JPS62243628A - Production of surface-modified wholly aromatic polyamide formed product - Google Patents
Production of surface-modified wholly aromatic polyamide formed productInfo
- Publication number
- JPS62243628A JPS62243628A JP8703086A JP8703086A JPS62243628A JP S62243628 A JPS62243628 A JP S62243628A JP 8703086 A JP8703086 A JP 8703086A JP 8703086 A JP8703086 A JP 8703086A JP S62243628 A JPS62243628 A JP S62243628A
- Authority
- JP
- Japan
- Prior art keywords
- aromatic polyamide
- wholly aromatic
- formed product
- molded product
- treatment
- 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
- 239000004760 aramid Substances 0.000 title claims abstract description 35
- 229920003235 aromatic polyamide Polymers 0.000 title claims abstract description 35
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- 150000001875 compounds Chemical class 0.000 claims abstract description 20
- 125000003368 amide group Chemical group 0.000 claims abstract description 12
- 125000003700 epoxy group Chemical group 0.000 claims abstract description 11
- 239000003513 alkali Substances 0.000 claims abstract description 7
- 229910052751 metal Inorganic materials 0.000 claims abstract description 4
- 239000002184 metal Substances 0.000 claims abstract description 4
- 150000003839 salts Chemical class 0.000 claims abstract description 4
- -1 alkaline earth metal salt Chemical class 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 16
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 8
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 claims description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 2
- KXDAEFPNCMNJSK-UHFFFAOYSA-N Benzamide Chemical compound NC(=O)C1=CC=CC=C1 KXDAEFPNCMNJSK-UHFFFAOYSA-N 0.000 claims 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 abstract description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 abstract description 8
- 239000002585 base Substances 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 7
- 239000004952 Polyamide Substances 0.000 abstract description 3
- 239000002798 polar solvent Substances 0.000 abstract description 3
- 229920002647 polyamide Polymers 0.000 abstract description 3
- 230000008961 swelling Effects 0.000 abstract description 3
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 abstract description 2
- 229910000104 sodium hydride Inorganic materials 0.000 abstract description 2
- 239000012312 sodium hydride Substances 0.000 abstract description 2
- 238000005406 washing Methods 0.000 abstract description 2
- 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 abstract 1
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 abstract 1
- 238000001035 drying Methods 0.000 abstract 1
- 239000000835 fiber Substances 0.000 description 16
- 229920005989 resin Polymers 0.000 description 13
- 239000011347 resin Substances 0.000 description 13
- 239000011159 matrix material Substances 0.000 description 11
- 239000010410 layer Substances 0.000 description 9
- 229920001971 elastomer Polymers 0.000 description 8
- 239000005060 rubber Substances 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 239000004744 fabric Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000002759 woven fabric Substances 0.000 description 5
- 239000004593 Epoxy Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000011342 resin composition Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 150000004984 aromatic diamines Chemical group 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- MHSKRLJMQQNJNC-UHFFFAOYSA-N terephthalamide Chemical compound NC(=O)C1=CC=C(C(N)=O)C=C1 MHSKRLJMQQNJNC-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- 229920000271 Kevlar® Polymers 0.000 description 2
- 229920000265 Polyparaphenylene Polymers 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 150000001555 benzenes Chemical class 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000004761 kevlar Substances 0.000 description 2
- 239000004816 latex Substances 0.000 description 2
- 229920000126 latex Polymers 0.000 description 2
- 238000006263 metalation reaction Methods 0.000 description 2
- 238000001465 metallisation Methods 0.000 description 2
- NAYYNDKKHOIIOD-UHFFFAOYSA-N phthalamide Chemical compound NC(=O)C1=CC=CC=C1C(N)=O NAYYNDKKHOIIOD-UHFFFAOYSA-N 0.000 description 2
- 229920003366 poly(p-phenylene terephthalamide) Polymers 0.000 description 2
- 239000012779 reinforcing material Substances 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000004753 textile Substances 0.000 description 2
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 1
- RDIGYBZNNOGMHU-UHFFFAOYSA-N 3-amino-2,4,5-tris(oxiran-2-ylmethyl)phenol Chemical compound OC1=CC(CC2OC2)=C(CC2OC2)C(N)=C1CC1CO1 RDIGYBZNNOGMHU-UHFFFAOYSA-N 0.000 description 1
- CXXSQMDHHYTRKY-UHFFFAOYSA-N 4-amino-2,3,5-tris(oxiran-2-ylmethyl)phenol Chemical compound C1=C(O)C(CC2OC2)=C(CC2OC2)C(N)=C1CC1CO1 CXXSQMDHHYTRKY-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 244000046038 Ehretia acuminata Species 0.000 description 1
- 235000009300 Ehretia acuminata Nutrition 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- 206010061592 cardiac fibrillation Diseases 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- GLUUGHFHXGJENI-UHFFFAOYSA-N diethylenediamine Natural products C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 1
- 239000012971 dimethylpiperazine Substances 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 230000002600 fibrillogenic effect Effects 0.000 description 1
- SAVROPQJUYSBDD-UHFFFAOYSA-N formyl(dimethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)=CO SAVROPQJUYSBDD-UHFFFAOYSA-N 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical group 0.000 description 1
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000012669 liquid formulation Substances 0.000 description 1
- SIAPCJWMELPYOE-UHFFFAOYSA-N lithium hydride Chemical compound [LiH] SIAPCJWMELPYOE-UHFFFAOYSA-N 0.000 description 1
- 229910000103 lithium hydride Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- JVXXKQIRGQDWOJ-UHFFFAOYSA-N naphthalene-2-carboxamide Chemical compound C1=CC=CC2=CC(C(=O)N)=CC=C21 JVXXKQIRGQDWOJ-UHFFFAOYSA-N 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 125000004193 piperazinyl group Chemical group 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 1
- 229960001755 resorcinol Drugs 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 239000004846 water-soluble epoxy resin Substances 0.000 description 1
Landscapes
- Treatments Of Macromolecular Shaped Articles (AREA)
- Polyamides (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は表面変性全芳香族ポリアミド成形物の製造方法
に関する。更に詳しくはポリエポキシ化合物な有する層
を成形させた表面変性全芳香族ポリアミド成形物の製造
方法（二関するものであり、全芳香族ポリアミド成形物
の表面特性、例えば全芳香族ポリアミド成形物とマトリ
ックス樹脂との接着性を改善する方法を提供するもので
ある。DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention relates to a method for producing a surface-modified wholly aromatic polyamide molded article. More specifically, a method for producing a surface-modified wholly aromatic polyamide molded product formed by molding a layer containing a polyepoxy compound (this method is related to the surface characteristics of a wholly aromatic polyamide molded product, such as a wholly aromatic polyamide molded product and a matrix). The present invention provides a method for improving adhesion with resin.
（従来の技術）
従来、全芳香族ポリアミド成形物はその高い比強度、比
弾性率、優れた耐熱性を有することから、ゴム、熱硬化
性、熱可塑性樹脂に添加され、その樹脂組成物の力学的
性質、耐熱性等の向上が検討されている。(Prior Art) Conventionally, fully aromatic polyamide molded products have been added to rubber, thermosetting, and thermoplastic resins because of their high specific strength, specific modulus, and excellent heat resistance, and have been added to resin compositions. Improvements in mechanical properties, heat resistance, etc. are being considered.
（発明が解決しようとする問題点）
しかしながら、かかる性能を有する全芳香族ポリアミド
成形物からなる樹脂組成物の例として、たとえば繊維強
化樹脂では、全芳香族ポリアミド繊維とマトリックス樹
脂との接着性が悪く、また、マトリックス樹脂°中への
分散性が悪いため、良好な力学的性質を示さない。(Problems to be Solved by the Invention) However, as an example of a resin composition made of a wholly aromatic polyamide molded product having such performance, for example, in a fiber reinforced resin, the adhesiveness between the wholly aromatic polyamide fiber and the matrix resin is low. Furthermore, it does not exhibit good mechanical properties due to poor dispersibility in the matrix resin.
かかる欠点を解消するためＣ二、これまで種々の検討が
なされている。たとえばプラズマを用いる方法では、良
い接着性を示すものもあるが、これらの方法では繊維の
損傷がさけられず、また、再現性、均一性などの点で工
業的（二は問題があると考えられる。一方、化学処理に
より該全芳香族ポリアミド成形物表面に形成されたエポ
キシ基とマトリックス樹脂との化学結合力によって接着
性を向上させた例もあるが（特開昭ｔ７−／９６／３６
号公報、同！ターフＱ／ｊ７号公報および同！デー／♂
’１２３１１号公報）、これらの方法（＝よる接着性の
向上は、必ずしも満足できるものではない。In order to eliminate such drawbacks, various studies have been made so far. For example, some methods using plasma show good adhesion, but these methods do not avoid damage to the fibers, and they are considered to be problematic in terms of reproducibility and uniformity. On the other hand, there are examples in which adhesion was improved by the chemical bonding force between the epoxy groups formed on the surface of the wholly aromatic polyamide molded product through chemical treatment and the matrix resin (Japanese Unexamined Patent Publication No. 7-196-36).
No. Publication, same! Turf Q/j No.7 Publication and the same! Day／♂
'12311), the improvement in adhesion achieved by these methods is not necessarily satisfactory.
特（＝、特開昭タター７４ｔ／ｊ７号公報および同５９
−／ｆ４ｔ２３’１号公報に開示されている方法では、
繊維表面への反応が不十分であると推測される。Special (=, Japanese Patent Application Publication No. 74t/j 7 and 59
-/f4t23'1 In the method disclosed in Publication No. 1,
It is assumed that the reaction to the fiber surface is insufficient.
さらに、化学処理（二より該全芳香族ポリアミド成形物
の表向をアルカリまたは酸でエツチングする方法も検討
されているが、この方法では反応が不充分で、所期の目
的は達せられていない。Furthermore, chemical treatment (secondary method of etching the surface of the fully aromatic polyamide molded product with alkali or acid has been considered, but this method does not produce sufficient reaction and the intended purpose has not been achieved. .
（問題点を解決するための手段）
本発明者は、前記問題を解決するため鋭意研究の結果、
全芳香族ポリアミド成形物の表面のアミド基をアルカリ
又はアルカリ土類金属塩とし膨潤させ、次いでポリエポ
キシ化合物と処理することで前記問題を解決できること
を見い出し、本発明に到達した。(Means for Solving the Problems) As a result of intensive research to solve the above problems, the inventors have found that:
We have discovered that the above problem can be solved by swelling the amide groups on the surface of a wholly aromatic polyamide molded product with an alkali or alkaline earth metal salt, and then treating it with a polyepoxy compound, and have thus arrived at the present invention.
すなわち、本発明は、全芳香族ポリアミド成形物を、芳
香族炭化水素及び脂肪族炭化水素のアルカリ又はアルカ
リ土類金属塩の存在下処理し、該成形物表面のアミド基
を金属塩とし、該成形物表面を膨潤させ、次いで／分子
内（二３個以上のエポキシ基を有するポリエポキシ化合
物と処理することを特徴とする表面変性全芳香族ポリア
ミド成形物の製造方法である。That is, the present invention treats a wholly aromatic polyamide molded product in the presence of an alkali or alkaline earth metal salt of an aromatic hydrocarbon and an aliphatic hydrocarbon, converts the amide group on the surface of the molded product into a metal salt, and This is a method for producing a surface-modified wholly aromatic polyamide molded article, characterized in that the surface of the molded article is swollen and then treated with a polyepoxy compound having 23 or more epoxy groups.
本発明に用いる全芳香族ポリアミド成形物とは以下の成
形物を意味し、種々の形態、例えばフィラメント、織物
、編物、スフ、ファイブリッド、バルブ、フィルム、粉
末などの形で利用可能である。特に繊維又は織物の形で
使用されるときその効果が最もよく発揮される。The wholly aromatic polyamide molded product used in the present invention refers to the following molded products, and can be used in various forms, such as filaments, woven fabrics, knitted fabrics, staples, fibrids, bulbs, films, and powders. In particular, its effects are best exhibited when used in the form of fibers or fabrics.
本発明の表面特性の改善された全芳香族ポリアミド成形
物を製造するには該成形物をアルカリ又はアルカリ土類
金属を含む塩基の存在ド、アミド基を金属塩とし、該成
形物表面Ｊ―を膨潤させた後ポリエポキシ化合物と処理
すればよい。該成形物を効果的に膨潤させるには非プロ
トン性極性溶媒を溶媒として用いるのが好ましい。In order to produce a wholly aromatic polyamide molded article with improved surface properties according to the present invention, the molded article is treated in the presence of a base containing an alkali or alkaline earth metal, and the amide group is treated as a metal salt. After swelling, it may be treated with a polyepoxy compound. In order to effectively swell the molded article, it is preferable to use an aprotic polar solvent as the solvent.
ここで、非プロトン性極性溶媒としてはジメチルスルホ
キシド、Ｎ、Ｎ−ジメチルアセトアミド、Ｎ、Ｎ−ジメ
チルホルムアミド、Ｎ−メチルピロリドン、ヘキサメチ
ルホスホリックトリアミド等が例示される。Here, examples of the aprotic polar solvent include dimethyl sulfoxide, N,N-dimethylacetamide, N,N-dimethylformamide, N-methylpyrrolidone, and hexamethylphosphoric triamide.
アミド基のプロトン引き抜き即ち、アミド基のメタル化
に用いる塩基としてはナトリクム、カリクム、リチウム
の水素化物、ナトリワムアミド、カリワムーｔ−プトキ
シドメチルリチクム、プチルリチクム等などの強塩基の
中から任意に選ぶことができ、含水状態でナトリクム、
カリクムの水酸化物を用いることも可能である。これら
溶媒と塩基の組み合せは上記のものから任意に採用する
ことができるが、特にジメチルスルホキシドを溶媒に用
いて、上記塩基と反応した結果生成するジムジルアニオ
ン（ＣＨ，，８ＣＨ，○）でアミド基をメタル化するの
が効果的で好ましく用いられる。アミド基がメタル化さ
れた全芳香族ポリアミドは該溶媒中に可溶となり、成形
物の表面が膨潤する。The base used for the proton withdrawal of the amide group, that is, the metalation of the amide group, can be arbitrarily selected from strong bases such as natricum, kalicum, lithium hydride, natriwamamide, kaliwamu t-ptoxide methyllyticum, butyllyticum, etc. Sodium cum in a hydrated state can be
It is also possible to use hydroxide of Calicum. Combinations of these solvents and bases can be arbitrarily adopted from those listed above, but in particular dimethyl sulfoxide is used as a solvent to react with the base, resulting in the formation of an amide with the dimyl anion (CH,, 8CH, ○). It is effective and preferably used to metalize the group. The wholly aromatic polyamide whose amide groups are metallized becomes soluble in the solvent, and the surface of the molded product swells.
メタル化に際し、必要となる塩基の量は、該成形物のア
ミド基の敞を規定することが難しいためいちがいＣ二は
決められないが、濃度としては一般（二０．０７〜／モ
ル／１の間である。The amount of base required for metallization cannot be determined for each C2 because it is difficult to specify the structure of the amide group in the molded product, but the concentration is generally (20.07~/mol/ It is between 1.
メタル化温度は用いた溶媒の凝固点から沸点までの間で
特に制限はなく、通常室温（２ｔ℃）付近で反応を行な
うことができる。メタル化時間も特に制限はなく！砂嵐
上であれば充分であり、特に好ましくは６０秒以上であ
る。The metalation temperature is not particularly limited within the range from the freezing point to the boiling point of the solvent used, and the reaction can usually be carried out around room temperature (2t°C). There is no particular limit to the metalization time! It is sufficient if it is above a sandstorm, and particularly preferably 60 seconds or more.
次いで、ポリエポキシ化合物で処理し、該エポキシ化合
物を含む層を形成させた後、アミド基を再生させればよ
い。ここで言うポリエポキシ化合物とは７つの構造単位
（二３個以上のエポキシ基を有する化合物を意味し、こ
れらの例としては、Ｎ。Next, the amide group may be regenerated after treatment with a polyepoxy compound to form a layer containing the epoxy compound. The polyepoxy compound referred to herein means a compound having seven structural units (23 or more epoxy groups, examples of which include N.
Ｎ、Ｎ；Ｎ’−テトラグリシジルメチレンジアニリン、
トリグリシジル−ｐ−アミノフェノール、トリグリシジ
ル−ｍ−アミノフェノール、／、へコ９．２−テ）う（
ｐ−グリンジルフエノキン）エタン等が例示される。ポ
リエポキシ化合物との処理温度時間に特に制限はなく、
反応温度は室温から用いた溶媒の沸点の間で任意（二選
ばれ、処理時間も７分から７時間程度の間で選ばれ、こ
れら条件は該ポリアミド表面の損傷しない範囲、即ち、
表面からθ、θ／〜／μのポリエポキシ層となるように
選ばれる。N, N; N'-tetraglycidylmethylene dianiline,
triglycidyl-p-aminophenol, triglycidyl-m-aminophenol, /, heco9.2-te)
Examples include p-grindylphenoquine) ethane. There are no particular restrictions on the temperature and time of treatment with polyepoxy compounds;
The reaction temperature was selected from any range between room temperature and the boiling point of the solvent used, and the treatment time was also selected from about 7 minutes to 7 hours.
The polyepoxy layer is selected so as to form a polyepoxy layer of θ, θ/~/μ from the surface.
かように該ポリエポキシ化合物を含む、全芳香族ポリア
ミド層を形成させた後、金属化全芳香族ポリアミド１−
を形成させた後、誼属化金芳香族ポリアミドが溶解しな
い溶媒、例えば含水アセトン、などで洗浄するか、或い
は処理に用いた溶媒を沸点以上に加熱又は減圧上加熱し
留去すればよい。After forming the wholly aromatic polyamide layer containing the polyepoxy compound in this way, the metallized wholly aromatic polyamide 1-
After forming, it may be washed with a solvent in which the aromatic polyamide is not dissolved, such as aqueous acetone, or it may be distilled off by heating the solvent used for the treatment above its boiling point or under reduced pressure.
この後処理で、一部アミド基とエポキシ基が反応する場
合もあるが、何ら本発明の効果を妨げるものではない。Although some of the amide groups and epoxy groups may react during this post-treatment, this does not impede the effects of the present invention in any way.
本発明に用いられる全芳香族ポリアミドは、アミド結合
の少なくとも２５モル％以上が芳香族環性ジアミン、芳
香族環性ジカルボン酸成分より得られるものである。そ
の構造例としては、ポリパラベンズアミド、ポリパラフ
ェニレンテレフタルアミド、ポリ−４ｔ、４ｔ′−ジア
ミノベンズアニリドテレフタルアミド、ポリパラフェニ
レン−λ、６−ナフタリツクアミド、コポリパラフェニ
レン／ ４ｔ、に’（３，３’−ジメチルビフェニレン
）−テレフタルアミド、コポリパラフェニレン、／Ｚ、
ｊ−ビリジレンーテレフタルアミド、ポリオＩＶソフエ
ニレンフタルアミド、ポリメタフェニレンフタルアミド
、ポリパラフェニレンフタルアミド、ポリオルソフェニ
レンイソフタルアミド、ポリメタフェニレンイソフタル
アミド、ポリパラフェニレンイソフタルアミド、ポリオ
ルソフェニレンテレフタルアミド、ポリメタフェニレン
テレフタルアミド、ポリ−７゜！−ナフタレンフタルア
ミド、ポリーク、タージフエ二しンーオルソーフダルア
ミド、ポリーｇ、ｇ’−ジフェニレンイソフタルアミド
、ポリ−７，４ｔ−ナフタレンフタルアミド、ポリー／
、４ｔ−ナフタレンインフタルアミド、ポリー／、ｊ−
ナフタレンイソフタルアミド等、およびこれらの芳香族
ジアミンのベンゼン核の一部をハロゲンで置換した化合
物、さらには、これらの芳香族ジアミンのベンゼン核の
一部をピペラジン、λ、！−ジメチルピペラジン、コ、
ｊ−ジエチルピペラジンで置換した化合物等に代表され
る脂環式アミンを含む芳香族ポリアミド、または芳香族
ジアミンが３．３′−オキシジフェニレンジアミン、ｊ
、４ｔ’−オキシジフェニレンジアミン等のエーテル基
、アルキル基、−５−１−ＳＯ，−１−Ｃ−１−ＮＨ−
等の基（二より結合された２個の）エニル基を含む芳香
族ポリアミド、または−ｈｙＪ＞の芳香族ポリアミドの
コポリマー、たとえば、ポリ−３，３’−オキシジフェ
ニレンテレフタルアミド／ポリパラフェニレンテレフタ
ルアミド共電合体、ポリ−３，ｑ′−オキシジフェニレ
ンテレフタルアミド／ポリパラフェニレンテレフタルア
ミド共■合体等を挙げることができる。In the wholly aromatic polyamide used in the present invention, at least 25 mol% or more of the amide bonds are obtained from aromatic cyclic diamine and aromatic cyclic dicarboxylic acid components. Examples of its structures include polyparabenzamide, polyparaphenylene terephthalamide, poly-4t, 4t'-diaminobenzanilide terephthalamide, polyparaphenylene-λ, 6-naphthalicamide, copolyparaphenylene/4t, 3,3'-dimethylbiphenylene)-terephthalamide, copolyparaphenylene, /Z,
j-Pyridylene-terephthalamide, Polio IV sophenylene phthalamide, polymetaphenylene phthalamide, polyparaphenylene phthalamide, polyorthophenylene isophthalamide, polymetaphenylene isophthalamide, polyparaphenylene isophthalamide, polyorthophenylene terephthalamide , polymetaphenylene terephthalamide, poly-7゜! - naphthalene phthalamide, polyc, tadiphenylamide, polyg, g'-diphenylene isophthalamide, poly-7,4t-naphthalene phthalamide, poly/
, 4t-naphthalene inphthalamide, poly/, j-
Naphthalene isophthalamide, etc., and compounds in which a portion of the benzene nucleus of these aromatic diamines is substituted with halogen, and furthermore, a portion of the benzene nucleus of these aromatic diamines is replaced with piperazine, λ,! -dimethylpiperazine,
Aromatic polyamide containing an alicyclic amine, such as a compound substituted with j-diethylpiperazine, or an aromatic diamine containing 3,3'-oxydiphenylenediamine, j
, ether group such as 4t'-oxydiphenylenediamine, alkyl group, -5-1-SO, -1-C-1-NH-
or copolymers of aromatic polyamides of -hyJ>, such as poly-3,3'-oxydiphenylene terephthalamide/polyparaphenylene Examples include terephthalamide co-electrolyte, poly-3,q'-oxydiphenylene terephthalamide/polyparaphenylene terephthalamide co-electrolyte, and the like.
これらの全芳香族ポリアミドの製造法は、本発明を実施
する上で制限されるものではなく、たとえば、該当する
ジアミンおよびジ酸クロライドから、特公昭３ｊ−／４
ｔ３９９号公報等で知られる低温溶＃を直合法礪二より
容易に製造できる。The method for producing these wholly aromatic polyamides is not limited in carrying out the present invention, and for example, from the corresponding diamine and diacid chloride,
The low-temperature melt # known from Publication No. t399 etc. can be easily produced by the direct method.
本発明（二相いるパラ配向的全芳香族ポリアミド成形物
は、特公昭４ｔコ一♂／！号公報、特公昭Ｊ−０−／コ
ダ／ｊ号公報、特公昭！θ−１２θθ６号公報、特開昭
４ｔ７−３９４ｔｊ♂号公報、特公昭！ワーフ２♂？４
号公報等の各公報に記載の方法により、さらに高モジュ
ラス繊維は、特公昭！Ｏ−／コタ♂グ号公報、特公昭３
０−１３３６３号公報、特開昭Ｑ７−４ｔ３４ｔ／デ号
公報等の各公報に記載の方法により製造できる。因Ｃユ
市販のものとしては、デュポン社のケブラーコタ及びケ
ブラー４ｔ？（いずれもデュポン社商標で、ポリパラフ
ェニレンテレフタルアミド繊維といわれる）がある。The present invention (para-oriented wholly aromatic polyamide molded product having two phases is disclosed in Japanese Patent Publication No. 4T Ko-1/!, Publication No. J-0-/Koda/J, Publication No. 6 of Japanese Patent Publication Sho!θ-12θθ6, Japanese Patent Publication No. 4t7-394tj♂, Special Publication Showa! Wharf 2♂?4
Further, high modulus fibers can be produced by the methods described in each publication such as No. O-/Kotagu No. Publication, Special Publication Show 3
It can be produced by the methods described in various publications such as JP-A No. 0-13363 and Japanese Patent Application Laid-Open No. 1997-07-4T34T/DE. Commercially available products include DuPont's Kevlar Kota and Kevlar 4T? (Both are trademarks of the DuPont Company and are called polyparaphenylene terephthalamide fibers.)
又、特別な例としては、特公昭ｊ４ｔ−４ｔ３ｔ／２号
公報、他（：より提案された新規な構造の繊維にも、本
発明の方法は有効である。Further, as a special example, the method of the present invention is also effective for fibers with novel structures proposed by Japanese Patent Publication No. 4T-4T3T/2 and others.
該成形物表向のエポキシ基は通常のエポキシ基の検出法
で行うことができ（例えば、Ｆ、Ｄ、 ５ｎｅｌｌａｎ
ｄ Ｌ、Ｓ、 ｇｔｔｒｅ ′＠、 −ｇｎｃｙｃｌｏ
ｐｅｄｉａ ｏｆ ＩｎｄｕｓｔｒｉａｌＣｈｅｍｉｃ
ａｌ Ａｎａｌｙｓｉｓ’、 Ｖｏｌ、 ／２． ｐａ
ｇｅ／９２−２３３ 、 Ｉｎｔｅｒｓｃｉｅｎ
ｃｅ Ｐｕｂｌｉｓｈｅｒｓ、 Ｎｅｗ Ｙｏｒ
ｋ。The epoxy group on the surface of the molded product can be detected by a normal epoxy group detection method (for example, F, D, 5nellan
d L, S, gttre ′@, -gncyclo
pedia of Industrial Chemistry
al Analysis', Vol, /2. pa
ge/92-233, Interscient
ce Publishers, New York
k.
／り７／ 参照）、または、化学分析磁子分光法（Ｅｓ
ｃＡ）などの方法でも検出できる。/ri7/) or chemical analytical magneton spectroscopy (Es
It can also be detected by methods such as cA).
このようにして処理された全芳香族ポリアミド成形物は
そのままの形で種々の用途への強化材として用いること
ができる。The wholly aromatic polyamide molded product treated in this way can be used as is as a reinforcing material for various applications.
（作用）
本発明による全芳香族ポリアミド成形物の製造方法の特
徴は該成形物表面を膨潤させ、次いでポリエポキシ化合
物と処理することにより、該ポリエポキシ化合物が膨潤
した層に入り込み、後処理段階で再凝固されるとき、該
ポリアミド表面層（二ポリエポキシ化合物を含んだ層が
形成され、これらエポキシ基が全芳香族ポリアミドの分
子鎖をまたいで架橋し、強固な網目構造を形成すること
（二、ある。即ち、成形物とマトリックス界面での接着
性の向上だけでは該成形物のフィブリル化が起きるため
大幅な接着性が望めなかったものが、表面を強固な網目
構造形成によるかしめ効果でフィブリル化を抑えること
で一層の接看力の向上が可能（＝なったものである。(Function) The feature of the method for producing a wholly aromatic polyamide molded product according to the present invention is that the surface of the molded product is swollen and then treated with a polyepoxy compound, so that the polyepoxy compound enters the swollen layer, and the post-treatment step When the polyamide surface layer (a layer containing a dipolyepoxy compound is formed), these epoxy groups cross-link across the molecular chains of the fully aromatic polyamide to form a strong network structure ( Second, there is. In other words, although it was not possible to achieve significant adhesion by simply improving the adhesion at the interface between the molded product and the matrix because the molded product would become fibrillated, the caulking effect created by forming a strong network structure on the surface By suppressing fibrillation, it is possible to further improve the patient's viewing ability.
従って、マトリックス樹脂にエボキン樹脂を用いた場合
ではマトリックス樹脂と反応するエポキシ基が表面層）
二存在することによるアンカー効果も加わり、さらに接
着性の向上が見られたと推定される。また、該ポリアミ
ド成形物表面の水素結合の消失（二よりマトリックス樹
脂との親和性が高まるため、凝集を引き起こすことなく
マトリックス樹脂中（＝均一に分散すると考えられ、強
化の効果も大きくなると予想される。Therefore, when Evokin resin is used as the matrix resin, the epoxy group that reacts with the matrix resin is the surface layer)
It is presumed that the anchoring effect due to the presence of the two compounds also contributed to the further improvement in adhesion. In addition, the disappearance of hydrogen bonds on the surface of the polyamide molded product (secondarily, it increases the affinity with the matrix resin, so it is thought that it will be uniformly dispersed in the matrix resin without causing aggregation, and the reinforcing effect is expected to be greater. Ru.
（実施例）
以ド、本発明を−ｊ−明確（二するために実施例を挙げ
て説明するが、本発明の範囲をこれらの実施例（：限足
するものでないことはいうまでもない。(Examples) Hereinafter, the present invention will be explained with reference to examples in order to clarify the present invention, but it goes without saying that these examples do not limit the scope of the present invention. .
実施例／
ジメチルスルホキシド（ＤＭ８０）Ｊ−θθ−中にナト
リクムハイドライドｉ、ｓ ｔ ｒを添加し、窒素気流
中で７θ℃にて４ｔＯ分間加熱して完全に溶解した後、
３ＩＣまで冷却した。Example/Sodium hydride i, str was added to dimethyl sulfoxide (DM80) J-θθ-, and after completely dissolving by heating at 7θ°C for 4tO minutes in a nitrogen stream,
Cooled to 3 IC.
長さ／５備、巾／θ口のポリパラフェニレンテレフタル
アミド繊維（ケプラー、デュポン社）製の織布を上記Ｄ
Ｍ８０系に添加し、３５℃で／θ分間ナトリウム化反応
を行った。次いで、ＤＭＳＯ！θθ−とＮ、Ｎ、Ｎ′、
Ｎ′−テトラグリシジルメチレンジアニリン！θ？とか
らなる溶液に、上記ナトリクム化繊布を浸漬し、５０℃
で３θ分間反応させた。この織布を多量のアセトンで５
回洗浄し過剰のエボキン樹脂を除去した後、真空下で乾
燥した。The above D
It was added to the M80 system, and the sodium conversion reaction was carried out at 35°C for /θ minutes. Next, DMSO! θθ− and N, N, N′,
N'-tetraglycidylmethylene dianiline! θ? The sodium synthetic fiber fabric was immersed in a solution consisting of
The reaction was carried out for 3θ minutes. This woven fabric was washed with a large amount of acetone.
After washing twice to remove excess Evoquin resin, it was dried under vacuum.
繊維表面のエポキシ基は塩酸ジメチルホルムアミド法（
プラスチック横座（１）、“エポキシ樹脂＃橋本邦之編
著、日刊工業新聞社、昭和ダタ年第６７版参照）により
検出した。Epoxy groups on the fiber surface were removed using the hydrochloric acid dimethylformamide method (
Detected using Plastic Yokoza (1), “Epoxy resin #edited by Kuniyuki Hashimoto, Nikkan Kogyo Shimbun, Showa Data, 67th edition).
この織布（＝ビスフェノールＡ型エポキシ樹脂（ＤＦＡ
Ｒ３ｆ３、ダクケミカル製）／θ０亜量部とトリエチレ
ンテトラミン／３．３重量部から成る樹脂組成物を塗布
し、２枚貼り合わせ減圧上室温で３時間プレスし、次い
で常圧、７００℃で２時間硬化させた。This woven fabric (= bisphenol A epoxy resin (DFA)
A resin composition consisting of R3f3 (manufactured by Dak Chemical Co., Ltd.)/θ0 and 3.3 parts by weight of triethylenetetramine was applied, and the two sheets were bonded together and pressed at room temperature under reduced pressure for 3 hours, and then pressed at normal pressure at 700°C for 2 hours. Allowed to cure for hours.
この硬化物を巾／夕１、長さ／夕０１に切断し、万能引
張り試験機（ＡＵＴＯＧＲＡＰ）ｌ Ｄ Ｓ Ｓ −ｊ
００島津製）にてヘッドスピード１００−でＴ−はく
離試験を行なった。Ｔ−はく離強度は２．３ Ｋ９／／
５ａｍであった。This cured product was cut into width 1 and length 01, and then tested using a universal tensile testing machine (AUTOGRAP).
A T-peel test was carried out at a head speed of 100 mm (manufactured by Shimadzu Corporation). T-peel strength is 2.3 K9//
It was 5am.
比較例／
表面変性を実施していない織布について、実施例／と同
様な方法にて成形し、Ｔ−はく離試験を行なったところ
、Ｔ−はく離強度はθ、 ９ Ｋｑ／／ 、ｊｍａであ
った。Comparative Example: A woven fabric without surface modification was molded in the same manner as in Example and subjected to a T-peel test. The T-peel strength was θ, 9 Kq//, jma. Ta.
実施例コ
実施例／と同様にしてメタル化処理したＰ Ｐ Ｔ Ａ
繊維織物を、Ｄ Ｍ Ｓ ＯＪ−θθ−に／θ０？のト
リグリンジルーＰ−アミノフェノールを溶解した処理液
（＝、３０℃で！分間’＆ｔｌし、次いで、アセトン洗
浄、水洗浄した後、減圧ド乙０℃で乾燥した。Example: P P T A metallized in the same manner as Example/
Textile fabric to DMS OJ-θθ-/θ0? The treatment solution in which triglyceride-P-aminophenol was dissolved was heated at 30°C for 1 minute, then washed with acetone and water, and then dried under reduced pressure at 0°C.
次いで、次の如き配合により調製したレゾルンンーホル
マリンーラテックス（ＲＦ’／Ｌ）処理液に浸漬し、マ
ングルで液を絞り出した後、７５０℃で３分間乾燥し、
次いで／♂θ℃、２分間、次いでコ３θ℃、２分間のキ
ユアリングを施した。Next, it was immersed in a resolun-formalin-latex (RF'/L) treatment solution prepared with the following formulation, and after squeezing out the solution with a mangle, it was dried at 750 ° C. for 3 minutes.
Then, curing was performed at /♂θ°C for 2 minutes, and then at ♂θ°C for 2 minutes.
このときのＲＦ／Ｌ重合体組成物の付着量は、対繊維６
．７係であった。At this time, the amount of the RF/L polymer composition attached to the fiber was 6
．． I was in Section 7.
（ＲＦ／Ｌ処理剤処方）
レゾルシン ／へ〇部水
２３♂、４ｔ
ホルマリン
（３７チ水溶液） ／ ｔ、ａＮａ
ＯＨＯ，！
スチレン／ブタジェン／ビニルピリジン共重合体ラテッ
クス（固形分４ｔ／％） ｒ ＜ｔ ４ｔ、０
合 計 ！０り、９部次い
で、処理織物と厚さ約θ、７８の未加流ゴムシートを合
わせ、加圧プレスで／ ４’ ０ ’ＣＸ ／ ５ ＝
＋加硫した。得られた試料を３ ｃｍ 幅に切り、／♂
θ０剥離法により、ゴム／繊物間の接着力を測定した。(RF/L treatment agent formulation) Resorcin/parts water
23♂, 4t
Formalin (37% aqueous solution) / t, aNa
OHO,! Styrene/butadiene/vinylpyridine copolymer latex (solid content 4t/%) r <t 4t, 0
total ! Then, the treated fabric was combined with an unwashed rubber sheet having a thickness of about θ and 78 cm, and was pressed using a pressure press.
+ Vulcanized. Cut the obtained sample into 3 cm wide pieces,
The adhesive strength between the rubber and the textile material was measured by the θ0 peeling method.
用いられたゴムンートの組成は、次の如くである。The composition of the rubber compound used is as follows.
＃／（天然ゴム） ２θ 部ハイカー＃
１５θコ
（ＳＢＲ共重合ゴム） ３θ力−ボンＦｇＦ
タ０ステアリン酸
２．θ芳香族柔軟化剤 ７０
曲 鉛 華
ｊ、θ老化防止剤Ａ Ｉ Ｖ ／、
ｊ−加硫促進剤ＤＭ 、２．０合
計 ／７３ 部ゴム
／織物間の剥離強度は７．ｊ ｈであり、剥離はＲＦ／
Ｌ重合体の暗褐色を呈し、実体顕微鏡による観察でも、
全く繊維の露出は見られず、剥離はＲＦ／Ｌ重合体組成
物層とゴムとの間で生じていることが確認された。#/(Natural Rubber) 2θ Part Hiker #
15θ (SBR copolymer rubber) 3θ force-Bon FgF
Ta0 stearic acid
2. θ aromatic softener 70
Song lead flower
j, θ anti-aging agent A IV /,
j-vulcanization accelerator DM, 2.0 total /73 parts Rubber/fabric peel strength is 7. j h, and the peeling is RF/
The L polymer exhibits a dark brown color, and even when observed with a stereomicroscope,
No fibers were exposed at all, and it was confirmed that peeling occurred between the RF/L polymer composition layer and the rubber.
比較例コ
実施例コで用いたＰＰＴＡ繊維織物を、本発明の処理な
せず、従来の方法であるエポキシ処理を施し、次いで、
実施例−同様にＲＦ／Ｌ処理を実施した後、ゴムとの接
着力を測定した。Comparative Example The PPTA fiber fabric used in Example C was not subjected to the treatment of the present invention, but was subjected to a conventional epoxy treatment, and then,
Example - After carrying out RF/L treatment in the same manner, the adhesive strength with rubber was measured.
ここで、エポキシ処理液処方は、下記のとおりであり、
織布を該液に浸漬後、コｑθ℃×３ａ１１の熱処理を施
した。Here, the epoxy treatment liquid prescription is as follows,
After the woven fabric was immersed in the liquid, it was subjected to heat treatment at coqθ°C x 3a11.
（エポキシ処理液処方）
キャタリストタオ ２．θ俤（帝国
化学製品、水溶性エポキシ樹脂）ＮａＯＨＯ，／
ペレックス０ＴＰ（ｊ４ｓｏｌｎ）
２−θ水
９５．９合 計
１００．０係繊維（二付着したＲＦ／Ｌ重合体組成
物層の蝋は、対繊維６．７係であって、実施例コでは、
本発明の効果の一つとして、処理液との濡れがよいこと
が分る。(Epoxy treatment liquid formulation) Catalyst Tao 2. θtou (Teikoku Kagaku, water-soluble epoxy resin) NaOHO, / Perex 0TP (j4soln)
2-theta water
95.9 total
The wax of the attached RF/L polymer composition layer was 6.7% of the fibers, and in Example Co.
It can be seen that one of the effects of the present invention is that it has good wettability with the processing liquid.
剥離強度はλ、ｌに９で、実施例λの半分以下であり、
剥離面は繊維の色がＲＦ／Ｌに汚染されたＰＰＴＡ繊維
の色である黄褐色を呈し、実体顕微蹴観察でも、明瞭な
繊維の露出が見られた。The peel strength is 9 for λ, l, which is less than half of that of Example λ,
On the peeled surface, the color of the fibers was yellowish brown, which is the color of PPTA fibers contaminated with RF/L, and clear exposure of the fibers was observed even when observed under a stereoscopic microscope.
（発明の効果）
本発明の製造方法により得られた表面変性全芳香族ポリ
アミド成形物はこれを複合材の分野における強化材とし
て用いた場合、該成形物とマトリックス樹脂間の接着性
にすぐれ、またマトリックス樹脂への分散性が良好であ
る。即ち、本発明（二より得られた表面変性全芳香族ポ
リアミド成形物を添加した樹脂組成物ではその力学的性
質、例えば強度・弾性率等が大幅に改善される。(Effects of the Invention) When the surface-modified wholly aromatic polyamide molded product obtained by the production method of the present invention is used as a reinforcing material in the field of composite materials, it has excellent adhesion between the molded product and the matrix resin, Further, the dispersibility in the matrix resin is good. That is, in the resin composition to which the surface-modified wholly aromatic polyamide molded product obtained in accordance with the present invention (2) is added, its mechanical properties, such as strength and elastic modulus, are significantly improved.
Claims (1)
脂肪族炭化水素のアルカリ又はアルカリ土類金属塩の存
在下処理し、該成形物表面アミド基を金属塩とし、該成
形物表面を膨潤させ、次いで１分子内に３個以上のエポ
キシ基を有するポリエポキシ化合物と処理することを特
徴とする表面変性全芳香族ポリアミド成形物の製造方法 ２ 全芳香族ポリアミドがポリパラベンズアミド又はポ
リパラフェニレンテレフタルアミドである特許請求の範
囲第１項記載の表面変性全芳香族ポリアミド成形物の製
造方法[Claims] 1. A wholly aromatic polyamide molded product is treated in the presence of an alkali or alkaline earth metal salt of an aromatic hydrocarbon and an aliphatic hydrocarbon to convert the amide groups on the surface of the molded product into a metal salt, and Method 2 for producing a surface-modified wholly aromatic polyamide molded product, characterized in that the surface of the molded product is swollen and then treated with a polyepoxy compound having three or more epoxy groups in one molecule. A method for producing a surface-modified wholly aromatic polyamide molded product according to claim 1, which is benzamide or polyparaphenylene terephthalamide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8703086A JPS62243628A (en) | 1986-04-17 | 1986-04-17 | Production of surface-modified wholly aromatic polyamide formed product |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8703086A JPS62243628A (en) | 1986-04-17 | 1986-04-17 | Production of surface-modified wholly aromatic polyamide formed product |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS62243628A true JPS62243628A (en) | 1987-10-24 |
Family
ID=13903553
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8703086A Pending JPS62243628A (en) | 1986-04-17 | 1986-04-17 | Production of surface-modified wholly aromatic polyamide formed product |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62243628A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01217036A (en) * | 1988-01-14 | 1989-08-30 | E I Du Pont De Nemours & Co | Production of polyamide anion solution |
| US5275625A (en) * | 1991-03-01 | 1994-01-04 | E. I. Du Pont De Nemours And Company | Surface treated aramid fibers and a process for making them |
| US5279899A (en) * | 1992-03-17 | 1994-01-18 | Monsanto Company | Sulfonated polyamides |
| WO2000022209A1 (en) * | 1998-10-09 | 2000-04-20 | E.I. Du Pont De Nemours And Company | Grafted poly(p-phenylene terephthalamide) fibers |
| JP2001303456A (en) * | 2000-02-16 | 2001-10-31 | Du Pont Toray Co Ltd | Method of surface-treatment for aramid fiber and surface-treated fiber |
-
1986
- 1986-04-17 JP JP8703086A patent/JPS62243628A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01217036A (en) * | 1988-01-14 | 1989-08-30 | E I Du Pont De Nemours & Co | Production of polyamide anion solution |
| US5275625A (en) * | 1991-03-01 | 1994-01-04 | E. I. Du Pont De Nemours And Company | Surface treated aramid fibers and a process for making them |
| US5443896A (en) * | 1991-03-01 | 1995-08-22 | E. I. Du Pont De Nemours And Company | Surface treated aramid fibers and a process for making them |
| US5279899A (en) * | 1992-03-17 | 1994-01-18 | Monsanto Company | Sulfonated polyamides |
| WO2000022209A1 (en) * | 1998-10-09 | 2000-04-20 | E.I. Du Pont De Nemours And Company | Grafted poly(p-phenylene terephthalamide) fibers |
| JP2001303456A (en) * | 2000-02-16 | 2001-10-31 | Du Pont Toray Co Ltd | Method of surface-treatment for aramid fiber and surface-treated fiber |
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