JPH05222612A - Polyamideimide copolymer fiber and its production - Google Patents
Polyamideimide copolymer fiber and its productionInfo
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- JPH05222612A JPH05222612A JP5694192A JP5694192A JPH05222612A JP H05222612 A JPH05222612 A JP H05222612A JP 5694192 A JP5694192 A JP 5694192A JP 5694192 A JP5694192 A JP 5694192A JP H05222612 A JPH05222612 A JP H05222612A
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Abstract
Description
【0001】[0001]
【産業上の利用分野】本発明は耐熱性、難燃性に優れた
共重合ポリアミドイミド繊維およびその製造法に関する
ものである。さらに詳しくは、本発明は著しく熱寸法安
定性に優れた耐熱性で高強力繊維に関するものであり、
該繊維は作業服やカーペット、カーテン、寝具等のイン
テリア用および高温バッグフィルター等の産業資材に利
用されるものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a copolyamideimide fiber having excellent heat resistance and flame retardancy and a method for producing the same. More specifically, the present invention relates to a heat-resistant and high-strength fiber having extremely excellent thermal dimensional stability,
The fibers are used for work clothes, interiors such as carpets, curtains and bedding, and industrial materials such as high temperature bag filters.
【0002】[0002]
【従来の技術】従来より耐熱性で高強力繊維としてはテ
レフタル酸クロリドとp−フェニレンジアミンとから合
成されるパラ型アラミド繊維やイソフタル酸クロリドと
m−フェニレンジアミンとから合成されるメタ型アラミ
ド繊維、ガラス繊維及び炭素繊維等が知られているが、
いずれも特殊な方法で製造するため高価な設備や煩雑な
作業が必要であった。2. Description of the Related Art Conventionally, as heat-resistant and high-strength fibers, para-type aramid fibers synthesized from terephthalic acid chloride and p-phenylenediamine and meta-type aramid fibers synthesized from isophthalic acid chloride and m-phenylenediamine. , Glass fiber and carbon fiber are known,
Since all of them are manufactured by a special method, expensive equipment and complicated work are required.
【0003】一方耐熱性ポリマーの代表とされるポリイ
ミド系の繊維についても、例えばポリ(4,4’−オキ
シジフェニレンピロメリットイミド)の繊維化が提案さ
れているが、紡糸、延伸後に高温加熱処理して脱水閉環
する必要があるため、ボイドが発生し易く、強度が不充
分であるばかりでなく製造コストが高いという欠点があ
った。On the other hand, regarding polyimide fibers represented by heat-resistant polymers, for example, poly (4,4'-oxydiphenylenepyromellitimide) fibers have been proposed, but they are heated at a high temperature after spinning and drawing. Since it is necessary to treat and perform dehydration ring closure, there are drawbacks that voids are likely to occur, strength is insufficient, and manufacturing cost is high.
【0004】[0004]
【発明が解決しようとする課題】そこで本発明は、従来
の設備を用いて安価に製造できる耐熱性、難燃性及び熱
寸法安定性に優れた高強力繊維を得ることを課題として
いる。SUMMARY OF THE INVENTION Therefore, an object of the present invention is to obtain a high-strength fiber excellent in heat resistance, flame retardancy, and thermal dimensional stability, which can be manufactured at low cost using conventional equipment.
【0005】[0005]
【課題を解決するための手段】前記課題を解決するた
め、本発明者らは高分子量化が容易で剛直構造を有し且
つ汎用の有機溶剤に可溶な耐熱性ポリマーが上記の課題
を解決するのに有効であると考え鋭意検討した結果、特
殊な構造を有するポリアミドイミドが上記の目的を達成
できることを見いだし本発明を完成するに到った。即ち
本発明は下記化5で表される単位および化6で表される
単位を繰り返し単位とする共重合ポリアミドイミドを紡
糸又は紡糸後延伸することによって得られることを特徴
をする共重合ポリアミドイミド繊維および下記化5で表
される単位および化6で表される単位を繰り返し単位と
する共重合ポリアミドイミドに溶剤を含んだ状態で紡糸
後、必要により延伸することを特徴とする共重合ポリア
ミドイミド繊維の製造方法である。In order to solve the above-mentioned problems, the present inventors have solved the above-mentioned problems by using a heat-resistant polymer which has a rigid structure and is easily soluble in a general-purpose organic solvent, and which has a rigid structure. As a result of diligent studies, it was found that a polyamide-imide having a special structure can achieve the above object, and the present invention has been completed. That is, the present invention is characterized by being obtained by spinning or spinning and then stretching a copolymerized polyamideimide having a unit represented by the following chemical formula 5 and a unit represented by the following chemical formula 6 as a repeating unit. And a copolyamideimide fiber comprising a unit represented by the following chemical formula 5 and a unit represented by the following chemical formula 6 as a repeating unit, which is spun in a solvent-containing state and then stretched if necessary. Is a manufacturing method.
【0006】[0006]
【化5】 [Chemical 5]
【0007】[0007]
【化6】 (化5および化6においてArは二価の芳香族基であ
り、そのうち25〜95モル%は3,3’−ジアルキル
ビフェニレン基である。またRは炭素数1〜60のアル
キレン基を示し、lは0〜30モル%、mは0又は1、
nは1〜10の整数を示す。)[Chemical 6] (In the chemical formulas 5 and 6, Ar is a divalent aromatic group, 25 to 95 mol% of which is a 3,3′-dialkylbiphenylene group. R represents an alkylene group having 1 to 60 carbon atoms, l is 0 to 30 mol%, m is 0 or 1,
n shows the integer of 1-10. )
【0008】本発明において用いられる共重合ポリアミ
ドイミドを製造する方法としては、イソシアネート法或
は酸クロリド法など通常の方法で合成することができ
る。イソシアネート法で用いる原料としてはトリメリッ
ト酸無水物、ベンゾフェノンテトラカルボン酸無水物、
3,3’−ジメチルジフェニル4,4’−ジイソシアネ
ート、3,3’−ジエチルジフェニル4,4’−ジイソ
シアネート等がある。As a method for producing the copolyamideimide used in the present invention, it can be synthesized by a usual method such as an isocyanate method or an acid chloride method. Raw materials used in the isocyanate method include trimellitic anhydride, benzophenone tetracarboxylic anhydride,
There are 3,3'-dimethyldiphenyl 4,4'-diisocyanate, 3,3'-diethyldiphenyl 4,4'-diisocyanate and the like.
【0009】前記共重合ポリアミドイミドの製造におい
て、本発明の目的を損なわない限り、他の酸成分またな
アミン成分を共重合してもよい。共重合可能な他のアミ
ン成分としてはp−フェニレンジアミン、m−フェニレ
ンジアミン、4,4’−ジアミノジフェニルエーテル、
4,4’−ジアミノジフェニルメタン、4,4’−ジア
ミノジフェニルスルホン、4,4’−ジアミノベンゾフ
ェノン、2,2’−ビス(4アミノフェニル)プロパ
ン、2,4−トリレンジアミン、2,6−トリレンジア
ミン、p−キシレリンジアミン、イソホロンジアミン、
ヘキサメチレンジアミン等が挙げられる。In the production of the copolymerized polyamide-imide, other acid component or amine component may be copolymerized as long as the object of the present invention is not impaired. Other copolymerizable amine components include p-phenylenediamine, m-phenylenediamine, 4,4′-diaminodiphenyl ether,
4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfone, 4,4'-diaminobenzophenone, 2,2'-bis (4aminophenyl) propane, 2,4-tolylenediamine, 2,6- Tolylenediamine, p-xylelline diamine, isophorone diamine,
Hexamethylenediamine and the like can be mentioned.
【0010】共重合可能な他の酸成分としては、テレフ
タル酸、イソフタル酸、4,4’−ビフェニルジカルボ
ン酸、ピロメリット酸、3,3’4,4’−ベンゾフェ
ノンテトラカルボン酸、3,3’4,4’−ビフェニル
スルホンテトラカルボン酸、3,3’4,4’−ビフェ
ニルテトラカルボン酸、アジピン酸、セバシン酸、マレ
イン酸、フマール酸、ダイマー酸、スチルベンジカルボ
ン酸等が挙げられる。Other copolymerizable acid components include terephthalic acid, isophthalic acid, 4,4'-biphenyldicarboxylic acid, pyromellitic acid, 3,3'4,4'-benzophenonetetracarboxylic acid, 3,3. Examples include '4,4'-biphenyl sulfone tetracarboxylic acid, 3,3'4,4'-biphenyl tetracarboxylic acid, adipic acid, sebacic acid, maleic acid, fumaric acid, dimer acid, stilbene dicarboxylic acid.
【0011】またアミン成分として以下のイソシアネー
トも利用できる。例えば2,4−トリレンジイソシアネ
ート、4,4’−ジフェニルメタンジイソシアネート、
イソホロンジイソシアネート、ヘキサメチレンジイソシ
アネート等が挙げられ、酸成分として以下の酸無水物、
酸塩化物等も利用できる。例えばベンゾフェノンテトラ
カルボン酸無水物、ジフェニルスルホンテトラカルボン
酸無水物、ビフェニルテトラカルボン酸無水物、ピロメ
リット酸無水物等が挙げられる。The following isocyanates can also be used as the amine component. For example, 2,4-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate,
Isophorone diisocyanate, hexamethylene diisocyanate and the like, the following acid anhydride as an acid component,
Acid chloride and the like can also be used. Examples thereof include benzophenone tetracarboxylic acid anhydride, diphenyl sulfone tetracarboxylic acid anhydride, biphenyl tetracarboxylic acid anhydride, and pyromellitic acid anhydride.
【0012】本発明で用いられる共重合ポリアミドイミ
ドの特長の1つは3,3’−ジアルキルビフェニル残基
を25〜95モル%、好ましくは50〜90モル%含有
することにある。この理由は該アミン残基の剛直な分子
構造の効果により繊維にしたときの強度、弾性率及び熱
寸法安定性への寄与と溶剤への溶解性のバランスによっ
て決められた範囲である。即ち3,3’−ジアルキルビ
フェニル残基が25モル%以下であると剛直な分子構造
成分が少なく強度、弾性率及び熱寸法安定性が充分発揮
されず、一方95モル%を越えると溶解性が悪くなって
紡糸が困難になる。One of the features of the copolyamideimide used in the present invention is that it contains 25 to 95 mol% of 3,3'-dialkylbiphenyl residues, preferably 50 to 90 mol%. The reason for this is the range determined by the balance between the contribution to the strength, elastic modulus and thermal dimensional stability when formed into a fiber due to the effect of the rigid molecular structure of the amine residue, and the solubility in a solvent. That is, when the 3,3'-dialkylbiphenyl residue is 25 mol% or less, the rigid molecular structure component is small and the strength, elastic modulus and thermal dimensional stability are not sufficiently exhibited, while when it exceeds 95 mol%, the solubility is increased. It becomes worse and makes spinning difficult.
【0013】なお本発明で用いられる共重合ポリアミド
イミドはエポキシ化合物で変性することによって更にそ
の優位性が発揮される。エポキシ化合物による変性は紡
糸後延伸、熱処理によりポリアミドイミドを架橋させ耐
熱性、耐薬品性を一段と向上させると同時に接炎時のド
リップを抑える効果がある。The copolyamideimide used in the present invention exhibits its superiority by being modified with an epoxy compound. The modification with an epoxy compound has the effect of cross-linking the polyamide-imide by drawing after spinning and heat treatment to further improve heat resistance and chemical resistance, and at the same time suppress drip during flame contact.
【0014】本発明に使用されるエポキシ化合物として
は、本発明の目的を損なわない限り2官能又は3官能以
上の芳香族、脂肪族又は脂環族のいずれのエポキシ化合
物の1種又は2種以上の混合物として用いることができ
るが、少量で架橋密度を上げ、本来の目的である耐熱
性、難燃性で高強力な繊維を得るには多官能性のフェノ
ールノボラック型エポキシ化合物が好ましく、その配合
量は1〜30重量%、特に2.5〜20重量%が好まし
い。As the epoxy compound used in the present invention, one or more kinds of bifunctional or trifunctional or more aromatic, aliphatic or alicyclic epoxy compounds are used unless the object of the present invention is impaired. A polyfunctional phenol novolac type epoxy compound is preferable for increasing the crosslink density in a small amount to obtain heat resistant, flame retardant and high-strength fibers, which are the original purpose, and its blending. The amount is preferably 1 to 30% by weight, particularly preferably 2.5 to 20% by weight.
【0015】本発明で用いられる共重合ポリアミドイミ
ド又はエポキシ変性共重合ポリアミドイミドの対数粘度
はポリマーの濃度が0.5g/100mlのNメチル2
ピロリドン溶液を25℃で測定したときに0.5〜2.
5dl/g、好ましくは1.0〜2.0dl/gであ
る。The copolyamideimide or the epoxy-modified copolyamideimide used in the present invention has a logarithmic viscosity of N-methyl 2 at a polymer concentration of 0.5 g / 100 ml.
0.5-2. When the pyrrolidone solution is measured at 25 ° C.
It is 5 dl / g, preferably 1.0 to 2.0 dl / g.
【0016】本発明において、共重合ポリアミドイミド
又はエポキシ変性共重合ポリアミドイミドより得られる
繊維としての特性及び加工性を向上させるために油剤、
帯電防止剤、着色剤、酸化防止剤、無機充填剤などの各
種添加剤を適当量配合することができる。In the present invention, an oil agent for improving the properties and processability of the fiber obtained from the copolyamideimide or the epoxy-modified copolyamideimide,
Various additives such as an antistatic agent, a colorant, an antioxidant and an inorganic filler can be blended in appropriate amounts.
【0017】本発明において、前記共重合ポリアミドイ
ミド又はエポキシ変性共重合ポリアミドイミドより繊維
を得る方法としては、従来の設備を用いて湿式紡糸法、
乾式紡糸法のいずれの方法を採用しても製造することが
できる。これらの場合溶剤としてはジメチルホルムアミ
ド、ジメチルアセトアミド、Nメチル2ピロリドン、ジ
メチルスルホオキシド、ジメチル尿素等の極性溶剤を使
用することが好ましいが、これらと併用して、トルエ
ン、キシレン等の炭化水素系、アセトン、メチルエチル
ケトン、メチルイソブチルケトン、シクロヘキサノン等
のケトン系、ジオキサン、エチレングリコールジメチル
エーテル、テトラヒドロフラン等のエーテル系、酢酸エ
チル、酢酸nブチル、γブチロラクトン等のエステル系
等の溶剤を混合して用いることもできる。また前記共重
合ポリアミドイミド又はエポキシ変性共重合ポリアミド
イミドに含有させる溶剤の量は30重量%以下が好まし
い。なお湿式紡糸法で製造する場合、凝固浴としては該
共重合ポリアミドイミド又はエポキシ変性共重合ポリア
ミドイミドの非溶剤で且つ上記溶剤と相溶する溶剤であ
れば何でも使用できるが水を用いるのが最も好ましい。In the present invention, as a method of obtaining fibers from the above-mentioned copolymerized polyamideimide or epoxy-modified copolymerized polyamideimide, a wet spinning method using conventional equipment,
It can be produced by any of the dry spinning methods. In these cases, it is preferable to use polar solvents such as dimethylformamide, dimethylacetamide, N-methyl-2-pyrrolidone, dimethylsulfoxide, and dimethylurea as the solvent, but in combination with these, hydrocarbon solvents such as toluene and xylene, It is also possible to mix and use a solvent such as a ketone-based solvent such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, an ether-based solvent such as dioxane, ethylene glycol dimethyl ether and tetrahydrofuran, and an ester-based solvent such as ethyl acetate, n-butyl acetate and γ-butyrolactone. .. The amount of the solvent contained in the copolymerized polyamideimide or the epoxy-modified copolymerized polyamideimide is preferably 30% by weight or less. In the case of producing by the wet spinning method, as the coagulation bath, any solvent which is a non-solvent of the copolymerized polyamideimide or the epoxy-modified copolymerized polyamideimide and which is compatible with the above solvent can be used, but water is most used. preferable.
【0018】本発明の共重合ポリアミドイミド及びエポ
キシ変性共重合ポリアミドイミド繊維は未延伸の状態で
も用途によっては使用できるが、強度、弾性率を向上さ
せるためには延伸が必要である。延伸は未延伸糸が溶剤
を含んでいない場合、300〜400℃で約4倍まで可
能であり、難燃性(LOI値)が31、引っ張り強度で
5g/d以上、引っ張り弾性率で300g/d以上の高
強度で難燃性の繊維が得られる。The copolyamideimide and epoxy-modified copolyamideimide fibers of the present invention can be used depending on the application even in an unstretched state, but they need to be stretched to improve strength and elastic modulus. When the undrawn yarn does not contain a solvent, it can be drawn up to about 4 times at 300 to 400 ° C., flame retardancy (LOI value) is 31, tensile strength is 5 g / d or more, and tensile elastic modulus is 300 g / d. Fibers with high strength and flame retardancy of d or more can be obtained.
【0019】更に高強度にするために高延伸する場合
は、共重合ポリアミドイミド及びエポキシ変性共重合ポ
リアミドイミドの溶剤または膨潤剤を未延伸糸に対して
30重量%以下の範囲で予め含ませた後延伸すればよ
い。溶剤又は膨潤剤の量が30重量%を越えると吸湿に
より未延伸糸が白化したり、ブロッキングして延伸作業
が困難になるので好ましくない。前記溶剤又は膨潤剤と
しては、上記溶剤をそのまま用いることができるが、溶
剤の揮散による効果の低下を防ぐといった点からNメチ
ル2ピロリドンやジメチルスルホオキシドのような沸点
の高い溶剤が好ましい。同様な理由から前記以外の溶剤
としてフェノール、クレゾール等のフェノール系溶剤や
スルホラン、アセトフェノン等が挙げられる。In the case of high drawing for higher strength, the solvent or swelling agent for the copolyamideimide and the epoxy-modified copolyamideimide is contained in advance in an amount of 30% by weight or less based on the undrawn yarn. It may be post-stretched. When the amount of the solvent or the swelling agent exceeds 30% by weight, the undrawn yarn is whitened due to moisture absorption or blocking occurs, which makes drawing work difficult, which is not preferable. As the solvent or the swelling agent, the above-mentioned solvent can be used as it is, but a solvent having a high boiling point such as N-methyl-2pyrrolidone or dimethyl sulfoxide is preferable from the viewpoint of preventing the effect from being reduced by volatilization of the solvent. For the same reason, examples of solvents other than the above include phenolic solvents such as phenol and cresol, sulfolane, and acetophenone.
【0020】溶剤又は膨潤剤を未延伸糸に含浸させる方
法としては、延伸前に未延伸糸を溶剤又は膨潤剤に浸漬
させる方法、湿式紡糸の場合は凝固浴に溶剤又は膨潤剤
を混合させる方法、乾式防止の場合は乾燥凝固条件を調
整するなどの方法で制御することができる。溶剤又は膨
潤剤を含浸させた未延伸糸は5倍以上の高延伸が可能と
なり強度、弾性率が向上するばかりでなく、300℃以
下での低温延伸が可能となる利点がある。As a method of impregnating the undrawn yarn with the solvent or the swelling agent, the undrawn yarn is immersed in the solvent or the swelling agent before drawing, and in the case of wet spinning, the solvent or the swelling agent is mixed with the coagulation bath. In the case of dry prevention, it can be controlled by a method such as adjusting dry coagulation conditions. The unstretched yarn impregnated with the solvent or the swelling agent has the advantage that it can be highly stretched 5 times or more, and not only the strength and elastic modulus are improved, but also low temperature stretching at 300 ° C. or less is possible.
【0021】[0021]
【実施例】以下、実施例によって本発明を更に具体的に
説明するが、本発明はこれらの実施例によって限定され
るものではない。なお共重合ポリアミドイミド繊維の特
性は下記の方法によって測定した。 対数粘度;ポリマー0.5gのNメチル2ピロリドン1
00ml溶液を25℃で測定した。 引っ張り強伸度;東洋ボールドウイン社製のテンシロン
を用いて20℃、65%RHの雰囲気下で、引っ張り速
度を20mm/分として測定した。 難燃性(LOI);JIS−K7201に記載の方法に
従って測定した。The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. The characteristics of the copolyamideimide fiber were measured by the following methods. Logarithmic viscosity; 0.5 g of polymer N methyl 2 pyrrolidone 1
The 00 ml solution was measured at 25 ° C. Tensile strength and elongation: Tensileon manufactured by Toyo Baldwin Co., Ltd. was used, and the tensile speed was measured at 20 mm / min in an atmosphere of 20 ° C. and 65% RH. Flame retardance (LOI); measured according to the method described in JIS-K7201.
【0022】実施例1 反応容器にトリメリット酸無水物1モル、2,4−トリ
レンジイソシアネート0.2モル、o−トリジンジイソ
シアネート0.8モルをNメチル2ピロリドン2Kgと
共に仕込み、攪拌しながら200℃まで約1時間で昇温
した。その後、200℃で約5時間攪拌を続け反応を停
止した。得られたポリマーの対数粘度は1.56であっ
た。このポリマー溶液から水を凝固浴として湿式法で紡
糸して110dの未延伸糸を得た。この未延伸糸を35
0℃の加熱ゾーンを通しつつ3.5倍延伸した。延伸糸
の引っ張り強度は8g/d,引っ張り弾性率は450g
/d、LOI値は31であった。Example 1 A reaction vessel was charged with 1 mol of trimellitic anhydride, 0.2 mol of 2,4-tolylene diisocyanate and 0.8 mol of o-tolidine diisocyanate together with 2 Kg of N-methyl-2pyrrolidone, and stirred to 200 The temperature was raised to ° C in about 1 hour. Then, stirring was continued at 200 ° C. for about 5 hours to stop the reaction. The inherent viscosity of the obtained polymer was 1.56. This polymer solution was spun by a wet method using water as a coagulating bath to obtain 110d undrawn yarn. This undrawn yarn is
It was stretched 3.5 times while passing through a heating zone of 0 ° C. Tensile strength of drawn yarn is 8g / d, Tensile elastic modulus is 450g
/ D, LOI value was 31.
【0023】実施例2 反応容器にトリメリット酸無水物0.8モル、ベンゾフ
ェノンテトラカルボン酸無水物0.2モル、2,4−ト
リレンジイソシアネート0.5モル、o−トリジンジイ
ソシアネート0.5モルをNメチル2ピロリドン2Kg
と共に仕込み、攪拌しながら200℃まで約1時間で昇
温した。その後200℃で約2時間攪拌を続け反応を停
止した。得られたポリマーの対数粘度は1.48であっ
た。このポリマー溶液から実施例1と同じ方法で75d
の未延伸糸を得、380℃の加熱ゾーンを通しながら
4.2倍延伸した。得られた延伸糸の引っ張り強度は1
8.5g/d,引っ張り弾性率は1050g/d、LO
I値は32であった。Example 2 In a reaction vessel, 0.8 mol of trimellitic anhydride, 0.2 mol of benzophenone tetracarboxylic acid anhydride, 0.5 mol of 2,4-tolylene diisocyanate and 0.5 mol of o-tolidine diisocyanate. N methyl 2 pyrrolidone 2Kg
The mixture was charged with the mixture and heated to 200 ° C. in about 1 hour with stirring. Then, stirring was continued at 200 ° C. for about 2 hours to stop the reaction. The polymer obtained had an inherent viscosity of 1.48. 75d from this polymer solution in the same manner as in Example 1.
The unstretched yarn of was obtained and stretched 4.2 times while passing through a heating zone of 380 ° C. The tensile strength of the obtained drawn yarn is 1
8.5 g / d, tensile elastic modulus is 1050 g / d, LO
The I value was 32.
【0024】比較例1 反応容器にトリメリット酸無水物1モル、o−トリジン
ジイソシアネート1モルをNメチル2ピロリドン2Kg
と共に仕込み実施例1と同じ条件で反応させたが、重合
の進行にともなって溶液が白濁しポリマーが析出してき
たために紡糸ができなかった。Comparative Example 1 1 mol of trimellitic anhydride and 1 mol of o-tolidine diisocyanate were placed in a reaction vessel and 2 kg of N-methyl-2pyrrolidone was added.
The reaction was carried out under the same conditions as in Example 1, but as the polymerization proceeded, the solution became cloudy and the polymer was precipitated, so that spinning was not possible.
【0025】比較例2 反応容器にトリメリット酸無水物0.5モル、ベンゾフ
ェノンテトラカルボン酸無水物0.5モル、2,4−ト
リレンジイソシアネート0.5モル、o−トリジンジイ
ソシアネート0.5モルをnメチル3ピロリドン2Kg
と共に仕込み実施例1と同じ条件で反応させたが、重合
の進行にともなって溶液が白濁しポリマーが析出してき
たために紡糸ができなかった。Comparative Example 2 0.5 mol of trimellitic anhydride, 0.5 mol of benzophenone tetracarboxylic anhydride, 0.5 mol of 2,4-tolylene diisocyanate and 0.5 mol of o-tolidine diisocyanate were placed in a reaction vessel. N-methyl 3 pyrrolidone 2Kg
The reaction was carried out under the same conditions as in Example 1, but as the polymerization proceeded, the solution became cloudy and the polymer was precipitated, so that spinning was not possible.
【0026】実施例3 実施例1において得られた重合反応終了後のポリマー溶
液を100℃まで降温させた後、フェノールノボラック
型エポキシ樹脂をポリマー固形分に対して5重量%添加
して100℃を保ったまま2時間反応させた。得られた
ポリマーの対数粘度は1.62であった。このポリマー
溶液から実施例1と同じ方法で紡糸を行い110dの未
延伸糸を得た。この未延伸糸を350℃の加熱ゾーンを
通しつつ3.5倍延伸した。得られた延伸糸の引っ張り
強度は8.5g/d,引っ張り弾性率は440g/dと
実施例1の延伸糸とほぼ同程度の機械的特性を示した
が、この延伸糸はNメチル2ピロリドンや濃硫酸に溶解
せず著しく耐薬品性が向上し、またLOIも31と実施
例1の延伸糸とほぼ同程度であり、燃焼時ドリップアウ
ト現象がみられず架橋効果による非溶融化が認められ
た。Example 3 After the temperature of the polymer solution obtained in Example 1 after the completion of the polymerization reaction was lowered to 100 ° C., 5% by weight of phenol novolac type epoxy resin was added to the polymer solid content, and the temperature was raised to 100 ° C. The reaction was carried out for 2 hours while maintaining the temperature. The polymer obtained had an inherent viscosity of 1.62. This polymer solution was spun in the same manner as in Example 1 to obtain 110d undrawn yarn. The undrawn yarn was drawn 3.5 times while passing through a heating zone at 350 ° C. The stretched yarn obtained had a tensile strength of 8.5 g / d and a tensile elastic modulus of 440 g / d, which showed mechanical properties almost the same as those of the stretched yarn of Example 1. The stretched yarn had N-methyl-2-pyrrolidone. The chemical resistance was remarkably improved without being dissolved in concentrated sulfuric acid, and LOI was 31 and was almost the same as that of the drawn yarn of Example 1. No drip-out phenomenon was observed during combustion, and non-melting due to the crosslinking effect was recognized. Was given.
【0027】実施例4 実施例3で得られたエポキシ変性共重合ポリアミドイミ
ド溶液を紡糸してNメチル2ピロリドンの25重量%水
溶液中で1.6倍延伸させながら凝固させた後120℃
で1分乾燥して溶剤含有量が18重量%の未延伸糸をつ
くった。この未延伸糸を270℃の加熱ゾーンを通しつ
つ4.5倍延伸して合計7.2倍の延伸糸を作った。得
られた延伸糸の引っ張り強度は13g/d,引っ張り弾
性率は620g/dであり溶剤を含んだことによる延伸
性の向上効果が認められた。Example 4 The epoxy-modified copolyamideimide solution obtained in Example 3 was spun and coagulated in a 25% by weight aqueous solution of N-methyl-2pyrrolidone while stretching 1.6 times, and then 120 ° C.
And dried for 1 minute to prepare an undrawn yarn having a solvent content of 18% by weight. This undrawn yarn was drawn 4.5 times while passing through a heating zone of 270 ° C. to make a drawn yarn of 7.2 times in total. The stretched yarn thus obtained had a tensile strength of 13 g / d and a tensile elastic modulus of 620 g / d, and the effect of improving the stretchability due to the inclusion of a solvent was confirmed.
【0028】[0028]
【発明の効果】本発明の共重合ポリアミドイミド繊維は
3,3’−ジアルキルベンジジン残基を溶解性の損なわ
ない範囲で共重合させているためにその剛直な分子構造
によって高強度、高弾性率で高温下での寸法安定性及び
難燃性にも優れ、且つ従来の設備をそのま用いることが
できるので安価に製造できる等、産業界に寄与すること
大である。EFFECT OF THE INVENTION Since the copolyamideimide fiber of the present invention is copolymerized with 3,3′-dialkylbenzidine residues within the range that does not impair the solubility, it has a high strength and a high elastic modulus due to its rigid molecular structure. Therefore, it is excellent in dimensional stability under high temperature and flame retardancy, and can be manufactured at low cost because conventional equipment can be used as it is, which is a great contribution to the industrial world.
Claims (2)
れる単位を繰り返し単位とする共重合ポリアミドイミド
を紡糸又は紡糸後延伸することによって得られることを
特徴をする共重合ポリアミドイミド繊維。 【化1】 【化2】 (化1および化2においてArは二価の芳香族基であ
り、そのうち25〜95モル%は3,3’−ジアルキル
ビフェニレン基である。またRは炭素数1〜60のアル
キレン基を示し、lは0〜30モル%、mは0又は1、
nは1〜10の整数を示す。)1. A copolyamideimide obtained by spinning or spinning after spinning a copolyamideimide having a repeating unit of the unit represented by the following chemical formula 1 and the unit represented by the following chemical formula 2. fiber. [Chemical 1] [Chemical 2] (In Chemical Formula 1 and Chemical Formula 2, Ar is a divalent aromatic group, 25 to 95 mol% of which is a 3,3′-dialkylbiphenylene group. R represents an alkylene group having 1 to 60 carbon atoms, l is 0 to 30 mol%, m is 0 or 1,
n shows the integer of 1-10. )
れる単位を繰り返し単位とする共重合ポリアミドイミド
に溶剤を含んだ状態で紡糸後、必要により延伸すること
を特徴とする共重合ポリアミドイミド繊維の製造方法。 【化3】 【化4】 (化3および化4においてArは二価の芳香族基であ
り、そのうち25〜95モル%は3,3’−ジアルキル
ビフェニレン基である。またRは炭素数1〜60のアル
キレン基を示し、lは0〜30モル%、mは0又は1、
nは1〜10の整数を示す。)2. A copolymerized polyamideimide having a unit represented by the following chemical formula 3 and a unit represented by the following chemical formula 4 as a repeating unit, which is spun in a state containing a solvent and then stretched if necessary. Method for producing polymerized polyamide-imide fiber. [Chemical 3] [Chemical 4] (In Chemical Formula 3 and Chemical Formula 4, Ar is a divalent aromatic group, 25 to 95 mol% of which is a 3,3′-dialkylbiphenylene group. R represents an alkylene group having 1 to 60 carbon atoms, l is 0 to 30 mol%, m is 0 or 1,
n shows the integer of 1-10. )
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP5694192A JPH05222612A (en) | 1992-02-06 | 1992-02-06 | Polyamideimide copolymer fiber and its production |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP5694192A JPH05222612A (en) | 1992-02-06 | 1992-02-06 | Polyamideimide copolymer fiber and its production |
Publications (1)
Publication Number | Publication Date |
---|---|
JPH05222612A true JPH05222612A (en) | 1993-08-31 |
Family
ID=13041572
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP5694192A Pending JPH05222612A (en) | 1992-02-06 | 1992-02-06 | Polyamideimide copolymer fiber and its production |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH05222612A (en) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0770714A1 (en) * | 1994-05-13 | 1997-05-02 | Toyo Boseki Kabushiki Kaisha | Polyamide-imide fibers for a bug filter |
WO2006033262A1 (en) * | 2004-09-21 | 2006-03-30 | Toyo Boseki Kabushiki Kaisha | Polyamide-imide resin for melt molding |
WO2007013552A1 (en) * | 2005-07-29 | 2007-02-01 | Toyo Boseki Kabushiki Kaisha | Polyamide imide fiber, non-woven fabric composed of the fiber, process for manufacture of the non-woven fabric, and separator for electronic component |
JP2007059388A (en) * | 2005-07-29 | 2007-03-08 | Toyobo Co Ltd | Separator for electronic component |
-
1992
- 1992-02-06 JP JP5694192A patent/JPH05222612A/en active Pending
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0770714A1 (en) * | 1994-05-13 | 1997-05-02 | Toyo Boseki Kabushiki Kaisha | Polyamide-imide fibers for a bug filter |
US5681656A (en) * | 1994-05-13 | 1997-10-28 | Toyo Boseki Kabushiki Kaisha | Polyamide-imide fibers for a bag filter |
WO2006033262A1 (en) * | 2004-09-21 | 2006-03-30 | Toyo Boseki Kabushiki Kaisha | Polyamide-imide resin for melt molding |
WO2007013552A1 (en) * | 2005-07-29 | 2007-02-01 | Toyo Boseki Kabushiki Kaisha | Polyamide imide fiber, non-woven fabric composed of the fiber, process for manufacture of the non-woven fabric, and separator for electronic component |
JP2007059388A (en) * | 2005-07-29 | 2007-03-08 | Toyobo Co Ltd | Separator for electronic component |
US9023534B2 (en) | 2005-07-29 | 2015-05-05 | Toyo Boseki Kabushiki Kaisha | Polyamide imide fiber, non-woven fabric composed of the fiber, process for manufacture of the non-woven fabric, and separator for electronic component |
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