JPH11116278A - Production of fluororesin coated body - Google Patents
Production of fluororesin coated bodyInfo
- Publication number
- JPH11116278A JPH11116278A JP28727697A JP28727697A JPH11116278A JP H11116278 A JPH11116278 A JP H11116278A JP 28727697 A JP28727697 A JP 28727697A JP 28727697 A JP28727697 A JP 28727697A JP H11116278 A JPH11116278 A JP H11116278A
- Authority
- JP
- Japan
- Prior art keywords
- fluororesin
- low
- resin
- vapor
- molecular weight
- 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
Landscapes
- Physical Vapour Deposition (AREA)
- Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
- Surface Treatment Of Glass (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、撥水性、撥油性、
離型性、潤滑性、耐食性、耐薬品性等が必要な資材に多
岐に亘り利用される低分子量フッ素樹脂の被覆方法に関
するものである。TECHNICAL FIELD The present invention relates to water repellency, oil repellency,
The present invention relates to a method for coating a low molecular weight fluororesin which is widely used for materials requiring release properties, lubricity, corrosion resistance, chemical resistance and the like.
【０００２】[0002]
【従来の技術および発明が解決しようとする課題】フッ
素樹脂は撥水性、撥油性、離型性、潤滑性、耐薬品性等
に優れた材料として知られており、フッ素樹脂のコーテ
ィングにより、これらの性質を他の各種材料表面に付与
することが従来よりなされてきた。フッ素樹脂のコーテ
ィングには、例えば、特開平５−９７４７７号公報、特
開平５−９７４７８号公報、特開平４−４８０６８号公
報、特開平１−３０４９３６号公報、特開昭５８−７１
９７７号公報等に開示されているように、塗布、浸漬、
真空蒸着、スパッタリング、プラズマ重合等の手法を用
いて行われる。2. Description of the Related Art Fluororesins are known as materials having excellent water repellency, oil repellency, releasability, lubricity, chemical resistance and the like. Has been conventionally imparted to the surface of various other materials. Examples of the fluororesin coating include, for example, JP-A-5-97477, JP-A-5-97478, JP-A-4-48068, JP-A-1-304936, and JP-A-58-71.
977, etc., coating, dipping,
This is performed using a technique such as vacuum deposition, sputtering, or plasma polymerization.
【０００３】しかしながら、塗布、浸漬による方法で
は、フッ素樹脂を液状とするために溶媒が必要であり、
ＰＴＦＥのような溶媒に溶けにくいフッ素樹脂には適用
できない。また、真空蒸着、スパッタリング、プラズマ
重合では、真空装置、プラズマ発生装置等の設備にコス
トがかかり、更に、装置内に入らないような大きいもの
には施工することができない。これ以外にもフッ素樹脂
の粉体を焼き付ける方法もあるが、焼き付け温度が比較
的高く、基材が限定される。However, the method of coating and dipping requires a solvent to make the fluororesin liquid,
It cannot be applied to fluororesins which are hardly soluble in solvents such as PTFE. Further, in vacuum deposition, sputtering, and plasma polymerization, equipment such as a vacuum device and a plasma generator is costly, and furthermore, it cannot be applied to a large device that does not enter the device. There is another method of baking fluororesin powder, but the baking temperature is relatively high and the substrate is limited.
【０００４】[0004]
【課題を解決するための具体的手段】本発明者らは、上
記の問題点を解決するため鋭意検討の結果、大気圧下で
蒸発可能なフッ素樹脂を用いて、安価で簡便に、しかも
被覆する基材の大きさに関係なくフッ素樹脂をコーティ
ングする方法を見出し本発明に到達した。The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, using a fluororesin which can be evaporated under atmospheric pressure, the coating is inexpensive, simple, and easy. The present inventors have found a method of coating a fluororesin irrespective of the size of a substrate to be formed, and have reached the present invention.
【０００５】すなわち本発明は、加温蒸発が可能な低分
子量フッ素樹脂を圧力１０〜２００ＫＰａの範囲で蒸着
することを特徴とする含フッ素樹脂被覆体の製造方法を
提供するものである。That is, the present invention provides a method for producing a fluorine-containing resin coating, which comprises depositing a low-molecular-weight fluororesin capable of being heated and evaporated at a pressure of 10 to 200 KPa.
【０００６】本発明において、使用する加温蒸発可能な
低分子量フッ素樹脂とは、５００〜４０００の平均分子
量を持つフッ素樹脂を指し、テロメリゼーション、特公
平１−４９４０４号公報、特公平６−６７８５９号公報
に開示される方法等で製造された低分子量ＰＴＦＥ、低
分子量ＦＥＰ、低分子量ＰＦＡ、低分子量ＣＴＦＥ等で
ある。特に、特公平１−４９４０４号公報、特公平６−
６７８５９号公報記載の方法による低分子量フッ素樹脂
は、Ｆ2、ＮＦ3、ハロゲン化フッ化物および希ガスのフ
ッ化物の少なくとも１種と接触反応させることを特徴と
しており、該低分子量フッ素樹脂の末端基がＣＦ3とな
っている割合が他法による低分子量フッ素樹脂と比較し
て多く、撥水性、撥油性、離型性、潤滑性、耐薬品性等
が優れているため好適に使用される。本発明において、
５００以下の分子量を有する低分子量フッ素樹脂は、室
温において液状であるため適当ではない。また、４００
０以上の分子量を有する低分子量フッ素樹脂は、常圧下
で加温蒸発が困難なため適当ではない。[0006] In the present invention, the low molecular weight fluororesin capable of being heated and evaporated is a fluororesin having an average molecular weight of 500 to 4000, and is referred to as telomerization, Japanese Patent Publication No. 1-49404, and Japanese Patent Publication No. And low-molecular-weight PTFE, low-molecular-weight FEP, low-molecular-weight PFA, low-molecular-weight CTFE, etc., produced by the method disclosed in Japanese Patent No. 67859. In particular, Japanese Patent Publication No. 1-49404,
The low-molecular-weight fluororesin according to the method described in Japanese Patent No. 67859 is characterized by contacting and reacting with at least one of F 2 , NF 3 , a halogenated fluoride and a rare gas fluoride. The ratio in which the group is CF 3 is larger than that of a low molecular weight fluororesin obtained by another method, and is preferably used because it has excellent water repellency, oil repellency, mold release properties, lubricity, chemical resistance and the like. . In the present invention,
Low molecular weight fluororesins having a molecular weight of 500 or less are not suitable because they are liquid at room temperature. Also, 400
A low molecular weight fluororesin having a molecular weight of 0 or more is not suitable because it is difficult to evaporate under normal pressure while heating.
【０００７】本発明において、圧力は、１０〜２００Ｋ
Ｐａの範囲で蒸着するのが好ましい。圧力が１０ＫＰａ
以下だと特別な真空容器が必要となり、また、２００Ｋ
Ｐａ以上だと圧力容器を必要とし装置経済上好ましくな
い。蒸着環境、低分子量フッ素樹脂の平均分子量等によ
り適宜決めればよいが、通常は大気圧（１００ＫＰａ）
が好ましい。常圧付近での蒸着においては、蒸発した低
分子量フッ素樹脂分子の平均自由行程が極めて小さくな
るため、被覆すべき基材まで低分子量フッ素樹脂の蒸気
を到達させる工夫が必要である。そのためには、温度が
低下する前に基材まで低分子量フッ素樹脂蒸気を運ぶ必
要がある。具体的には熱風で蒸気を基材に吹き付ける方
法が有効であり、蒸気の温度低下を防止し、かつ基材ま
での到達時間を短縮できる。 本発明に用いる蒸着装置
は、低分子量フッ素樹脂を蒸発させる部分と蒸発気化し
た該低分子量フッ素樹脂を基材に吹き付ける部分より構
成される。図１にその概略図を示すが、図２のような一
体型の装置の方がコンパクトでより実用的である。In the present invention, the pressure is 10 to 200K.
It is preferable to deposit in the range of Pa. Pressure is 10KPa
If it is below, a special vacuum container is required, and 200K
If the pressure is Pa or more, a pressure vessel is required, which is not preferable in terms of equipment economy. It may be appropriately determined depending on the deposition environment, the average molecular weight of the low molecular weight fluororesin, and the like, but is usually atmospheric pressure (100 KPa).
Is preferred. In vapor deposition at around normal pressure, the mean free path of the evaporated low molecular weight fluororesin molecules is extremely small, so it is necessary to make the vapor of the low molecular weight fluororesin reach the substrate to be coated. For that purpose, it is necessary to carry the low molecular weight fluororesin vapor to the substrate before the temperature decreases. Specifically, a method of blowing steam to the base material with hot air is effective, which can prevent the temperature of steam from lowering and shorten the time required to reach the base material. The vapor deposition apparatus used in the present invention includes a portion for evaporating the low molecular weight fluororesin and a portion for spraying the vaporized low molecular weight fluororesin onto the base material. FIG. 1 is a schematic diagram showing an integrated device as shown in FIG. 2, which is more compact and more practical.
【０００８】低分子量フッ素樹脂を蒸発させる方法に
は、抵抗加熱、熱風加熱、熱線照射等があり、蒸発させ
る温度範囲は、低分子量フッ素樹脂の分子量等により適
宜決めればよいが、蒸気圧が５〜１００ＫＰａとなる温
度範囲が好ましい。これより高い温度ではフッ素樹脂が
熱分解を起こし、有害なガスを発生するおそれがあるた
め好ましくない。また、蒸発した低分子量フッ素樹脂を
基材に吹き付ける場合、吹き付けに使用する熱風の温度
は、低分子量フッ素樹脂を蒸発させる温度より高く設定
する必要があり、具体的には１０〜１００℃高めに設定
することが好ましい。低分子量フッ素樹脂を蒸発させる
温度より低い温度では粉状の析出物が多くなり、成膜性
が悪くなる。熱風の線速は、１〜５０ｍ／ｓｅｃ、基材
の温度は、２０〜２５０℃の範囲に保つことが好まし
い。ノズルから基材までの距離は、膜質に最も影響を及
ぼし、通常５〜３０ｍｍが好ましい。これより短い距離
では基材の温度上昇が激しくなり、また、これより長い
距離では粉状の析出物が多くなり、膜が剥がれやすくな
る。蒸着時間は、低分子量フッ素樹脂の蒸気濃度、熱風
の線速、基材の温度、蒸着すべき膜厚に応じ適宜選択す
ればよい。[0008] The method of evaporating the low molecular weight fluororesin includes resistance heating, hot air heating, heat ray irradiation, and the like. The temperature range for evaporating may be appropriately determined according to the molecular weight of the low molecular weight fluororesin. A temperature range of １００100 KPa is preferred. If the temperature is higher than this, the fluororesin may be thermally decomposed to generate harmful gas, which is not preferable. When spraying the evaporated low molecular weight fluororesin on the base material, the temperature of the hot air used for spraying needs to be set higher than the temperature at which the low molecular weight fluororesin evaporates. It is preferable to set. If the temperature is lower than the temperature at which the low-molecular-weight fluororesin evaporates, the amount of powdery precipitates increases, and the film formability deteriorates. It is preferable that the linear velocity of the hot air be kept in the range of 1 to 50 m / sec and the temperature of the substrate be kept in the range of 20 to 250 ° C. The distance from the nozzle to the substrate has the greatest effect on the film quality, and is usually preferably 5 to 30 mm. If the distance is shorter than this, the temperature of the base material rises sharply. If the distance is longer than this, powdery precipitates increase and the film tends to peel off. The deposition time may be appropriately selected according to the vapor concentration of the low molecular weight fluororesin, the linear velocity of the hot air, the temperature of the substrate, and the film thickness to be deposited.
【０００９】以上述べたように、本発明によれば、撥水
性、撥油性、離型性、潤滑性、耐薬品性等に優れたフッ
素樹脂皮膜を安価で簡便に、しかも被覆する基材の大き
さに関係なくコーティングすることができる。As described above, according to the present invention, a fluororesin film excellent in water repellency, oil repellency, releasability, lubricity, chemical resistance, and the like is inexpensive, simple, and a base material for coating. Coating can be performed regardless of size.
【００１０】[0010]
【実施例】以下、実施例に従って本発明を具体的に説明
する。本発明はこれら実施例に限定されるものではな
い。Hereinafter, the present invention will be described in detail with reference to examples. The present invention is not limited to these examples.
【００１１】実施例１〜８ 図１に示すような常圧蒸着装置の容器内に、平均分子量
３０００の低分子量ＰＴＦＥ１を仕込み、容器をヒータ
ー２により３４０℃に加熱した。配管３より窒素ガスを
流量５００ｓｃｃｍに設定して流し込み、容器内に気化
した低分子量ＰＴＦＥをノズル４の方へ導き、所定の線
速の熱風によりガラス基板５に吹き付けた。これらの条
件およびその評価を表１に示した。評価は、各条件で得
られた被覆した基板について、水に対する接触角（２５
℃）を協和界面科学（株）製ＣＡ−Ｄ型を用いて測定す
る方法で実施した。Examples 1 to 8 A low-molecular-weight PTFE 1 having an average molecular weight of 3000 was charged into a container of an atmospheric pressure vapor deposition apparatus as shown in FIG. 1, and the container was heated to 340 ° C. by a heater 2. Nitrogen gas was set to flow at a flow rate of 500 sccm from the pipe 3, and the vaporized low-molecular-weight PTFE was introduced into the container toward the nozzle 4, and was blown onto the glass substrate 5 by hot air at a predetermined linear velocity. Table 1 shows these conditions and their evaluation. Evaluation was performed on the coated substrate obtained under each condition, with the contact angle (25
° C) using a CA-D type manufactured by Kyowa Interface Science Co., Ltd.
【００１２】実施例９〜１０ 図２に示すような常圧蒸着装置の上部に微細な孔の開い
た容器６内に、平均分子量３０００の低分子量ＰＴＦＥ
７を仕込み、容器が３４０℃に加熱するようにヒータ８
を設定し、ファン９で熱風を起こし、気化した低分子量
ＰＴＦＥを所定の線速でガラス基板１０に吹き付けた。
これらの条件および評価を表１に示す。評価方法は、実
施例１〜８と同様に実施した。Examples 9 to 10 A low molecular weight PTFE having an average molecular weight of 3000 was placed in a container 6 having fine holes in the upper part of an atmospheric pressure vapor deposition apparatus as shown in FIG.
7 and a heater 8 so that the container is heated to 340 ° C.
, Hot air was generated by the fan 9, and the vaporized low molecular weight PTFE was sprayed on the glass substrate 10 at a predetermined linear velocity.
Table 1 shows these conditions and evaluations. The evaluation method was performed in the same manner as in Examples 1 to 8.
【００１３】比較例１ 比較として実施例で使用したのと同一のガラス基板をブ
ランクとして用意し、実施例と同様の方法で評価した。Comparative Example 1 As a comparison, the same glass substrate as used in the examples was prepared as a blank, and evaluated in the same manner as in the examples.
【００１４】[0014]
【表１】 [Table 1]
【００１５】[0015]
【発明の効果】本発明によれば、大気圧下で蒸発可能な
フッ素樹脂を用いて、撥水性、撥油性、離型性、潤滑
性、耐薬品性等に優れたフッ素樹脂皮膜を安価で簡便
に、しかも被覆する基材の大きさに関係なくコーティン
グすることができる。According to the present invention, a fluororesin film excellent in water repellency, oil repellency, releasability, lubricity, chemical resistance and the like can be produced at low cost by using a fluororesin which can be evaporated under atmospheric pressure. Coating can be performed simply and regardless of the size of the substrate to be coated.
【図１】本発明の撥水皮膜の製造に使用した常圧蒸着装
置の一例を示す概略図である。FIG. 1 is a schematic view showing an example of a normal-pressure deposition apparatus used for producing a water-repellent film of the present invention.
【図２】本発明の撥水皮膜の製造に使用した一体型常圧
蒸着装置の一例を示す概略図である。FIG. 2 is a schematic view showing an example of an integrated normal-pressure deposition apparatus used for producing a water-repellent film of the present invention.
１、７ 低分子量ＰＴＦＥ ２、８ ヒーター ３ 配管 ４ ノズル ５、１０ ガラス基板 ６ 容器 ９ ファン 1,7 Low molecular weight PTFE 2,8 Heater 3 Piping 4 Nozzle 5,10 Glass substrate 6 Container 9 Fan
Claims (2)
圧力１０〜２００ＫＰａの範囲で蒸着してなる含フッ素
樹脂被覆体の製造方法。1. A method for producing a fluorine-containing resin coating, wherein a low-molecular-weight fluororesin capable of being heated and evaporated is deposited at a pressure of 10 to 200 KPa.
子量が、平均分子量５００〜４０００であることを特徴
とする請求項１記載のフッ素樹脂被覆体の製造方法。2. The method according to claim 1, wherein the low-molecular-weight fluororesin according to claim 1 has an average molecular weight of 500 to 4,000.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28727697A JPH11116278A (en) | 1997-10-20 | 1997-10-20 | Production of fluororesin coated body |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28727697A JPH11116278A (en) | 1997-10-20 | 1997-10-20 | Production of fluororesin coated body |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH11116278A true JPH11116278A (en) | 1999-04-27 |
Family
ID=17715315
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP28727697A Pending JPH11116278A (en) | 1997-10-20 | 1997-10-20 | Production of fluororesin coated body |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH11116278A (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006087665A (en) * | 2004-09-24 | 2006-04-06 | Toppan Printing Co Ltd | Liquid medicine transpiration container |
| JP2006299002A (en) * | 2005-04-18 | 2006-11-02 | Shinko Giken Kk | Surface treatment agent and surface-treated elastomer material |
| US7413774B2 (en) | 2003-06-27 | 2008-08-19 | Applied Microstructures, Inc. | Method for controlled application of reactive vapors to produce thin films and coatings |
| US7638167B2 (en) | 2004-06-04 | 2009-12-29 | Applied Microstructures, Inc. | Controlled deposition of silicon-containing coatings adhered by an oxide layer |
| US7695775B2 (en) | 2004-06-04 | 2010-04-13 | Applied Microstructures, Inc. | Controlled vapor deposition of biocompatible coatings over surface-treated substrates |
| US7776396B2 (en) | 2004-06-04 | 2010-08-17 | Applied Microstructures, Inc. | Controlled vapor deposition of multilayered coatings adhered by an oxide layer |
| US7879396B2 (en) | 2004-06-04 | 2011-02-01 | Applied Microstructures, Inc. | High aspect ratio performance coatings for biological microfluidics |
| JP2011223030A (en) * | 2000-08-30 | 2011-11-04 | Epcos Ag | Electronic component and manufacturing method thereof |
| US8987029B2 (en) | 2006-06-05 | 2015-03-24 | Applied Microstructures, Inc. | Protective thin films for use during fabrication of semiconductors, MEMS, and microstructures |
| US9725805B2 (en) | 2003-06-27 | 2017-08-08 | Spts Technologies Limited | Apparatus and method for controlled application of reactive vapors to produce thin films and coatings |
-
1997
- 1997-10-20 JP JP28727697A patent/JPH11116278A/en active Pending
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011223030A (en) * | 2000-08-30 | 2011-11-04 | Epcos Ag | Electronic component and manufacturing method thereof |
| US7413774B2 (en) | 2003-06-27 | 2008-08-19 | Applied Microstructures, Inc. | Method for controlled application of reactive vapors to produce thin films and coatings |
| US9725805B2 (en) | 2003-06-27 | 2017-08-08 | Spts Technologies Limited | Apparatus and method for controlled application of reactive vapors to produce thin films and coatings |
| US7638167B2 (en) | 2004-06-04 | 2009-12-29 | Applied Microstructures, Inc. | Controlled deposition of silicon-containing coatings adhered by an oxide layer |
| US7695775B2 (en) | 2004-06-04 | 2010-04-13 | Applied Microstructures, Inc. | Controlled vapor deposition of biocompatible coatings over surface-treated substrates |
| US7776396B2 (en) | 2004-06-04 | 2010-08-17 | Applied Microstructures, Inc. | Controlled vapor deposition of multilayered coatings adhered by an oxide layer |
| US7879396B2 (en) | 2004-06-04 | 2011-02-01 | Applied Microstructures, Inc. | High aspect ratio performance coatings for biological microfluidics |
| JP2006087665A (en) * | 2004-09-24 | 2006-04-06 | Toppan Printing Co Ltd | Liquid medicine transpiration container |
| JP2006299002A (en) * | 2005-04-18 | 2006-11-02 | Shinko Giken Kk | Surface treatment agent and surface-treated elastomer material |
| JP4530901B2 (en) * | 2005-04-18 | 2010-08-25 | シンコー技研株式会社 | Surface treatment agent and surface-treated elastomer material |
| US8987029B2 (en) | 2006-06-05 | 2015-03-24 | Applied Microstructures, Inc. | Protective thin films for use during fabrication of semiconductors, MEMS, and microstructures |
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