JP2716810C - - Google Patents
Info
- Publication number
- JP2716810C JP2716810C JP2716810C JP 2716810 C JP2716810 C JP 2716810C JP 2716810 C JP2716810 C JP 2716810C
- Authority
- JP
- Japan
- Prior art keywords
- polyamide resin
- filament
- acid
- weight
- layered silicate
- 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
- 239000004952 Polyamide Substances 0.000 claims description 19
- 229920002647 polyamide Polymers 0.000 claims description 19
- 239000011528 polyamide (building material) Substances 0.000 claims description 19
- BPQQTUXANYXVAA-UHFFFAOYSA-N silicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 13
- 239000011347 resin Substances 0.000 claims description 10
- 229920005989 resin Polymers 0.000 claims description 10
- 239000011342 resin composition Substances 0.000 claims description 10
- 239000011229 interlayer Substances 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 239000000203 mixture Substances 0.000 description 8
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N Caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 6
- KARVSHNNUWMXFO-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane;hydrate Chemical compound O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O KARVSHNNUWMXFO-UHFFFAOYSA-N 0.000 description 6
- 229910052901 montmorillonite Inorganic materials 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000789 fastener Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000009987 spinning Methods 0.000 description 3
- WNLRTRBMVRJNCN-UHFFFAOYSA-N Adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N HCl Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000002734 clay mineral Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000004043 dyeing Methods 0.000 description 2
- 238000010409 ironing Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000002965 rope Substances 0.000 description 2
- 230000002522 swelling Effects 0.000 description 2
- GUOSQNAUYHMCRU-UHFFFAOYSA-N 11-Aminoundecanoic acid Chemical compound NCCCCCCCCCCC(O)=O GUOSQNAUYHMCRU-UHFFFAOYSA-N 0.000 description 1
- PBLZLIFKVPJDCO-UHFFFAOYSA-N 12-aminododecanoic acid Chemical compound NCCCCCCCCCCCC(O)=O PBLZLIFKVPJDCO-UHFFFAOYSA-N 0.000 description 1
- XUWHAWMETYGRKB-UHFFFAOYSA-N 2-Piperidinone Chemical compound O=C1CCCCN1 XUWHAWMETYGRKB-UHFFFAOYSA-N 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N 2-Pyrrolidone Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- QUBNFZFTFXTLKH-UHFFFAOYSA-N 2-aminododecanoic acid Chemical compound CCCCCCCCCCC(N)C(O)=O QUBNFZFTFXTLKH-UHFFFAOYSA-N 0.000 description 1
- 229940000687 6-Aminocaproic Acid Drugs 0.000 description 1
- XDOLZJYETYVRKV-UHFFFAOYSA-N 7-aminoheptanoic acid Chemical compound NCCCCCCC(O)=O XDOLZJYETYVRKV-UHFFFAOYSA-N 0.000 description 1
- VWPQCOZMXULHDM-UHFFFAOYSA-N 9-aminononanoic acid Chemical compound NCCCCCCCCC(O)=O VWPQCOZMXULHDM-UHFFFAOYSA-N 0.000 description 1
- 241000251468 Actinopterygii Species 0.000 description 1
- SLXKOJJOQWFEFD-UHFFFAOYSA-N Aminocaproic acid Chemical compound NCCCCCC(O)=O SLXKOJJOQWFEFD-UHFFFAOYSA-N 0.000 description 1
- 206010003736 Attention deficit/hyperactivity disease Diseases 0.000 description 1
- BTCSSZJGUNDROE-UHFFFAOYSA-N GABA Chemical compound NCCCC(O)=O BTCSSZJGUNDROE-UHFFFAOYSA-N 0.000 description 1
- NAQMVNRVTILPCV-UHFFFAOYSA-N Hexamethylenediamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 1
- QQVIHTHCMHWDBS-UHFFFAOYSA-N Isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 1
- GEYOCULIXLDCMW-UHFFFAOYSA-N O-Phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 1
- 101710029643 PDSS1 Proteins 0.000 description 1
- FKHIFSZMMVMEQY-UHFFFAOYSA-N Talc Chemical compound [Mg+2].[O-][Si]([O-])=O FKHIFSZMMVMEQY-UHFFFAOYSA-N 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 1
- 102100005713 UBASH3B Human genes 0.000 description 1
- 101710012487 UBASH3B Proteins 0.000 description 1
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- WMGSQTMJHBYJMQ-UHFFFAOYSA-N aluminum;magnesium;silicate Chemical compound [Mg+2].[Al+3].[O-][Si]([O-])([O-])[O-] WMGSQTMJHBYJMQ-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 229960002684 aminocaproic acid Drugs 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 201000006287 attention deficit hyperactivity disease Diseases 0.000 description 1
- VJCJAQSLASCYAW-UHFFFAOYSA-N azane;dodecanoic acid Chemical compound [NH4+].CCCCCCCCCCCC([O-])=O VJCJAQSLASCYAW-UHFFFAOYSA-N 0.000 description 1
- ACWNVEXNIHQIOQ-UHFFFAOYSA-N azanium;12-aminododecanoate Chemical compound [NH4+].NCCCCCCCCCCCC([O-])=O ACWNVEXNIHQIOQ-UHFFFAOYSA-N 0.000 description 1
- CJYXCQLOZNIMFP-UHFFFAOYSA-N azocan-2-one Chemical compound O=C1CCCCCCN1 CJYXCQLOZNIMFP-UHFFFAOYSA-N 0.000 description 1
- VNSBYDPZHCQWNB-UHFFFAOYSA-N calcium;aluminum;dioxido(oxo)silane;sodium;hydrate Chemical compound O.[Na].[Al].[Ca+2].[O-][Si]([O-])=O VNSBYDPZHCQWNB-UHFFFAOYSA-N 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000008395 clarifying agent Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- QFTYSVGGYOXFRQ-UHFFFAOYSA-N dodecane-1,12-diamine Chemical compound NCCCCCCCCCCCCN QFTYSVGGYOXFRQ-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 229910052621 halloysite Inorganic materials 0.000 description 1
- 238000009998 heat setting Methods 0.000 description 1
- 229910000271 hectorite Inorganic materials 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 150000003951 lactams Chemical class 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000000391 magnesium silicate Substances 0.000 description 1
- 229910052919 magnesium silicate Inorganic materials 0.000 description 1
- 235000019792 magnesium silicate Nutrition 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002074 melt spinning Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000002794 monomerizing Effects 0.000 description 1
- SXJVFQLYZSNZBT-UHFFFAOYSA-N nonane-1,9-diamine Chemical compound NCCCCCCCCCN SXJVFQLYZSNZBT-UHFFFAOYSA-N 0.000 description 1
- 229910000273 nontronite Inorganic materials 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 230000000379 polymerizing Effects 0.000 description 1
- 229910000275 saponite Inorganic materials 0.000 description 1
- 229910052604 silicate mineral Inorganic materials 0.000 description 1
- REYJJPSVUYRZGE-UHFFFAOYSA-N stearylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 description 1
- KLNPWTHGTVSSEU-UHFFFAOYSA-N undecane-1,11-diamine Chemical compound NCCCCCCCCCCCN KLNPWTHGTVSSEU-UHFFFAOYSA-N 0.000 description 1
- 229910052902 vermiculite Inorganic materials 0.000 description 1
- 239000010455 vermiculite Substances 0.000 description 1
- 235000019354 vermiculite Nutrition 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
Description
【発明の詳細な説明】
[発明の目的]
(産業上の利用分野)
本発明は、フィラメント用ポリアミド樹脂組成物及びそのフィラメントに関し
、さらに詳しくは優れた強度・伸度を有し、かつ剛性・引き抜き力に優れ、かつ
熱収縮・熱水収縮性、寸法安定性に優れ、衣料用として良好な風合を持つモノ及
びマルチフィラメント用樹脂組成物並びにモノ及びマルチフィラメントに関する
。
(従来の技術)
ポリアミド樹脂は、その優れた強度・伸度等の特性から、釣り糸、歯ブラシ、
マジックファスナーなどのモノフィラメント及びタイヤコード、衣料などのマル
チフィラメントに幅広く利用されている。
しかしながら、従来のポリアミド樹脂は、一部の釣り糸、歯ブラシ等に用いら
れるブリッスル(荒毛)、マジックファスナー、タイヤコード、絨毬、人工芝な
どの用途では、その剛性、弾性率が十分でなく、さらに弾性率の高い材料が望ま
れている。また衣料用では剛性のあるフィラメントで、つや消し風合のものが望
まれている。また、染色時やアイロン処理等、加熱された時の収縮率が小さく、
寸法の安定した材料が望まれている。
(発明が解決しようとする課題)
本発明は、従来のポリアミド樹脂組成物からなるフィラメントの問題点を改良
し、優れた強度・伸度を有し、かつ、剛性、引き抜き力、熱収縮、熱水収縮性、
寸法安定性にも優れ、また、衣料用として風合の優れたモノ及びマルチフィラメ
ント用樹脂組成物並びにモノ及びマルチフィラメントを提供することを目的とす
る。
[発明の構成]
(課題を解決するための手段及び作用)
本発明は、ポリアミド樹脂(A)100重量音と(A)成分中に均一に分散さ
れている層状珪酸塩(B)0.05〜30重量部のポリアミド樹脂組成物及び該
ポリアミド樹脂組成物からなるフィラメントである。
ポリアミド樹脂(A)は、分子中に酸アミド結合(−CONH−)を有する重
合体であり、具体的には、ε−カプロラクタム、6−アミノカプロン酸、ω−エ
ナントラクタム、7−アミノヘプタン酸、11−アミノウンデカン酸、9−アミ
ノノナン酸、α−ピロリドン、α−ピペリドンなどから得られる重合体又は共重
合体;ヘキサメチレンジアミン、ノナメチレンジアミン、ウンデカメチレンジア
ミン、ドデカメチレンジアミン、メタキシリレンジアミンなどのジアミンとテレ
フタル酸、イソフタル酸、アジピン酸、セバシン酸などのジカルボン酸とを重縮
合して得られる重合体若しくは共重合体又はこれらのブレンド物を例示すること
ができる。
ポリアミド樹脂(A)の、平均分子量は10,000〜30,000が好まし
い。
平均分子量が10,000以下では、フィラメントの紡糸・延伸が困難であり
、30,000以上になるとポリアミド自体の生産が難しくなるので好ましくな
い。
層状珪酸塩(B)は、ポリアミド樹脂(A)に、その優れた引張り伸び特性を
損なうことなく、剛性、高弾性、高引き抜き力特性及び優れた風合を付与するた
めの成分である。
層状珪酸塩(B)は、(A)成分中に分散させた際、平均的に20Å以上の層
間距離を保ち、均一に分散するものであることが好ましい。ここで層間距離とは
層状珪酸塩の平板の重心間の距離を言い、均一に分散するとは層状珪酸塩の一枚
一枚が、若しくは平均的な重なりが5層以下の多層物が平行に、またはランダム
に、もしくは平行とランダムが混在した状態で50重量%以上が、好ましくは
70重量%以上が局所的な塊を形成することなく分散する状態を言う。ここで、
層状珪酸塩は、厚みが6〜20Åで、一辺が0.002〜1μmの層状一単位を
示す。
このような層状珪酸塩の原料としては、珪酸マグネシウム又は珪酸アルミニウ
ムの層から構成される層状フィロ又は珪酸鉱物を例示することができる。具体的
には、モンモリロナイト、サポナイト、バイデライト、ノントロナイト、ヘクト
ライト、スティブンサイトなどのスメクタイト系粘土鉱物及びバーミキュライト
、ハロイサイトなどを例示することができ、これらは天然のものであっても、合
成されたものであってもよい。これらのなかでもモンモリロナイトが好ましい。
(A)成分と(B)成分の組成は、(A)成分100重量部に対して(B)成
分が0.05〜30重量部である。(B)成分の組成が0.05重量部未満であ
ると、剛性、弾性、引き抜き力の向上が顕著でなく、30重量部を超えると生産
が難しくなるため好ましくない。
本発明の組成物又はフィラメントの製造時に、目的に応じて、染料、顔料、可
塑剤、耐熱剤、透明剤、滑剤、帯電防止剤などを適宜、適量を配合することがで
きる。
層状珪酸塩(B)が多層状粘土鉱物である場合には、(ジ)オクタデシルアミ
ン、フェニレンジアミンのようなアミン、4−アミノ−n−酪酸、12−アミノ
ドデカン酸のようなアミノ酸又はε−カプロラクタムのようなラクタム類の膨潤
化剤と接触させて、予め層間を拡げて層間にモノマーを取り込みやすくした後、
ポリアミドモノマーと混合し、重合する方法(特開昭62−74957号公報参
照)がある。また、膨潤化剤を用い、予め層間を20Å以上に拡げて、これをポ
リアミド樹脂若しくはこれを含む樹脂と溶融混練して均一に分散させる方法によ
ってもよい。
本発明のフィラメントは、その原料組成物を単軸などの溶融押出機にて溶融状
態とし、さらに、その吐出量を定量的に実施するギヤポンプ等により、紡糸口金
から押し出し、空気又は水などで冷却しながら、所定の引き取り速度で引き取る
こと等によって製造することができる。
さらに得られたフィラメントは、用途によって種々の倍率で延伸することがで
きるし、また、上記溶融紡糸時に、同時に延伸することができる。
フィラメントの形状は、単糸・複数糸又は複数糸の撚り合わせたものであって
もよいし、その断面は、円形に限らず、中空・星形などの異形断面であってもよ
い。
(発明の効果)
本発明のフィラメントは、各種のモノ及びマルチフィラメントに用いることが
でき、特に、ブラシ用ブリッスル、釣り糸、マジックファスナー、タイヤコード
、人工芝、絨毬、自動車座席用シート、魚網、ロープ、ザイル、フィルター用糸
などの用途に剛性の強い製品を与える。また染色やアイロン処理等、加熱された
時の収縮率が小さく、寸法及び織物としての形状の安定した製品を与える。また
腰の強い特殊な風合いを持つ衣料用の繊維としても用いることができる。
(実施例)
実施例1
層状珪酸塩の一単位の厚みが平均的に9.5Åで一辺の平均長さが約0.1μ
mのモンモリロナイト100gを10lの水に分散させ、これに51.2gの1
2−アミノドデカン酸と24mlの濃塩酸を加え、5分間撹拌したのち、濾過した
。さらにこれを十分洗浄したのち、真空乾燥した。この操作により、12−ドデ
カン酸アンモニウム[NH3 +(CH2)11COO-]とモンモリロナイトの複合体を調製した
。複合体中の層状珪酸塩分は80重量%となった。
次に、撹拌機付の反応容器に、10kgのε−カプロラクタム、1kgの水及び9
0gの前記複合体を入れ、100℃で反応系内が均一な状態になるように撹拌し
た。さらに温度を260℃に上昇させ、15kg/cm2の加圧下で1時間撹拌した。
その後、放圧し、水分を反応容器から揮散させながら、常圧下で2時間反応させ
た。反応終了後、反応容器の下部ノズルから、ストランド状に取り出した反応物
を水冷し、カッティングを行い、ポリアミド樹脂(平均分子量15,000)及
びモンモリロナイトからなるペレットを得た。このペレットを熱水中に浸漬し、
未反応のモノマー(約10%)を抽出、除去したのち、真空中で乾燥して、ポリ
アミド樹脂組成物を得た。
このようにして得られた材料について、次のような評価試験を行った。
(1)モノフィラメント評価試験
試験材料を、下記条件の押出機に投入し、直径1.47mm8穴のノズルから溶
融押し出し、7℃の冷却水中で冷却し、第1ローラーで引張り、さらに、第2ロ
ーラーの引き取り速度を第1ローラーの3.9倍として延伸し(延伸温度250
℃)、さらに第3ローラーの引き取り速度を、第1ローラーの5倍とし、さらに
延伸し(延伸温度300℃)、最後に、第4ローラーを第3ローラーと同一の引
き取り速度で引き取り、その間を雰囲気温度220℃とし、熱固定してモノフィ
ラメントを得た。
(押出し機条件)
スクリュー径:30mm
シリンダー設定温度:C1 C2 C3 C4 N
℃ 220 240 260 270 260
得られたモノフィラメントにつき次の評価試験を行った。
1)繊度
2)引張り強度・伸度・弾性率 JISL 1070、L1073に準じて測定
3)引き抜き力
第1図に示す治具を作成し、10mm径の孔よりフィラメントをカギ状治具で引
き抜く時の力をロードセルで測定し、その最大値を引き抜き力とした。
4)熱水収縮率
試料を23℃相対湿度65%中に重量が一定になるまで静置し、その後、長さ
1,000mmに切断する。これを100℃水中に15分間浸漬し、その直後の寸
法を測定する。そしてこの熱水収縮率を百分率にて算出する。
(2)マルチフィラメント評価試験
試料を(株)島津製作所製 紡糸機(スクリュー直径30mm、L/D=23、圧
縮比3.5)、同社製巻取機(STS−1、表面駆動方式、1錘1ボビン)、同
社製延伸撚糸機(SD−4)にて、紡糸・延伸撚糸を行いマルチフィラメントを
得た。詳細条件は、下記のとおりである。
(紡糸条件)
1)押出機設定温度:℃
C1 C2 C3 AD H D
210 230 250 260 260 250
2)ノズル:径0.45mm×30孔
3)引き取り速度:700m/min
4)フィルター:40/40/75/125/250/325メッシュ
5)冷却風速度:0.6m/s
6)油剤:丸菱油化(株)製 Spinner F-160TS
(延伸撚糸条件)
1)延伸温度:170℃(ホットピン)
2)延伸倍率:4倍
3)延伸速度:100m/min
以上のようにして、240d/30f目標のマルチフィラメントを作成した。
得られたマルチフィラメントにつき、次の評価試験を行った。
1)繊度
2)マルチフィラメント引張り弾性率
JIS L1070及び同L1073に準じて測定した。
3)糸の輝き、てらつきを目視にて評価。
結果を表に示す。
実施例2
実施例1において、撹拌機付の反応器に、10kgのε−カプロラクタム、1kg
の水及び180gの12−アミノドデカン酸アンモニウムとモンモリロナイトの
複合体を添加した以外は、実施例1と同様の実験を行った。結果を表に示す。
比較例1
実施例1において、撹拌機付の反応器に10kgのε−カプロラクタム、1kgの
水のみを装入し、複合体を添加せずに、実施例1と同様の実験を行った。結果を
表に示す。
DETAILED DESCRIPTION OF THE INVENTION [Object of the Invention] (Field of Industrial Application) The present invention relates to a polyamide resin composition for filaments and filaments thereof, and more particularly, to a polyamide resin composition having excellent strength and elongation and having rigidity and elongation. The present invention relates to a mono- and multi-filament resin composition and mono- and multi-filaments having excellent pulling force, excellent heat shrinkage / hot water shrinkage, and dimensional stability, and having a good feeling for clothing. (Prior art) Polyamide resins are used for fishing line, toothbrush,
It is widely used for monofilaments such as magic fasteners and multifilaments such as tire cords and clothing. However, conventional polyamide resins have insufficient rigidity and elastic modulus in applications such as bristles (rough hair), magic fasteners, tire cords, valleys, and artificial turf used for some fishing lines, toothbrushes, and the like. A material having a higher elastic modulus is desired. In addition, a stiff filament having a matte texture is desired for clothing. In addition, shrinkage when heated, such as during dyeing or ironing, is small,
Materials with stable dimensions are desired. (Problems to be Solved by the Invention) The present invention improves the problems of filaments made of a conventional polyamide resin composition, has excellent strength and elongation, and has rigidity, pull-out force, heat shrinkage, and heat. It is an object of the present invention to provide a mono- and multi-filament resin composition, and a mono- and multi-filament, which are excellent in water shrinkage and dimensional stability, and excellent in texture for clothing. [Structure of the Invention] (Means and Actions for Solving the Problems) The present invention relates to a polyamide resin (A) 100 weight tone and a layered silicate (B) 0.05 uniformly dispersed in the component (A). It is a polyamide resin composition of up to 30 parts by weight and a filament comprising the polyamide resin composition. The polyamide resin (A) is a polymer having an acid amide bond (—CONH—) in the molecule, and specifically includes ε-caprolactam, 6-aminocaproic acid, ω-enantholactam, 7-aminoheptanoic acid, Polymer or copolymer obtained from 11-aminoundecanoic acid, 9-aminononanoic acid, α-pyrrolidone, α-piperidone, etc .; hexamethylenediamine, nonamethylenediamine, undecamethylenediamine, dodecamethylenediamine, metaxylylenediamine Examples thereof include a polymer or copolymer obtained by polycondensing a diamine such as terephthalic acid, isophthalic acid, adipic acid, and secarboxylic acid with a dicarboxylic acid, or a blend thereof. The average molecular weight of the polyamide resin (A) is preferably from 10,000 to 30,000. If the average molecular weight is 10,000 or less, it is difficult to spin and draw the filament, and if it is 30,000 or more, the production of polyamide itself becomes difficult, which is not preferable. The layered silicate (B) is a component for imparting rigidity, high elasticity, high pull-out force characteristics, and excellent feeling to the polyamide resin (A) without impairing its excellent tensile elongation characteristics. When the layered silicate (B) is dispersed in the component (A), it is preferable that the layered silicate maintains an interlayer distance of 20 ° or more on average and is uniformly dispersed. Here, the interlayer distance refers to the distance between the centers of gravity of the plate of the layered silicate, and to uniformly disperse, the layered silicate is one by one, or a multilayer having an average overlap of 5 layers or less is parallel. Or, a state in which 50% by weight or more, preferably 70% by weight or more is dispersed without forming a local mass at random or in a state where parallel and random are mixed. here,
The layered silicate has a thickness of 6 to 20 ° and represents one layered unit having a side of 0.002 to 1 μm. As a raw material of such a layered silicate, a layered phyllo or a silicate mineral composed of a layer of magnesium silicate or aluminum silicate can be exemplified. Specifically, montmorillonite, saponite, beidellite, nontronite, hectorite, smectite clay minerals such as stevensite and vermiculite, halloysite, etc. can be exemplified. May be done. Of these, montmorillonite is preferred. The composition of the component (A) and the component (B) is such that the component (B) is 0.05 to 30 parts by weight based on 100 parts by weight of the component (A). If the composition of the component (B) is less than 0.05 part by weight, the rigidity, elasticity, and pull-out force are not significantly improved, and if it exceeds 30 parts by weight, production becomes difficult, which is not preferable. At the time of producing the composition or filament of the present invention, an appropriate amount of a dye, a pigment, a plasticizer, a heat-resistant agent, a clarifying agent, a lubricant, an antistatic agent, and the like can be appropriately added according to the purpose. When the layered silicate (B) is a multilayer clay mineral, (di) an amine such as octadecylamine or phenylenediamine, an amino acid such as 4-amino-n-butyric acid or 12-aminododecanoic acid, or ε-. After contacting with a lactam swelling agent such as caprolactam to expand the layers in advance and make it easier to take in monomers between the layers,
There is a method of mixing with a polyamide monomer and polymerizing (see JP-A-62-74957). Alternatively, a method of using a swelling agent to preliminarily expand the interlayer to 20 ° or more, and melt-knead this with a polyamide resin or a resin containing the same to uniformly disperse them may be used. The filament of the present invention is obtained by melting the raw material composition in a melt extruder such as a single-screw extruder from a spinneret by a gear pump or the like for quantitatively controlling the discharge amount, and cooling with air or water. Meanwhile, it can be manufactured by taking at a predetermined take-up speed or the like. Further, the obtained filament can be drawn at various magnifications depending on the application, and can be drawn simultaneously with the melt spinning. The shape of the filament may be a single yarn, a plurality of yarns or a combination of a plurality of yarns, and the cross section is not limited to a circular shape, and may be an irregular cross section such as a hollow or star shape. (Effect of the Invention) The filament of the present invention can be used for various types of monofilaments and multifilaments. In particular, bristles for brushes, fishing lines, magic fasteners, tire cords, artificial turf, valleys, automobile seats, fish nets, Gives rigid products to applications such as ropes, ropes, and filter yarns. In addition, the shrinkage ratio when heated such as dyeing or ironing is small, and a product having a stable size and shape as a woven fabric is provided. Also, it can be used as a fiber for clothing having a strong and special texture. (Example) Example 1 The thickness of one unit of the layered silicate is 9.5 mm on average, and the average length of one side is about 0.1 μm.
m of montmorillonite was dispersed in 10 l of water, and 51.2 g of 1
2-Aminododecanoic acid and 24 ml of concentrated hydrochloric acid were added, and the mixture was stirred for 5 minutes and filtered. After sufficiently washing this, it was vacuum-dried. By this operation, a complex of ammonium 12-dodecanoate [NH 3 + (CH 2 ) 11 COO − ] and montmorillonite was prepared. The layered silicate content in the composite was 80% by weight. Next, 10 kg of ε-caprolactam, 1 kg of water and 9 kg were added to a reaction vessel equipped with a stirrer.
0 g of the composite was added and stirred at 100 ° C. so that the inside of the reaction system became uniform. The temperature was further raised to 260 ° C., and the mixture was stirred for 1 hour under a pressure of 15 kg / cm 2 .
Thereafter, the pressure was released, and the reaction was carried out at normal pressure for 2 hours while evaporating water from the reaction vessel. After completion of the reaction, the reaction product taken out in a strand form from the lower nozzle of the reaction vessel was water-cooled and cut to obtain a pellet comprising a polyamide resin (average molecular weight of 15,000) and montmorillonite. Immerse these pellets in hot water,
After unreacted monomers (about 10%) were extracted and removed, they were dried in a vacuum to obtain a polyamide resin composition. The materials thus obtained were subjected to the following evaluation tests. (1) Monofilament evaluation test The test material was put into an extruder having the following conditions, melted and extruded from a nozzle having a diameter of 1.47 mm, 8 holes, cooled in 7 ° C cooling water, pulled by a first roller, and further pulled by a second roller. Of the first roller 3.9 times as fast as the first roller (stretching temperature 250
° C), the take-up speed of the third roller is set to five times that of the first roller, and the film is further stretched (stretching temperature: 300 ° C). Finally, the fourth roller is taken out at the same take-up speed as the third roller. The atmosphere temperature was set to 220 ° C., and heat setting was performed to obtain a monofilament. (Extruder conditions) Screw diameter: 30 mm Cylinder set temperature: C1 C2 C3 C4 N ° C. 220 240 260 270 260 The following evaluation test was performed on the obtained monofilament. 1) Fineness 2) Tensile strength, elongation, and elastic modulus Measured according to JISL 1070, L1073 3) Pulling force When a jig shown in Fig. 1 is created and a filament is pulled out from a 10 mm diameter hole with a hook-shaped jig Was measured with a load cell, and the maximum value was defined as the pull-out force. 4) Hot water shrinkage The sample is allowed to stand at 23 ° C. and a relative humidity of 65% until the weight becomes constant, and then cut into a length of 1,000 mm. This is immersed in water at 100 ° C. for 15 minutes, and the dimensions immediately after that are measured. Then, this hot water shrinkage is calculated in percentage. (2) Multifilament evaluation test Samples were taken from a spinning machine (Screw diameter: 30 mm, L / D = 23, compression ratio: 3.5) manufactured by Shimadzu Corporation, and a winder manufactured by the company (STS-1, surface drive system, 1 A multifilament was obtained by spinning / drawing and twisting with a draw-twisting machine (SD-4) manufactured by the company. The detailed conditions are as follows. (Spinning conditions) 1) Extruder setting temperature: ° C C 1 C 2 C 3 ADHD 210 230 250 260 260 250 2) Nozzle: 0.45 mm diameter x 30 holes 3) Take-off speed: 700 m / min 4) Filter: 40/40/75/125/250/325 mesh 5) Cooling air velocity: 0.6 m / s 6) Oil agent: Spinner F-160TS manufactured by Marubishi Yuka Co., Ltd. (Drawing and twisting conditions) 1) Drawing temperature: 170 ° C (hot pin) 2) Stretching ratio: 4 times 3) Stretching speed: 100 m / min As described above, a target multifilament of 240d / 30f was prepared. The following evaluation test was performed on the obtained multifilament. 1) Fineness 2) Multifilament tensile elastic modulus Measured according to JIS L1070 and L1073. 3) The shine and flicker of the yarn were visually evaluated. The results are shown in the table. Example 2 In Example 1, 10 kg of ε-caprolactam, 1 kg
The same experiment as in Example 1 was performed except that water and 180 g of a complex of ammonium 12-aminododecanoate and montmorillonite were added. The results are shown in the table. Comparative Example 1 In Example 1, 10 kg of ε-caprolactam and only 1 kg of water were charged into a reactor equipped with a stirrer, and the same experiment as in Example 1 was performed without adding the complex. The results are shown in the table.
【図面の簡単な説明】 第1図は引き抜き力測定用治具の説明図である。[Brief description of the drawings] FIG. 1 is an explanatory view of a jig for measuring a pull-out force.
Claims (1)
重量部とからなり、層状珪酸塩は、厚みが6〜20Åで、一辺が0.002〜1
μmの一単位を示し、それぞれ平均20Å以上の層間距離を保って均一に分散し
ている、フィラメント用ポリアミド樹脂組成物。 2.請求項1記載のポリアミド樹脂組成物からなるフィラメント。[Claims] 1. 100 parts by weight of polyamide resin (A) and layered silicate (B) 0.05 to 30
Parts by weight, and the layered silicate has a thickness of 6 to 20 ° and a side of 0.002 to 1
A polyamide resin composition for filaments, which indicates one unit of μm and is uniformly dispersed while maintaining an interlayer distance of 20 ° or more on average. 2. A filament comprising the polyamide resin composition according to claim 1.
Family
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