JP2000007869A - Fluorine-containing resin composition having improved antistaining property - Google Patents
Fluorine-containing resin composition having improved antistaining propertyInfo
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- JP2000007869A JP2000007869A JP18043298A JP18043298A JP2000007869A JP 2000007869 A JP2000007869 A JP 2000007869A JP 18043298 A JP18043298 A JP 18043298A JP 18043298 A JP18043298 A JP 18043298A JP 2000007869 A JP2000007869 A JP 2000007869A
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- fluorine
- perfluoro
- containing resin
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Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は防汚性が改良された
非パーフルオロ系含フッ素樹脂組成物および非パーフル
オロ系含フッ素樹脂成形品に関する。The present invention relates to a non-perfluoro fluorine-containing resin composition and a non-perfluoro fluorine-containing resin molded article having improved antifouling properties.
【０００２】[0002]
【従来の技術】含フッ素樹脂は耐候性、耐薬品性、耐熱
性などに優れており、特にハイドロフルオロ系含フッ素
樹脂およびクロロフルオロ系含フッ素樹脂などの非パー
フルオロ系含フッ素樹脂は、パーフルオロ系含フッ素樹
脂に比べて金属、セラミックス、他の合成樹脂などとの
接着性に優れているため、これらの特性を活かして各種
の成形品のの材料として広く使用されている。2. Description of the Related Art Fluorine-containing resins are excellent in weather resistance, chemical resistance, heat resistance and the like. In particular, non-perfluoro-type fluorine-containing resins such as hydrofluoro-type fluorinated resins and chlorofluoro-type fluorinated resins, Compared with fluoro-based fluororesins, they have better adhesiveness to metals, ceramics, other synthetic resins, etc., and are widely used as materials for various molded products by utilizing these characteristics.
【０００３】こうした非パーフルオロ系含フッ素樹脂
は、汎用樹脂に比して撥水撥油性に優れており、ある程
度高い防汚性（汚れの拭き取り容易性や付着しにくさな
ど）を有しているが、パーフオロ系含フッ素樹脂には劣
っている。[0003] Such a non-perfluoro fluorine-containing resin is excellent in water and oil repellency as compared with general-purpose resins, and has a somewhat high antifouling property (e.g., easy wiping of dirt and difficulty in adhesion). However, it is inferior to the perfluoro-based fluororesin.
【０００４】[0004]
【発明が解決しようとする課題】本発明は防汚性が改良
され、汚れが付きにくく、また拭き取りにより容易に汚
れを除去できる非パーフルオロ系含フッ素樹脂成形品お
よびそれを与える含フッ素樹脂組成物を提供することを
目的とする。DISCLOSURE OF THE INVENTION The present invention relates to a non-perfluoro-based fluororesin molded article having improved antifouling properties, less susceptibility to dirt, and easy removal of dirt by wiping, and a fluororesin composition providing the same. The purpose is to provide things.
【０００５】[0005]
【課題を解決するための手段】本発明は、ハイドロフル
オロ系含フッ素樹脂およびクロロフルオロ系含フッ素樹
脂よりなる群から選ばれた少なくとも１種の非パーフル
オロ系含フッ素樹脂に低分子量のパーフルオロ系含フッ
素重合体を配合してなる含フッ素樹脂組成物および、該
含フッ素樹脂組成物を溶融成形して得られる成形品に関
する。SUMMARY OF THE INVENTION The present invention relates to a low-molecular-weight perfluoropolymer comprising at least one non-perfluorofluorinated resin selected from the group consisting of hydrofluorofluorinated resins and chlorofluorofluorinated resins. The present invention relates to a fluorinated resin composition containing a fluorinated polymer and a molded article obtained by melt-molding the fluorinated resin composition.
【０００６】低分子量パーフルオロ系含フッ素重合体と
しては、たとえば数平均分子量が１０００〜１００００
の含フッ素樹脂、および常温で液状の数平均分子量が１
０００〜１００００のパーフルオロポリエーテルが好ま
しい。As the low molecular weight perfluoro series fluoropolymer, for example, the number average molecular weight is 1,000 to 10,000.
And a number average molecular weight of 1 which is liquid at room temperature
000-10,000 perfluoropolyethers are preferred.
【０００７】低分子量パーフルオロ系含フッ素重合体は
非パーフルオロ系含フッ素樹脂１００重量部（以下、
「部」という）に対して０．０５〜１０部配合するのが
好ましい。The low-molecular-weight perfluoro-based fluoropolymer is composed of 100 parts by weight of a non-perfluoro-based fluororesin (hereinafter, referred to as a perfluoro-based resin)
It is preferable to mix 0.05 to 10 parts with respect to “part”.
【０００８】また、本発明の含フッ素樹脂成形品は、低
分子量パーフルオロ系含フッ素重合体の表面濃度が成形
品中の低分子量パーフルオロ系含フッ素重合体の含有量
の少なくとも３倍であることが好ましい。Further, in the fluororesin molded article of the present invention, the surface concentration of the low molecular weight perfluoro series fluoropolymer is at least three times the content of the low molecular weight perfluoro series fluoropolymer in the molded article. Is preferred.
【０００９】[0009]
【発明の実施の形態】本発明が対象とする非パーフルオ
ロ系含フッ素樹脂はハイドロフルオロ系含フッ素樹脂ま
たはクロロフルオロ系含フッ素樹脂である。ハイドロフ
ルオロ系含フッ素樹脂としては、たとえばテトラフルオ
ロエチレン（ＴＦＥ）、トリフルオロエチレン、ビニリ
デンフルオライド（ＶｄＦ）、ビニルフルオライド、ヘ
キサフルオロプロピレン（ＨＦＰ）、エチレンおよびプ
ロピレンの少なくとも１つの単量体を重合して得られる
重合体があげられる。もちろんＴＦＥやＨＦＰなどのパ
ーフルオロ系単量体およびエチレンやプロピレンなどの
非フッ素系単量体は共単量体である。具体的には、たと
えばＴＦＥ−エチレン共重合体（ＥＴＦＥ）、ポリビニ
リデンフルオロライド（ＰＶｄＦ）、ポリビニルフルオ
ライド、ポリトリフルオロエチレン、ＴＦＥ−ＶｄＦ共
重合体、ＴＦＥ−ＨＦＰ−ＶｄＦ共重合体、ＴＦＥ−Ｈ
ＦＰ−エチレン共重合体などがあげられ、特に樹脂の強
度が強く、コロナ放電などの表面処理が容易な点からＥ
ＴＦＥ、ＰＶｄＦが好ましい。BEST MODE FOR CARRYING OUT THE INVENTION The non-perfluoro fluorine-containing resin to which the present invention is directed is a hydrofluoro fluorine-containing resin or a chlorofluoro fluorine-containing resin. Examples of the hydrofluorofluorinated resin include at least one monomer of tetrafluoroethylene (TFE), trifluoroethylene, vinylidene fluoride (VdF), vinyl fluoride, hexafluoropropylene (HFP), ethylene and propylene. Examples include polymers obtained by polymerization. Of course, perfluoro monomers such as TFE and HFP and non-fluorine monomers such as ethylene and propylene are comonomers. Specifically, for example, TFE-ethylene copolymer (ETFE), polyvinylidene fluoride (PVdF), polyvinyl fluoride, polytrifluoroethylene, TFE-VdF copolymer, TFE-HFP-VdF copolymer, TFE -H
FP-ethylene copolymer, and the like. In particular, E is used because of its strong resin and easy surface treatment such as corona discharge.
TFE and PVdF are preferred.
【００１０】クロロフルオロ系含フッ素樹脂としては、
たとえばクロロトリフルオロエチレン（ＣＴＦＥ）の単
独または前記の含フッ素単量体または非フッ素系単量体
との共重合体があげられる。これらのうち、ポリクロロ
トリフルオロエチレン（ＰＣＴＦＥ）、ＣＴＦＥ−エチ
レン共重合体（ＥＣＴＦＥ）が成形性に優れ、表面処理
が容易な点で好ましい。As the chlorofluoro fluorine-containing resin,
For example, chlorotrifluoroethylene (CTFE) alone or a copolymer with the above-mentioned fluorine-containing monomer or non-fluorine-based monomer can be mentioned. Among them, polychlorotrifluoroethylene (PCTFE) and CTFE-ethylene copolymer (ECTFE) are preferable because of excellent moldability and easy surface treatment.
【００１１】本発明において、低分子量パーフルオロ系
含フッ素重合体は非パーフルオロ系含フッ素樹脂に防汚
性を付与する防汚性付与剤の働きをする。本発明で好ま
しく用いられる低分子量パーフルオロ系含フッ素重合体
としては、前記のとおり、低分子量の樹脂性のパーフル
オロ系含フッ素重合体と常温で液体のパーフルオロポリ
エーテルがあげられる。In the present invention, the low molecular weight perfluoro-based fluoropolymer functions as an antifouling agent for imparting antifouling properties to the non-perfluoro-based fluororesin. As described above, low-molecular-weight perfluoro-based fluoropolymers preferably used in the present invention include, as described above, low-molecular-weight resinous perfluoro-based fluoropolymers and perfluoropolyethers which are liquid at room temperature.
【００１２】樹脂性の低分子量パーフルオロ系含フッ素
重合体は３８０℃の溶融粘度が１．５×１０6ポイズ以
下であるのが非パーフルオロ系含フッ素樹脂を溶融混練
または溶融成形後に防汚性を向上させる点で好ましい。
さらに溶融混練または溶融成形の際熱分解しにくい点か
ら数平均分子量でいうと、１０００〜１００００である
のが好ましい。具体例としては、ＴＦＥ、ＨＦＰまたは
パーフルオロ（アルキルビニルエーテル）の少なくとも
１つの単量体を重合して得られる樹脂性の重合体があげ
られ、たとえばポリテトラフルオロエチレン（ＰＴＦ
Ｅ）、ＴＦＥ−ＨＦＰ（ＦＥＰ）、ＴＦＥ−パーフルオ
ロ（アルキルビニルエーテル）共重合体（ＰＦＡ）など
があげられる。The resinous low molecular weight perfluoro-based fluoropolymer has a melt viscosity at 380 ° C. of 1.5 × 10 6 poise or less. It is preferable in that the property is improved.
Further, the number average molecular weight is preferably 1,000 to 10,000 from the viewpoint of difficulty in thermal decomposition during melt kneading or melt molding. Specific examples thereof include resinous polymers obtained by polymerizing at least one monomer of TFE, HFP or perfluoro (alkyl vinyl ether). For example, polytetrafluoroethylene (PTF
E), TFE-HFP (FEP), TFE-perfluoro (alkyl vinyl ether) copolymer (PFA) and the like.
【００１３】これらのうち、防汚効果がもっとも長期間
得られる点からＰＴＦＥが好ましく、特に数平均分子量
２０００〜１００００の低分子量ＰＴＦＥが好ましい。Of these, PTFE is preferred from the viewpoint that the antifouling effect can be obtained for the longest period, and low molecular weight PTFE having a number average molecular weight of 2,000 to 10,000 is particularly preferred.
【００１４】もう一方のパーフルオロポリエーテル（Ｐ
ＦＰＥ）としては、一般式（Ｉ）：The other perfluoropolyether (P
FPE) has the general formula (I):
【００１５】[0015]
【化１】 Embedded image
【００１６】（式中、Ｒは−ＣＦ2−、−ＣＦ2−ＣＦ2
−または−ＣＦ（ＣＦ3）−である）で表される単位か
らなり、数平均分子量が１０００〜１００００、特に２
０００〜１００００のものが好ましい。これらのＰＦＰ
Ｅは常温で液状であり、いわゆるフッ素オイルと称され
るものである。数平均分子量が１０００未満となると防
汚性は奏されるが、非パーフルオロ系含フッ素樹脂との
溶融混練や溶融成形の際、揮発したり熱分解が発生し、
量的な損失が生ずるほか、発泡や成形性の低下など物性
や加工面でも悪影響が生ずることがある。一方、１００
００を超えて大きくなると防汚性は奏されるが、非パー
フルオロ系含フッ素樹脂への分散性が悪く、引張強度の
低下や透明性の低下を招く。[0016] (wherein, R -CF 2 -, - CF 2 -CF 2
Or a unit represented by —CF (CF 3 ) —) having a number average molecular weight of 1,000 to 10,000, particularly 2
000 to 10,000 are preferred. These PFPs
E is liquid at normal temperature and is so-called fluorine oil. When the number average molecular weight is less than 1000, antifouling properties are exhibited, but during melt kneading or melt molding with a non-perfluoro fluorine-containing resin, volatilization or thermal decomposition occurs,
In addition to loss of quantity, adverse effects may also occur on physical properties and processing such as foaming and deterioration of moldability. On the other hand, 100
When it is larger than 00, the antifouling property is exhibited, but the dispersibility in the non-perfluoro-based fluorine-containing resin is poor, which causes a decrease in tensile strength and a decrease in transparency.
【００１７】本発明に使用可能なＰＦＰＥとしては、た
とえばダイキン工業（株）製の商品名デムナムシリー
ズ、ＮＯＫクリューバー社製の商品名バリエルタシリー
ズ、旭硝子（株）製の商品名フォンブリンシリーズ、デ
ュポン社製の商品名ＫＲＹＴＯＸシリーズなどのうち、
数平均分子量が１０００〜１００００のものがあげられ
る。Examples of the PFPE usable in the present invention include Demnum series (trade name, manufactured by Daikin Industries, Ltd.), Valierta series (trade name, manufactured by NOK Kluber), and Fomblin series (trade name, manufactured by Asahi Glass Co., Ltd.). , Of the product name KRYTOX series manufactured by DuPont,
Those having a number average molecular weight of 1,000 to 10,000 are mentioned.
【００１８】低分子量パーフルオロ系含フッ素重合体
は、前記のいずれの形態であっても、マトリックスであ
る非パーフルオロ系含フッ素樹脂１００部に対して０．
０５〜１０部、好ましくは０．１〜５部、特に好ましく
は０．３〜１部配合する。０．０５部よりも少ないと目
的とする防汚性、すなわち撥水撥油性が得られず、一
方、配合量を増やしても撥水撥油性が増大しないほか、
加工性が低下する。In any of the above-mentioned forms, the low-molecular-weight perfluoro-based fluoropolymer is used in an amount of 0.1 to 100 parts of the matrix non-perfluoro-based fluororesin.
The amount is from 0.05 to 10 parts, preferably from 0.1 to 5 parts, particularly preferably from 0.3 to 1 part. If the amount is less than 0.05 part, the desired antifouling property, that is, water / oil repellency cannot be obtained. On the other hand, even if the amount is increased, the water / oil repellency does not increase.
Workability decreases.
【００１９】低分子量パーフルオロ系含フッ素重合体を
マトリックス樹脂である非パーフルオロ系含フッ素樹脂
に配合して樹脂組成物を調製する方法は、所定量の低分
子量パーフルオロ系含フッ素重合体を樹脂性の場合は粉
末の形で、液状の場合はそのまま添加し、たとえば二軸
混練り機により、マトリックス樹脂の融点以上で溶融混
練すればよい。A method for preparing a resin composition by blending a low-molecular-weight perfluoro-based fluoropolymer with a non-perfluoro-based fluororesin as a matrix resin is to prepare a predetermined amount of a low-molecular-weight perfluoro-based fluoropolymer. If it is resinous, it may be added in the form of a powder, if it is liquid, it may be added as it is, and may be melt-kneaded at a temperature equal to or higher than the melting point of the matrix resin by, for example, a biaxial kneader.
【００２０】本発明の含フッ素樹脂組成物には、必要に
応じて各種の添加剤を配合してもよい。添加剤として
は、たとえばマイカ、アルミナ、シリカ、酸化チタン、
酸化亜鉛、酸化セリウム、有機または無機顔料などがあ
げられる。The fluororesin composition of the present invention may contain various additives as necessary. Examples of additives include mica, alumina, silica, titanium oxide,
Examples include zinc oxide, cerium oxide, organic or inorganic pigments, and the like.
【００２１】本発明はまた、前記含フッ素樹脂組成物を
溶融成形して得られる防汚性が改良された含フッ素樹脂
成形品に関する。The present invention also relates to a fluorine-containing resin molded article obtained by melt-molding the fluorine-containing resin composition and having improved antifouling properties.
【００２２】成形方法としては従来公知の溶融成形法が
採用でき、たとえば溶融押出成形法、加熱圧縮成形法な
どが利用できる。As a molding method, a conventionally known melt molding method can be employed, and for example, a melt extrusion molding method, a heat compression molding method, or the like can be used.
【００２３】本発明の成形品においては樹脂性の低分子
量パーフルオロ系含フッ素重合体であっても常温で液体
の低分子量パーフルオロポリエーテルであっても、同じ
く防汚効果を奏する。In the molded article of the present invention, the same antifouling effect can be obtained regardless of whether it is a resinous low molecular weight perfluoropolyether or a low molecular weight perfluoropolyether which is liquid at normal temperature.
【００２４】本発明における防汚作用は、溶融混練され
た低分子量パーフルオロ系含フッ素重合体が成形品の溶
融成形時または使用時に成形品の表面に集まり、表面濃
度が内部に比して高くなるため、パーフルオロ系含フッ
素重合体の極めて優れた撥水撥油性が奏されることに基
づく。The antifouling effect of the present invention is as follows. The melt-kneaded low-molecular weight perfluoro-based fluoropolymer gathers on the surface of the molded article during the melt molding or use of the molded article, and the surface concentration is higher than the inside. Therefore, it is based on the fact that the perfluoro-based fluoropolymer exhibits extremely excellent water and oil repellency.
【００２５】本発明の含フッ素樹脂成形品における低分
子量パーフルオロ系含フッ素重合体の成形品表面濃度
は、成形品の該低分子量重合体の含有量の少なくとも３
倍、好ましくは５〜３０倍、特に好ましくは１０〜３０
倍である。あまり表面濃度が高くなりすぎても含フッ素
樹脂成形品から低分子量パーフルオロ系含フッ素重合体
が脱落しやすくなり、防汚効果が長期間得られなくな
る。また、低分子量パーフルオロ系含フッ素重合体の成
形品表面濃度は３重量％以上あれば防汚性が奏され、好
適には５〜４０重量％である。このように本発明の成形
品における防汚性の発現は低分子量パーフルオロ系含フ
ッ素重合体が成形品表面にブリードまたは偏在すること
によりえられるが、ブリードの仕方は低分子量パーフル
オロ系含フッ素重合体が樹脂性であるか液状であるかに
よって若干異なる。The surface concentration of the low molecular weight perfluoro-based fluoropolymer in the fluororesin molded product of the present invention is at least 3 times the content of the low molecular weight polymer in the molded product.
Times, preferably 5 to 30 times, particularly preferably 10 to 30 times.
It is twice. If the surface concentration is too high, the low-molecular-weight perfluoro-based fluoropolymer easily falls off from the fluororesin molded article, and the antifouling effect cannot be obtained for a long time. If the surface concentration of the molded article of the low molecular weight perfluoro-based fluoropolymer is 3% by weight or more, antifouling properties are exhibited, and preferably 5 to 40% by weight. Thus, the development of the antifouling property of the molded article of the present invention is obtained by the bleeding or uneven distribution of the low molecular weight perfluoro-based fluoropolymer on the surface of the molded article. It differs slightly depending on whether the polymer is resinous or liquid.
【００２６】樹脂性の低分子量パーフルオロ系含フッ素
重合体はマトリックス樹脂である非パーフルオロ系含フ
ッ素樹脂の溶融成形時に表面付近にブリードして表面濃
度を高め、防汚性を付与する。成形後のブリードは期待
できないが、長期間の防汚性の維持が可能であり、また
繰り返し拭き取ることによる磨耗により新たに表面が更
新され、さらに長期間の防汚性が期待できる。The resinous low molecular weight perfluoro-based fluorinated polymer bleeds near the surface during melt molding of the non-perfluoro-based fluorinated resin as the matrix resin to increase the surface concentration and impart antifouling properties. Although bleeding after molding cannot be expected, the antifouling property can be maintained for a long period of time, and the surface is newly renewed by abrasion due to repeated wiping, and further antifouling property can be expected for a long time.
【００２７】一方、液状のパーフルオロポリエーテル
（ＰＴＰＥ）は溶融成形後も成形品表面へのブリードが
生ずるので、即時の防汚性の発現がえられる。また、成
形温度の比較的低いＰＶｄＦなどの非パーフルオロ系含
フッ素樹脂をマトリックス樹脂とする場合に好適であ
る。On the other hand, liquid perfluoropolyether (PTPE) bleeds to the surface of the molded product even after the melt molding, so that an immediate antifouling property can be obtained. It is also suitable when a non-perfluoro fluorine-containing resin such as PVdF having a relatively low molding temperature is used as the matrix resin.
【００２８】本発明の含フッ素樹脂成形品は種々の形状
をとることができ、たとえばシート状、フィルム状、繊
維状、板状、各種製品などが好適な形状である。特にフ
ィルム状にしたものを各種製品の表面の貼着する形態が
有効である。The fluororesin molded article of the present invention can take various shapes, for example, sheet, film, fiber, plate, and various products are suitable shapes. In particular, a form in which a film is adhered to the surface of various products is effective.
【００２９】具体的製品としては、たとえばハウス栽培
用の農業用フィルム、マーキングフィルム、剥離フィル
ムなどの単独使用の製品；たとえば各種コンロなどの厨
房設備の表面カバーフィルム；各種家具の表面保護フィ
ルム；アルミサッシ、壁紙、ドア、窓ガラスなどの建築
物の内外装材の表面保護フィルム；座席シート、ドアな
どの車輌・船舶の内外装材の表面保護フィルム；炊飯
器、湯沸しポットなどの電気・ガス製品の表面保護フィ
ルム；電線、ケーブルなどの被覆フィルム；トンネル、
防音壁、各種標識、看板、煙突など屋外構造物の表面保
護フィルム；各種ガラス製品の表面保護フィルムまたは
飛散防止フィルム；太陽電池モジュールの表面保護フィ
ルムなどがあげられるが、これらに限られるものではな
く、汚れが付着する製品、設備の表面保護や被覆に使用
できる。Specific products include, for example, products for single use such as agricultural films for house cultivation, marking films and release films; surface cover films for kitchen equipment such as various stoves; surface protective films for various furniture; aluminum Surface protection film for interior and exterior materials of buildings such as sashes, wallpapers, doors, and window glasses; Surface protection film for interior and exterior materials of vehicles and ships such as seats and doors; Electric and gas products such as rice cookers and water heaters Surface protective film; Covering film for wires, cables, etc .; Tunnel,
Surface protection films for outdoor structures such as soundproof walls, various signs, signs, and chimneys; surface protection films or shatterproof films for various glass products; surface protection films for solar cell modules, but are not limited thereto. It can be used for surface protection and coating of products and equipment to which dirt adheres.
【００３０】[0030]
【実施例】本発明を実施例および比較例をあげて説明す
るが、本発明はかかる実施例のみに限定されるものでは
ない。EXAMPLES The present invention will be described with reference to examples and comparative examples, but the present invention is not limited to these examples.
【００３１】実施例１〜３ テトラフルオロエチレン−エチレン共重合体（ＥＴＦ
Ｅ。２９７℃、５ｋｇ荷重のときのメルトフローレート
が１０ｇ／１０分）１００部に常温で液状のパーフルオ
ロポリエーテル（構造式：Examples 1 to 3 Tetrafluoroethylene-ethylene copolymer (ETF)
E. 297 ° C., melt flow rate under 5 kg load: 10 g / 10 min) 100 parts perfluoropolyether liquid (structural formula:
【００３２】[0032]
【化２】 Embedded image
【００３３】。数平均分子量８０００）を表１に示す量
配合し二軸混練り機（（株）東洋精機製作所製のラボプ
ラストミル）を用いてシリンダ温度３００℃にて１５分
間混練して本発明の含フッ素樹脂組成物をえた。[0033] (Number average molecular weight 8000) as shown in Table 1 and kneaded for 15 minutes at a cylinder temperature of 300 ° C. using a twin-screw kneader (Labo Plast Mill manufactured by Toyo Seiki Seisaku-sho, Ltd.) for 15 minutes. A resin composition was obtained.
【００３４】ついでこの樹脂組成物をプレス成形（金型
温度３００℃、圧力８０ｋｇｆ／ｃｍ2）し、厚さ２ｍ
ｍのシートとした。Then, the resin composition was press-molded (mold temperature: 300 ° C., pressure: 80 kgf / cm 2 ), and the thickness was 2 m.
m sheet.
【００３５】このシートにつき、溶媒接触角および拭き
取り性をつぎの試験法に従って調べた。結果を表１に示
す。The sheet was examined for solvent contact angle and wiping properties according to the following test methods. Table 1 shows the results.
【００３６】（溶媒接触角）表面接触角計（協和界面科
学（株）製の接触角計ＣＡ−ＤＴ）を用い、キシレン６
部に対してｎ−ブタノール１部を混合した溶媒に対する
静的な接触角を測定する。２５°以上であれば防汚性に
優れているといえる。(Solvent contact angle) Xylene 6 was measured using a surface contact angle meter (contact angle meter CA-DT manufactured by Kyowa Interface Science Co., Ltd.).
The static contact angle to a solvent in which 1 part of n-butanol is mixed with one part is measured. If it is 25 ° or more, it can be said that the antifouling property is excellent.
【００３７】（拭き取り性）シートの表面に油性ペン
（寺西化学工業（株）製のマジックインキ黒Ｎｏ．５０
０）を用いて３ｃｍの線を引き、１０秒後に乾いた綿で
１０回擦り、拭き取ることができた面積を目視で確認す
る。(Wipeability) An oil-based pen (Magic Ink Black No. 50 manufactured by Teranishi Chemical Industry Co., Ltd.) was applied to the surface of the sheet.
A line of 3 cm is drawn using 0), and 10 seconds later, it is rubbed 10 times with dry cotton, and the area that can be wiped off is visually confirmed.
【００３８】評価はつぎの５段階とした。 １：５％未満しか拭き取れなかった。 ２：５％以上３０％未満が拭き取れた。 ３：３０％以上６０％未満が拭き取れた。 ４：６０％以上９５％未満が拭き取れた。 ５：９５％以上が拭き取れた。 ３以上であれば防汚性に優れているといえる。The evaluation was based on the following five levels. Only less than 1: 5% could be wiped off. 2: 5% or more and less than 30% were wiped off. 3: 30% or more and less than 60% were wiped off. 4: 60% or more and less than 95% were wiped off. 5: 95% or more was wiped off. If it is 3 or more, it can be said that the antifouling property is excellent.
【００３９】実施例４〜５ 実施例１と同じＥＴＦＥ１００部に低分子量ＰＴＦＥ
（数平均分子量２５００）粉末を表１に示す量配合し、
実施例１と同様にして二軸混練り機（シリンダ温度３３
０℃、混練時間１５分間）により混練りし、本発明の含
フッ素樹脂組成物を得た。Examples 4 and 5 Low molecular weight PTFE was added to 100 parts of the same ETFE as in Example 1.
(Number average molecular weight 2500) Powder was blended in the amount shown in Table 1,
A twin-screw kneader (cylinder temperature 33
(0 ° C., kneading time: 15 minutes) to obtain a fluororesin composition of the present invention.
【００４０】この樹脂組成物を実施例１と同様にしてプ
レス成形（金型温度３３０℃、圧力８０ｋｇｆ／ｃ
ｍ2）し、厚さ２ｍｍのシートとし、実施例１と同様に
して溶媒接触角および拭き取り性を調べた。結果を表１
に示す。This resin composition was press-molded in the same manner as in Example 1 (die temperature 330 ° C., pressure 80 kgf / c).
m 2 ) to obtain a sheet having a thickness of 2 mm, and the solvent contact angle and the wiping property were examined in the same manner as in Example 1. Table 1 shows the results
Shown in
【００４１】比較例１ 実施例１で用いたＥＴＦＥをそのまま同実施例と同様に
して混練・プレス成形し、厚さ２ｍｍのシートを得、溶
媒接触角および拭き取り性を調べた。結果を表１に示
す。Comparative Example 1 The ETFE used in Example 1 was kneaded and press-molded as it was in the same manner as in Example 1, to obtain a sheet having a thickness of 2 mm, and the solvent contact angle and the wiping property were examined. Table 1 shows the results.
【００４２】比較例２ パーフルオロポリエーテルに代えてポリクロロトリフル
オロエチレン（数平均分子量２５００）を表１に示す量
配合したほかは実施例１と同様にして混練後プレス成形
し、厚さ２ｍｍのシートを得、溶媒接触角および拭き取
り性を調べた。結果を表１に示す。Comparative Example 2 Kneading and press molding were carried out in the same manner as in Example 1, except that polychlorotrifluoroethylene (number average molecular weight 2500) was used instead of perfluoropolyether in the amount shown in Table 1. Was obtained, and the solvent contact angle and the wiping property were examined. Table 1 shows the results.
【００４３】[0043]
【表１】 [Table 1]
【００４４】実施例６〜８ 実施例１で用いたＥＴＦＥ１００部に同実施例で用いた
パーフルオロポリオール（ＰＦＰＥ）を表２に示す量配
合し、ヘンシェルミキサで室温にて１０分間混合して混
合粉末を得た。Examples 6 to 8 Perfluoropolyol (PFPE) used in Example 1 was mixed with 100 parts of ETFE used in Example 1 in an amount shown in Table 2, and mixed with a Henschel mixer at room temperature for 10 minutes. A powder was obtained.
【００４５】この混合粉末を二軸押出機（池貝（株）製
のＰＣＭ４６）を用いて溶融押出（シリンダ温度３００
℃、押出速度１５ｋｇ／時間）し、ペレットとした。こ
のペレットを脱気後、溶融押出機（池貝（株）製のＥＳ
５０）により押出成形（シリンダ温度３３０℃、押出速
度１０ｋｇ／時間）して厚さ５０μｍのフィルムとし
た。The mixed powder was melt-extruded using a twin-screw extruder (PCM46, manufactured by Ikegai Co., Ltd.) (cylinder temperature: 300).
° C, extrusion speed 15 kg / hour) to obtain pellets. After degassing the pellets, a melt extruder (ESIGAGI's ES
Extrusion molding (cylinder temperature: 330 ° C., extrusion speed: 10 kg / hour) was performed to obtain a film having a thickness of 50 μm.
【００４６】このフィルムにつき、溶媒接触角および拭
き取り性を実施例１と同様にして調べ、また対水接触角
および添加剤（パーフルオロポリエーテル）の表面濃度
をつぎの方法で調べた。結果を表２に示す。With respect to this film, the solvent contact angle and the wiping property were examined in the same manner as in Example 1, and the contact angle with water and the surface concentration of the additive (perfluoropolyether) were examined by the following methods. Table 2 shows the results.
【００４７】（対水接触角）前記の接触角計を用い、水
に対する静的な接触角を測定する。９７℃以上なら防汚
性に優れているといえる。(Contact angle with water) The static contact angle with water is measured using the contact angle meter described above. If it is 97 ° C or more, it can be said that the antifouling property is excellent.
【００４８】（添加剤の表面濃度）（株）島津製作所製
ＥＳＣＡ−７５０を用い、フィルムについてＸＰＳ測定
を行なう。各元素の１ｓ軌道から放出された電子数を検
出し、ＰＴＦＥを混合したサンプル（実施例９〜１２）
については、添加剤がないサンプル（比較例３）を基準
にして、フッ素濃度の増加分から添加剤の表面濃度を求
める。パーフルオロポリエーテルを添加したサンプル
（実施例６〜８）については酸素濃度の増加分から添加
剤の表面濃度を求める。このときの表面の分析深さは、
約１００Åである。(Surface Concentration of Additive) The film is subjected to XPS measurement using ESCA-750 manufactured by Shimadzu Corporation. Samples in which the number of electrons emitted from the 1s orbital of each element was detected and PTFE was mixed (Examples 9 to 12)
As for (2), the surface concentration of the additive is determined from the increase in the fluorine concentration based on the sample without the additive (Comparative Example 3). For the samples to which perfluoropolyether was added (Examples 6 to 8), the surface concentration of the additive was determined from the increase in the oxygen concentration. The analysis depth of the surface at this time is
It is about 100 °.
【００４９】実施例９〜１０ パーフルオロポリエーテルに代えて低分子量ＰＴＦＥ
（数平均分子量２５００）を用いたほかは実施例６と同
様にしてペレット化および溶融押出し成形して厚さ５０
μｍのフィルムを得た。Examples 9-10 Low molecular weight PTFE in place of perfluoropolyether
(Number average molecular weight 2500) Pelletization and melt extrusion were carried out in the same manner as in Example 6 except for using a thickness of 50.
A μm film was obtained.
【００５０】このフィルムにつき、溶媒接触角、対水接
触角、添加剤の表面濃度および拭き取り性を実施例６と
同様にして調べた。結果を表２に示す。The film was examined for solvent contact angle, water contact angle, additive surface concentration and wiping properties in the same manner as in Example 6. Table 2 shows the results.
【００５１】実施例１１〜１２ パーフルオロポリエーテルに代えて低分子量ＰＴＦＥ
（数平均分子量６０００）を用いたほかは実施例６と同
様にしてペレット化および溶融押出し成形して厚さ５０
μｍのフィルムを得た。Examples 11 to 12 Instead of perfluoropolyether, low molecular weight PTFE
(Number average molecular weight: 6000) Pelletization and melt extrusion were carried out in the same manner as in Example 6 except that a thickness of 50 was used.
A μm film was obtained.
【００５２】このフィルムにつき、溶媒接触角、対水接
触角、添加剤の表面濃度および拭き取り性を実施例６と
同様にして調べた。結果を表２に示す。For this film, the solvent contact angle, the contact angle with water, the surface concentration of the additive and the wiping property were examined in the same manner as in Example 6. Table 2 shows the results.
【００５３】比較例３ 実施例６で用いたＥＴＦＥのみを溶融押出して厚さ５０
μｍのフィルムを得た。このフィルムにつき実施例６と
同様にして溶媒接触角、対水接触角および拭き取り性を
調べた。結果を表２に示す。Comparative Example 3 Only ETFE used in Example 6 was melt extruded to a thickness of 50
A μm film was obtained. This film was examined for solvent contact angle, water contact angle and wiping properties in the same manner as in Example 6. Table 2 shows the results.
【００５４】[0054]
【表２】 [Table 2]
【００５５】[0055]
【発明の効果】本発明によれば、パーフルオロ系含フッ
素樹脂に比べて劣る非パーフルオロ系含フッ素樹脂の防
汚性を高め、その優れた加工性や物性を低下させること
なく防汚性が改良された成形品が提供できる。According to the present invention, the antifouling property of a non-perfluoro-based fluororesin which is inferior to that of a perfluoro-based fluororesin is improved, and the excellent antifouling property is obtained without deteriorating its workability and physical properties. Can be provided.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 塩月 敬三 大阪府摂津市西一津屋１番１号 ダイキン 工業株式会社淀川製作所内 (72)発明者 中田 裕 大阪府摂津市西一津屋１番１号 ダイキン 工業株式会社淀川製作所内 Ｆターム(参考） 4J002 BD121 BD122 BD131 BD141 BD151 BD152 BD161 ──────────────────────────────────────────────────続 き Continued on the front page (72) Keizo Shiozuki 1-1, Nishiichitsuya, Settsu-shi, Osaka Daikin Industries, Ltd. Yodogawa Works (72) Inventor Hiroshi Nakata 1-1-1, Nishiichitsuya, Settsu-shi, Osaka Daikin F-term in Yodogawa Seisakusho Co., Ltd. (reference) 4J002 BD121 BD122 BD131 BD141 BD151 BD152 BD161
Claims (10)
クロロフルオロ系含フッ素樹脂よりなる群から選ばれた
少なくとも１種の非パーフルオロ系含フッ素樹脂に低分
子量のパーフルオロ系含フッ素重合体を配合してなる防
汚性が改良された含フッ素樹脂組成物。1. A low-molecular-weight perfluoro-based fluorinated polymer is blended with at least one non-perfluoro-based fluorinated resin selected from the group consisting of a hydrofluoro-based fluorinated resin and a chlorofluoro-based fluorinated resin. A fluorine-containing resin composition having improved antifouling properties.
テトラフルオロエチレン、トリフルオロエチレン、クロ
ロトリフルオロエチレン、ビニリデンフルオライド、ビ
ニルフルオライド、ヘキサフルオロプロピレン、エチレ
ンおよびプロピレンよりなる群から選ばれた少なくとも
１つの単量体を重合して得られる重合体である請求項１
記載の含フッ素樹脂組成物。2. The non-perfluoro fluorine-containing resin,
Tetrafluoroethylene, trifluoroethylene, chlorotrifluoroethylene, vinylidene fluoride, vinyl fluoride, hexafluoropropylene, a polymer obtained by polymerizing at least one monomer selected from the group consisting of ethylene and propylene Certain claim 1
The fluorine-containing resin composition according to the above.
テトラフルオロエチレン−エチレン共重合体、ポリビニ
リデンフルオライド、ポリクロロトリフルオロエチレ
ン、ポリビニルフルオライド、ポリトリフルオロエチレ
ン、テトラフルオロエチレン−ビニリデンフルオライド
共重合体、テトラフルオロエチレン−ヘキサフルオロプ
ロピレン−ビニリデンフルオライド共重合体、テトラフ
ルオロエチレン−ヘキサフルオロプロピレン−エチレン
共重合体またはクロロトリフルオロエチレン−エチレン
共重合体である請求項１または２記載の含フッ素樹脂組
成物。3. The non-perfluoro fluorine-containing resin,
Tetrafluoroethylene-ethylene copolymer, polyvinylidene fluoride, polychlorotrifluoroethylene, polyvinyl fluoride, polytrifluoroethylene, tetrafluoroethylene-vinylidene fluoride copolymer, tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride The fluororesin composition according to claim 1 or 2, which is a ride copolymer, a tetrafluoroethylene-hexafluoropropylene-ethylene copolymer or a chlorotrifluoroethylene-ethylene copolymer.
合体が、テトラフルオロエチレン、ヘキサフルオロプロ
ピレンおよびパーフルオロ（アルキルビニルエーテル）
よりなる群から選ばれた少なくとも１つの単量体を重合
して得られる重合体である請求項１〜３のいずれかに記
載の含フッ素樹脂組成物。4. The low-molecular-weight perfluoro-based fluoropolymer comprises tetrafluoroethylene, hexafluoropropylene and perfluoro (alkyl vinyl ether).
The fluororesin composition according to any one of claims 1 to 3, which is a polymer obtained by polymerizing at least one monomer selected from the group consisting of:
合体が、ポリテトラフルオロエチレン、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
重合体または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である請求項１〜４のいずれかに記
載の含フッ素樹脂組成物。5. The low-molecular-weight perfluoro-based fluoropolymer is polytetrafluoroethylene, tetrafluoroethylene-perfluoro (alkyl vinyl ether) copolymer or tetrafluoroethylene-hexafluoropropylene copolymer. 5. The fluorine-containing resin composition according to any one of 1 to 4.
合体が、低分子量パーフルオロポリエーテルである請求
項１〜３のいずれかに記載の含フッ素樹脂組成物。6. The fluorine-containing resin composition according to claim 1, wherein the low-molecular-weight perfluoro-based fluoropolymer is a low-molecular-weight perfluoropolyether.
合体の数平均分子量が１０００〜１００００である請求
項５または６記載の含フッ素樹脂組成物。7. The fluorine-containing resin composition according to claim 5, wherein the low molecular weight perfluoro-based fluoropolymer has a number average molecular weight of 1,000 to 10,000.
０重量部に対して低分子量パーフルオロ系含フッ素重合
体を０．０５〜１０重量部配合してなる請求項１〜７の
いずれかに記載の含フッ素樹脂組成物。8. The non-perfluoro fluorine-containing resin 10
The fluorine-containing resin composition according to any one of claims 1 to 7, wherein 0.05 to 10 parts by weight of a low molecular weight perfluoro-based fluoropolymer is blended with respect to 0 parts by weight.
素樹脂組成物を溶融成形して得られる防汚性が改良され
た含フッ素樹脂成形品。9. A fluororesin molded article having improved antifouling properties obtained by melt-molding the fluororesin composition according to claim 1.
体の成形品表面の濃度が成形品中の該低分子量パーフル
オロ系含フッ素重合体の含有量の少なくとも３倍である
請求項９記載の含フッ素樹脂成形品。10. The method according to claim 9, wherein the concentration of the low-molecular-weight perfluoro-based fluoropolymer on the surface of the molded article is at least three times the content of the low-molecular-weight perfluoro-based fluoropolymer in the molded article. Fluororesin molded product.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18043298A JP2000007869A (en) | 1998-06-26 | 1998-06-26 | Fluorine-containing resin composition having improved antistaining property |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18043298A JP2000007869A (en) | 1998-06-26 | 1998-06-26 | Fluorine-containing resin composition having improved antistaining property |
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| Publication Number | Publication Date |
|---|---|
| JP2000007869A true JP2000007869A (en) | 2000-01-11 |
Family
ID=16083158
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|---|---|---|---|
| JP18043298A Pending JP2000007869A (en) | 1998-06-26 | 1998-06-26 | Fluorine-containing resin composition having improved antistaining property |
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| Country | Link |
|---|---|
| JP (1) | JP2000007869A (en) |
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| JP2009242710A (en) * | 2008-03-31 | 2009-10-22 | Daikin Ind Ltd | Molded body of polytetrafluoroethylene, mixed powder and method for producing molded body |
| JP2015131879A (en) * | 2014-01-09 | 2015-07-23 | ダイキン工業株式会社 | Rubber modifier, rubber composition and molded product |
| JP2018076534A (en) * | 2018-01-09 | 2018-05-17 | ダイキン工業株式会社 | Modifier for rubber, rubber composition and molded article |
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1998
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009534511A (en) * | 2006-04-25 | 2009-09-24 | ソルヴェイ・ソレクシス・エッセ・ピ・ア | Thermoplastic fluoropolymer composition |
| JP2009242710A (en) * | 2008-03-31 | 2009-10-22 | Daikin Ind Ltd | Molded body of polytetrafluoroethylene, mixed powder and method for producing molded body |
| JP2015131879A (en) * | 2014-01-09 | 2015-07-23 | ダイキン工業株式会社 | Rubber modifier, rubber composition and molded product |
| JP2018076534A (en) * | 2018-01-09 | 2018-05-17 | ダイキン工業株式会社 | Modifier for rubber, rubber composition and molded article |
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