JP2516241B2 - Fluorine-containing resin dispersion - Google Patents
Fluorine-containing resin dispersionInfo
- Publication number
- JP2516241B2 JP2516241B2 JP11844988A JP11844988A JP2516241B2 JP 2516241 B2 JP2516241 B2 JP 2516241B2 JP 11844988 A JP11844988 A JP 11844988A JP 11844988 A JP11844988 A JP 11844988A JP 2516241 B2 JP2516241 B2 JP 2516241B2
- Authority
- JP
- Japan
- Prior art keywords
- molecular weight
- dispersion
- fluorine
- fluororesin
- low molecular
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Landscapes
- Lubricants (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Paints Or Removers (AREA)
Description
【発明の詳細な説明】 ［産業上の利用分野］ 本発明は新規な液状含フッ素樹脂分散体に関するもの
であり、各種材料の表面に適用し、潤滑性、離型性、撥
水・撥油性の面を形成したり、塗料、インク等に添加す
ることにより、前記の各種物性を付与することのできる
ものである。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a novel liquid fluororesin dispersion, which is applied to the surface of various materials and has lubricity, releasability, water repellency and oil repellency. The above-mentioned various physical properties can be imparted by forming the surface of (1) or by adding it to paint, ink or the like.
［従来技術］ テトラフルオロエチレン樹脂（PTFE）をはじめとして
含フッ素樹脂は、潤滑性、非粘着性、撥水・撥油性など
の優れた特性を有しており、これらの特性の要求される
各種用途に使用されているが、その使用形態の一つに液
体に分散させた分散体があり、従来から知られているこ
の種の分散体はテトラフルオロエチレンの乳化重合の際
得られる水性分散体に界面活性剤を添加、濃縮したもの
（特公昭32−1844号）、あるいはテトラフルオロエチレ
ンを1,1,2−トリクロロ−1,2,2−トリフルオロエタン中
でテロメリゼーションして得たもの（米国特許第306726
2号）等があるが、水性分散体はPTFE自体が高分子量（1
06〜107程度）であり、コーティング等により得られた
表面の物性、特に潤滑性能が必ずしも十分ではなかっ
た。また、テロメリゼーションにより得られる分散体は
原料のテトラフルオロエチレンを溶解する溶媒が1,1,2
−トリクロロ−1,2,2−トリフルオロエタンに限定され
るため、この溶媒以外の分散体が得られず、用途面で制
約を受けるものである。[Prior Art] Fluorine-containing resins such as tetrafluoroethylene resin (PTFE) have excellent properties such as lubricity, non-adhesiveness, water repellency, and oil repellency. Although it is used for applications, one of its usage forms is a dispersion dispersed in a liquid, and a conventionally known dispersion of this kind is an aqueous dispersion obtained during emulsion polymerization of tetrafluoroethylene. Obtained by adding a surfactant to and concentrating (Japanese Patent Publication No. 32-1844) or tetrafluoroethylene by telomerization in 1,1,2-trichloro-1,2,2-trifluoroethane. Things (US Pat. No. 306726
No. 2), etc., but PTFE itself has a high molecular weight (1
0 6 to 10 7 ), and the physical properties of the surface obtained by coating or the like, particularly the lubricating performance, were not always sufficient. In addition, the dispersion obtained by telomerization uses 1,1,2 as the solvent that dissolves the starting material tetrafluoroethylene.
Since it is limited to -trichloro-1,2,2-trifluoroethane, a dispersion other than this solvent cannot be obtained, which limits the application.
［問題点を解決するための手段］ 本発明者らは上記問題点解決のため、鋭意検討の結
果、含フッ素樹脂のうち、平均粒子径２μ以下で、且つ
分子量の低い粉末は、各種の溶媒に均一に分散し、分散
安定性も良好であり、各種基材への含浸、コーティング
等により得られる表面は潤滑性能等の物性に優れている
ことを見いだし本発明に到達した。[Means for Solving Problems] As a result of intensive studies for solving the above problems, the present inventors have found that among fluorine-containing resins, powders having an average particle diameter of 2 μm or less and a low molecular weight are various solvents. They have found that they are evenly dispersed in water, have good dispersion stability, and have excellent physical properties such as lubrication performance on the surface obtained by impregnation into various base materials and coating.
すなわち本発明は、平均粒径0.5〜２μの分子量1,500
〜10,000の低分子量含フッ素樹脂粉末をノニオン系界面
活性剤および増粘剤を含有する水性媒体中に分散させて
なる含フッ素樹脂分散体および平均粒径0.5〜２μの分
子量1,500〜10,000の低分子量含フッ素樹脂粉末を増粘
剤を含有する有機溶剤媒体中に分散させてなる含フッ素
樹脂分散体である。本発明において使用する含フッ素樹
脂は、低分子量のものを用いる必要があり、分子量1,50
0〜10,000、より好ましくは1,500〜2,000のものを用い
る。また、粒子径も、より小さい方がよく、平均粒子径
で0.5〜２μ、より好ましくは0.5〜１μのものを用い
る。分子量がこれより大きいと、含浸、コーティング等
により得た含フッ素樹脂面の物性、特に潤滑性能が十分
ではなく、また、粒子径がこれより大きくなると溶媒に
対する分散安定性が悪くなり好ましくない。このような
微細な含フッ素樹脂粉末を得るにはワックス状の含フッ
素樹脂低分子量物を粉砕により微細化する方法がある
が、３μ程度までは粉砕できるが、さらに粉砕すること
は容易ではない。本発明者らは、すでにサブミクロンオ
ーダーの低分子量含フッ素樹脂粉末の製造法として含フ
ッ素樹脂をフッ素化剤の存在下で加熱反応させ、発生す
る反応生成ガスからその中に含まれているより低分子量
化された含フッ素樹脂を冷却、析出させる方法を提案し
ており（特願昭61−285962号）、このようにして得られ
る含フッ素樹脂低分子量物を好適に使用できる。以下、
この含フッ素樹脂低分子量物の製造についてより詳しく
説明する。That is, the present invention has a molecular weight of 1,500 with an average particle size of 0.5 to 2 μ.
To 10,000 low molecular weight fluororesin powder dispersed in an aqueous medium containing a nonionic surfactant and a thickener and a low molecular weight 1,500 to 10,000 molecular weight of 0.5 to 2μ A fluororesin dispersion obtained by dispersing fluororesin powder in an organic solvent medium containing a thickener. The fluorine-containing resin used in the present invention needs to have a low molecular weight, and has a molecular weight of 1,50.
The one used is from 0 to 10,000, and more preferably from 1,500 to 2,000. Also, the particle size is preferably smaller, and the average particle size is 0.5 to 2 μ, and more preferably 0.5 to 1 μ. If the molecular weight is higher than this, the physical properties of the fluorine-containing resin surface obtained by impregnation, coating, etc., in particular, the lubricating performance is not sufficient, and if the particle size is larger than this, the dispersion stability in the solvent is unfavorable. In order to obtain such a fine fluororesin powder, there is a method of pulverizing a waxy fluororesin low molecular weight substance by pulverization, but it can be pulverized up to about 3 μ, but further pulverization is not easy. The present inventors have already performed a reaction for heating a fluororesin in the presence of a fluorinating agent as a method for producing a submicron-order low-molecular-weight fluororesin powder, and a reaction product gas generated from the reaction product gas contained therein. A method for cooling and precipitating a low-molecular-weight fluororesin has been proposed (Japanese Patent Application No. 61-285962), and the fluoropolymer low-molecular weight product thus obtained can be preferably used. Less than,
The production of this fluororesin low molecular weight product will be described in more detail.
原料の含フッ素樹脂としては、PTFE、テトラフルオロ
エチレン−ヘキサフルオロプロピレン共重合体（FE
P）、テトラフルオロエチレン−パーフルオロアルコキ
シエチレン共重合体（PFA）、ポリクロロトリフルオロ
エチレン（PCTFE）、エチレン−テトラフルオロエチレ
ン共重合体（ETFE）、ポリビニリデンフルオライド（PV
dF）、ポリビニルフルオライド（PVF）等の汎用の含フ
ッ素樹脂が好適に用いられ、粉末、ペレット、シート、
スクラップあるいはフィラー入りのものなど、いかなる
形状のものでも使用できるが、あらかじめフッ素化剤、
放射線あるいは加熱などの手段により低分子量化したも
のを用いる方が、反応速度が速く、高収率で目的の低分
子量物を得ることができる。フッ素化剤としては、フッ
素（F2）、三フッ化窒素（NF3）、三フッ化塩素（Cl
F3）などが使用され、反応条件は使用する樹脂により異
なるが、原料の含フッ素樹脂を融点以上に加熱し、雰囲
気温度は原料温度よりいくぶん低めの200〜550℃におい
ておこなわれる。雰囲気温度が200℃以下では含フッ素
樹脂の低分子量物は容易に気体とならない。また、原料
温度が600℃以上、雰囲気温度が550℃以上では反応生成
ガス中の含フッ素樹脂の低分子量物が分解するために収
率よく含フッ素樹脂の低分子量物を得ることができな
い。また、使用するフッ素化剤の添加量は、含フッ素樹
脂の種類、形状にもよるが、含フッ素樹脂100重量部に
対してフッ素原子として0.01重量部以上となるように供
給（存在）させればよく、0.01重量部より少ないと低分
子量化反応は容易に進行しない。一方、過剰に存在する
場合は、含フッ素樹脂の低分子量化が進みすぎ、収率よ
く目的とする低分子量物を得ることができないので、大
略10重量部程度までの範囲で選択するのが好ましい。こ
の場合、窒素、アルゴン、ヘリウム、四フッ化炭素等の
不活性ガスで稀釈使用する。Examples of the raw material fluorine-containing resin include PTFE, tetrafluoroethylene-hexafluoropropylene copolymer (FE
P), tetrafluoroethylene-perfluoroalkoxyethylene copolymer (PFA), polychlorotrifluoroethylene (PCTFE), ethylene-tetrafluoroethylene copolymer (ETFE), polyvinylidene fluoride (PV
General-purpose fluorine-containing resins such as dF) and polyvinyl fluoride (PVF) are preferably used, and powders, pellets, sheets,
Any shape, such as scrap or filler, can be used, but the fluorinating agent,
When the one having a low molecular weight by means of radiation or heating is used, the reaction rate is faster and the desired low molecular weight product can be obtained in a high yield. Fluorinating agents include fluorine (F 2 ), nitrogen trifluoride (NF 3 ), chlorine trifluoride (Cl
F 3 ), etc. are used, and the reaction conditions vary depending on the resin used, but the fluorine-containing resin as a raw material is heated to a temperature equal to or higher than the melting point, and the ambient temperature is slightly lower than the raw material temperature at 200 to 550 ° C. When the ambient temperature is 200 ° C or lower, the low molecular weight fluoropolymer does not easily turn into a gas. Further, when the raw material temperature is 600 ° C. or higher and the atmospheric temperature is 550 ° C. or higher, the low molecular weight substance of the fluororesin in the reaction product gas is decomposed, so that the low molecular weight substance of the fluororesin cannot be obtained in good yield. The addition amount of the fluorinating agent to be used depends on the type and shape of the fluororesin, but is supplied (present) so as to be 0.01 part by weight or more as a fluorine atom with respect to 100 parts by weight of the fluororesin. If the amount is less than 0.01 part by weight, the reaction for lowering the molecular weight does not easily proceed. On the other hand, when it is present in excess, the molecular weight of the fluorine-containing resin is too low, and the target low molecular weight product cannot be obtained in good yield. Therefore, it is preferable to select it in the range of up to about 10 parts by weight. . In this case, it is diluted with an inert gas such as nitrogen, argon, helium or carbon tetrafluoride.
使用する反応器は、気体と固体が接触する形態のもの
であれば、いかなるものでも使用できるが、例えば多段
の反応棚を具備する強制循環式の反応器、流動層などの
気固接触が良好に行える反応器が好ましい。Any reactor can be used as long as it is in a form in which gas and solid are in contact with each other. For example, a forced circulation type reactor equipped with a multi-stage reaction shelf, a gas-solid contact such as a fluidized bed is good. Preferred reactors.
含フッ素樹脂の低分子量物を収率よく得るために、含
フッ素樹脂の低分子量物を気体状で含む高温の反応生成
ガスを100℃以下好ましくは室温以下に冷却し、含フッ
素樹脂の低分子量物を析出、分離または捕集するための
冷却器および分離器または捕集器が必要である。冷却の
方法としては、空気、水、冷媒、液化ガスなどが考えら
れ、反応生成ガスの冷却速度をコントロールすることに
より析出する粒子の粒径をコントロールすることが可能
である。分離または捕集の方法としては、重力を利用し
た沈降室形、慣性力を利用した衝突板形、遠心力を利用
したサイクロン、バッグフィルターなどが採用される。
また、反応器内の圧力は高圧になればなるほど反応は速
やかに進行するが常圧でも十分な反応速度を持ってい
る。かかる方法で得られる含フッ素樹脂の低分子量物
は、微小な球状あるいは薄片状の粉末であり、冷却速度
を大とすることにより、より粒子径を小さくすることが
可能である。なお、生成物は活性なフッ素ラジカルの存
在下で分解を行っているため、末端はCF3化されてお
り、極めて安定である。In order to obtain the low molecular weight product of the fluororesin in good yield, the high-temperature reaction product gas containing the low molecular weight product of the fluororesin in a gaseous state is cooled to 100 ° C. or lower, preferably room temperature or lower, to obtain the low molecular weight of the fluororesin. Coolers and separators or collectors for depositing, separating or collecting material are needed. As a cooling method, air, water, a refrigerant, a liquefied gas or the like can be considered, and it is possible to control the particle size of the precipitated particles by controlling the cooling rate of the reaction product gas. As a method of separation or collection, a sedimentation chamber type utilizing gravity, a collision plate type utilizing inertial force, a cyclone utilizing centrifugal force, a bag filter, etc. are adopted.
Further, the higher the pressure in the reactor, the faster the reaction proceeds, but at normal pressure it has a sufficient reaction rate. The low molecular weight substance of the fluorine-containing resin obtained by such a method is a fine spherical or flaky powder, and the particle diameter can be further reduced by increasing the cooling rate. Since the product is decomposed in the presence of active fluorine radicals, it has a CF 3 terminal and is extremely stable.
本発明においては、このようにして得られた含フッ素
樹脂の低分子量微粉末を溶媒に分散させるものである
が、溶媒として水を用いる場合には低分子量微粉末を水
に良好に濡らすため、界面活性剤を使用することが必要
であり、ノニオン系の界面活性剤が好適に使用される。
具体的には、サンモリンII（三洋化成工業株式会社製、
ポリオキシエチレンアルキルエーテル）、ノニポール10
0（三洋化成工業株式会社製、ポリオキシンエチレンノ
ニルフェニルエーテル）、ノニオンNS−212、（日本油
脂株式会社製、ポリオキシエチレンノニルフェルエーテ
ル）等の非イオン系界面活性剤が挙げられる。本発明に
おいて低分子量含フッ素樹脂粉末の量は特に制限はない
が分散体中１〜30重量％の範囲が推奨される。この範囲
より少ない場合には低分子量の含フッ素樹脂の特性が十
分に発揮されず、また、この範囲より多い場合にはグリ
ース状になり、分散液として使用することが困難とな
る。In the present invention, the low molecular weight fine powder of the fluororesin thus obtained is dispersed in a solvent, but when water is used as the solvent, the low molecular weight fine powder is satisfactorily wetted by water, It is necessary to use a surfactant, and a nonionic surfactant is preferably used.
Specifically, San Morin II (manufactured by Sanyo Chemical Industries,
Polyoxyethylene alkyl ether), nonipol 10
Nonionic surfactants such as 0 (manufactured by Sanyo Chemical Industry Co., Ltd., polyoxine ethylene nonyl phenyl ether), Nonion NS-212, (Nippon Yushi Co., Ltd., polyoxyethylene nonyl phenyl ether) and the like can be mentioned. In the present invention, the amount of the low molecular weight fluororesin powder is not particularly limited, but a range of 1 to 30% by weight in the dispersion is recommended. When the amount is less than this range, the characteristics of the low molecular weight fluorine-containing resin are not sufficiently exhibited, and when the amount is more than this range, it becomes grease-like and it becomes difficult to use as a dispersion liquid.
界面活性剤の添加量は用いる界面活性剤の種類、低分
子量含フッ素樹脂の量にもよるが大略0.1〜５重量％の
範囲が好ましい。この範囲より少ないと樹脂が水に十分
に濡れないため、良好に分散しない。また、この範囲よ
り多くしても添加量に見合った効果はなく、経済的でな
いため避けるべきである。このようにして調製した分散
体は均一な分散を示すが、静置状態では比較的短時間で
粒子が沈降する。沈降した状態が短時間の場合には、攪
拌により再分散し、均一な分散体となるが、長時間放置
した場合には沈降した粒子同志が強く凝集して、攪拌に
よっても再分散が困難となることもあり、本発明におい
ては分散安定性を増し、また、長時間放置の後一旦沈降
しても粒子同志の凝集を防ぎ、攪拌により容易に再分散
させるため、増粘剤を添加したものである。増粘剤とし
ては、当然であるが、用いる溶媒と親和性のあるものを
用いる必要があり、水を分散媒として用いる場合には水
溶性の増粘剤、すなわち、デンプン、アラビアゴム、ア
ルギン酸、カゼイン等の天然糊料、メチルセルロース、
ヒドロキシエチルセルロース、カルボキシメチルセルロ
ース等の繊維素誘導体、ポリビニルアルコール、ポリア
クリル酸塩、ポリエチレンオキシド等の合成糊料、ある
いはデキストリン等の加工デンプン等が用いられる。こ
れら増粘剤の添加量はその種類によっても異なるが、分
散体の粘度が５〜30センチポイズ程度となるように添加
する。この場合では、その添加量は0.1〜１重量％程度
となる。この程度の添加量で、その分散安定性は飛躍的
に向上し、十分に実用的であるが、勿論、目的によって
は、より粘度の高い分散体とすることも可能であって、
特に添加量の上限はない。本発明の第２は、分散媒とし
て有機溶剤を用いるものである。用いる有機溶剤は良好
に分散させるため比重、表面張力を考慮して選択するこ
とが好ましい。すなわち、比重が大きい程、粒子が沈降
しにくく、また、表面張力が小さい程粒子と液が濡れや
すく、より容易に分散させることができる。1,1,2−ト
リクロロ−1,2,2−トリフルオロエタン（フロン113）は
比重1.565と高く、また、表面張力も19.0dyn/cm（25
℃）と低く、最も好ましい溶剤の１つである。このほか
ｎ−ヘプタン、ｎ−ヘキサンも表面張力はそれぞれ20.3
dyn/cm（20℃）、18.4dyn/cm（20℃）であり、濡れ性が
良好であり、容易に分散する。しかし、これらは比重が
それぞれ0.69、0.67といずれも小さく、粒子は短時間で
沈降する。従って、本発明においては水媒体を用いる場
合と同様に増粘剤を添加するものであり、使用する増粘
剤としては水素添加ひまし油ステアリン酸アルミニウ
ム、オクタン酸アルミニウム等の金属せっけん、アルミ
ニウムジイソプロポキシドモノアセト酢酸エチル、有機
ベントナイト、酸化ポリエチレン、長鎖ポリアミノアミ
ド、ポリカルボン酸アルキルアミン、あるいは天然ゴ
ム、塩化ゴム等のラテックス、また、水相溶性の有機溶
剤の場合には、ヒドロキシプロピルセルロース等が挙げ
られる。用いる有機溶剤との親和性等を考慮して選択さ
れる。また、その添加量は得られる分散体の粘度が５〜
30センチポイズの範囲となるようにする。これら増粘剤
は分散体の状態では、その分散安定性、粒子沈降時の再
分散性の向上に優れた効果を発揮するものであるが、こ
の分散体を各種基材上にコーティングしたり、あるい
は、含浸させたりして、含フッ素樹脂を付着させる際の
基材および粒子同士間のバインダーとしても機能するも
のであり、その使用形態によって、より基材への付着強
度、粒子間の結合を強固にすることが望ましい場合に
は、増粘剤の量を適宜増やせばよい。使用する有機溶剤
としては前記したもののほかに、エタノール（比重0.7
9、表面張力22.1dyn/cm）、トルエン（比重0.87、表面
張力30.9dyn/cm）等の各種の有機溶剤が使用可能であ
り、比重が小さく粒子が沈降しやすい場合でも増粘剤の
添加により、著しく分散安定性を改善することができ、
また、表面張力が30dyn/cm以下の有機溶剤であれば、よ
く混合すれば十分に濡らすことができ、均一分散が可能
である。しかし、比較的表面張力の大きい有機溶剤の場
合には、より簡単に、より確実に分散させるため、界面
活性剤の添加は有効であり、非イオン系の界面活性剤が
特に有効である。このように、本発明は各種溶媒の含フ
ッ素樹脂分散体を提供するものであるが、使用態様によ
って、溶媒の沸点や蒸気圧を適当に選ぶことにより最適
の分散体が選定できる。蒸気圧の大きい有機溶媒を用い
る場合には、含浸、コーティングした際、熱処理するこ
となく溶剤を速やかに揮発させることができる。本発明
の含フッ素樹脂分散体の好適な使用例としては、潤滑、
離型性を要する材料部位に含浸、スプレーなどの方法に
よって含フッ素樹脂を塗工すること以外に次のような使
用例がある。すなわち、含フッ素樹脂微粉末を他の樹脂
やゴムなどに分散させて複合材料とする方法、塗料やイ
ンクなどに添加して耐候性、非粘着性などを向上させる
方法、オイルやグリースなどに添加して極圧性、耐久性
などを向上させる方法などがあり、含フッ素樹脂粉末を
そのまま基材中に均一に分散させることは困難である
が、本発明の分散体を用い、これらの基材中に添加、混
合したものは溶媒を蒸発させることにより容易に基材中
に分散させたものを得ることができる。The amount of the surfactant added depends on the type of the surfactant used and the amount of the low molecular weight fluorine-containing resin, but is preferably in the range of approximately 0.1 to 5% by weight. If the amount is less than this range, the resin is not sufficiently wetted with water and is not dispersed well. Moreover, even if it exceeds this range, there is no effect commensurate with the added amount and it is uneconomical and should be avoided. The dispersion prepared in this manner shows a uniform dispersion, but when settled, the particles settle in a relatively short time. When the sedimented state is for a short time, it is redispersed by stirring to form a uniform dispersion, but when left for a long time, the sedimented particles are strongly aggregated, making it difficult to redisperse even by stirring. In the present invention, a thickener is added in order to increase the dispersion stability and prevent the particles from aggregating even if they settle after standing for a long time and easily redisperse by stirring. Is. As the thickener, of course, it is necessary to use one having an affinity with the solvent used, and when water is used as the dispersion medium, a water-soluble thickener, that is, starch, gum arabic, alginic acid, Natural paste such as casein, methyl cellulose,
A fibrin derivative such as hydroxyethyl cellulose or carboxymethyl cellulose, a synthetic paste such as polyvinyl alcohol, polyacrylate, polyethylene oxide, or a modified starch such as dextrin is used. The addition amount of these thickeners varies depending on the kind, but they are added so that the viscosity of the dispersion becomes about 5 to 30 centipoise. In this case, the added amount is about 0.1 to 1% by weight. With this amount of addition, the dispersion stability is dramatically improved and is sufficiently practical, but of course, depending on the purpose, it is also possible to make a dispersion having a higher viscosity,
There is no particular upper limit to the amount added. The second aspect of the present invention is to use an organic solvent as the dispersion medium. The organic solvent used is preferably selected in consideration of specific gravity and surface tension in order to disperse well. That is, as the specific gravity is larger, the particles are less likely to settle, and as the surface tension is smaller, the particles and the liquid are more easily wetted, and the particles can be more easily dispersed. 1,1,2-Trichloro-1,2,2-trifluoroethane (Freon 113) has a high specific gravity of 1.565 and a surface tension of 19.0 dyn / cm (25
(° C), which is one of the most preferable solvents. In addition, the surface tension of n-heptane and n-hexane is 20.3 respectively.
They are dyn / cm (20 ° C) and 18.4 dyn / cm (20 ° C), have good wettability, and disperse easily. However, their specific gravities are as low as 0.69 and 0.67, respectively, and the particles settle in a short time. Therefore, in the present invention, a thickener is added as in the case of using an aqueous medium, and as the thickener to be used, hydrogenated castor oil aluminum stearate, metal soap such as aluminum octanoate, aluminum diisopropoxy is used. Ethyl domonoacetoacetate, organic bentonite, polyethylene oxide, long-chain polyaminoamide, polycarboxylic acid alkylamine, or latex of natural rubber, chlorinated rubber, etc., and in the case of water-miscible organic solvent, hydroxypropyl cellulose, etc. Is mentioned. It is selected in consideration of the affinity with the organic solvent used. Further, the amount of addition is such that the viscosity of the obtained dispersion is 5
Keep it in the range of 30 centipoise. These thickeners, in the state of a dispersion, exhibit excellent effects in improving the dispersion stability and redispersibility of particles when settling, coating the dispersion on various substrates, Alternatively, it also functions as a binder between the base material and particles when adhering the fluororesin by being impregnated, and depending on the usage form, the adhesive strength to the base material and the bond between the particles may be improved. When it is desired to make the composition strong, the amount of the thickener may be appropriately increased. As the organic solvent to be used, in addition to those mentioned above, ethanol (specific gravity 0.7
9, various organic solvents such as surface tension 22.1 dyn / cm), toluene (specific gravity 0.87, surface tension 30.9 dyn / cm) can be used, and even if the specific gravity is small and the particles tend to settle, the addition of a thickener , Can significantly improve dispersion stability,
In addition, if the organic solvent has a surface tension of 30 dyn / cm or less, it can be sufficiently wet and can be uniformly dispersed if mixed well. However, in the case of an organic solvent having a relatively large surface tension, the addition of a surfactant is effective and the nonionic surfactant is particularly effective in order to disperse it more easily and more reliably. Thus, the present invention provides a fluorine-containing resin dispersion of various solvents, and the optimum dispersion can be selected by appropriately selecting the boiling point and vapor pressure of the solvent depending on the usage mode. When an organic solvent having a large vapor pressure is used, the solvent can be quickly volatilized without heat treatment when impregnated and coated. Suitable examples of use of the fluorine-containing resin dispersion of the present invention include lubrication,
In addition to coating the fluorine-containing resin by a method such as impregnation or spraying on a material portion that requires releasability, there are the following usage examples. That is, a method of dispersing a fine powder of fluorine-containing resin in another resin or rubber to form a composite material, a method of adding it to paint or ink to improve weather resistance, non-adhesiveness, etc., and adding to oil or grease Therefore, it is difficult to uniformly disperse the fluororesin powder as it is in the base material, but using the dispersion of the present invention, The product added and mixed with can be easily dispersed in the substrate by evaporating the solvent.
以下実施例により本発明をより具体的に説明する。 Hereinafter, the present invention will be described more specifically with reference to Examples.
実施例１、比較例１、２ 特願昭61−285962号の方法と同様にして含フッ素樹脂
低分子量の微粉末を得た。すなわち、5mm角のPTFEペレ
ットをニッケル製反応器に仕込み窒素ガスで稀釈したフ
ッ素ガスを導入し450℃で反応を行い、PTFEの主鎖切断
を行った。得られたワックスを粗粉砕ののち、ジェット
ミルで微粉砕し、融点315℃、分子量8500、平均粒子径
３μｍの粉末を得た（比較例１）。この粗粉砕ワックス
を窒素で10％に稀釈したフッ素ガス中50℃で反応をおこ
ない、反応生成ガスを吸引し冷却器で約40℃に冷却し低
分子量物を析出、補集した。このようにして得たPTFE微
粉末（融点265℃、特許第3,067,262号に示されている融
点と分子量の関係式より算出した分子量1,500、平均粒
子径0.5μ）（実施例１）10gを用い、200mlのビーカー
中で、非イオン系界面活性剤として、三洋化成工業
（株）製ノニポール100（ポリオキシエチレンノニルフ
ェニルエーテル）0.1重量％を添加した水に、強力に攪
拌しながら、添加混合し、全重量100gの分散体を得た。
また、このものにカルボキシメチルセルロースを0.5重
量％となるよう攪拌しながら添加した。また、有機溶剤
として1,1,2−トリクロロ−1,2,2−トリフルオロエタン
（フロン113）、1,1,1−トリクロロエタン、ｎ−ヘキサ
ン、エタノール、トルエンを用い、分散体を得た。同様
にして各種の含フッ素樹脂粉末についても分散体を得
た。その組成を第１表に示した。また、分散体の粘度を
測定した。さらにこの分散体をキャップ付試験管にいれ
分散状態の観察を行った。その結果を第２表に示す。Example 1, Comparative Examples 1 and 2 In the same manner as in the method of Japanese Patent Application No. 61-285962, a fluororesin low molecular weight fine powder was obtained. That is, 5 mm square PTFE pellets were charged into a nickel reactor, fluorine gas diluted with nitrogen gas was introduced, the reaction was carried out at 450 ° C., and the main chain of PTFE was cut. The wax thus obtained was roughly pulverized and then finely pulverized with a jet mill to obtain a powder having a melting point of 315 ° C., a molecular weight of 8500 and an average particle diameter of 3 μm (Comparative Example 1). This coarsely pulverized wax was reacted in fluorine gas diluted with nitrogen to 10% at 50 ° C., the reaction product gas was sucked and cooled to about 40 ° C. in a cooler to deposit and collect low molecular weight substances. Thus obtained PTFE fine powder (melting point 265 ° C., molecular weight 1,500 calculated from the relational expression of melting point and molecular weight shown in Patent No. 3,067,262, average particle diameter 0.5 μ) (Example 1) using 10 g, In a 200 ml beaker, as a nonionic surfactant, Sanyo Kasei Co., Ltd. nonipol 100 (polyoxyethylene nonyl phenyl ether) 0.1% by weight of water was added to the mixture while stirring vigorously, A total weight of 100 g of dispersion was obtained.
Also, carboxymethyl cellulose was added to this while stirring so as to be 0.5% by weight. A dispersion was obtained by using 1,1,2-trichloro-1,2,2-trifluoroethane (CFC113), 1,1,1-trichloroethane, n-hexane, ethanol and toluene as the organic solvent. . In the same manner, dispersions were obtained for various fluorine-containing resin powders. The composition is shown in Table 1. In addition, the viscosity of the dispersion was measured. Further, this dispersion was put into a test tube with a cap and the dispersed state was observed. Table 2 shows the results.
なお、表中の分散安定性、再分散性の評価は、次のと
おりとした。The evaluations of dispersion stability and redispersibility in the table are as follows.
分散安定性○：均一に分散し10時間放置後も粒子の沈降
がみられない △：均一に分散するが３分間後には粒子の沈
降がみられる ×：均一に分散しない 再分散性 ○：粒子沈降後再度攪拌により容易に均一分
散する △：強攪拌により均一再分散する ×：強攪拌により再分散しない ［発明の効果］ 本発明の含フッ素樹脂分散体は微細かつ低分子量の粒
子を用いたものであり、水、有機溶剤に良好に分散する
とともに、増粘剤の添加効果により、長期にわたり、そ
の分散安定性が持続し、しかも一旦粒子が沈降したのち
においても、容易に再分散させることができ、これを適
用して各種基材に潤滑性等の優れた物性を付与すること
ができるものである。Dispersion stability ○: Evenly dispersed and no particle sedimentation even after standing for 10 hours Δ: Evenly dispersed but particle sedimentation is observed after 3 minutes ×: Not evenly dispersed Redispersibility ○: Particle After settling, it is easily and uniformly dispersed by stirring again. Δ: Uniformly redispersed by strong stirring ×: Not redispersed by strong stirring [Effects of the Invention] The fluororesin dispersion of the present invention uses fine and low-molecular weight particles, which disperse well in water and an organic solvent, and due to the addition effect of the thickener, Dispersion stability is maintained, and even after particles have once settled, they can be easily redispersed, and by applying this, various physical properties such as lubricity can be imparted to various base materials. is there.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ 技術表示箇所 //(Ｃ１０Ｍ 173/00 (Ｃ１０Ｍ 173/00 107:38 107:38 129:16 129:16 145:40 145:40 159:10 159:10 129:40） 129:40） (Ｃ１０Ｍ 169/04 (Ｃ１０Ｍ 169/04 105:12 105:12 105:04 105:04 105:52 105:52 145:40 145:40 159:10 159:10 129:40 129:40 107:38） 107:38） Ｃ１０Ｎ 20:06 Ｃ１０Ｎ 20:06 Ｚ 30:00 30:00 Ａ ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 6 Identification code Office reference number FI technical display location // (C10M 173/00 (C10M 173/00 107: 38 107: 38 129: 16 129: 16 145 : 40 145: 40 159: 10 159: 10 129: 40) 129: 40) (C10M 169/04 (C10M 169/04 105: 12 105: 12 105: 04 105: 04 105: 52 105: 52 145: 40 145: 40 159: 10 159: 10 129: 40 129: 40 107: 38) 107: 38) C10N 20:06 C10N 20:06 Z 30:00 30:00 A
Claims (2)
の低分子量含フッ素樹脂粉末をノニオン系界面活性剤お
よび増粘剤を含有する水性媒体中に分散させてなる含フ
ッ素樹脂分散体。1. A molecular weight of 1,500 to 10,000 having an average particle size of 0.5 to 2 μ.
A fluororesin dispersion obtained by dispersing the low molecular weight fluororesin powder of 1. in an aqueous medium containing a nonionic surfactant and a thickener.
の低分子量含フッ素樹脂粉末を増粘剤を含有する有機溶
剤媒体中に分散させてなる含フッ素樹脂分散体。2. A molecular weight of 1,500 to 10,000 having an average particle size of 0.5 to 2 μ.
A fluororesin dispersion obtained by dispersing the low molecular weight fluororesin powder of 1. in an organic solvent medium containing a thickener.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11844988A JP2516241B2 (en) | 1988-05-16 | 1988-05-16 | Fluorine-containing resin dispersion |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11844988A JP2516241B2 (en) | 1988-05-16 | 1988-05-16 | Fluorine-containing resin dispersion |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01289896A JPH01289896A (en) | 1989-11-21 |
| JP2516241B2 true JP2516241B2 (en) | 1996-07-24 |
Family
ID=14736920
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11844988A Expired - Fee Related JP2516241B2 (en) | 1988-05-16 | 1988-05-16 | Fluorine-containing resin dispersion |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2516241B2 (en) |
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| JP6315602B2 (en) * | 2015-03-25 | 2018-04-25 | 住鉱潤滑剤株式会社 | Aqueous lubricant composition |
| JP7038508B2 (en) * | 2017-09-13 | 2022-03-18 | 三菱鉛筆株式会社 | Fluorine resin water dispersion |
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| JP7078441B2 (en) * | 2018-04-05 | 2022-05-31 | 三菱鉛筆株式会社 | Polytetrafluoroethylene aqueous dispersion |
| JP7193681B1 (en) | 2021-05-31 | 2022-12-20 | Ｊｆｅスチール株式会社 | Chemicals, oil country tubular goods, and oil country tubular goods threaded joints |
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-
1988
- 1988-05-16 JP JP11844988A patent/JP2516241B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI842856B (en) * | 2019-03-22 | 2024-05-21 | 新加坡商Ａｇｃ亞太有限公司 | Composition comprising fluororesin and methods of producing the composition and a fluororesin dispersion |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH01289896A (en) | 1989-11-21 |
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