯電圧・測定
例を表１に示す。測定は市販帯電電位測定器により指定
の条件で行った。 200ｇのおもりをのせたキムワイプで
試験片表面を一方向に軽く３回摩擦した後、直ちに測定
した。無処理のＰＴＦＥではこの測定値は−3.0 KV以上
となった。表１でこの値と比較すると稀釈剤としての２
−メチル−２−プロパノールだけが顕著な効果を示すこ
とが分る。ＰＦＡ試験片でも同じ測定を行ったが、ほぼ
同様の結果となった。Experimental Example 1 It is essential that the antistatic mechanism of the coating type antistatic agent has a large hygroscopic property as a substance, but it is also an important condition that it has excellent adhesion to the surface to be coated. ..
Therefore, the surfactant is used because the surface activity becomes the dominant factor, but when this adhesiveness cannot be sufficiently obtained in an aqueous solution, it is diluted with an organic solvent. But PFA and P
With respect to TFE, a surfactant having a paraffin chain as a hydrophobic group cannot obtain the required adhesiveness even when diluted with methanol or isopropyl alcohol which has been conventionally used for a coating type antistatic agent. Table 1 shows the frictional electrification voltage / measurement example in the PTFE test piece in the case of using the diluent of the present invention with respect to the antistatic agent A, using dilution with water or many organic solvents as a comparative example. The measurement was carried out using a commercially available charging potential measuring instrument under the specified conditions. The surface of the test piece was lightly rubbed in one direction three times with a Kimwipe having a weight of 200 g, and then immediately measured. With untreated PTFE, the measured value was -3.0 KV or more. Compared to this value in Table 1, 2 as a diluent
It can be seen that only -methyl-2-propanol has a marked effect. The same measurement was performed on the PFA test piece, but almost the same result was obtained.
【００２０】[0020]
【表１】 [Table 1]
【００２１】実験例２ 第４級アンモニウム塩帯電防止剤を２−メチル−２−プ
ロパノールで稀釈した処理剤の効果を示すために、上述
のＡ, Ｂ, Ｃ, Ｄ剤について、コロナ放電による帯電圧
および減衰特性を市販の帯電電荷減衰度測定器により、
指定の条件でＰＦＡ試験片について測定した。また同様
の試験片で表面固有抵抗の測定を行った。この測定は市
販の超絶縁抵抗計により超高抵抗測定用試料箱でなされ
た。これらの結果を摩擦帯電圧と共に表２に示す。尚稀
釈後の帯電防止剤の純分濃度は４種のいずれもが 0.1％
になるようにした。稀釈剤で本発明と記載したものは２
−メチル−２−プロパノール（99.5％）であって水を比
較液とした。帯電電荷減衰特性試験は印加電圧を＋10K
V、−10KVについて行ったが両者はほぼ同じ結果を示し
たので−10KVの場合のみを記載する。また表面固有抵抗
は印加電圧 250Ｖの場合を示した。Experimental Example 2 In order to show the effect of the treatment agent prepared by diluting the quaternary ammonium salt antistatic agent with 2-methyl-2-propanol, the above-mentioned agents A, B, C and D were subjected to a zone by corona discharge. The voltage and attenuation characteristics can be measured with a commercially available electrified charge attenuation meter.
The PFA test piece was measured under the specified conditions. The surface resistivity was measured with the same test piece. This measurement was carried out in a sample box for measuring ultra-high resistance with a commercially available ultra-insulation resistance meter. The results are shown in Table 2 together with the friction electrification voltage. The pure content of the antistatic agent after dilution was 0.1% for all four types.
I tried to become. The diluent described as the present invention is 2
-Methyl-2-propanol (99.5%) and water as the comparison solution. The applied voltage is + 10K in the electrostatic charge decay characteristic test
V and -10KV were performed, but both showed almost the same result, so only the case of -10KV is described. The surface resistivity is shown for an applied voltage of 250V.
【００２２】[0022]
【表２】 [Table 2]
【００２３】パーフルオロアルキル基をもつＣ剤を水で
稀釈した場合、帯電防止性能はもっとも優れているが、
本発明の稀釈剤でもほぼ近い性能を示す。また本発明の
稀釈剤によれば、Ａ剤とＢ剤はかなりこれらに近い性能
を示し、Ｄ剤はやや劣るが、使用可能なレベルにある。
Ｄ剤の濃度を 0.5％として本発明の処理を行うと摩擦帯
電位は 0.1KV程度となり、帯電防止特性がかなり改善さ
れる。When the agent C having a perfluoroalkyl group is diluted with water, the antistatic property is the best,
The diluent of the present invention shows almost similar performance. Further, according to the diluent of the present invention, the agents A and B exhibit performances very close to these, and the agent D is slightly inferior, but at a usable level.
When the treatment of the present invention is carried out with the concentration of the D agent being 0.5%, the triboelectric charge potential becomes about 0.1 KV, and the antistatic property is considerably improved.
【００２４】実験例３ 本発明による帯電防止剤塗布でべとつき等による環境か
らの塵埃汚染を起すか否かを調べるために、放射性の
99mTcで標識した平均粒径 0.2 mμの炭素粒を分散させ
た雰囲気を作成し、これを比較試料片と一緒に本発明で
処理されたＰＦＡ試料片及び未処理の試料片に吹付けて
汚染を比較した。比較試料片としては同面積の銅片を使
用した。これらの試料片はこの雰囲気に対して露出条件
が出来るだけ揃うように配置され、雰囲気吹付終了後、
試験片の放射能を測定して銅片を基準の１として炭素塵
相対付着量を求めた。試料片の帯電防止処理条件は実験
例２と同じである。結果を表３に示す。Experimental Example 3 In order to investigate whether or not the application of the antistatic agent according to the present invention causes dust pollution from the environment due to stickiness, etc.
An atmosphere was prepared in which carbon particles labeled with 99 m Tc and having an average particle size of 0.2 mμ were dispersed, and this was sprayed together with a comparative sample piece onto a PFA sample piece treated according to the present invention and an untreated sample piece to be contaminated. Were compared. A copper piece having the same area was used as a comparative sample piece. These sample pieces are arranged so that the exposure conditions for this atmosphere are as uniform as possible, and after the atmosphere has been sprayed,
The radioactivity of the test piece was measured, and the relative amount of carbon dust was determined using the copper piece as a reference 1. The antistatic treatment conditions for the sample piece are the same as in Experimental Example 2. The results are shown in Table 3.
【００２５】[0025]
【表３】 [Table 3]
【００２６】本発明によるＰＦＡ表面の帯電防止処理は
未処理品との比較で明らかに雰囲気中の塵埃の付着汚染
を減少せしめていることが分る。しかもその汚染量は銅
片と同じで、塗布された帯電防止剤の粘着性に起因する
付着はほとんど起っていない。It can be seen that the antistatic treatment on the surface of PFA according to the present invention obviously reduces the adhesion contamination of dust in the atmosphere as compared with the untreated product. Moreover, the amount of contamination is the same as that of the copper pieces, and the adhesion due to the tackiness of the applied antistatic agent hardly occurs.
【００２７】実験例４ 本発明の処理がプラスチック表面を汚染した微粒子を除
去する有効な手段であることを明らかにするために、上
例のようにして放射性の 99mTcで標識した炭素微粒子で
汚染した試料片を作成し、これに本発明の処理を行い、
同一組成の液でリンスして、この処理の前後の試料片の
放射能の比較で汚染微粒子に対する除去率を求め表４に
示した。表１から分るように稀釈する２−メチル−２−
プロパノールに小量の水を加えても、帯電防止性能はあ
まり低下しない。この添加は処理液の凝固点を実用上問
題のないレベルまで下げるとともに、表面の水溶性の無
機塩類等の汚染を溶出除去する効果もあるので、この実
施例では稀釈剤はすべて水５％が加えられている。さら
に非イオン性界面活性剤の添加効果、並びに超音波（28
kc）による洗浄力強化効果をも検討した。汚染試料片は
すべてＰＦＡで、室温の処理液へ３分浸漬した。Experimental Example 4 In order to clarify that the treatment of the present invention is an effective means for removing the particulates contaminated on the plastic surface, it is contaminated with radioactive carbon particles labeled with radioactive 99m Tc as in the above example. Prepared sample piece, and subjected to the treatment of the present invention,
After rinsing with a liquid having the same composition, the removal rate for contaminated fine particles was determined by comparing the radioactivity of the sample pieces before and after this treatment and is shown in Table 4. 2-Methyl-2-dilute as can be seen from Table 1.
Adding a small amount of water to propanol does not significantly reduce the antistatic performance. This addition has the effect of lowering the freezing point of the treatment liquid to a level at which there is no practical problem, and has the effect of eluting and removing the contamination of water-soluble inorganic salts on the surface. Therefore, in this example, 5% of water was added as the diluent. Has been. Furthermore, the effect of adding a nonionic surfactant and ultrasonic (28
The effect of enhancing the detergency by kc) was also examined. All the contaminated sample pieces were soaked with PFA in the treatment liquid at room temperature for 3 minutes.
【００２８】[0028]
【表４】 [Table 4]
【００２９】Ｃ剤を純水で稀釈したものは実験例２のよ
うに帯電防止性能はもっとも優れているのに微粒子洗浄
効果は純水そのものと大差はない。帯電防止剤そのもの
は微粒子除去効果もあるとはいえない。しかし本発明の
稀釈剤ではＣ剤の場合に限り若干洗浄効果を助けるよう
である。フッ素樹脂の微粒子除去には適量の非イオン系
界面活性剤の添加と超音波が特に有効と思われる。The agent C diluted with pure water has the best antistatic performance as in Experimental Example 2, but the particle cleaning effect is not so different from that of pure water itself. It cannot be said that the antistatic agent itself has the effect of removing fine particles. However, the diluent of the present invention seems to slightly assist the cleaning effect only in the case of the agent C. It seems that the addition of an appropriate amount of nonionic surfactant and ultrasonic waves are particularly effective for removing fine particles of the fluororesin.
【００３０】実験例５ 稀釈液に含有させ得る水の量を明らかにするため、帯電
防止性のもっとも優れていたＣ剤に関し、その 0.1％を
含む処理剤において稀釈液の含水量と摩擦帯電圧並びに
99mTc標識炭素微粒子汚染試料での除去率を求めた。処
理液にそれぞれ0.01％のポリオキシエチレングリコール
モノメチルエーテルを加え、28kHz の超音波処理をＰＦ
Ａ試料片に対して行った。結果を表５に示す。Experimental Example 5 In order to clarify the amount of water that can be contained in the diluted solution, regarding the agent C that was most excellent in antistatic property, the water content of the diluted solution and the frictional electrification voltage in the treating agent containing 0.1% thereof. And
The removal rate of the 99m Tc-labeled carbon fine particle contaminated sample was obtained. Add 0.01% polyoxyethylene glycol monomethyl ether to each treatment solution and apply 28 kHz ultrasonic treatment to PF.
A sample piece was tested. The results are shown in Table 5.
【００３１】[0031]
【表５】 [Table 5]
【００３２】帯電防止性能は２−メチル−２−プロパノ
ール80％以下で急に悪くなる。尚この結果からポリオキ
シエチレンエーテル型非イオン系界面剤の添加は帯電防
止性能に影響を与えず、微粒子除去効果は十分に得られ
ることが分る。The antistatic performance suddenly deteriorates at 80% or less of 2-methyl-2-propanol. From these results, it can be seen that the addition of the polyoxyethylene ether type nonionic interfacial agent does not affect the antistatic performance and the effect of removing fine particles is sufficiently obtained.
【００３３】実験例６ 本発明の処理方法はフッ素樹脂に対して強力な帯電防止
効果と微粒子除去効果を示すので、一般のプラスチック
に対しても本発明に係る帯電防止剤は極めて小量で有効
な効果が得られる筈である。もっとも効果が弱かったＤ
剤の0.01％とポリオキシエチレンアルキルエーテルの0.
01％を含む95％２−メチル−２−プロパノール液で３分
の超音波処理を行った５種のプラスチック試料による、
摩擦帯電圧と 99mTc標識炭素微粒子に対する除去率の測
定結果を表６に示す。いずれのプラスチックについても
良好な結果が得られている。Experimental Example 6 Since the treatment method of the present invention has a strong antistatic effect and a fine particle removing effect on a fluororesin, the antistatic agent of the present invention is effective for general plastics in a very small amount. It should have a great effect. The effect was the weakest D
0.01% of the agent and 0 of polyoxyethylene alkyl ether.
According to 5 kinds of plastic samples that have been sonicated for 3 minutes with 95% 2-methyl-2-propanol solution containing 01%,
Table 6 shows the measurement results of the friction electrification voltage and the removal rate for 99m Tc-labeled carbon fine particles. Good results have been obtained for all plastics.
【００３４】[0034]
【表６】 [Table 6]
【００３５】[0035]
【発明の効果】以上述べたように、本発明による処理液
ならびに処理方法によれば一つの処理で同時に帯電防止
と微粒子除去洗浄を行うことが出来、フッ素樹脂のよう
に一般に濡れが悪くて帯電防止の難しいものを含めて、
ほとんどのプラスチック分野に適用出来る。また帯電防
止剤が最小量で効果的に表面に作用するので、処理後環
境雰囲気からの塵埃汚染を有効に抑止出来る効果があ
り、クリーンルーム内で使用するプラスチック器具類の
清浄度を保つ上で極めて効果的である。As described above, according to the treatment liquid and the treatment method of the present invention, it is possible to simultaneously perform antistatic treatment and fine particle removal and washing in one treatment, and it is generally difficult to wet due to poor wetting like fluororesin. Including difficult ones,
Applicable to most plastic fields. In addition, since the antistatic agent effectively acts on the surface with a minimum amount, it has the effect of effectively suppressing dust contamination from the environmental atmosphere after treatment, and is extremely effective in maintaining the cleanliness of plastic equipment used in a clean room. It is effective.
Claims (4)
塩を、濃度80重量％以上の２−メチル−２−プロパノー
ルで希釈したプラスチック表面処理剤。1. A plastic surface treating agent prepared by diluting a quaternary ammonium salt as an antistatic agent with 2-methyl-2-propanol having a concentration of 80% by weight or more.
(1): Ｒ−Ａ−（CH2 ）3 −Ｎ+ （CH3 ）2 （Ｃ2 Ｈ4 OH）・Ｘ- (1) 〔式中、Ｒはパラフィン鎖またはパーフルオロアルキル
基、Ａは−CONH−または−SO2 NH−で表される２価の
基、ＸはNO3 , 1/2SO4 , I, Br, Cl, ClO4 または1/3P
O4 をそれぞれ示す〕で示されるものである請求項１に
記載のプラスチック表面処理剤。2. A quaternary ammonium salt has the following general formula:
(1): R-A- ( CH 2) 3 -N + (CH 3) 2 (C 2 H 4 OH) · X - (1) [wherein, R paraffinic chain or a perfluoroalkyl group, A is A divalent group represented by -CONH- or -SO 2 NH-, X is NO 3 , 1 / 2SO 4 , I, Br, Cl, ClO 4 or 1 / 3P
Each of which represents O 4 ], The plastic surface treating agent according to claim 1.
ル型非イオン系界面活性剤が添加されている請求項１ま
たは２に記載のプラスチック表面処理剤。3. The plastic surface treating agent according to claim 1, wherein a polyoxyethylene ether type nonionic surfactant is added to the diluent.
ックを浸漬して該プラスチック表面に付着した微粒子を
除去した後、該処理剤の乾燥を行い、プラスチック表面
上に帯電防止膜を形成することを特徴とするプラスチッ
ク表面の処理方法。4. The treatment agent according to claim 1 is dipped in plastic to remove fine particles adhering to the surface of the plastic, and then the treatment agent is dried to form an antistatic film on the surface of the plastic. A method for treating a plastic surface, which comprises:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP33757791A JP3242683B2 (en) | 1991-11-27 | 1991-11-27 | Plastic surface treatment agent and treatment method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP33757791A JP3242683B2 (en) | 1991-11-27 | 1991-11-27 | Plastic surface treatment agent and treatment method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH05302077A true JPH05302077A (en) | 1993-11-16 |
| JP3242683B2 JP3242683B2 (en) | 2001-12-25 |
Family
ID=18309961
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP33757791A Expired - Fee Related JP3242683B2 (en) | 1991-11-27 | 1991-11-27 | Plastic surface treatment agent and treatment method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3242683B2 (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001088024A1 (en) * | 2000-05-16 | 2001-11-22 | Dow Global Technologies Inc. | Polymeric films having anti-static properties |
| US6372829B1 (en) | 1999-10-06 | 2002-04-16 | 3M Innovative Properties Company | Antistatic composition |
| DE10141707A1 (en) * | 2001-08-25 | 2003-03-13 | Chemetall Gmbh | Process for the antistatic coating of plastic molding surfaces, plastic or lacquer coatings |
| WO2003046091A1 (en) * | 2001-11-27 | 2003-06-05 | Zeller + Gmelin Gmbh & Co. Kg | Use of a coating composition in the production of a temporary protective coating on plastic surfaces |
| US6740413B2 (en) | 2001-11-05 | 2004-05-25 | 3M Innovative Properties Company | Antistatic compositions |
| US6924329B2 (en) | 2001-11-05 | 2005-08-02 | 3M Innovative Properties Company | Water- and oil-repellent, antistatic compositions |
| US7678941B2 (en) | 2001-05-10 | 2010-03-16 | 3M Innovative Properties Company | Polyoxyalkylene ammonium salts and their use as antistatic agents |
| JP2010121093A (en) * | 2008-11-21 | 2010-06-03 | Nof Corp | Coating-type antistatic agent |
| JP2019119832A (en) * | 2018-01-10 | 2019-07-22 | 株式会社アースクリーンテクノ | Antistatic agent, concentration antistatic agent, and static elimination method |
-
1991
- 1991-11-27 JP JP33757791A patent/JP3242683B2/en not_active Expired - Fee Related
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6372829B1 (en) | 1999-10-06 | 2002-04-16 | 3M Innovative Properties Company | Antistatic composition |
| US6706920B2 (en) | 1999-10-06 | 2004-03-16 | 3M Innovative Properties Company | Antistatic composition |
| WO2001088024A1 (en) * | 2000-05-16 | 2001-11-22 | Dow Global Technologies Inc. | Polymeric films having anti-static properties |
| US7678941B2 (en) | 2001-05-10 | 2010-03-16 | 3M Innovative Properties Company | Polyoxyalkylene ammonium salts and their use as antistatic agents |
| US7893144B2 (en) | 2001-05-10 | 2011-02-22 | 3M Innovative Properties Company | Polyoxyalkylene ammonium salts and their use as antistatic agents |
| US7754277B2 (en) | 2001-08-25 | 2010-07-13 | Chemetall Gmbh | Method for anti-statically coating the surfaces of plastic moulded parts or plastic or paint coatings |
| DE10141707A1 (en) * | 2001-08-25 | 2003-03-13 | Chemetall Gmbh | Process for the antistatic coating of plastic molding surfaces, plastic or lacquer coatings |
| DE10141707B4 (en) * | 2001-08-25 | 2008-07-24 | Chemetall Gmbh | Process for the antistatic coating of plastic molded parts surfaces, molded parts coated with plastic or / and varnish and use of the plastic and / or painted surfaces treated by the process |
| US6740413B2 (en) | 2001-11-05 | 2004-05-25 | 3M Innovative Properties Company | Antistatic compositions |
| US6924329B2 (en) | 2001-11-05 | 2005-08-02 | 3M Innovative Properties Company | Water- and oil-repellent, antistatic compositions |
| WO2003046091A1 (en) * | 2001-11-27 | 2003-06-05 | Zeller + Gmelin Gmbh & Co. Kg | Use of a coating composition in the production of a temporary protective coating on plastic surfaces |
| JP2010121093A (en) * | 2008-11-21 | 2010-06-03 | Nof Corp | Coating-type antistatic agent |
| JP2019119832A (en) * | 2018-01-10 | 2019-07-22 | 株式会社アースクリーンテクノ | Antistatic agent, concentration antistatic agent, and static elimination method |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3242683B2 (en) | 2001-12-25 |
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