JPH0551701B2 - - Google Patents
Info
- Publication number
- JPH0551701B2 JPH0551701B2 JP18642584A JP18642584A JPH0551701B2 JP H0551701 B2 JPH0551701 B2 JP H0551701B2 JP 18642584 A JP18642584 A JP 18642584A JP 18642584 A JP18642584 A JP 18642584A JP H0551701 B2 JPH0551701 B2 JP H0551701B2
- Authority
- JP
- Japan
- Prior art keywords
- fluorination
- degree
- vinylidene fluoride
- fiber structure
- fiber
- 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 - Lifetime
Links
- 239000000835 fiber Substances 0.000 claims description 69
- 238000003682 fluorination reaction Methods 0.000 claims description 54
- 239000007789 gas Substances 0.000 claims description 26
- 229920001577 copolymer Polymers 0.000 claims description 24
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 22
- 229910052731 fluorine Inorganic materials 0.000 claims description 22
- 239000011737 fluorine Substances 0.000 claims description 22
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 claims description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- 239000002904 solvent Substances 0.000 description 14
- 239000002994 raw material Substances 0.000 description 13
- 238000000034 method Methods 0.000 description 12
- 229920005989 resin Polymers 0.000 description 11
- 239000011347 resin Substances 0.000 description 11
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 9
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 7
- 239000005977 Ethylene Substances 0.000 description 7
- 239000004744 fabric Substances 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 7
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 6
- 239000002759 woven fabric Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000004745 nonwoven fabric Substances 0.000 description 5
- 239000002184 metal Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- PYVHTIWHNXTVPF-UHFFFAOYSA-N F.F.F.F.C=C Chemical compound F.F.F.F.C=C PYVHTIWHNXTVPF-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- MIZLGWKEZAPEFJ-UHFFFAOYSA-N 1,1,2-trifluoroethene Chemical compound FC=C(F)F MIZLGWKEZAPEFJ-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- CHDVXKLFZBWKEN-UHFFFAOYSA-N C=C.F.F.F.Cl Chemical compound C=C.F.F.F.Cl CHDVXKLFZBWKEN-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 229910000792 Monel Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- BXKDSDJJOVIHMX-UHFFFAOYSA-N edrophonium chloride Chemical compound [Cl-].CC[N+](C)(C)C1=CC=CC(O)=C1 BXKDSDJJOVIHMX-UHFFFAOYSA-N 0.000 description 1
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 description 1
- 238000004334 fluoridation Methods 0.000 description 1
- 229920002313 fluoropolymer Polymers 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- -1 polytetrafluoroethylene chains Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
- Artificial Filaments (AREA)
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、フツ素樹脂繊維構造体の製造方法、
特に耐溶剤性に優れたフツ素樹脂繊維構造体の製
造方法に関するものである。[Detailed Description of the Invention] [Industrial Application Field] The present invention provides a method for producing a fluororesin fiber structure;
In particular, the present invention relates to a method for producing a fluororesin fiber structure having excellent solvent resistance.
一般にフツ素樹脂は比較的優れた耐蝕性、耐溶
剤性を有するものが多く、特に四フツ化エチレン
樹脂は、有機溶剤、酸、アルカリに対する耐性が
極めて優れている。しかし四フツ化エチレン樹脂
は融点が327℃以上と高くかつ大きな分子量を有
しているので、繊維、フイルム等を製造するため
に、成型法として一般的な溶融成型法を利用する
ことが困難である。
In general, many fluororesins have relatively excellent corrosion resistance and solvent resistance, and tetrafluoroethylene resins in particular have extremely excellent resistance to organic solvents, acids, and alkalis. However, because tetrafluoroethylene resin has a high melting point of 327°C or higher and a large molecular weight, it is difficult to use the general melt molding method to manufacture fibers, films, etc. be.
このため従来において四フツ化エチレン樹脂よ
り成る繊維等を得るためには、四フツ化エチレン
樹脂の微粉末に潤滑油を加えてペースト状にし、
これを繊維状に押出成型した後焼結する方法が採
用されているが、このような方法では製造過程に
帰因して、得られる繊維等が多孔質のものとなる
ことを回避できず、また樹脂の着色も大きい欠点
がある。 Therefore, conventionally, in order to obtain fibers made of tetrafluoroethylene resin, lubricating oil is added to fine powder of tetrafluoroethylene resin to form a paste.
A method has been adopted in which this is extruded into a fiber shape and then sintered, but due to the manufacturing process, it cannot be avoided that the resulting fibers etc. become porous. Another major drawback is the coloring of the resin.
然るに、フツ素樹脂のうちフツ化ビニリデン系
樹脂、具体的にはポリフツ化ビニリデンまたはフ
ツ化ビニリデン共重合体は極めて良好な成型性を
有していて溶融成型法により容易に繊維化するこ
とができる。このフツ化ビニリデン系樹脂は、一
般に耐蝕性には優れているけれども、極性の大き
い溶剤、例えばジメチルアセトアミド、ジメチル
ホルムアミド、ジメチルスルホキシド、シクロヘ
キサノン等には高温で容易に溶解し、従つて耐溶
剤性に乏しい問題点がある。 However, among fluororesins, vinylidene fluoride resins, specifically polyvinylidene fluoride or vinylidene fluoride copolymers, have extremely good moldability and can be easily made into fibers by melt molding. . Although vinylidene fluoride resin generally has excellent corrosion resistance, it easily dissolves in highly polar solvents such as dimethylacetamide, dimethylformamide, dimethyl sulfoxide, and cyclohexanone at high temperatures, and therefore has poor solvent resistance. There are some shortcomings.
このように従来の方法では耐溶剤性に優れしか
も非多孔質の繊維を得ることは困難であつた。 As described above, it has been difficult to obtain non-porous fibers with excellent solvent resistance using conventional methods.
一方、ポリフツ化ビニリデンよりなるフイルム
をフツ素ガスによつてフツ素化処理することによ
り、当該重合体を四フツ化エチレン様の樹脂に変
換させることが報告されている（篠原、岩崎、岡
崎：「日本化学会第29秋季年会講演予稿集」
3H13、1973年10月）。しかしながら、この方法に
よつて得られるフイルムは、その全体の殆どが四
フツ化エチレン化したものとなるため、全く機械
的強度に欠け、手で持つことによつても容易に破
砕される程度に脆弱なものである。 On the other hand, it has been reported that by fluorinating a film made of polyvinylidene fluoride with fluorine gas, the polymer can be converted into a tetrafluoroethylene-like resin (Shinohara, Iwasaki, Okazaki: "Proceedings of the 29th Autumn Annual Meeting of the Chemical Society of Japan"
3H13, October 1973). However, since most of the film obtained by this method is made of tetrafluoroethylene, it lacks mechanical strength and is easily crushed even when held by hand. It is fragile.
本発明は以上のような事情を背景になされたも
のであり、優れた耐溶剤性を有し、非多孔質であ
つてしかも実用的に十分大きい強度を有するフツ
素樹脂繊維構造体を極めて容易に製造することの
できる方法を提供することを目的としている。
The present invention was made against the background of the above-mentioned circumstances, and it is an extremely easy method to produce a fluororesin fiber structure that has excellent solvent resistance, is non-porous, and has sufficient strength for practical use. The purpose is to provide a method that can be manufactured to
本発明の特徴とするところは、フツ化ビニリデ
ンを50モル％以上含有するフツ化ビニリデン共重
合体より成り、その繊維径が1μm〜５mmである繊
維体よりなる繊維構造体を、酸素濃度が１重量％
以下であるフツ素ガスに接触させてフツ素化処理
することにより、当該繊維構造体を形成している
フツ化ビニリデン共重合体のフツ素化度をその値
が75％を越えない範囲において２〜40％増加せし
め、繊維構造体を構成する繊維体の表面部分のフ
ツ素化度が内部のフツ素化度より高い状態とする
点にある。
The present invention is characterized in that a fibrous structure made of a vinylidene fluoride copolymer containing 50 mol% or more of vinylidene fluoride and having a fiber diameter of 1 μm to 5 mm is used at an oxygen concentration of 1 μm to 5 mm. weight%
The degree of fluorination of the vinylidene fluoride copolymer forming the fiber structure can be increased by fluorination treatment by contacting with the following fluorine gas within a range that does not exceed 75%. The point is that the degree of fluorination of the surface portion of the fiber body constituting the fiber structure is higher than the degree of fluorination of the inside.
以下本発明について具体的に説明する。 The present invention will be specifically explained below.
本発明においては、フツ化ビニリデンを50モル
％以上の割合で含有するフツ化ビニリデン共重合
体により、その繊維径が1μm〜５mmである繊維体
による繊維構造体を得、これに、酸素濃度が１重
量％以下であるフツ素ガスを接触せしめることに
よつてフツ素化処理を行ない、このフツ素化処理
によつて当該繊維構造体を形成しているフツ化ビ
ニリデン共重合体のフツ素化度を２〜40％増加せ
しめるがその値が75％を越えないようにし、もつ
て当該繊維構造体を構成する繊維体の表面部分の
フツ素化度が内部のフツ素化度より高い状態とす
ることによつてフツ素樹脂繊維構造体を製造す
る。 In the present invention, a fibrous structure is obtained by using a vinylidene fluoride copolymer containing vinylidene fluoride in a proportion of 50 mol% or more, and the fiber structure has a fiber diameter of 1 μm to 5 mm. Fluorination treatment is carried out by contacting with 1% by weight or less of fluorine gas, and by this fluorination treatment, the vinylidene fluoride copolymer forming the fiber structure is fluorinated. The degree of fluorination is increased by 2 to 40%, but the value does not exceed 75%, and the degree of fluorination on the surface of the fiber body constituting the fiber structure is higher than the degree of fluorination inside. A fluororesin fiber structure is manufactured by doing this.
以上において「繊維構造体」とは、繊維、及び
繊維の二次加工品である織布、編物、各種形状の
不織布等並びにこれらの織布、編物、各種形状の
不織布等を金属、プラスチツク等の基材に積層さ
せた積層体を含む概念を表わす語である。 In the above, "fiber structures" refer to fibers, secondary processed products of fibers such as woven fabrics, knitted fabrics, non-woven fabrics of various shapes, etc., as well as these woven fabrics, knitted fabrics, non-woven fabrics of various shapes, etc. made of metals, plastics, etc. This term refers to a concept that includes a laminate layered on a base material.
本発明において原料繊維構造体として用いるフ
ツ化ビニリデン共重合体は、具体的には、50モル
％以上のフツ化ビニリデンと、三フツ化エチレ
ン、四フツ化エチレン、三フツ化塩化エチレン等
のフツ化ビニリデンと共重合可能なエチレン系単
量体の一種以上とを共重合させて得られる共重合
体である。フツ化ビニリデン分子はフツ素ガスに
対し適度の反応性を保有しているので、原料繊維
構造体が、フツ化ビニリデンを50モル％以上含有
するフツ化ビニリデン共重合体よりなることによ
り、フツ素化度が75％を越えることを容易に確実
に防止することができ、過剰なフツ素化が抑止さ
れて機械的強度が大幅に低下することが防止され
る。 Specifically, the vinylidene fluoride copolymer used as the raw material fiber structure in the present invention contains 50 mol% or more of vinylidene fluoride and ethylene trifluoride, ethylene tetrafluoride, ethylene trifluoride chloride, etc. It is a copolymer obtained by copolymerizing vinylidene oxide and one or more copolymerizable ethylene monomers. Vinylidene fluoride molecules have moderate reactivity with fluorine gas, so if the raw material fiber structure is made of a vinylidene fluoride copolymer containing 50 mol% or more of vinylidene fluoride, it is possible to It is possible to easily and reliably prevent the degree of fluorination from exceeding 75%, suppressing excessive fluorination and preventing a significant decrease in mechanical strength.
フツ化ビニリデン共重合体よりなる繊維構造体
の作製方法は特に限定されるものではない。例え
ば溶融押出法により所望の口径のノズルから延伸
して、または延伸せずに繊維を作製してもよい
し、また溶媒を用いて湿式で作製してもよい。原
料繊維構造体を構成する繊維体としては、繊維径
が1μm〜５mmの範囲のものが用いられる。この繊
維体によつて各種の織物、編物、不織布等の二次
加工品が作製され、またこれらの織布、編物、不
織布等を金属、プラスチツク等の基材に融着また
は接着させることによつて積層体が作製される。 The method for producing the fibrous structure made of vinylidene fluoride copolymer is not particularly limited. For example, fibers may be produced by melt extrusion through a nozzle of a desired diameter or without stretching, or may be produced wet using a solvent. The fibers constituting the raw material fiber structure have a fiber diameter in the range of 1 μm to 5 mm. Various secondary processed products such as woven, knitted, and nonwoven fabrics are made from this fibrous body, and these woven fabrics, knitted fabrics, and nonwoven fabrics are fused or adhered to base materials such as metals and plastics. A laminate is produced.
上述の如きフツ化ビニリデン共重合体の繊維構
造体はフツ素ガスによりフツ素化処理されるが、
このフツ素化処理に用いられるフツ素ガスは、酸
素含量が少ないものであり、具体的には酸素濃度
が１重量％以下、好ましくは0.5重量％以下のフ
ツ素ガスが用いられる。 The fiber structure of vinylidene fluoride copolymer as described above is fluorinated with fluorine gas,
The fluorine gas used in this fluorination treatment has a low oxygen content, and specifically, a fluorine gas having an oxygen concentration of 1% by weight or less, preferably 0.5% by weight or less is used.
フツ素化処理を行なうための処理ガスとして
は、純粋なフツ素ガスを用いてもよいが希釈され
たフツ素ガスを用いてもよい。特にフツ素化処理
において重合体分子の切断や架橋反応を併発する
おそれがあるときは、原料繊維構造体を形成して
いるフツ化ビニリデン共重合体の種類ないしその
フツ素ガスに対する耐性に応じ、適当な希釈ガス
によつて希釈された適宜の濃度のフツ素ガスを選
ぶべきである。一般に、処理ガスにおけるフツ素
ガスの濃度は１％以上のものが適当である。希釈
ガスとしては、フツ素ガスおよびフツ化ビニリデ
ン共重合体よりなる繊維構造体の何れに対しても
不活性なもの、例えば窒素ガス、アルゴンガス、
ヘリウムガス等が適当である。 As the processing gas for performing the fluorination treatment, pure fluorine gas may be used, but diluted fluorine gas may also be used. In particular, when there is a risk that cutting of polymer molecules or crosslinking reactions may occur during fluorination treatment, depending on the type of vinylidene fluoride copolymer forming the raw material fiber structure and its resistance to fluorine gas, An appropriate concentration of fluorine gas diluted with an appropriate diluent gas should be selected. Generally, the concentration of fluorine gas in the processing gas is preferably 1% or more. The diluent gas may be one that is inert to both fluorine gas and the fiber structure made of vinylidene fluoride copolymer, such as nitrogen gas, argon gas,
Helium gas etc. are suitable.
フツ素化処理の温度は、用いるフツ化ビニリデ
ン共重合体の繊維構造体の種類、そのフツ素ガス
に対する耐性、フツ素ガスの濃度等により大きく
異なるが、通常は室温から200℃位までの範囲内
とされる。またフツ素化処理は、減圧下で行なつ
てもよいし加圧下で行なうこともできる。 The temperature for fluorination treatment varies greatly depending on the type of fiber structure of the vinylidene fluoride copolymer used, its resistance to fluorine gas, the concentration of fluorine gas, etc., but it is usually in the range from room temperature to around 200℃. considered to be within. Further, the fluorination treatment may be performed under reduced pressure or under increased pressure.
フツ素化処理の手段は、バツチ方式でもフロー
方式でもよく、また所期のフツ素化度の増加を得
るために、フツ素化処理を一度に行なつてもよい
しあるいは数回に分けて順次フツ素化度を上げる
ようにして行なつてもよい。 The means of fluorination treatment may be either a batch method or a flow method, and in order to obtain the desired increase in the degree of fluorination, the fluorination treatment may be performed at once or divided into several times. The degree of fluorination may be increased sequentially.
上述のフツ素化処理は、これによつて原料繊維
構造体を形成している重合体のフツ素化度を２〜
40％増加させるものであることが必要であり、フ
ツ素化度の増加は特に４〜25％であることが好ま
しい。ここに「フツ素化度」とは重合体のエチレ
ン単位における水素原子がフツ素原子によつて
今、原料繊維構造体の重合体におけるエチレン
単位の平均分子量をＭ、フツ素化処理前の重合体
の重量をW0、フツ素化処理後の重合体の重量を
Ｗとするとき、エチレン単位（―CH2−CH2）―にお
ける４個の水素原子のうちのｘ個がフツ素原子に
より置換されたとすると、エチレンを基礎とした
ときのエチレン単位の重量増加分について、次式
(1)が成立する。 The above-mentioned fluorination treatment increases the degree of fluorination of the polymer forming the raw material fiber structure from 2 to 2.
It is necessary that the degree of fluorination is increased by 40%, and it is particularly preferable that the increase in the degree of fluorination is from 4 to 25%. Here, "degree of fluorination" means that the hydrogen atoms in the ethylene units of the polymer are replaced by fluorine atoms. When the weight of the combined product is W 0 and the weight of the polymer after fluorination treatment is W, x of the four hydrogen atoms in the ethylene unit (-CH 2 - CH 2 )- are due to fluorine atoms. Assuming that the substitution is made, the weight increase of the ethylene unit when based on ethylene is calculated by the following formula:
(1) holds true.
（19−１）ｘ＝（M′−28） ……(1)
この式(1)において、左辺の19はフツ素の原子
量、１は水素の原子量を表わし、右辺のM′はフ
ツ素化処理によつて増加したエチレン単位の平均
分子量、28はエチレンの分子量を表わす。而して
M′＝MW／W0であるから、結局次式(2)が成立す
る。 (19-1) x = (M'-28) ...(1) In this formula (1), 19 on the left side represents the atomic weight of fluorine, 1 represents the atomic weight of hydrogen, and M' on the right side represents the atomic weight of fluorine. The average molecular weight of ethylene units increased by the treatment, 28, represents the molecular weight of ethylene. Then
Since M′=MW/W 0 , the following equation (2) holds true.
ｘ＝１／18（MW／W0−28） ……(2)
従つて、フツ素化処理後の重合体のフツ素化度
はx/4となる。 x=1/18 (MW/W 0 -28) ...(2) Therefore, the degree of fluorination of the polymer after the fluorination treatment is x/4.
またフツ素化処理は、増加されたフツ素化度の
値が75％を越えるものであつてはならない。 Furthermore, the fluorination treatment must not increase the degree of fluorination by more than 75%.
仮にフツ化ビニリデン共重合体の繊維構造体を
完全にフツ素化して最終フツ素化度を100％にし
たとすると、繊維構造体の物質は四フツ化エチレ
ン樹脂に変化してしまう。しかしこの物質は、ポ
リ四フツ化エチレン鎖の分子間力の欠除に帰因し
て実用上強度が全くなく、指でつまむだけでも破
砕する程度のもので到底実用に供することができ
ない。 If the fiber structure of vinylidene fluoride copolymer were to be completely fluorinated to have a final degree of fluorination of 100%, the substance of the fiber structure would change to tetrafluoroethylene resin. However, this material has no practical strength at all due to the lack of intermolecular force in the polytetrafluoroethylene chains, and it can only be crushed by pinching it with fingers, so it cannot be put to practical use.
本発明は以上のような方法であるから、フツ素
化処理においてはフツ素ガスを接触させるため、
原料繊維構造体はその表面、特に結晶化していな
い無定形部分から優先的に選択的にフツ素化され
るようになるが、原料繊維構造体の繊維体の繊維
径が1μm〜５mmであり、かつ当該繊維構造体を形
成しているフツ化ビニリデン共重合体のフツ素化
度をその値が75％を越えない範囲において２〜40
％増加せしめられるため、得られるフツ素樹脂繊
維構造体を構成する繊維体においては、その表面
部分のフツ素化度がその内部のフツ素化度より高
い状態となり、従つて、後述する実施例の説明か
らも明かなように、全体として同一のフツ素化度
を有するフツ素樹脂の繊維構造体に比して、遥か
に大きな耐溶剤性を有するものとなる。しかも当
該繊維構造体は、表面部分はフツ素化度が高くて
も内部はフツ素化度が低い状態のものであるので
機械的強度が大幅に低下するようなことはなく、
実用上十分な強度を有することができる。本発明
におけるフツ素化処理において、フツ素化度の増
加が２％未満では以上のような効果を確実に得る
ことができず、またフツ素化度の増加が40％を越
えるようになると、仮に全体のフツ素化度が75％
以下であつても、表面における脆弱な高フツ素化
度部分の厚さが大きくなるために機械的強度が低
下し、実用上無用なものとなるおそれが大きい。
そして、フツ素化処理に用いられるフツ素ガスの
酸素濃度が１重量％を越える場合には、酸素がフ
ツ化ビニリデン共重合体の高分子体を酸化切断し
て−COFの形の末端を形成するようになるため、
所期の目的を十分に達成することができない。
Since the present invention is a method as described above, in the fluorination treatment, in order to contact with fluorine gas,
The raw material fiber structure is preferentially and selectively fluorinated from its surface, especially from the non-crystallized amorphous portion, but when the fiber diameter of the fiber body of the raw material fiber structure is 1 μm to 5 mm, and the degree of fluorination of the vinylidene fluoride copolymer forming the fiber structure is 2 to 40 within a range that does not exceed 75%.
%, in the fibers constituting the obtained fluoroplastic fiber structure, the degree of fluorination on the surface portion thereof is higher than the degree of fluorination on the inside thereof. As is clear from the explanation, the fiber structure has much greater solvent resistance than a fluororesin fiber structure having the same degree of fluorination as a whole. Furthermore, the fiber structure has a high degree of fluorination on the surface, but a low degree of fluorination on the inside, so the mechanical strength does not decrease significantly.
It can have practically sufficient strength. In the fluorination treatment of the present invention, if the increase in the degree of fluorination is less than 2%, the above effects cannot be reliably obtained, and if the increase in the degree of fluorination exceeds 40%, If the overall fluoridation degree is 75%
Even if it is less than that, the thickness of the fragile highly fluorinated portion on the surface will increase, so the mechanical strength will decrease, and there is a large possibility that it will become practically useless.
When the oxygen concentration of the fluorine gas used for fluorination treatment exceeds 1% by weight, oxygen oxidizes and cleaves the polymer of the vinylidene fluoride copolymer to form terminals in the form of -COF. In order to be able to
The intended purpose cannot be fully achieved.
更に本発明においては、原料繊維構造体として
は成型性の良好なフツ化ビニリデン共重合体のも
のを用いるため、有利な溶融押出成型法を利用し
て、所要の形態を有する透明で非多孔質の繊維構
造体を製造することができ、しかもフツ素化処理
は当該原料繊維構造体の形態については何ら悪影
響を与えずまた着色させるようなこともないの
で、結局所望の形態で着色もない非多孔質で既述
のように耐溶剤性の抜群に大きいフツ素樹脂繊維
構造体を得ることができる。また耐溶剤性の大き
い四フツ化エチレン樹脂は他の樹脂、金属等と融
着しにくいものであるが、フツ化ビニリデン共重
合体はそのような融着が比較的容易であるので、
本発明方法において、フツ化ビニリデン共重合体
より成る繊維から得られる織布、編物、不織布等
を金属、プラスチツク等の基材に一体的に融着し
て積層体としたものを原料繊維構造体として用
い、これをフツ素化処理することによつて耐溶剤
性の大きい積層体を容易に製造することができ
る。 Furthermore, in the present invention, since a vinylidene fluoride copolymer with good moldability is used as the raw material fiber structure, an advantageous melt extrusion method is used to create a transparent, non-porous structure having the desired morphology. Moreover, the fluorination treatment does not have any adverse effect on the morphology of the raw fiber structure and does not cause it to become colored. It is possible to obtain a fluororesin fiber structure that is porous and has excellent solvent resistance as described above. In addition, ethylene tetrafluoride resin, which has high solvent resistance, is difficult to fuse with other resins, metals, etc., but vinylidene fluoride copolymer is relatively easy to fuse with.
In the method of the present invention, the raw material fiber structure is a laminate obtained by integrally fusing woven fabrics, knitted fabrics, nonwoven fabrics, etc. obtained from fibers made of vinylidene fluoride copolymer to a base material such as metal or plastic. A laminate with high solvent resistance can be easily produced by using this as a fluorination treatment.
本発明方法においては、以上のように原料繊維
構造体の形態がそのまま保存されるので、最終的
に織布等の繊維の二次加工品を得るときには、予
めフツ化ビニリデン共重合体より成る織布を作成
してこれをフツ素化処理するようにしてもよい
が、予めフツ化ビニリデン共重合体の繊維をフツ
素化処理し、その後加工して織布を作製するよう
にしてもよい。 In the method of the present invention, as described above, the form of the raw material fiber structure is preserved as it is, so when a secondary processed product of fibers such as a woven fabric is finally obtained, a woven fabric made of vinylidene fluoride copolymer is prepared in advance. Although a cloth may be prepared and then fluorinated, it is also possible to fluoride the vinylidene fluoride copolymer fibers in advance and then process them to produce a woven cloth.
このように本発明によつて得られる耐溶剤性の
優れたフツ素樹脂繊維構造体は、耐溶剤性の要求
される布、漁網、パツキン材料等として有用で
ある。 As described above, the fluororesin fiber structure with excellent solvent resistance obtained by the present invention is useful as cloth, fishing nets, packing materials, etc. that require solvent resistance.
実施例 １
フツ化ビニリデン―四フツ化エチレン共重合体
（モル比90：10、平均分子量67.6）を溶融成型法
により成型して繊維径約25μmの原料繊維を作製
し、その0.6452gをモネル社製のリアクター内に
入れ、リアクター内を１×10-2mmHgに脱気した
後常圧となるまで、酸素0.5重量％を含む純度99
重量％以上のフツ素ガスを導入した。このフツ素
ガスの量は処理される繊維の量に対して大過剰の
量である。そしてリアクターの温度を30分間かけ
て昇温して60℃とし、昇温後１時間の間フツ素化
処理を行ない、フツ素樹脂繊維を得た。
Example 1 A raw material fiber with a fiber diameter of approximately 25 μm was produced by molding vinylidene fluoride-ethylene tetrafluoride copolymer (mole ratio 90:10, average molecular weight 67.6) by a melt molding method, and 0.6452 g of it was sold to Monel Co., Ltd. After the inside of the reactor was degassed to 1 x 10 -2 mmHg, the purity 99 containing 0.5% by weight of oxygen was heated until the pressure reached normal pressure.
More than % by weight of fluorine gas was introduced. This amount of fluorine gas is in large excess relative to the amount of fibers to be treated. Then, the temperature of the reactor was raised to 60°C over 30 minutes, and fluorination treatment was carried out for 1 hour after the temperature was raised to obtain fluororesin fibers.
フツ素化処理終了後直ちにフツ素樹脂繊維の重
量を測定したところ、0.6944gであり、この重量
増加により当該フツ素樹脂繊維のフツ素化度は62
％と計算された。そして、原料繊維のフツ素化度
は55％であるので、フツ素化処理によるフツ素化
度の増加は７％となる。 Immediately after the fluorination treatment was completed, the weight of the fluororesin fiber was measured and found to be 0.6944g, and due to this weight increase, the degree of fluorination of the fluororesin fiber was 62.
It was calculated as %. Since the degree of fluorination of the raw material fiber is 55%, the increase in the degree of fluorination due to the fluorination treatment is 7%.
上記の原料繊維はジメチルホルムアミド及びジ
メチルアセトアミドの何れに対しても温度60℃で
完全に溶解するものであつたが、フツ素化処理さ
れたフツ素樹脂繊維は、同一の条件で何れの溶媒
にも全く溶解せず、耐溶剤性が顕著に大きいもの
であることが明らかとなつた。 The raw material fibers mentioned above were completely soluble in both dimethylformamide and dimethylacetamide at a temperature of 60°C, but the fluorinated fluororesin fibers were completely soluble in both dimethylformamide and dimethylacetamide under the same conditions. It was revealed that the solvent did not dissolve at all, and the solvent resistance was significantly high.
更に、得られたフツ素樹脂繊維の引張強度を引
張試験機「テンシロン」により、引張スピード10
mm／min（温度21℃）で測定したところ、16Kg／
mm2であつて実用上十分大きな強度を保有すること
が確認された。 Furthermore, the tensile strength of the obtained fluororesin fiber was measured using a tensile tester "Tensilon" at a tensile speed of 10.
When measured at mm/min (temperature 21℃), it was 16Kg/min.
mm 2 and was confirmed to have a strength sufficiently large for practical use.
Claims (1)
ツ化ビニリデン共重合体より成り、その繊維径が
1μm〜５mmである繊維体よりなる繊維構造体を、
酸素濃度が１重量％以下であるフツ素ガスに接触
させてフツ素化処理することにより、当該繊維構
造体を形成しているフツ化ビニリデン共重合体の
フツ素化度をその値が75％を越えない範囲におい
て２〜40％増加せしめ、繊維構造体を構成する繊
維体の表面部分のフツ素化度が内部のフツ素化度
より高い状態とすることを特徴とするフツ素樹脂
繊維構造体の製造方法。1 Consists of a vinylidene fluoride copolymer containing 50 mol% or more of vinylidene fluoride, whose fiber diameter is
A fibrous structure consisting of a fibrous body with a size of 1 μm to 5 mm,
The degree of fluorination of the vinylidene fluoride copolymer forming the fiber structure can be increased to 75% by fluorination treatment by contacting with fluorine gas having an oxygen concentration of 1% by weight or less. A fluororesin fiber structure characterized in that the degree of fluorination of the surface portion of the fiber body constituting the fiber structure is higher than the degree of fluorination of the inside. How the body is manufactured.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18642584A JPS6170072A (en) | 1984-09-07 | 1984-09-07 | Production of fluorocarbon resin fiber structure |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18642584A JPS6170072A (en) | 1984-09-07 | 1984-09-07 | Production of fluorocarbon resin fiber structure |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6170072A JPS6170072A (en) | 1986-04-10 |
| JPH0551701B2 true JPH0551701B2 (en) | 1993-08-03 |
Family
ID=16188197
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP18642584A Granted JPS6170072A (en) | 1984-09-07 | 1984-09-07 | Production of fluorocarbon resin fiber structure |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6170072A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR3011504B1 (en) * | 2013-10-04 | 2015-10-23 | Arkema France | TEXTILE ARTICLE IN PVDF |
| CN103642159A (en) * | 2013-11-11 | 2014-03-19 | 青岛佰众化工技术有限公司 | PVDF self-reinforced composite material |
| JP6090683B1 (en) * | 2016-11-09 | 2017-03-08 | 株式会社デュエル | Polyvinylidene fluoride monofilament and method for producing polyvinylidene fluoride monofilament |
-
1984
- 1984-09-07 JP JP18642584A patent/JPS6170072A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6170072A (en) | 1986-04-10 |
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