JPS63249716A - Production of fibrillated fiber and pulpy particle - Google Patents
Production of fibrillated fiber and pulpy particleInfo
- Publication number
- JPS63249716A JPS63249716A JP7747687A JP7747687A JPS63249716A JP S63249716 A JPS63249716 A JP S63249716A JP 7747687 A JP7747687 A JP 7747687A JP 7747687 A JP7747687 A JP 7747687A JP S63249716 A JPS63249716 A JP S63249716A
- Authority
- JP
- Japan
- Prior art keywords
- yarn
- weight
- blowing agent
- fibers
- temperature
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000000835 fiber Substances 0.000 title claims description 81
- 239000002245 particle Substances 0.000 title claims description 23
- 238000004519 manufacturing process Methods 0.000 title claims description 11
- 239000004604 Blowing Agent Substances 0.000 claims abstract description 40
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000005345 coagulation Methods 0.000 claims abstract description 26
- 230000015271 coagulation Effects 0.000 claims abstract description 26
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 21
- 239000004760 aramid Substances 0.000 claims abstract description 18
- 229920003235 aromatic polyamide Polymers 0.000 claims abstract description 18
- 239000002904 solvent Substances 0.000 claims abstract description 17
- 229920000642 polymer Polymers 0.000 claims abstract description 15
- 238000005406 washing Methods 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 12
- 239000004088 foaming agent Substances 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 5
- 238000005520 cutting process Methods 0.000 claims description 4
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 2
- 239000004156 Azodicarbonamide Substances 0.000 claims 1
- XOZUGNYVDXMRKW-AATRIKPKSA-N azodicarbonamide Chemical group NC(=O)\N=N\C(N)=O XOZUGNYVDXMRKW-AATRIKPKSA-N 0.000 claims 1
- 235000019399 azodicarbonamide Nutrition 0.000 claims 1
- 125000004432 carbon atom Chemical group C* 0.000 claims 1
- 239000000126 substance Substances 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 32
- 230000001112 coagulating effect Effects 0.000 abstract description 5
- 239000000243 solution Substances 0.000 description 23
- 238000009987 spinning Methods 0.000 description 13
- 238000005470 impregnation Methods 0.000 description 12
- 206010061592 cardiac fibrillation Diseases 0.000 description 7
- 230000002600 fibrillogenic effect Effects 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 238000012545 processing Methods 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 6
- 238000010008 shearing Methods 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 229920003366 poly(p-phenylene terephthalamide) Polymers 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 241000209094 Oryza Species 0.000 description 3
- 235000007164 Oryza sativa Nutrition 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 239000002954 polymerization reaction product Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000013557 residual solvent Substances 0.000 description 3
- 235000009566 rice Nutrition 0.000 description 3
- WRDNCFQZLUCIRH-UHFFFAOYSA-N 4-(7-azabicyclo[2.2.1]hepta-1,3,5-triene-7-carbonyl)benzamide Chemical compound C1=CC(C(=O)N)=CC=C1C(=O)N1C2=CC=C1C=C2 WRDNCFQZLUCIRH-UHFFFAOYSA-N 0.000 description 2
- ICGLPKIVTVWCFT-UHFFFAOYSA-N 4-methylbenzenesulfonohydrazide Chemical compound CC1=CC=C(S(=O)(=O)NN)C=C1 ICGLPKIVTVWCFT-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- -1 etc. Substances 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 238000005187 foaming Methods 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000012779 reinforcing material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 235000002639 sodium chloride Nutrition 0.000 description 2
- MHSKRLJMQQNJNC-UHFFFAOYSA-N terephthalamide Chemical compound NC(=O)C1=CC=C(C(N)=O)C=C1 MHSKRLJMQQNJNC-UHFFFAOYSA-N 0.000 description 2
- LXEJRKJRKIFVNY-UHFFFAOYSA-N terephthaloyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)C=C1 LXEJRKJRKIFVNY-UHFFFAOYSA-N 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 description 1
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 1
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 150000004984 aromatic diamines Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000010009 beating Methods 0.000 description 1
- 238000010504 bond cleavage reaction Methods 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 235000010216 calcium carbonate Nutrition 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 235000011148 calcium chloride Nutrition 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 239000002783 friction material Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000007602 hot air drying Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000000386 microscopy Methods 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
- 150000002832 nitroso derivatives Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229920003190 poly( p-benzamide) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 239000012783 reinforcing fiber Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Landscapes
- Artificial Filaments (AREA)
- Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)
- Paper (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、耐熱性1機械的特性に優れたフィブリル化線
維及び・ぐルプ状粒子を製造する方法に関するものであ
シ、更に詳しくは、樹脂補強材、摩擦材1合成紙原料等
の用途に好適な、高度にフィブリル化した繊維及び・母
ルプ状粒子を工業的に製造する方法に関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a method for producing fibrillated fibers and gruppy particles having excellent heat resistance and mechanical properties. This invention relates to a method for industrially producing highly fibrillated fibers and matrix particles suitable for use as resin reinforcing materials, friction material 1 synthetic paper raw materials, etc.
/ IJ (p−フェニレンテレフタルアミド>VC代
表される・母う配向芳香族ポリアミドは、耐熱性。/IJ (p-phenylene terephthalamide>VC typified by matrix oriented aromatic polyamide is heat resistant.
機械的特性、電気的特性等に優れ、繊維、フィルム、シ
ート状物、・臂ルプ状粒子等として有用であることが知
られている。It has excellent mechanical properties, electrical properties, etc., and is known to be useful as fibers, films, sheet-like materials, and lap-like particles.
例えば、特公昭50−8478号公報には、 /fう系
芳香族ポリアミドの光学異方性溶液から得られる高強度
高モジュラスの繊維について記載されておシ、また/や
う系芳香族ポリアミドの光学異方性ドープから直接得ら
れるフィブリッドについても記載されている。For example, Japanese Patent Publication No. 50-8478 describes a fiber with high strength and high modulus obtained from an optically anisotropic solution of an aromatic polyamide. Fibrids obtained directly from anisotropic doping have also been described.
また、・々う配向芳香族ポリアミドの光学異方性ドープ
から、−立腹状物あるいはモノフィラメントを得て1次
いで該成形物を機械的剪断力によってフィブリル化した
・9ルプ状粒子を得る方法が開示されている。しかしな
がら、該公報の開示は。Furthermore, a method for obtaining 9-lupe-shaped particles is disclosed, in which a 9-belt-shaped material or monofilament is obtained from an optically anisotropic dope of a 2-oriented aromatic polyamide, and then the formed product is fibrillated by mechanical shearing force. has been done. However, the disclosure of this publication is.
密度が小さく脆くて崩れ易い膜状物やモノフィラメント
を出発物にすることに限られておシ、シかもそのフィブ
リル化の程度は必ずしも満足できる水準でないことが判
明した。また、該公報にかかる出願に対する特許異議申
立事件における答弁書に開示されているように、光学異
方性ドープからマルチフィラメントを一旦つ〈シ、それ
を叩尊することくよってフィブリル化したI4ルプ状粒
子を製造することも可能であるが、かかる方法によって
得られる・臂ルプ状粒子においても機械的剪断力による
故か、フィラメントの表面部分での毛羽立ち程度のもの
が多く、あるいは、フィブリル化の程度を高めるために
、充分処叩解、スリ潰し等の機械的剪断力を加えること
によりて粒子径の小さなパルプ状粒子となシ、充分な性
能を発揮し得ないものである。It has been found that the degree of fibrillation is not necessarily at a satisfactory level even though it is limited to starting materials such as film-like materials or monofilaments, which have low density and are brittle and easily disintegrated. In addition, as disclosed in the answer to the patent opposition case against the application related to the publication, I4 fibers are made from optically anisotropic dope and then fibrillated by removing the multifilament from the optically anisotropic dope. It is also possible to produce fiber-shaped particles, but even in the fiber-shaped particles obtained by this method, there are many cases where the surface portion of the filament is only fluffy, probably due to mechanical shearing force, or there is no fibrillation. In order to improve the quality of the product, mechanical shearing force such as thorough beating or grinding must be applied to produce pulp-like particles with a small particle size, otherwise sufficient performance cannot be achieved.
上記、従来技術の現状に鑑み、本発明は、ノfルプ状粒
子の製造に極めて有用であシ、それ自体。In view of the above-mentioned current state of the prior art, the present invention is extremely useful for producing spherical particles, and as such.
補強材として有用な・ぐう配向芳香族ポリアミドのフィ
ブリル化繊維、及び高度にフィブリル化した好適な粒子
径を有する・!ルグ状粒子t−製造する方法を提供する
ものである。Fibrillated fibers of oriented aromatic polyamide useful as reinforcing materials and highly fibrillated with suitable particle sizes! A method for manufacturing rug-shaped particles is provided.
本発明は、上記目的を達成する為に、従来の機械的な剪
断力で繊維の外部からフィブリル化する方法に代わシ、
繊維の内部からの破砕力により、繊維全体に亘りて均一
にフィブリル化する方法につき鋭意検討を重ねた結果、
繊維内部に発泡剤を含浸させたのち、該発泡剤を発泡さ
せる化学的な反応を利用する方法に、よって、高度にフ
ィブリル化した繊維及び/4ルプ状粒子が得られること
を見出し、この知見をもとに更に研究を進め、本発明を
完成するに至ったものである。In order to achieve the above object, the present invention provides an alternative to the conventional method of fibrillating fibers from the outside using mechanical shearing force.
As a result of extensive research into a method of uniformly fibrillating the entire fiber using crushing force from within the fiber, we found that
We discovered that highly fibrillated fibers and /4 loop-shaped particles can be obtained by impregnating the inside of fibers with a blowing agent and then using a chemical reaction to foam the blowing agent. Based on this, further research was conducted and the present invention was completed.
即ち1本発明は、パラ配向芳香族ポリアミドを濃度97
〜101重量%の濃硫酸に、少くとも14重量%の?リ
マー濃度となるように溶解した光学異方性ドープを紡糸
口金より気体中に、ついで凝固浴中に押し出し、凝固時
または/および残存する硫酸系溶媒が対乾燥繊維に対し
て5重′に%以上の洗浄初期に凝固糸条から実質的に張
力を解放し、少くとも50重量%以上の水分を含む糸条
と1発泡剤を水と混和性のある溶媒に溶かした溶液とを
張力の実質的解放下に接触させて発泡剤を繊維中に、乾
燥繊維重量に基づいて少くとも0.5重量%以上となる
ように含浸させたのち該溶液から取り出し、ついで、乾
燥しつつまたは一旦該発泡剤の分解温度以下の温度で乾
燥したのち、該発泡剤の分解温度以上の温度に加熱する
ことを特徴とするフィブリル化繊維の製造法及びパラ配
向芳香族ポリアミドを濃度97〜101重i%の磯硫酸
に、少くとも14重量%のポリマー濃度となるように溶
解した光学異方性ドーグを紡糸口金より気体中に、つい
で凝固浴中に押し出し、凝固時または/および残存する
硫酸系溶媒が対乾燥繊維に対して5重量:%以上の洗浄
初期に凝固糸条から実質的に張力を解放し、少くとも5
0重t%以上の水分を含む糸条と1発泡剤を水と混和性
のある溶媒に溶かした溶液とを張力の実質的解放下に接
触させて発泡剤を繊維中に、乾燥繊維重量に基づいて少
くとも0.5重量%以上となるように含浸させたのち該
溶液から取出し、予め30w以下の長さに切断したのち
または切断に先立って、乾燥しつつ又は一旦該発泡剤の
分解温度以下の温度で乾燥したのち該発泡剤の分解温度
以上の温度に加熱することを特徴とするAlルプ状粒子
の製造法である。That is, 1 the present invention uses para-oriented aromatic polyamide at a concentration of 97%.
~101% by weight of concentrated sulfuric acid with at least 14% by weight of ? The optically anisotropic dope dissolved to a reamer concentration is extruded from a spinneret into a gas and then into a coagulation bath, and during coagulation and/or the remaining sulfuric acid solvent is reduced to 5% with respect to the dry fiber. At the initial stage of washing, the tension is substantially released from the coagulated thread, and a solution of the thread containing at least 50% by weight of water and a blowing agent dissolved in a water-miscible solvent is removed to substantially reduce the tension. The foaming agent is impregnated into the fibers in an amount of at least 0.5% by weight based on the weight of the dry fibers by contacting the fibers with a target, and then removed from the solution, and then while drying or once the foaming agent is impregnated into the fibers. A process for producing fibrillated fibers characterized by drying at a temperature below the decomposition temperature of the blowing agent and then heating to a temperature above the decomposition temperature of the blowing agent, and a method for producing fibrillated fibers comprising drying the fibrillated fiber at a temperature below the decomposition temperature of the blowing agent. Optically anisotropic Dogue dissolved in iso-sulfuric acid to a polymer concentration of at least 14% by weight is extruded from a spinneret into a gas and then into a coagulation bath, and during coagulation and/or the remaining sulfuric acid solvent is removed. Substantially relieves tension from the coagulated yarns at the initial stage of washing with a concentration of at least 5% by weight based on dry fibers;
A yarn containing water of 0% by weight or more and a solution of a blowing agent dissolved in a solvent miscible with water are brought into contact with each other under substantial release of tension to infuse the blowing agent into the fibers by the weight of the dry fibers. After impregnating the foaming agent to a concentration of at least 0.5% by weight based on the foaming agent, the foaming agent is taken out from the solution, cut into lengths of 30W or less, or before cutting, while drying or once the decomposition temperature of the foaming agent is reduced. This is a method for producing Al loop-like particles, which is characterized by drying at a temperature below and then heating to a temperature higher than the decomposition temperature of the blowing agent.
本発明でいう、ノヤラ配向芳香族ポリアミドとは。What is the Noyara-oriented aromatic polyamide referred to in the present invention?
アミド結合が芳香族環のパラ位又はそれに準じた配向位
(4,4’−ビフェニレン、1,5−ナフタレン。The amide bond is at the para position of the aromatic ring or at a similar orientation position (4,4'-biphenylene, 1,5-naphthalene).
2.6−リフタレンなどのような反対方向に同軸又は平
行位に延びる配向位)で結合されるぐシ返し単位から実
質的になるもので、例えば、ポ’J(p−フェニレンテ
レ7タルアミド)(以下PPTA(!:略称する。)、
ポリ(p−ベンズアミド)、Iす(4,4’−ベンズア
ニリドテレ7タルアミド)、ポIJ (p −フェニレ
ン−4,4′−ビフェニレンジヵル?ンアミド)、ポリ
(p−7エニレンー2,6−ナフタレンジカルゲンアミ
ド)等ポリパラ配向型又はパラ配向型に近い構造を有す
る芳香族ポリアミドを挙げることができる。これらのポ
リアミドは。2.6-rifthalene, etc., consisting essentially of repeating units bonded in coaxial or parallel orientations in opposite directions, such as p'J (p-phenylenetele 7-thalamide). (Hereinafter referred to as PPTA (!: abbreviated),
Poly(p-benzamide), Isu(4,4'-benzanilidetele-7talamide), Poly(p-phenylene-4,4'-biphenylene dicarbonamide), Poly(p-7enylene-2, Examples include aromatic polyamides having a polypara-oriented structure or a structure close to a para-oriented structure, such as 6-naphthalene dicargenamide). These polyamides.
芳香族ジアミンと芳香族ソカルゲン酸クロリドから従来
公知の低温溶液重合法で製造するのが好都合である。特
に/す(p−フェニレンテレタルアミr)は単純なモノ
マーから重合することが可能なので安価であり、工業的
見地から好ましい。It is convenient to produce it from an aromatic diamine and an aromatic socargenic acid chloride by a conventionally known low temperature solution polymerization method. In particular, /su (p-phenylene teretal amyl) can be polymerized from simple monomers, is inexpensive, and is therefore preferred from an industrial standpoint.
本発明において、/4う系芳香族ポリアミドの重合度は
、あまシ低いと機械的性質の良好な・ヤルプ粒子が得ら
れなくなるため、好ましくは2.5以上、より好ましく
は3.5以上の対数粘度η1nh(硫酸100m1にポ
リ−f−0,5,9を溶解して30℃で測定した値)を
与える重合度のものが選ばれる。In the present invention, the degree of polymerization of the /4-based aromatic polyamide is preferably 2.5 or more, more preferably 3.5 or more, since if it is too low, Yalp particles with good mechanical properties cannot be obtained. A polymer having a degree of polymerization that gives a logarithmic viscosity η1nh (a value measured at 30° C. by dissolving poly-f-0,5,9 in 100 ml of sulfuric acid) is selected.
本発明においては、繊維形成のために、パラ配向芳香族
ポリアミドを硫酸に溶解した光学異方性ドーグが用いら
れる。In the present invention, optically anisotropic DOG, which is prepared by dissolving para-oriented aromatic polyamide in sulfuric acid, is used for fiber formation.
この際用いられる硫酸の濃度は97〜101重i−%で
重量ことが必要である。97重量%以下の濃度では、パ
ラ配向芳香族ポリアミドに対する溶解能が低下し、優れ
た物性の繊維を得るのが困難となる。一方101重量%
以上においても同様に。The concentration of sulfuric acid used in this case must be 97 to 101% by weight. If the concentration is less than 97% by weight, the ability to dissolve para-oriented aromatic polyamide decreases, making it difficult to obtain fibers with excellent physical properties. On the other hand, 101% by weight
The same applies to the above.
ノ母う配向芳香族ポリアミドの溶解力は低下するので好
ましくない。The solubility of the oriented aromatic polyamide is undesirable because it lowers its solvency.
又、ドープ中のポリマー濃度は14重量%以上が必要で
ある。濃度が14重量%以下では光学異方性ドープとす
ることが難かしいぼかシでなく。Further, the polymer concentration in the dope needs to be 14% by weight or more. When the concentration is 14% by weight or less, it is difficult to form an optically anisotropic dope without blurring.
ドープの粘度が高くなり操作性を著しく低下させる。一
方高すぎる濃度、例えば22重#%以上では、ドーグの
粘度が高くなりすぎるため、ドープ温度を高く設定する
必要があシ、紡糸操作上困難を伴いやすい。従って、高
過ぎないよう選ばれるべきである。紡糸用ドーグのポリ
マー濃度は最も好ましくは16〜20重量%である。The viscosity of the dope increases, significantly reducing operability. On the other hand, if the concentration is too high, for example, 22 wt.% or more, the viscosity of the dope becomes too high, which necessitates setting the dope temperature high, which tends to cause difficulties in the spinning operation. Therefore, it should be chosen not to be too expensive. The polymer concentration of the spinning doug is most preferably between 16 and 20% by weight.
光学異方性の確認は、スライドグラス上にドープを薄く
伸ばしたプレパラートを、偏光顕微鏡の直交ニコルの間
に入れると、直交ニコルの暗視野が明視野に変化するこ
とにより行なわれるが、ドープを溶解する際に剪断力下
で配向して光を乱反射し、金属様または真珠様の光沢が
見られることによっても確められる。Optical anisotropy can be confirmed by placing a thin dope-stretched preparation on a slide glass between crossed nicols of a polarizing microscope, and the dark field of the crossed nicols changes to bright field. It can also be confirmed by the fact that it orients itself under shearing force during melting and reflects light diffusely, producing a metallic or pearl-like luster.
ドーグの調製および使用に当っては、上記ポリマー濃度
範囲においては、ドープは室温付近では固化する場合が
あるため、室温から80℃程度の温度で取扱えばよい。When preparing and using DOG, in the above polymer concentration range, the dope may solidify near room temperature, so it may be handled at a temperature from room temperature to about 80°C.
しかしながら、ポリマーの分解を可及的に回避する観点
から、固化しない限シなるべく低い温度を選ぶことが好
ましい。However, from the viewpoint of avoiding decomposition of the polymer as much as possible, it is preferable to select a temperature as low as possible as long as it does not solidify.
このようにして調製され九紡糸用ドープは、上記のポリ
マー濃度、ドープ温度範囲で光学的異方性を有すること
が認められる。かかるドープは、紡糸口金を通して一旦
空気中に押し出され、ついで凝固浴中に導ひかれる。It is recognized that the nine-spinning dope prepared in this manner has optical anisotropy within the above polymer concentration and doping temperature ranges. The dope is once extruded into the air through a spinneret and then introduced into a coagulation bath.
凝固浴中の凝固しつつある、または凝固した糸条はほと
んど引き伸ばしが行なわれないため、吐出されたドープ
は口金直下の空気中において、引き取りのドラフト(引
き伸ばし)がかかり、引き伸ばされる。この引き伸ばし
におつて、引き伸ばし率が低いと充分に繊維の物性例え
ば強度、初期モジュラスを高めることが出来ず、また、
高すぎるとこの間でドープ流が切断されるため1通常は
。Since the coagulating or coagulated yarn in the coagulation bath is hardly stretched, the discharged dope is drawn in the air directly below the nozzle and is stretched. In this stretching, if the stretching rate is low, the physical properties of the fiber, such as strength and initial modulus, cannot be sufficiently increased;
If the temperature is too high, the dope flow will be cut off between these points.
引き伸はし率は4〜15倍、好ましくは5〜12倍の間
に設定される。ドーグの引き伸ばしが行なわれる空気中
の長さ、部ちドープの吐出される紡糸用口金の面から凝
固浴液表面までの距離は1通常約1〜50yntx、好
適には3〜20i111にの範囲に設定されるが、これ
に限定されるものではない。具体的には、紡糸用口金か
らのドーグの吐出速度、上記のドラフト率、フィラメン
トの融合機会を少くすること等を考慮して決定されれば
よい。The stretching ratio is set between 4 and 15 times, preferably between 5 and 12 times. The length in the air where the dope is stretched, the distance from the surface of the spinning nozzle where the dope is discharged to the surface of the coagulation bath is usually in the range of about 1 to 50 yntx, preferably 3 to 20 intx. set, but is not limited to this. Specifically, it may be determined by taking into consideration the discharge speed of Dogue from the spinning nozzle, the above-mentioned draft rate, reducing the chance of filament fusion, and the like.
ドープの吐出に際して用いられる紡糸用口金の孔径は、
製造しようとする繊維の太さ、及び上記のドラフト率の
設定により選定されるべきであつて、通常は0.05〜
0.10mの範囲のものが選択されるが、これに限られ
るものではない。更に紡糸用口金に設けられる孔数は、
製造しようとする繊維の構成によって決定されればよく
、特に本発明法を実施するに当って限定されるものでは
ない。The pore diameter of the spinning nozzle used for discharging the dope is
It should be selected depending on the thickness of the fiber to be manufactured and the above draft rate setting, and is usually 0.05~
A range of 0.10 m is selected, but the range is not limited to this. Furthermore, the number of holes provided in the spinning nozzle is
It may be determined depending on the structure of the fiber to be manufactured, and is not particularly limited when carrying out the method of the present invention.
本発明において、紡糸用口金と凝固浴が分離されている
ことが、密度が大きく(つま#)コイドの少なく)1機
械的性質のすぐれた繊維を得るうえで重要である。In the present invention, it is important to separate the spinning nozzle and the coagulation bath in order to obtain fibers with high density (fewer coids) and excellent mechanical properties.
本発明の実施に当って、凝固液としては1通常水または
濃度70%までの硫酸水溶液が有利に用いられる。しか
しながら1例えば、塩化アンモニウム、塩化カルシウム
、炭酸カルシウム、塩化ナトリウム、硫酸ナトリウム等
の如き塩、もしくはそれらの混合物の水溶液、アンモニ
ア水溶液、水酸化ナトリウム水溶液、または、メタノー
ル、エタノール、エチレングリコールの如き有機溶媒も
しくはこれらの水溶液等であってもよく、特に限定され
るものではない。In carrying out the invention, water or an aqueous sulfuric acid solution having a concentration of up to 70% is preferably used as the coagulating liquid. However, 1, for example, an aqueous solution of a salt such as ammonium chloride, calcium chloride, calcium carbonate, sodium chloride, sodium sulfate, etc., or a mixture thereof, an aqueous ammonia solution, an aqueous sodium hydroxide solution, or an organic solvent such as methanol, ethanol, ethylene glycol, etc. Alternatively, it may be an aqueous solution of these, and is not particularly limited.
凝固液の温度は、一般には15℃以下、より好ましくは
10℃以下に保持されることがよい。何故なら、凝固浴
温度の低り方が、内部に生成するボイドの童が少なくな
シ、密度が大きくなって。The temperature of the coagulating liquid is generally kept at 15°C or lower, more preferably at 10°C or lower. This is because the lower the temperature of the coagulation bath, the less voids are generated inside and the density becomes larger.
強度などの機械的性能も向上するからである。なお、凝
固浴温度の下限は特に限定されず、該凝固浴の組成によ
りて決まる融点(凝固点)までである。This is because mechanical performance such as strength is also improved. Note that the lower limit of the coagulation bath temperature is not particularly limited, and is up to the melting point (freezing point) determined by the composition of the coagulation bath.
凝固浴より引出された繊維は、従来の方法と同様の方法
により、水や水性アルカリにて溶剤や凝固浴液が実質的
に中和、洗浄除去される。The fibers pulled out from the coagulation bath are substantially neutralized and washed with water or aqueous alkali to remove the solvent and coagulation bath liquid by a method similar to the conventional method.
本発明の方法においては、凝固時残rR量の多い洗浄工
程で繊維に作用している張力を解放する。In the method of the present invention, the tension acting on the fibers is released during the washing step in which the amount of rR remaining at the time of coagulation is large.
このことは、密度が大きく従って緻密な構造をとってい
るにもかかわらず1含浸の効果を大きくする上で大切で
ある。その理由は、未だ詳しくは解明されていないが、
水で膨潤されているrル状の繊維の分子鎖の配向性、結
晶の生成などと微妙な関係を有しているものと推定され
る。This is important in increasing the effect of impregnation despite the high density and therefore dense structure. The reason for this has not yet been elucidated in detail, but
It is presumed that there is a delicate relationship with the orientation of the molecular chains of the ripple-shaped fibers swollen with water, the formation of crystals, etc.
繊維の製造において、凝固時に、その糸条から張力を実
質的に解放する仁とは、工業的な生産方法・条件下では
困難であるため凝固浴出の糸条の洗浄工程で、糸条を実
質的に無緊張下に水洗することが好ましい。このような
方法としては工業的には凝固浴の残存溶媒含有糸条をネ
ットコンベヤー上に振り込んで、ここで無緊張下に洗浄
するのが好都合である。凝固糸命物から張力を解放する
時期は、該糸条物中の残存溶媒量が対乾燥繊維比5重量
5以上、より好ましくは10重量%以上であるときであ
ることが、緻密繊維に発泡剤の含浸を有効とならしめる
ため肝要である。逆に、5重量%より少ない残存溶媒に
なるまで凝固、洗浄を進めてからはじめて張力を解放し
たのでは、含浸が十分に行きわたらない。In the production of fibers, it is difficult to effectively release the tension from the yarn during coagulation under industrial production methods and conditions. It is preferable to wash with water under substantially no tension. For such a method, it is industrially convenient to transfer the yarn containing the residual solvent in the coagulation bath onto a net conveyor and wash it there under no tension. The time to release the tension from the coagulated filament is when the amount of residual solvent in the filament is at least 5% by weight relative to the dry fiber, more preferably at least 10% by weight. This is important in order to make the impregnation with the agent effective. On the other hand, if the tension is released only after coagulation and washing have proceeded until the residual solvent is less than 5% by weight, the impregnation will not be sufficient.
凝固した繊維糸条は、前記凝固状態のときに適尚な引取
りロール等の装置を介して、紡浴中より取出され、振込
み装置により処理のためコンベヤー上に振落される。The coagulated fiber threads are taken out of the spinning bath in the coagulated state via a suitable device such as a take-off roll, and are shaken off by a transfer device onto a conveyor for processing.
処理コンベヤー上に堆積された糸山は、コンベヤーと共
に移動し、水洗工程に導かれ、溶媒を糸条から除いた後
、含浸処理工程で発泡剤の含浸が行われる。The yarn pile deposited on the treatment conveyor moves with the conveyor and is led to a water washing step to remove the solvent from the yarn, and then impregnated with a blowing agent in an impregnation treatment step.
水洗工程においては、好ましくは、水洗水は。In the washing step, preferably the washing water is
孔明き板よりシャワー状に、または噴霧ノズルより霧状
に、またはブラシ状の多数本の繊維に沿って、糸山上に
供給され、糸山中に含まれる凝固液を洗浄し、処理コン
ベヤーを貫流して該コンベヤー下に排出されるが、ここ
で、水洗水の供給方法は、本発明を実施する上で制限さ
れるものではなく、上記の例に限定されるものではない
。The coagulation liquid contained in the yarn pile is supplied onto the yarn pile in a shower form from a perforated plate, in a mist form from a spray nozzle, or along a large number of brush-like fibers, and then flows through a processing conveyor. However, the method of supplying the washing water is not limited in carrying out the present invention, and is not limited to the above example.
水洗きれた糸山状の糸条は、実質的に張力を解放した状
態で乾燥させることなく、少くとも50重量%以上の水
分を含有させたまま保持し、発泡剤を含む溶液と接触さ
せなければならない。水分量が50重量%未満ではいわ
ゆる生乾きの状態であシ、含浸剤を含有する溶液からの
繊維内部への拡散速度が著しく低下し、実用的な量を含
浸させることができない。The thread pile-like thread that has been washed with water must be kept in a water content of at least 50% by weight without being dried in a state where the tension is substantially released, and it must be brought into contact with a solution containing a blowing agent. No. If the moisture content is less than 50% by weight, the fiber is in a so-called half-dry state, and the rate of diffusion from the solution containing the impregnating agent into the interior of the fiber decreases significantly, making it impossible to impregnate a practical amount.
含浸の方法は水洗と同様の手段によって処理コンベヤー
上で糸山に発泡剤を含む溶液′t−噴精、シャワーリン
グ等により供給するか、コンベヤーごと処理液に浸漬す
ることにより行なわれる。The method of impregnation is carried out by supplying a solution containing a foaming agent to the thread pile on the processing conveyor by spraying, showering, etc., by the same means as washing with water, or by immersing the whole conveyor in the processing liquid.
本発明において用いられる発泡剤は、特に限定されるも
のではなく、加熱によって例えば酸素。The blowing agent used in the present invention is not particularly limited, and can be heated, for example, with oxygen.
窒素、二酸化炭素等のガスを発生するものであればよく
、具体的には1例えば重炭酸ソーダ、炭酸アンモニウム
などの無機系発泡剤、主に窒素ガスを主成分として発泡
させる有機系のアゾ化合物。Any foaming agent that generates gas such as nitrogen or carbon dioxide may be used. Specifically, for example, inorganic foaming agents such as sodium bicarbonate and ammonium carbonate, and organic azo compounds that foam mainly with nitrogen gas as a main component.
ニトロソ化合物、スルホニルヒドラジド化合物等があげ
られるが、このうち、アゾビスニトリル化合物
数5以下のアルキル基又はシクロヘキシル基である)、
スルホニルヒドラジド化合物(R−5o2NH−NH2
)は1発泡のコントロールが容易であること、取扱いが
容易であること等から特に好ましく用いられる。Examples include nitroso compounds, sulfonyl hydrazide compounds, etc.; among these, azobisnitrile compounds (having 5 or less alkyl groups or cyclohexyl groups),
Sulfonyl hydrazide compound (R-5o2NH-NH2
) is particularly preferably used because it is easy to control foaming and easy to handle.
本発明において、かかる発泡剤は水に混和性のある溶媒
に溶解された溶液として用いられることが重要である。In the present invention, it is important that the blowing agent is used as a solution dissolved in a water-miscible solvent.
水と混和性のない溶媒に溶解した溶液では、水分を50
重量%以上含有する糸条と接触した際、充分に繊維中に
拡散が行われず、その結果、高度なフィブリル化が難か
しくなるか、又は、拡散の為に長時間’tiし、効率的
な処理が行えなくなるからである。ここでいう水と混和
性のある溶媒とは、水はもちろんのこと、水に少くとも
5重量%以上溶解する溶媒をいい、例えばメタノール、
エタノール等のアルコール類、エーテル類、ジメチルホ
ルムアミド、N−メチルピロリドン等々のアミド系溶媒
、ジメチルスルホキシド等などが用いられる。又、特別
な場合として、それ自体は水と混和性のない溶媒であり
ても乳化剤。For solutions dissolved in water-immiscible solvents, the water content is reduced by 50%.
When it comes into contact with yarn containing more than % by weight, it may not be sufficiently diffused into the fibers, making it difficult to form a high degree of fibrillation, or it may take a long time for diffusion to become efficient. This is because processing cannot be performed. The term "solvent miscible with water" as used herein refers not only to water but also to a solvent that dissolves at least 5% by weight in water, such as methanol,
Alcohols such as ethanol, ethers, amide solvents such as dimethylformamide and N-methylpyrrolidone, dimethyl sulfoxide, and the like are used. In special cases, emulsifiers may also be used as solvents that are not themselves miscible with water.
界面活性剤等により分散液として用いられることもあシ
、本発明法として有用である。It is also useful for the method of the present invention to use it as a dispersion with a surfactant or the like.
かかる発泡剤の溶液は1通常発泡剤の濃度が。Such blowing agent solutions usually have a blowing agent concentration of 1.
5〜10重量%で用いられるがこれに限定されるもので
はない。本発明法の含浸処理において、場合によっては
、上述の処理液と糸条を接触させる時に、糸条の保持す
る水分により発泡剤の溶解度が低下し発泡剤の一部が析
出することがあるが、この場合であっても特に問題なく
含浸処理は行える。It is used in an amount of 5 to 10% by weight, but is not limited thereto. In the impregnation treatment of the present invention, in some cases, when the yarn is brought into contact with the above-mentioned treatment liquid, the solubility of the blowing agent may decrease due to the moisture retained in the yarn, and a portion of the blowing agent may precipitate. Even in this case, the impregnation treatment can be carried out without any particular problem.
含浸処理に当りてのその他の条件は、繊維に必要とされ
る発泡剤の含浸量に応じて適宜決定されればよいが、含
浸処理温度は、使用される発泡剤の分解温度以下で行わ
れる。Other conditions for the impregnation treatment may be determined as appropriate depending on the amount of blowing agent impregnated into the fiber required, but the impregnation treatment temperature should be below the decomposition temperature of the blowing agent used. .
本発明においては1発泡剤の含浸量は謔燥繊維重量に対
して少くとも0.5重量%以上であることが必要である
。0.5重量%未満では、後に加熱発泡させた場合、充
分にフィブリル化させるだけのガスの発生による破砕力
が得られず、フィブリル化が不完全となる為である。好
ましくは1重t%以上の含浸をするのがよい。In the present invention, it is necessary that the amount of one blowing agent impregnated is at least 0.5% by weight based on the weight of the dried fibers. If it is less than 0.5% by weight, when it is heated and foamed later, it will not be possible to obtain a crushing force due to the generation of gas sufficient to cause fibrillation, resulting in incomplete fibrillation. Preferably, the impregnation is 1% by weight or more.
本発明法においては上述の含浸が行われた後。In the method of the invention, after the above-mentioned impregnation has been carried out.
含浸溶液から取り出し、必要があれは付着する余分な溶
液を取り除く目的で水洗等の洗浄を施したのち、乾燥さ
れる。乾燥は繊維の密度を高め、構造を緻密化するため
に重要な工程である。通常。It is removed from the impregnating solution, washed with water or the like to remove excess solution if necessary, and then dried. Drying is an important process to increase fiber density and refine the structure. usually.
・母う配向芳香族ポリアミド繊維の製造過程においては
%120℃以上の温度によって乾燥されるが、本発明に
おいては、フィブリル化を起こさせるために含浸された
発泡剤の分解温度以上の温度で乾燥しつつ加熱するか又
は、−立見泡剤の分解温度以下の温度で乾燥し、ついで
分解温度以上の温度に加熱することがフィブリル化繊維
とするために必要である。発泡剤を含んだ未乾燥の繊維
は、乾燥しつつ発泡剤の分解温度以上に加熱する方法に
おいては、乾燥による構造の緻密化と1発泡剤の分解に
よって発生するガスの破砕力によって、主に繊維長方向
への割裂が生じ高度にフィブリル化した繊維となる。・In the manufacturing process of matrix-oriented aromatic polyamide fibers, they are dried at a temperature of 120°C or higher, but in the present invention, they are dried at a temperature higher than the decomposition temperature of the impregnated blowing agent to cause fibrillation. In order to form fibrillated fibers, drying at a temperature below the decomposition temperature of the standing foaming agent and then heating at a temperature above the decomposition temperature is necessary. In a method in which undried fibers containing a blowing agent are dried and heated above the decomposition temperature of the blowing agent, the structure is densified by drying and the crushing force of the gas generated by the decomposition of the blowing agent causes the fibers to decompose. Splitting occurs in the fiber length direction, resulting in highly fibrillated fibers.
一部、一旦発泡剤の分解温度以下で乾燥された繊維にお
いても、ついで発泡剤の分解温度以上に加熱することに
よって上述と同様のフィブリル化繊維を得ることが出来
る。Even in some fibers that have been once dried at a temperature below the decomposition temperature of the blowing agent, fibrillated fibers similar to those described above can be obtained by subsequently heating the fiber to a temperature above the decomposition temperature of the blowing agent.
本発明法においては、ノ9う配向芳香族ポリアミドが極
めて高度に配向しやすい構造を有し、繊維化過程で、繊
維長方向に高配向した繊維構造をとる結果、主に繊維長
方向への割裂が起こシ、高度にフィブリル化した繊維が
得られるものと考えられる。In the method of the present invention, the oriented aromatic polyamide has a structure that is highly oriented and is highly oriented in the fiber length direction during the fiberization process. It is believed that splitting occurs and highly fibrillated fibers are obtained.
本発明法においてパルプ状粒子全得るには、予め30m
以下の長さに切断した、発泡剤を含浸させた未乾燥繊維
を上述と全く同様の手段、方法によって発泡剤を分解さ
せること、及び上述のフィブリル化繊維を30m以下の
好適な長さに切断することによって行われる。In order to obtain all the pulp particles in the method of the present invention, 30 m
Cutting the undried fibers impregnated with a blowing agent into the following lengths and decomposing the blowing agent by the same means and method as described above, and cutting the fibrillated fibers described above into suitable lengths of 30 m or less. It is done by doing.
本発明法においては発泡剤を分解温度以上に加熱する手
段として、例えば擦過ロール、グラインドミルリファイ
ナ等の粉砕機等を用いて摩擦熱によって加熱して発泡さ
せフィブリル化させることも有効であって好ましく適用
されるものである。In the method of the present invention, it is also effective to heat the foaming agent to a temperature above its decomposition temperature by using a grinder such as a scraping roll or a grind mill refiner to heat the foaming agent using frictional heat to cause foaming and fibrillation. This is preferably applied.
以下、実施例によって本発明を更に詳細に説明するが、
これらの実施例は何ら本発明を限定するものではない。Hereinafter, the present invention will be explained in more detail with reference to Examples.
These examples do not limit the invention in any way.
実施例中、特にことわりのない限り「%」および「部」
はそれぞれ重量パーセントおよび重量部を表わす。また
1本発明法において用いられる種種のパラメーターの主
なものは以下の様にして測定されたものである。In the examples, "%" and "part" unless otherwise specified.
represent weight percent and weight part, respectively. Furthermore, the main parameters used in the method of the present invention are measured as follows.
〈固有粘度の測定法〉
固有粘度(ηinh )は、98.5重量%の濃硫酸に
濃度(C1= 0.511/diでポリマーまたは繊維
を溶かした溶液を30℃にて常法により測定する。<Method for measuring intrinsic viscosity> Intrinsic viscosity (ηinh) is measured by a conventional method at 30°C using a solution of polymer or fiber dissolved in 98.5% by weight concentrated sulfuric acid at a concentration (C1 = 0.511/di). .
参考例(ポリ−p−フェニレンテレフタルアミドの製造
方法)
低温重合法により1次の如くポIJ −p −7二二レ
ンテレフタルアミド(以下、「PPTA」ト略ス)を得
た。特公昭53−43986号公報に示された重合装置
中でN−メチルピロリドン1000部に無水塩化リチウ
ム70部を溶解し、次いでパラフ二二レンジアミン48
.6部を溶解した。8℃に冷却した後、テレフタル酸ジ
クロライド91.4部を粉末状で一度に加えた。数分後
に重合反応物はチーズ状に固゛化したので、特公昭53
−43986号公報記載の方法に従って重合装置より重
合反応物を排出し、直ちに2軸の密閉型ニーグーに移し
、同ニーダ−中で重合反応物を微粉砕した。次に。Reference Example (Method for producing poly-p-phenylene terephthalamide) Poly-IJ-p-7 2-2-2 terephthalamide (hereinafter referred to as "PPTA") was obtained by a low-temperature polymerization method. In the polymerization apparatus shown in Japanese Patent Publication No. 53-43986, 70 parts of anhydrous lithium chloride was dissolved in 1000 parts of N-methylpyrrolidone, and then 48 parts of paraphenyl diamine was dissolved in 1000 parts of N-methylpyrrolidone.
.. 6 parts were dissolved. After cooling to 8°C, 91.4 parts of terephthalic acid dichloride was added at once in powder form. After a few minutes, the polymerization reaction product solidified into a cheese-like shape, so it was
The polymerization reaction product was discharged from the polymerization apparatus according to the method described in Japanese Patent No. 43986, and immediately transferred to a twin-screw closed kneader, and the polymerization reaction product was pulverized in the same kneader. next.
微粉砕物をへフシエルミキサー中に移し、はぼ等量の水
を加えさらに粉砕した後、濾過し数回温水中で洗浄して
、110℃の熱風中で乾燥した。The finely pulverized product was transferred to a Hefsiel mixer, an approximately equal amount of water was added thereto, and the mixture was further pulverized, filtered, washed several times in hot water, and dried in hot air at 110°C.
ηlnhが560の淡黄色のPPTA 95部を得た。95 parts of pale yellow PPTA with ηlnh of 560 was obtained.
なお、異なったη1nhのPPTAは、N−メチルピロ
リドンとモノマー(/クラフェニレンジアミンおよびテ
レフタル酸ジクロライド)の比、または/および七ツマ
ー間の比等を変えることによって容易に得ることができ
る。Note that PPTA with different η1nh can be easily obtained by changing the ratio of N-methylpyrrolidone and monomers (claphenylenediamine and terephthalic acid dichloride), or the ratio between heptamers, etc.
実施例1
固有粘度(171nh %E 7.05のPPTA Q
、ポリマ−濃度が18.7%となるように99.7%の
濃硫酸に、温度を80℃に保ちながら溶解し、紡糸用の
ポリマー溶液(以下、「ドープ」と略称する)を調製し
た。このポリマー溶液は光学的異方性を示すことが直交
ニコル下の偏光顕微鏡観察で確認された。Example 1 PPTA Q with intrinsic viscosity (171 nh %E 7.05
A polymer solution for spinning (hereinafter referred to as "dope") was prepared by dissolving the polymer in 99.7% concentrated sulfuric acid while maintaining the temperature at 80°C so that the polymer concentration was 18.7%. . It was confirmed by polarizing microscopy observation under crossed Nicols that this polymer solution exhibited optical anisotropy.
このドーfを真空下2時間静置脱泡後、紡糸に用いた。This dough f was left to stand under vacuum for 2 hours to defoam, and then used for spinning.
r−プをギアポンプを通して300メツシユステンレス
金網を8重に巻いたキャンドルフィルターを用いて濾過
後、Q、07mxφの孔径、100個の孔数を有する紡
糸用口金から5朋の空気中を通して凝固浴中に押出した
。凝固液としては1.5℃に冷却された10%硫酸水溶
液を用いたついで、凝固浴中に導かれた糸条を変向ロー
ルにて変向し、ネルソンロールへ導いた。このとき繊維
中の残存硫酸量は乾燥繊維重量比16.2%であった。After passing the r-p through a gear pump and filtering it using a candle filter made of 8 layers of 300 mesh stainless wire mesh, it is passed through a spinning nozzle with a pore diameter of 07 m x φ and 100 holes into a coagulation bath through a spinning nozzle of 5 mm. I pushed it inside. A 10% aqueous sulfuric acid solution cooled to 1.5° C. was used as the coagulation liquid, and the yarn introduced into the coagulation bath was changed direction with a direction changing roll and then introduced into a Nelson roll. At this time, the amount of sulfuric acid remaining in the fiber was 16.2% by weight of the dry fiber.
ネルソンロールに引き取られた糸条は、次いで、特公昭
55−9088号公報に示さる装置により、すなわち、
糸条を一対のギヤ一二ッグロール(歯車状のロールが洩
〈噛み合い、その間で糸条を送シ出すロール)により反
転ネット上に振り込み1次いで処理ネットコンベヤー上
に反転させて乗せた。処理ネットコンベヤー上に乗せら
れた先山は、シャワ一方式による水洗水により洗浄し、
約220重量%の含水状態のまま含浸処理工程で、同じ
くシャワ一方式にて、アゾビスイソブチロニトリルe1
2%の濃度になる様に溶解したアセトン溶液を降らせて
10分間接触させて含浸したのち、過剰のアセトン溶液
を除くために水洗した。ついで80℃の熱風乾燥中を通
して乾燥後。The yarn taken up by the Nelson roll is then processed by the device disclosed in Japanese Patent Publication No. 55-9088, that is,
The yarn was transferred onto a reversing net using a pair of gear rolls (rolls in which gear-shaped rolls mesh with each other and the yarn is fed out between them), and then the yarn was reversed and placed on a processing net conveyor. The pile placed on the processing net conveyor is washed with water using a single shower.
In the impregnation treatment process with a water content of about 220% by weight, azobisisobutyronitrile e1 was added using the same shower method.
An acetone solution dissolved at a concentration of 2% was dropped onto the surface, and the surface was left in contact with the surface for 10 minutes to impregnate the surface, followed by washing with water to remove excess acetone solution. Then, it was dried through hot air drying at 80°C.
180℃の温度に保たれた熱風炉を帯留時間が5分とな
る様に速度を制御しながら通し、捲取機にて捲取った。The material was passed through a hot air stove maintained at a temperature of 180° C. while controlling the speed so that the retention time was 5 minutes, and then wound up using a winding machine.
尚、乾燥後の繊維中にはアゾビスイソブチロニトリルが
1.2%含まれることが、Fvr−IRのアゾ基の吸収
から認められた。得られた繊維は、各単糸共微細に割裂
したフィブリルが多数発生していることが肉眼観察でも
認められた。この繊維の物性は繊度154デニール/1
00フイラメント、引張強度19.7 II/d 、伸
度4.3%、初期モジュラス485 N/dであった。In addition, it was recognized from the absorption of the azo group of Fvr-IR that the fiber after drying contained 1.2% azobisisobutyronitrile. It was also observed with the naked eye that the obtained fibers had many finely split fibrils in each single filament. The physical properties of this fiber are fineness of 154 denier/1
00 filament, tensile strength of 19.7 II/d, elongation of 4.3%, and initial modulus of 485 N/d.
実施例2
実施例1で得られたフィブリル化繊維を総状に捲きもど
して4mとなる様に切断し、パルプ状粒子を得た。Example 2 The fibrillated fibers obtained in Example 1 were rolled back into a total shape and cut into a length of 4 m to obtain pulp particles.
このパルプ状のカナディアン戸水度は700であり、タ
ッーースタンダード抄紙機で抄紙して得られた紙の強度
は0.7ユ//llm2であった。The pulp-like Canadian hardness was 700, and the strength of the paper obtained by making the paper using a Tu-Standard paper machine was 0.7 U//llm2.
実施例3
実施例1と全く同じ装置及び方法1条件で含水率220
%の水洗糸を製造し、ついでp−トルエンスルホニルヒ
ドラジドの30%ジメチルスルホキシド溶液と20分間
接触させたのち水洗し、そのまま、5朋の長さになるよ
うに切断し短繊維を得た。Example 3 Moisture content 220 using exactly the same equipment and method 1 conditions as Example 1
% water-washed yarn was produced, and then brought into contact with a 30% dimethyl sulfoxide solution of p-toluenesulfonyl hydrazide for 20 minutes, washed with water, and then cut into 5 mm lengths to obtain short fibers.
この短繊維中には乾燥繊維重量に対してp−トルエンス
ルホニルヒドラジドが約2.4%含まれることがFT
−IRの吸収で認められた。FT indicates that this short fiber contains approximately 2.4% p-toluenesulfonyl hydrazide based on the dry fiber weight.
-Recognized by IR absorption.
ついでこの短繊維を、炉内温度が160℃の熱炉中に3
0分間投入し、乾燥及び加熱を行った。Next, this short fiber was placed in a heat furnace with an internal temperature of 160°C for 30 minutes.
It was put in for 0 minutes and then dried and heated.
得られた短繊維はフィブリル化したことによって互いに
絡みあい、・ヤルプ状粒子化していることが認められた
。It was observed that the obtained short fibers were fibrillated and intertwined with each other to form yalp-like particles.
このパルプ状粒子のカナディアン戸水度は480であっ
て、抄紙性にも優れていることが認められ。This pulp-like particle had a Canadian water rating of 480, and was recognized to have excellent paper-making properties.
タッーースタンダード抄紙機によって得られた紙の引張
強度は0.9 kg、/+m2であった。The tensile strength of the paper obtained by the Ta-Standard paper machine was 0.9 kg, /+m2.
実施例4
アゾジカルデンアミドの10%N−メチル−2−ピロリ
ドン溶液を用いた以外は実施例1と同じ処方で含浸水洗
糸を得たー
次いでこの含浸水洗糸を120℃で乾燥したのち、アゾ
ジカル?ンアミドの分解温度(200〜210℃)以上
となる様に250℃の熱処理炉中に5分間投入してポリ
パラフェニレンテレフタルアミドのフィブリル化繊維を
得た。Example 4 An impregnated washed thread was obtained using the same recipe as in Example 1 except that a 10% solution of azodicardenamide in N-methyl-2-pyrrolidone was used.The impregnated washed thread was then dried at 120°C. Azogical? Fibrillated fibers of polyparaphenylene terephthalamide were obtained by placing the fibers in a heat treatment furnace at 250°C for 5 minutes so that the temperature reached the decomposition temperature (200 to 210°C) of poly(paraphenylene terephthalamide) or higher.
実施例5
実施例3で得られた5龍の長さの含浸短繊維を風乾後、
2枚の研磨板が相対して逆転するグラインドミル内に入
れて回転させた。この際摩擦熱により内部は約140℃
に加熱された。20分間の処理の後には、切断が起きて
2u以下の長さになった微細な・辛ルプ状粒子が得られ
た。Example 5 After air-drying the impregnated short fibers obtained in Example 3,
It was placed in a grind mill in which two polishing plates faced each other and rotated in reverse. At this time, the temperature inside is approximately 140℃ due to frictional heat.
heated to. After 20 minutes of treatment, fine, spiny-like particles with a length of less than 2 u were obtained due to scission.
本発明によれば、繊維内部からの破砕力によって繊維全
体に亘りて均一にかつ高度にフィブリル化した繊維及び
/fルグ状籾粒子得られ、又、機械的な剪断力による方
法等の多大なエネルギーを必要とせず容易に・ぐルグ状
粒子が得られるものである。According to the present invention, it is possible to obtain fibers and/f rug-like rice particles that are uniformly and highly fibrillated throughout the fibers by crushing force from inside the fibers, and it is also possible to obtain fibers and/or rug-like rice grains that are highly fibrillated throughout the fibers, and also to obtain large amounts of fibrillated rice particles by using methods using mechanical shearing force. Gurg-like particles can be easily obtained without requiring energy.
更には、フィブリル化した連続したフィラメントとして
・母う配向芳香族ポリアミド繊維が得られる結果、その
ままゴムやベルトの補強用として極めて高い接着力を有
する補強用繊維として使用することが出来るものである
。Furthermore, as a result of obtaining a matrix-oriented aromatic polyamide fiber in the form of fibrillated continuous filaments, it can be used as is as a reinforcing fiber with extremely high adhesive strength for reinforcing rubber or belts.
Claims (3)
量%の濃硫酸に、少くとも14重量%のポリマー濃度と
なるように溶解した光学異方性ドープを紡糸口金より気
体中に、次いで凝固浴中に押し出して繊維化し、凝固時
および/または残存する硫酸系溶媒が対乾燥繊維に対し
て5重量%以上の洗浄初期に凝固糸条から実質的に張力
を解放し、少くとも50重量%以上の水分を含む糸条を
得、これと、発泡剤を水と混和性のある溶媒に溶かした
溶液とを張力の実質的解放下に接触させて発泡剤を糸条
の繊維中に、乾燥繊維重量に基づいて少くとも0.5重
量%以上となるように含浸させたのち該溶液から取り出
し、ついで、乾燥しつつ、または一旦該発泡剤の分解温
度以下の温度で乾燥したのち、該発泡剤の分解温度以上
の温度に加熱することを特徴とするフィブリル化繊維の
製造法。(1) An optically anisotropic dope prepared by dissolving a para-oriented aromatic polyamide in concentrated sulfuric acid with a concentration of 97 to 101% by weight to give a polymer concentration of at least 14% by weight is passed through a spinneret into a gas, and then into a coagulation bath. The tension is substantially released from the coagulated yarn during coagulation and/or at the initial stage of washing when the residual sulfuric acid solvent is 5% by weight or more based on the dry fiber, and is at least 50% by weight or more. A yarn containing moisture is obtained, and the yarn is contacted with a solution of a blowing agent in a water-miscible solvent under substantial release of tension to inject the blowing agent into the fibers of the yarn, forming a dry fiber. The blowing agent is impregnated to a concentration of at least 0.5% by weight based on the weight, removed from the solution, and then dried, or once dried at a temperature below the decomposition temperature of the blowing agent. A method for producing fibrillated fibers, which comprises heating to a temperature higher than the decomposition temperature of.
量%の濃硫酸に、少くとも14重量%のポリマー濃度と
なるように溶解した光学異方性ドープを紡糸口金より気
体中に、次いで凝固浴中に押し出して繊維化し、凝固時
および/または残存する硫酸系溶媒が対乾燥繊維に対し
て5重量%以上の洗浄初期に凝固糸条から実質的に張力
を解放し、少くとも50重量%以上の水分を含む糸条を
得、これと、発泡剤を水と混和性のある溶媒に溶かした
溶液とを張力の実質的解放下に接触させて発泡剤を繊維
中に、乾燥繊維重量に基づいて少くとも0.5重量%以
上となるように含浸させたのち該溶液から取出し、予め
30mm以下の長さに切断したのちまたは切断に先立っ
て、乾燥しつつ、または一旦該発泡剤の分解温度以下の
温度で乾燥したのち該発泡剤の分解温度以上の温度に加
熱することを特徴とするパルプ状粒子の製造法。(2) An optically anisotropic dope prepared by dissolving a para-oriented aromatic polyamide in concentrated sulfuric acid with a concentration of 97 to 101% by weight to give a polymer concentration of at least 14% by weight is passed through a spinneret into a gas, and then into a coagulation bath. The tension is substantially released from the coagulated yarn during coagulation and/or at the initial stage of washing when the residual sulfuric acid solvent is 5% by weight or more based on the dry fiber, and is at least 50% by weight or more. A yarn containing water of After impregnating the foaming agent with a concentration of at least 0.5% by weight, the blowing agent is taken out from the solution, cut into lengths of 30 mm or less, or before cutting, while drying, or once at the decomposition temperature of the blowing agent. A method for producing pulp-like particles, which comprises drying at a temperature below and then heating to a temperature equal to or higher than the decomposition temperature of the blowing agent.
リル化合物 (▲数式、化学式、表等があります▼但し、R、R′は
炭素 数5以下のアルキル基又はシクロヘキシル基である)、
スルホニルヒドラジド化合物(R−SO_2NH−NH
_2)の中から選択される1種又は2種以上である特許
請求の範囲第1項又は第2項の製造法。(3) The blowing agent is azodicarbonamide, azobisnitrile compound (▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ However, R and R' are an alkyl group or a cyclohexyl group having 5 or less carbon atoms),
Sulfonyl hydrazide compound (R-SO_2NH-NH
The manufacturing method according to claim 1 or 2, which is one or more selected from _2).
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP7747687A JPS63249716A (en) | 1987-04-01 | 1987-04-01 | Production of fibrillated fiber and pulpy particle |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP7747687A JPS63249716A (en) | 1987-04-01 | 1987-04-01 | Production of fibrillated fiber and pulpy particle |
Publications (1)
Publication Number | Publication Date |
---|---|
JPS63249716A true JPS63249716A (en) | 1988-10-17 |
Family
ID=13635037
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP7747687A Pending JPS63249716A (en) | 1987-04-01 | 1987-04-01 | Production of fibrillated fiber and pulpy particle |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS63249716A (en) |
-
1987
- 1987-04-01 JP JP7747687A patent/JPS63249716A/en active Pending
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