JPS6121141A - Molded fluororesin article - Google Patents
Molded fluororesin articleInfo
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- JPS6121141A JPS6121141A JP59142592A JP14259284A JPS6121141A JP S6121141 A JPS6121141 A JP S6121141A JP 59142592 A JP59142592 A JP 59142592A JP 14259284 A JP14259284 A JP 14259284A JP S6121141 A JPS6121141 A JP S6121141A
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- fluororesin
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Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は接着性を有するフッ素樹脂成型体に関するもの
である。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a fluororesin molded body having adhesive properties.
フッ素樹脂は耐熱性、耐薬品性、耐紫外線劣化性などに
他の樹脂には見られない優れた特性を有している。しか
し、接着性に乏しいため他の材料との複合化が困難であ
り、広汎に使用されていないのが現状である。このため
接着性に優れたフッ素樹脂、特にこれら優れた特性を損
う恐れのある接着剤を介さず容易に他の材料との熱接着
ができるフッ素樹脂の開発が望まれている。Fluororesins have excellent properties not found in other resins, such as heat resistance, chemical resistance, and resistance to UV deterioration. However, due to its poor adhesive properties, it is difficult to combine it with other materials, so it is currently not widely used. Therefore, it is desired to develop a fluororesin that has excellent adhesive properties, and in particular, a fluororesin that can be easily thermally bonded to other materials without using an adhesive that may impair these excellent properties.
従来、フッ素樹脂の接着性を改善するために多くの技術
が提案され、これらの技術による接着性の改善されたフ
ッ素樹脂が提供されている。例えば、 Ｎｅ１ｓｏｎ
Ｅ、Ｒ，らのＩｎｄ、Ｅｎｇ、ｃｈｅｍ、 、 ５０．
３２９（１９５８） に記載されたような金属ナトリ
ウム錯体による処理により表面のエツチングされたもの
。Conventionally, many techniques have been proposed to improve the adhesiveness of fluororesins, and fluororesins with improved adhesiveness have been provided using these techniques. For example, Nelson
E. R. et al., Ind, Eng, chem, 50.
329 (1958) whose surface has been etched by treatment with a metal sodium complex.
あるいは特公昭５Ｂ−２５７４２に記載されたようなス
パッタリングによシ表面に凹凸の形成されたもの、さら
にはＪ、 Ａｐｐｌ、 Ｐｏｌｙｍｅｒ Ｓｃｉ、、
１＜Ｓ。Alternatively, a material having irregularities formed on the surface by sputtering as described in Japanese Patent Publication No. 5B-25742, J. Appl. Polymer Sci.
1<S.
１４６５（１９７２）に記載されたような）（ａｌｌ
らの酸素プラズマかヘリウムプラズマで処理された四
フッ化エチレンと六フッ化プロピレンの共重合物の例が
ある。1465 (1972)) (all
Examples include copolymers of tetrafluoroethylene and hexafluoropropylene treated with oxygen plasma or helium plasma.
しかし、第１に挙げた方法によるフッ素樹脂は接着力が
経時的に低下し、特に紫外線照射により接着力が急激に
低下するという欠点がある。However, the fluororesin produced by the first method has a disadvantage in that its adhesive strength decreases over time, and particularly when exposed to ultraviolet rays, the adhesive strength decreases rapidly.
第２の方法によるものでは、流動性の悪い接着剤に対し
ては改良の効果が不十分であり、さらに表面の凹凸が摩
擦によって容易に消失するために取シ扱いに神経を使わ
ねばならないという欠点がある。In the second method, the improvement effect is insufficient for adhesives with poor fluidity, and furthermore, the unevenness of the surface easily disappears due to friction, so care must be taken when handling it. There are drawbacks.
第３の方法によるものは、 Ｈａｌｌらの示したデータ
によれば改良の効果が顕著ではない。すなわち彼らはＡ
４／：１１−ポキシ接着剤／ Ｆ Ｅ Ｐ ”Ｔｅｆｌ
ｏｎ“／エポキシ接着剤ｌＡｔ板の構成でＡ、／板の引
き離し強度を測定しているが、未処理のものに対し数倍
程度の接着強度しか得られていない。ＦＥＰ”Ｔｅｆｌ
ｏｎ″は未処理の場合エポキシ接着剤とはほとんど接着
せず、その接着強度が数倍になったからといって実用レ
ベルにははるかに程遠い。実際本発明者らが彼らと同様
の処理条件で処理を行なったサンプルでも、エポキシ接
着剤に対する剥離強度では全く実用にならないと思われ
るレベルであった。これは他の樹脂の接着性に較べてフ
ッ素樹脂のそれがプラズマ処理により極めて特異な傾向
を示すためであり、彼らがそれに気付かず通常の処理条
件で処理を行ったためである。According to the data presented by Hall et al., the improvement effect of the third method is not significant. That is, they are A
4/:11-Poxy adhesive/FEP”Tefl
The peel strength of the A,/ board was measured using the on"/epoxy adhesive lAt board configuration, but the adhesive strength was only several times that of the untreated one.FEP"Tefl
on'' hardly adheres to epoxy adhesive when untreated, and even though its adhesive strength has increased several times, it is still far from a practical level.In fact, the inventors of the present invention Even in the treated samples, the peel strength against epoxy adhesives was at a level that would be considered completely impractical.This is because the adhesive properties of fluororesin have a very unique tendency due to plasma treatment compared to the adhesive properties of other resins. This is because they did not notice this and proceeded with the processing under normal processing conditions.
また、前記第１．第２および第６の方法によるものすべ
て、熱接着性はほとんど改良されていない。In addition, the above-mentioned No. 1. The second and sixth methods all show little improvement in thermal adhesion.
本発明の目的は、接着性９特に熱接着性に優れ。 The object of the present invention is to provide excellent adhesive properties 9, particularly thermal adhesive properties.
かかる欠点の解決されたフッ素樹脂成型体を提供せんと
するものである。It is an object of the present invention to provide a fluororesin molded article that solves these drawbacks.
本発明は上記目的を達成するために次の構成。 The present invention has the following configuration to achieve the above object.
から１８の範囲にあり、かつ該表層の炭素原子数に対す
る酸素原子数の比（以下０ ／ Ｃと呼ぶ）と、男と壬
の関係が
０／Ｃ≦０．２−０．０９ ｘ （Ｆ ／ Ｃ）であり
、さらに該表層（以下、改質層と呼ぶ）以外の部分（以
下、基材樹脂と呼ぶ）は、Ｆ／Ｃが１．９から２．０の
範囲にあるフッ素樹脂成型体を特徴とするものである。to 18, and the relationship between the ratio of the number of oxygen atoms to the number of carbon atoms in the surface layer (hereinafter referred to as 0/C) and the relationship between 0/C≦0.2-0.09 x (F / C), and the portion (hereinafter referred to as base resin) other than the surface layer (hereinafter referred to as modified layer) is molded with a fluororesin having an F/C in the range of 1.9 to 2.0. It is characterized by the body.
本発明において、基材樹脂とは、Ｆ／Ｃが１．９から２
０の範囲のものを指し、この範囲内のものであれば特に
限定されるものではないが、具体的には、ポリテトラフ
ルオロエチレン、テトラフルオロエチレンとへキサフル
オロプロピレンとの共重合体（以下、ＦＥＰと呼ぶ）、
あるいはテトラフルオロエチレンとパーフルオロアルコ
キシエチレンとの共重合体（以下ＰＦＡと呼ぶ）、ある
いは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コキシエチレンの３元共重合
体（以下ＥＰＥと呼ぶ）等が、その代表的な樹脂として
挙げられる。特にＦＥＰ、ＰＦＡ、ＤＰＥなどの如くテ
トラフルオロエチレンと他のフッ素モノマとの共重合物
は、溶融成型によシフイルムおよびシート化が可能であ
り、透明性にも優れているためより好ましい。In the present invention, the base resin has an F/C of 1.9 to 2.
0, and is not particularly limited as long as it is within this range. Specifically, polytetrafluoroethylene, a copolymer of tetrafluoroethylene and hexafluoropropylene (hereinafter referred to as , FEP),
Alternatively, a copolymer of tetrafluoroethylene and perfluoroalkoxyethylene (hereinafter referred to as PFA), or a terpolymer of tetrafluoroethylene, hexafluoropropylene and perfluoroalkoxyethylene (hereinafter referred to as EPE), etc. It is mentioned as a typical resin. In particular, copolymers of tetrafluoroethylene and other fluorine monomers such as FEP, PFA, and DPE are more preferred because they can be melt-molded into films and sheets and have excellent transparency.
またＦ／Ｃが上記範囲内であればエチレン、クロロトリ
フロロエチレンなどと共重合されたものや９着色のだめ
の顔料や種々の添加剤９例えばカーボンブラック、グラ
ファイト、シリカ粉などを混合して成型されたものでも
よい。If the F/C is within the above range, molding may be done by mixing copolymerized materials with ethylene, chlorotrifluoroethylene, etc.9, coloring pigments, and various additives9, such as carbon black, graphite, silica powder, etc. It may be something that has been done.
次に本発明のフッ素樹脂成型体の改質層はＦ／Ｃが０．
８から１．８の範囲にあり、かつＯ／ＣとＦ／Ｃの関係
がＯ／Ｃ≦０．２−０．０９ Ｘ （Ｆ／Ｃ）であらね
ばならない。Ｆ／Ｃが１．８を越えると改質の効果が不
十分で十分な接着力が得られず、 Ｆ／Ｃが０．８未満
になるとやはり接着力が不十分になる。Next, the modified layer of the fluororesin molded product of the present invention has an F/C of 0.
8 to 1.8, and the relationship between O/C and F/C must be O/C≦0.2-0.09 X (F/C). If F/C exceeds 1.8, the effect of modification will be insufficient and sufficient adhesive strength will not be obtained, and if F/C is less than 0.8, adhesive strength will still be insufficient.
またＦ／Ｃが０．８から１．８の範囲にあっても０／Ｃ
が（０，２−０，０９Ｘ （Ｆ／Ｃ） ）の値を超すと
接着力が不十分であり、特に熱接着性の改良効果がない
。Also, even if F/C is in the range of 0.8 to 1.8, 0/C
If it exceeds the value of (0,2-0,09X (F/C)), the adhesive force will be insufficient, and there will be no improvement in thermal adhesion.
また、改質層の厚さは１００Ａ以上、１μｍ以下で、か
つ基材樹脂の厚さの１／２以下、好ましくは１０００′
Ａ以上、５ｏｏｏ；以下が十分な接着力を付与し、かつ
基材樹脂本来のもつ優れた特性を損わない点から望まし
い。Further, the thickness of the modified layer is 100A or more and 1μm or less, and 1/2 or less of the thickness of the base resin, preferably 1000A
A value of A or more and 5ooo or less is desirable from the viewpoint of providing sufficient adhesive strength and not impairing the excellent properties inherent to the base resin.
また改質層表面は平滑であることが好ましい。Further, the surface of the modified layer is preferably smooth.
表面に凹凸ができるなどして表面が粗くなると。When the surface becomes rough due to unevenness on the surface.
摩擦によって表面が摩耗し改質層の組成が変化したり、
あるいは接着時にこの凹凸中に気泡が残存したシし、接
着力の低下をきたす。これらのことから改質層の表面は
中心線平均粗さくＲａ） （Ｊ ＩＳ Ｅ ０６０
１）が０．０２ ｐ ｍ以下、より好ましくは０．０１
μｍ以下であり、さらに好ましくはフッ素樹脂成型体表
面を走査型電子顕微鏡にて倍率１５゜０００倍で撮影し
、それをイメージアナライザ（ケンブリッジＯインスト
ルメント製’ＱＵＡＮＴＩＭＥＴ”７２０）にて凹部の
大きさ、数量分布を測定する方法において、０．１μｍ
２ （平方ミクロン）以上の凹部が１００μｍ′当り
１０個未満、好ましくは０，０７μｍ２以上の四部が１
００μｍ２当シ１Ｄ個未満、さらに好ましくは０．０３
μが以上の凹部が１００μが当り１０個未満であること
が望ましい。The surface wears out due to friction, and the composition of the modified layer changes,
Alternatively, air bubbles may remain in these irregularities during adhesion, resulting in a decrease in adhesive strength. From these facts, the surface of the modified layer has a center line average roughness (Ra) (JIS E 060
1) is 0.02 p m or less, more preferably 0.01
μm or less, and more preferably, the surface of the fluororesin molded body is photographed at a magnification of 15°000 times using a scanning electron microscope, and the size of the recess is determined using an image analyzer ('QUANTIMET' 720 manufactured by Cambridge O Instrument). , in the method of measuring quantity distribution, 0.1 μm
Less than 10 recesses per 100 μm' with a size of 2 (microns squared) or more, preferably 1 in 4 parts with a size of 0.07 μm2 or more
Less than 1D pieces per 00μm2, more preferably 0.03
It is desirable that the number of concave portions with μ equal to or greater than 100 μ is less than 10.
なお、当然のことながら改質層は成型体の全表面に形成
してもよく、また接着性を必要とする表面の一部にのみ
形成してもよい。Note that, as a matter of course, the modified layer may be formed on the entire surface of the molded product, or may be formed only on a part of the surface that requires adhesiveness.
本発明の改質層を形成する方法は特に限定されるもので
はないが、基材樹脂そのものの表面処理により改質する
方法が好ましい。この方法では。Although the method of forming the modified layer of the present invention is not particularly limited, a method of modifying the base resin itself by surface treatment is preferred. in this way.
基材樹脂からなる成型体の表層の極めて薄い層を改質す
るため、フッ素樹脂のもつ優れた特性を損う事なく、接
着性のみを付与する事ができ極めて優れた方法と言える
。Since this method modifies the extremely thin surface layer of the molded body made of the base resin, it can be said to be an extremely excellent method as it can impart only adhesive properties without impairing the excellent properties of the fluororesin.
表面処理の方法としては、なかでも低温プラズマ処理に
よる処理が改質層の組成を広く変えることと、フッ素樹
脂本来のもつ特性を変えることなく９表層のみを改質で
きること、高温下、高湿下。Among the surface treatment methods, low-temperature plasma treatment can widely change the composition of the modified layer, it can modify only the surface layer without changing the inherent properties of the fluororesin, and it can be used under high temperature and high humidity conditions. .
紫外線照射による接着力の低下の少ない層を形成できる
ことから、より好ましい。This is more preferable since it is possible to form a layer with less deterioration in adhesive strength due to ultraviolet irradiation.
低温プラズマ処理とは、低圧力下のガス雰囲気中で高電
圧を印加した際に開始、持続する放電。Low-temperature plasma treatment is a discharge that starts and continues when high voltage is applied in a gas atmosphere under low pressure.
いわゆるグロー放電によって生じたプラズマを。Plasma generated by so-called glow discharge.
被処理樹脂にさられ、該樹脂の表面を改質する手法であ
る。これら一般的なプラズマ処理に関しては例えば、「
低温プラズマ化学」（穂積啓一部編。This is a method of exposing the resin to be treated and modifying the surface of the resin. Regarding these general plasma treatments, for example,
"Low-Temperature Plasma Chemistry" (edited by Kei Hozumi).
化学の領域、増刊１１１号、南江堂出版、１９７６年発
行）などに詳細に説明されている。It is explained in detail in Chemistry Area, Special Issue No. 111, Nankodo Publishing, published in 1976).
ところでフッ素樹脂は低温プラズマ処理によって極めて
容易にフッ素原子が引き抜かれ、該表層のＦ／Ｃが著し
く低下する。通常の低温プラズマ処理では処理強度は５
０ Ｗ 、 ｓｅｃ／／ｃｍ”以上が用いられるが、こ
の条件で処理した場合、Ｆ／Ｕは０．８未満となり、十
分な接着力の改善効果は認められない。従って本発明の
フッ素樹脂を製造するにあたっては０．０３ Ｗ −ｓ
ｅｃ ／ ｃｍ”以上Ｉ Ｄ Ｗ ｏ ｓｅｅ ／ ａ
ｍ”未満の処理強度、好ましくは０．２ Ｗ −ｓｅａ
／ ｅｍ”以上５Ｗ・Ｓｅｅ ／ ｃＸｎ” 以下
の処理強度で低温プラズマ処理する事が極めて重要であ
る。By the way, fluorine atoms are very easily extracted from fluororesin by low-temperature plasma treatment, and the F/C of the surface layer is significantly lowered. In normal low-temperature plasma treatment, the treatment intensity is 5
0 W, sec//cm" or more, but when treated under these conditions, F/U is less than 0.8, and a sufficient effect of improving adhesive strength is not observed. Therefore, the fluororesin of the present invention is 0.03 W-s for manufacturing
ec/cm” or more ID W o see/a
m” treatment intensity, preferably 0.2 W-sea
It is extremely important to perform low-temperature plasma treatment at a processing intensity of 5 W·See/cXn'' or higher.
ところで、低温プラズマ処理ではフッ素原子の引き抜き
のあと、酸素原子の取り込みが容易に起こる。すなわち
Ｆ／Ｃの低下に伴い０／Ｃが増大するが、０／Ｃが（０
，２−０，０９Ｘ （Ｆ／Ｃ） ３以下になるためには
前述の処理強度に加え、ガスの選定も重要である。By the way, in low-temperature plasma treatment, after fluorine atoms are extracted, oxygen atoms are easily incorporated. In other words, as F/C decreases, 0/C increases, but 0/C becomes (0
, 2-0,09
プラズマを得るだめのガスは、プラズマ中で非重合性の
ガスで、かつ１０−！−ルチ以上の酸素ガスを含まない
ガスである必要があり、 Ｃｏ、、 Ｃｏ、Ｈ，。The gas used to obtain the plasma is a non-polymerizable gas in the plasma, and 10-! - It must be a gas that does not contain more than 100% oxygen gas, such as Co, Co, H,.
Ｎ２． ＮＨ，、Ｎ、０． ＳＯ，、ＨＣＩ、 Ｈ，Ｓ
、 ＣＦ４ などの７レオンガスなど、あるいはこれ
らの混合ガスの処理強度を十分考慮することによシ用い
ることができるが、 ＮＨ，、Ｃｏおよびとれら同志の
混合ガスあるいはこれらのガスに他のガスを混合したも
のは広い処理強度範囲で使用でき特に好ましい。N2. NH,,N,0. SO,,HCI,H,S
, 7 Leon gas such as CF4, or a mixture of these gases can be used by taking sufficient consideration of the processing strength, but NH, Co, and a mixture of these gases or a mixture of these gases with other gases may be used. A mixture is particularly preferred since it can be used over a wide range of treatment strengths.
なお、処理するだめの処理装置、あるいは電源ならびに
電源周波数などは特に限定されるものではない。Note that there are no particular limitations on the processing device used for processing, the power supply, the power supply frequency, etc.
本発明の成型体は、形状が特に限定されるものではなく
、シート状、フィルム状、ブロック状。The shape of the molded product of the present invention is not particularly limited, and may be sheet-like, film-like, or block-like.
棒状、チューブ状など任意の形状のものであってもよい
。なお、形状がフィルム状々と薄い場合にはｔ厚さは１
μｍ以上、好ましくは１０μｍ以上であるのが望ましい
。It may be of any shape such as a rod or a tube. In addition, when the shape is thin like a film, t thickness is 1
It is desirable that the thickness be at least μm, preferably at least 10 μm.
（１）樹脂の組成分析
光電子分光装置（国際電気社製、ＥＳ−２００型）によ
って測定したＣ１８．Ｆ、８および０，６の積分強度比
を、検出感度で補正し、原子組成比Ｆ／ＣとＯ／Ｃを算
定した。(1) Resin composition analysis C18. measured with a photoelectron spectrometer (manufactured by Kokusai Denki Co., Ltd., model ES-200). The integrated intensity ratios of F, 8 and 0,6 were corrected by detection sensitivity, and the atomic composition ratios F/C and O/C were calculated.
測定条件は以下に示す通りである。The measurement conditions are as shown below.
−１〇−
温 度： ２０℃
真空度： ３ ｘ １０ Ｔｏｒｒ
（２） 熱接着によるフィルム同志の貼す合ワせヒー
トシーラを用い、処理面同志を合せ熱板温度を２１０°
Ｃ〜２５０℃で圧力１．５ｋｇ７が、ヒートシール時間
１０秒で接着した。-1〇- Temperature: 20°C Vacuum degree: 3 x 10 Torr (2) Laminating the films together by thermal adhesion Using a heat sealer, align the treated surfaces together and set the hot plate temperature to 210°.
A pressure of 1.5 kg7 was bonded at ~250° C. and a heat seal time of 10 seconds.
（３） 接着力の測定 万能力つ張シ試験機（東洋ボールドウィン製。(3) Measurement of adhesive strength Universal tension tester (manufactured by Toyo Baldwin).
テンシロン）を用い、Ｔビールを行った。引張速度は２
００に／ｍｉｎである。Tensilon) was used to make T-beer. The tensile speed is 2
00/min.
〔実施例〕
実施例１〜１４．比較例１〜１０
厚さ５０μｍ、巾１３ｍのＦＥＰフィルムを内部電極方
式のプラズマ処理装置に入れ、初期圧力（ｌ１０３Ｔｏ
ｒｒに排気後、第１表に示す種々のガスを導入して０．
４０ Ｔｏｒｒの圧力に保ち１１１０ＫＨ７Ｏ高周波電
力を投入し、処理速度１ｍ／ｍｉｎで第１表に示す高周
波電力で処理を行った。[Example] Examples 1 to 14. Comparative Examples 1 to 10 An FEP film with a thickness of 50 μm and a width of 13 m was placed in an internal electrode type plasma processing apparatus, and the initial pressure (l103To
After exhausting the rr, various gases shown in Table 1 were introduced and the temperature was reduced to 0.
The pressure was kept at 40 Torr, 1110 KH7O high frequency power was applied, and the treatment was performed with the high frequency power shown in Table 1 at a processing speed of 1 m/min.
該処理フィルムの改質層の組成分析を前述のＥＳＣＡに
より行った。The composition analysis of the modified layer of the treated film was performed by the above-mentioned ESCA.
同じ（ＥＳＣＡによシ該処理フィルムの基材のＦ／Ｃは
１．９から２０の範囲にあることを確認した。It was confirmed by ESCA that the F/C of the base material of the treated film was in the range of 1.9 to 20.
さらに該処理フィルムを前述の方法によシ熱接着を行な
い、その接着力を測定した。なお、熱接着温度は２１０
℃であるが、未処理のＦＥＰフィルムは２１０°Ｃでは
接着できず２６０°０ではじめて接着する。Furthermore, the treated film was thermally bonded by the method described above, and the adhesive strength was measured. The thermal bonding temperature is 210
℃, but untreated FEP film cannot be bonded at 210°C and only bonds at 260°C.
各実施例および比較例の処理条件とＦ／Ｃ，Ｏ／Ｃ。Processing conditions, F/C, and O/C for each example and comparative example.
０、２−０．０９ ｘ （Ｆ ／ Ｃ）および接着力の
関係を第１表に示す。The relationship between 0,2-0.09 x (F/C) and adhesive force is shown in Table 1.
さらに各実施例１〜１４および比較例１〜１０の接着強
度に対するＦ／ＣとＯ／Ｃの関係をプロットしたものを
第１図に示す。Further, FIG. 1 shows a plot of the relationship between F/C and O/C with respect to the adhesive strength of each of Examples 1 to 14 and Comparative Examples 1 to 10.
第１図中、白丸は５０μｍのＦＤＰフィルムが伸びる強
度すなわち約０．８ ｋｇ／ ｃｍ以上の接着強度を有
することを示し、黒丸はフィルムが伸びるまでには至ら
ない強度すなわち接着強度０．８ｑ／ｃＩｎ未満を示す
。In Figure 1, the white circles indicate the strength at which the 50 μm FDP film can be stretched, that is, the adhesive strength of approximately 0.8 kg/cm or more, and the black circles indicate the strength at which the film does not stretch, that is, the adhesive strength of 0.8 q/cm. Indicates less than cIn.
第１表、第１図よシ明らかなように改質層の組成はＦ／
Ｃが０．８から１．８の範囲にあり、かつ。As is clear from Table 1 and Figure 1, the composition of the modified layer is F/
C is in the range of 0.8 to 1.8, and.
０／Ｃが第１図の斜走破線であられす式（０，２−０，
０９Ｘ（Ｆ／Ｃ）３以下であることが良好な接着性を有
するために必要である。0/C is the diagonal dashed line in Figure 1.
09X(F/C) is required to be 3 or less in order to have good adhesion.
実施例１５．１６
厚さ５０μｍ、巾１３ｃＩＩＩのＰＦＡおよびＦｔＰＥ
フィルムをそれぞれ内部電極方式のプラズマで処理装置
に入れ、初期圧力０，０３Ｔｏｒｒに排気後。Example 15.16 PFA and FtPE with a thickness of 50 μm and a width of 13 cIII
Each film was placed in an internal electrode type plasma processing device and evacuated to an initial pressure of 0.03 Torr.
ＮＨ，ガスを導入して０．４０Ｔｏｒｒ の圧力に保ち
。Introduce NH gas and maintain the pressure at 0.40 Torr.
１１０ ＫＨｚの高周波電力を投入し、処理速度１ｍ／
ｍｉｎで処理を行なった。投入した高周波電力は共に６
Ｗである。Input high frequency power of 110 KHz, processing speed 1m/
Processing was performed at min. The high frequency power input was both 6
It is W.
該処理フィルムを前述の方法により熱接着を行ない、そ
の接着力を測定した。ＰＦＡの場合は熱板温度を２５０
℃、ＥＰＥの場合は２４０℃とした。この温度は共にそ
れぞれの樹脂の融点より約５０°Ｃ低い温度であり、未
処理のものでは全く接着しない。The treated film was thermally bonded by the method described above, and its adhesive strength was measured. For PFA, set the hot plate temperature to 250
℃, and in the case of EPE, it was 240℃. Both of these temperatures are approximately 50° C. lower than the melting points of the respective resins, and untreated materials do not adhere at all.
前述の実施例、比較例と同様の評価を行った結果を第２
表に示す。The results of the same evaluation as in the above-mentioned Examples and Comparative Examples are shown in the second example.
Shown in the table.
第 ２ 表
ＦＤＰの場合と同様、Ｆ／Ｃが０．８から１．８の範囲
にあり、かつＯ／Ｃ≦０．２−０．０９ｘ（Ｆ／Ｃ）の
関係を満足しており、接着強度も十分なものが得られた
。As in the case of FDP in Table 2, F/C is in the range of 0.8 to 1.8 and satisfies the relationship O/C≦0.2-0.09x (F/C), Sufficient adhesive strength was also obtained.
本発明のフッ素樹脂は、Ｆ／Ｃが０．８から１．８の範
囲にあり、かツＯ／ Ｃが（０，２−０，０９ｘ （Ｆ
／Ｃ） １以下の改質層を有するため、フッ素樹脂同志
、あるいは他の樹脂、金属、ガラスなどと熱接着あるい
は熱硬化性樹脂または熱可塑性樹脂からなる接着剤を介
しての接着が可能であり、高温・高湿下での接着力の低
下が少ない。さらにフッ素樹脂のもつ耐熱性、耐薬品性
、耐紫外線劣化性、耐湿性などの本来の性質を損うこと
なく、まだ従来の接着性改質技術では必ず付随する黄変
色がなく、透明性に優れている。The fluororesin of the present invention has an F/C in the range of 0.8 to 1.8, and an O/C of (0,2-0,09x (F
/C) Since it has a modified layer of 1 or less, it can be bonded to fluororesins, other resins, metals, glass, etc. through thermal bonding or adhesives made of thermosetting resins or thermoplastic resins. Yes, there is little decrease in adhesive strength under high temperature and high humidity conditions. Furthermore, without impairing the original properties of fluoropolymer such as heat resistance, chemical resistance, UV deterioration resistance, and moisture resistance, there is still no yellowing that always accompanies conventional adhesive modification technology, and transparency is maintained. Are better.
このため粘着テープ、搬送ベルトの離形用フィルム、マ
クネトロンのカバーレーフイルム、太陽電池のカバーレ
ーフイルム、複合フィルム、ガラス’ＩＦフィルム、ホ
ットメルト用フィルムなど種々の用途に用いることがで
きる。Therefore, it can be used in various applications such as adhesive tapes, release films for conveyor belts, coverlay films for Macnetron, coverlay films for solar cells, composite films, glass IF films, and hot melt films.
第１図は実施例１〜１４と比較例１〜１０の接着強度に
対するＦ／Ｃと０７Ｃの関係をあられす説明図である。FIG. 1 is an explanatory diagram showing the relationship between F/C and 07C with respect to the adhesive strength of Examples 1 to 14 and Comparative Examples 1 to 10.
Claims (1)
素原子数の比Ｆ／Ｃが０．８から１．８の範囲にあり、
かつ該表層の炭素原子数に対する酸素原子数の比Ｏ／Ｃ
とＦ／Ｃの関係が Ｏ／Ｃ≦０．２−０．０９×（Ｆ／Ｃ） であり、さらに該表層以外の部分はＦ／Ｃが１．９から
２．０の範囲にあるフツ素樹脂成型体。(1) At least a part of the surface layer has a ratio F/C of the number of fluorine atoms to the number of carbon atoms in the range of 0.8 to 1.8,
and the ratio of the number of oxygen atoms to the number of carbon atoms in the surface layer O/C
The relationship between O/C and F/C is O/C≦0.2-0.09×(F/C), and the area other than the surface layer has F/C in the range of 1.9 to 2.0. Molded resin body.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59142592A JPS6121141A (en) | 1984-07-10 | 1984-07-10 | Molded fluororesin article |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59142592A JPS6121141A (en) | 1984-07-10 | 1984-07-10 | Molded fluororesin article |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6121141A true JPS6121141A (en) | 1986-01-29 |
| JPH0254848B2 JPH0254848B2 (en) | 1990-11-22 |
Family
ID=15318887
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59142592A Granted JPS6121141A (en) | 1984-07-10 | 1984-07-10 | Molded fluororesin article |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6121141A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62223236A (en) * | 1986-03-26 | 1987-10-01 | Toray Ind Inc | Production of polyimide laminate |
| JPS6335632A (en) * | 1986-07-30 | 1988-02-16 | Kuraray Co Ltd | Sheet-like fluorinated polymer structure and its production |
| JPH02141224A (en) * | 1988-11-22 | 1990-05-30 | Shin Etsu Chem Co Ltd | Surface protective film |
| WO2003089231A1 (en) * | 2002-04-18 | 2003-10-30 | 3M Innovative Properties Company | Fluoropolymer-perfluoropolymer laminate____________ |
| US6849314B2 (en) | 2002-04-18 | 2005-02-01 | 3M Innovative Properties Company | Fluoropolymer blends and multilayer articles |
| JP2006272741A (en) * | 2005-03-29 | 2006-10-12 | Daiso Co Ltd | Epichlorohydrin rubber-fluorocarbon resin laminate, laminated hose, and method for producing laminate |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6392138B1 (en) * | 1998-10-06 | 2002-05-21 | Daikin Industries, Ltd. | Non-perfluoro fluorine-containing resin molded article having low-temperature heat-sealing property |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5465956U (en) * | 1977-10-17 | 1979-05-10 |
-
1984
- 1984-07-10 JP JP59142592A patent/JPS6121141A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5465956U (en) * | 1977-10-17 | 1979-05-10 |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62223236A (en) * | 1986-03-26 | 1987-10-01 | Toray Ind Inc | Production of polyimide laminate |
| JPS6335632A (en) * | 1986-07-30 | 1988-02-16 | Kuraray Co Ltd | Sheet-like fluorinated polymer structure and its production |
| JPH02141224A (en) * | 1988-11-22 | 1990-05-30 | Shin Etsu Chem Co Ltd | Surface protective film |
| WO2003089231A1 (en) * | 2002-04-18 | 2003-10-30 | 3M Innovative Properties Company | Fluoropolymer-perfluoropolymer laminate____________ |
| US6849314B2 (en) | 2002-04-18 | 2005-02-01 | 3M Innovative Properties Company | Fluoropolymer blends and multilayer articles |
| JP2006272741A (en) * | 2005-03-29 | 2006-10-12 | Daiso Co Ltd | Epichlorohydrin rubber-fluorocarbon resin laminate, laminated hose, and method for producing laminate |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0254848B2 (en) | 1990-11-22 |
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