JPH03115443A - Molded article of wholly aromatic polyamide - Google Patents
Molded article of wholly aromatic polyamideInfo
- Publication number
- JPH03115443A JPH03115443A JP1252217A JP25221789A JPH03115443A JP H03115443 A JPH03115443 A JP H03115443A JP 1252217 A JP1252217 A JP 1252217A JP 25221789 A JP25221789 A JP 25221789A JP H03115443 A JPH03115443 A JP H03115443A
- Authority
- JP
- Japan
- Prior art keywords
- aromatic polyamide
- wholly aromatic
- oxazoline
- oxazoline group
- molded article
- 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
- 229920003235 aromatic polyamide Polymers 0.000 title claims abstract description 47
- 239000004760 aramid Substances 0.000 title claims description 45
- 239000000126 substance Substances 0.000 claims abstract description 41
- 125000003504 2-oxazolinyl group Chemical group O1C(=NCC1)* 0.000 claims abstract description 40
- 239000000835 fiber Substances 0.000 abstract description 25
- 239000010408 film Substances 0.000 abstract description 20
- 229920000642 polymer Polymers 0.000 abstract description 9
- 230000001070 adhesive effect Effects 0.000 abstract description 7
- IMSODMZESSGVBE-UHFFFAOYSA-N 2-Oxazoline Chemical compound C1CN=CO1 IMSODMZESSGVBE-UHFFFAOYSA-N 0.000 abstract description 5
- 239000002245 particle Substances 0.000 abstract description 4
- 238000001125 extrusion Methods 0.000 abstract 1
- 239000000463 material Substances 0.000 description 20
- 229920005989 resin Polymers 0.000 description 18
- 239000011347 resin Substances 0.000 description 18
- 238000011282 treatment Methods 0.000 description 17
- 239000002759 woven fabric Substances 0.000 description 16
- 238000000034 method Methods 0.000 description 14
- 229920001971 elastomer Polymers 0.000 description 11
- 239000005060 rubber Substances 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- -1 aromatic cyclic diamine Chemical class 0.000 description 9
- WRDNCFQZLUCIRH-UHFFFAOYSA-N 4-(7-azabicyclo[2.2.1]hepta-1,3,5-triene-7-carbonyl)benzamide Chemical compound C1=CC(C(=O)N)=CC=C1C(=O)N1C2=CC=C1C=C2 WRDNCFQZLUCIRH-UHFFFAOYSA-N 0.000 description 8
- 239000011159 matrix material Substances 0.000 description 8
- 239000002131 composite material Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 239000000853 adhesive Substances 0.000 description 5
- 125000003118 aryl group Chemical group 0.000 description 5
- 238000005452 bending Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 125000000524 functional group Chemical group 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 239000004593 Epoxy Substances 0.000 description 4
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 4
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 4
- 239000004744 fabric Substances 0.000 description 4
- 230000002787 reinforcement Effects 0.000 description 4
- 239000004952 Polyamide Substances 0.000 description 3
- 150000004984 aromatic diamines Chemical class 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- QZUPTXGVPYNUIT-UHFFFAOYSA-N isophthalamide Chemical compound NC(=O)C1=CC=CC(C(N)=O)=C1 QZUPTXGVPYNUIT-UHFFFAOYSA-N 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 125000002971 oxazolyl group Chemical group 0.000 description 3
- 229920002647 polyamide Polymers 0.000 description 3
- 230000003014 reinforcing effect Effects 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Chemical compound C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 2
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000001555 benzenes Chemical class 0.000 description 2
- 229940106691 bisphenol a Drugs 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000001941 electron spectroscopy Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 125000000623 heterocyclic group Chemical group 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 239000004816 latex Substances 0.000 description 2
- 229920000126 latex Polymers 0.000 description 2
- 229920000620 organic polymer Polymers 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
- SCUZVMOVTVSBLE-UHFFFAOYSA-N prop-2-enenitrile;styrene Chemical compound C=CC#N.C=CC1=CC=CC=C1 SCUZVMOVTVSBLE-UHFFFAOYSA-N 0.000 description 2
- 239000011342 resin composition Substances 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 229920000638 styrene acrylonitrile Polymers 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- MHSKRLJMQQNJNC-UHFFFAOYSA-N terephthalamide Chemical compound NC(=O)C1=CC=C(C(N)=O)C=C1 MHSKRLJMQQNJNC-UHFFFAOYSA-N 0.000 description 2
- 229920005992 thermoplastic resin Polymers 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- OWRCNXZUPFZXOS-UHFFFAOYSA-N 1,3-diphenylguanidine Chemical compound C=1C=CC=CC=1NC(=N)NC1=CC=CC=C1 OWRCNXZUPFZXOS-UHFFFAOYSA-N 0.000 description 1
- PIPWSBOFSUJCCO-UHFFFAOYSA-N 2,2-dimethylpiperazine Chemical group CC1(C)CNCCN1 PIPWSBOFSUJCCO-UHFFFAOYSA-N 0.000 description 1
- JIAOVIBEPXQRNK-UHFFFAOYSA-N 2,5-diethylpiperazine Chemical group CCC1CNC(CC)CN1 JIAOVIBEPXQRNK-UHFFFAOYSA-N 0.000 description 1
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- WFUGQJXVXHBTEM-UHFFFAOYSA-N 2-hydroperoxy-2-(2-hydroperoxybutan-2-ylperoxy)butane Chemical compound CCC(C)(OO)OOC(C)(CC)OO WFUGQJXVXHBTEM-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical class C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- XRASRVJYOMVDNP-UHFFFAOYSA-N 4-(7-azabicyclo[4.1.0]hepta-1,3,5-triene-7-carbonyl)benzamide Chemical compound C1=CC(C(=O)N)=CC=C1C(=O)N1C2=CC=CC=C21 XRASRVJYOMVDNP-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241000736839 Chara Species 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical group OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 229920003369 Kevlar® 49 Polymers 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 238000007126 N-alkylation reaction Methods 0.000 description 1
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 1
- 229920000265 Polyparaphenylene Polymers 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 1
- CWRYPZZKDGJXCA-UHFFFAOYSA-N acenaphthene Chemical compound C1=CC(CC2)=C3C2=CC=CC3=C1 CWRYPZZKDGJXCA-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000007900 aqueous suspension 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
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000000805 composite resin Substances 0.000 description 1
- 238000003851 corona treatment Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 208000028659 discharge Diseases 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 1
- KKFHAJHLJHVUDM-UHFFFAOYSA-N n-vinylcarbazole Chemical compound C1=CC=C2N(C=C)C3=CC=CC=C3C2=C1 KKFHAJHLJHVUDM-UHFFFAOYSA-N 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 229920003986 novolac 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
- 230000003287 optical effect Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000002918 oxazolines Chemical class 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 229920005575 poly(amic acid) Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000012783 reinforcing fiber Substances 0.000 description 1
- 229920003987 resole Polymers 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 235000014692 zinc oxide Nutrition 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Landscapes
- Treatments Of Macromolecular Shaped Articles (AREA)
- Polyamides (AREA)
- Adhesives Or Adhesive Processes (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、新規な全芳香族ポリアミド成形物に関する。[Detailed description of the invention] (Industrial application field) The present invention relates to a novel wholly aromatic polyamide molded article.
更に詳しくは、本発明は、全芳香族ポリアミド樹脂成形
物をオキサゾリン基含有物質で処理することにより、表
面特性の改善された全芳香族ポリアミド樹脂成形物に関
する。More specifically, the present invention relates to a wholly aromatic polyamide resin molded article having improved surface characteristics by treating the wholly aromatic polyamide resin molded article with an oxazoline group-containing substance.
例えば、複合材料におけるマトリックス樹脂との接着性
を向上させた全芳香族ポリアミド繊維、または各種の接
着剤との接着性の向上した全芳香族ポリアミドフィルム
またはシートに関する。For example, the present invention relates to wholly aromatic polyamide fibers with improved adhesion to matrix resins in composite materials, or wholly aromatic polyamide films or sheets with improved adhesiveness to various adhesives.
（従来の技術）
全芳香族ポリアミド成形物は耐熱性の高い有機高分子材
料として数々の場で使用されている。特に、ｐ−フェニ
レンテレフタルアミド（ＰＰＴＡ）の高濃度硫酸溶液を
液晶紡糸して得られる糸（特開昭４７−３９４５８号公
報、特開昭４７−４３４１９号公報）は、高強度、高弾
性率の有機スーパー繊維として知られ、複合材料の補強
繊維としての利用が知られている。(Prior Art) Fully aromatic polyamide molded products are used in many places as highly heat-resistant organic polymer materials. In particular, yarns obtained by liquid crystal spinning a highly concentrated sulfuric acid solution of p-phenylene terephthalamide (PPTA) (Japanese Patent Laid-Open Nos. 47-39458 and 47-43419) have high strength and high elastic modulus. It is known as an organic super fiber, and is known to be used as a reinforcing fiber in composite materials.
例えば、ＰＰＴＡ繊維は、ゴム、熱可塑性樹脂、熱硬化
性樹脂に添加され、その樹脂組成物の力学特性を向上さ
せている。スチールに代わるタイヤ補強用のタイヤコー
ドとしても用いられている。For example, PPTA fibers have been added to rubbers, thermoplastics, and thermosets to improve the mechanical properties of the resin compositions. It is also used as a tire reinforcement cord instead of steel.
また、フィルムについては、ＰＰＴＡの光学異方性を示
す硫酸ドープを光学性等方性ドープに相変化させた後、
凝固させることにより力学性能の卓越したフィルム（特
開昭６２−３７１２４号公報、特開昭６２−３９６３４
号公報）が得られている。In addition, for the film, after phase-changing the sulfuric acid dope exhibiting optical anisotropy of PPTA to an optically isotropic dope,
By solidifying, films with excellent mechanical performance can be produced (Japanese Patent Application Laid-Open No. 62-37124, Japanese Patent Application Laid-open No. 62-39634).
(No. Publication) has been obtained.
これらのフィルムはその優れた耐熱性や機械強度を利用
して高密度・高精度の電気・電子材料に、あるいは複合
材料に使用されつつある。These films are being used in high-density, high-precision electrical and electronic materials, as well as in composite materials, due to their excellent heat resistance and mechanical strength.
しかしながら、例えばＰＰＴＡ＄！３ｉ維を強化剤とし
た繊維強化樹脂複合材料では、ＰＰＴＡ繊維とマトリッ
クス樹脂との接着性が悪く、また該繊維のマトリックス
樹脂中の分散性が悪いために、当初予想されたような良
好な力学特性を示さなかった。However, for example, PPTA$! In fiber-reinforced resin composite materials using 3i fibers as reinforcement, the adhesion between the PPTA fibers and the matrix resin is poor, and the dispersibility of the fibers in the matrix resin is poor, resulting in poor mechanical properties as initially expected. No characteristics were shown.
従って、補強効果を最大限に挙げることを目的とし、マ
トリックス樹脂との接着性を上げるために数多くの検討
がなされてきた。例えば、ゴム補強用には該繊維をレゾ
ルシン−ホルマリン−ラテックス（ＲＦＬ）処理したり
、全芳香族ポリアミド成形物表面に化学処理をしてエポ
キシ基等を形成し、これらとマトリックス樹脂の接着性
を向上させたり（特開昭５７−１９５１３６号公報、特
開昭５９−７４１５７号公報、特開昭５９−１８４２３
４号公報）、全芳香族ポリアミド成形物中のアミド基を
Ｎ−アルキル化したり（特開昭６１−８１４２６号公報
、Ｊ、Ｐｏｌｙｍｅｒ Ｓｃｉ、、 Ｐｏｌｙｍｅ
ｒ Ｃｈｅｍ、 Ｅｄ、、 １９、］、１３３
ｐ （１９Ｂり）、プラズマやコロナ放電などの物理的
な表面処理がなされてきた。Therefore, with the aim of maximizing the reinforcing effect, many studies have been made to improve the adhesiveness with the matrix resin. For example, for rubber reinforcement, the fibers are treated with resorcinol-formalin-latex (RFL), or the surface of fully aromatic polyamide molded products is chemically treated to form epoxy groups, etc., to improve the adhesion between these and matrix resins. (Japanese Patent Application Laid-Open No. 57-195136, JP-A No. 59-74157, JP-A-59-18423)
4), N-alkylation of the amide group in a wholly aromatic polyamide molded product (Japanese Patent Application Laid-Open No. 61-81426, J, Polymer Sci, Polyme
r Chem, Ed,, 19,], 133
Physical surface treatments such as p (19B), plasma and corona discharge have been performed.
（発明が解決しようとする課題）
しかしながら、これらの方法による接着性の向上は必ず
しも満足できるものではなかったり、反応活性の低い全
芳香族ポリアミドに対して、厳しい条件で改質するため
に成形物の高次構造を破壊したりし、せっかくの高い力
学特性を低下させたりすることが多かった。また、高価
な薬品を必要とする場合も多く、工業的ではなかった。(Problems to be Solved by the Invention) However, the improvement in adhesion by these methods is not necessarily satisfactory, and molded products are required to be modified under severe conditions for wholly aromatic polyamides with low reaction activity. In many cases, the higher-order structure of the material was destroyed, resulting in a decrease in its high mechanical properties. Moreover, it often required expensive chemicals and was not industrially viable.
本発明は、全芳香族ポリアミド成形物の性質、特に接着
性の向上を目的としてなされたものであり、鋭意検討し
た結果、特定の処理を施された変性全芳香族ポリアミド
樹脂成形物がこの目的を達成し得ることを見出し、本発
明を完成したものである。The present invention was made with the aim of improving the properties of wholly aromatic polyamide molded products, especially their adhesive properties.As a result of intensive studies, a modified wholly aromatic polyamide resin molded product subjected to a specific treatment has been developed for this purpose. The present invention has been completed based on the discovery that the following can be achieved.
（課題を解決するための手段）
すなわち、本発明は、全芳香族ポリアミド成形物をオキ
サプリン基含有物質で処理した、新規な成形物である。(Means for Solving the Problems) That is, the present invention is a novel molded product obtained by treating a wholly aromatic polyamide molded product with an oxapurine group-containing substance.
以下に本発明の詳細な説明する。The present invention will be explained in detail below.
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８５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。In the wholly aromatic polyamide used in the present invention, at least 85 mol% or more of the amide bonds are obtained from an aromatic cyclic diamine or an aromatic cyclic dicarboxylic acid component.
その具体例としては、ポリバラベンズアミド、ポリバラ
フェニレンテレフタルアミド、ポリ−４゜４゛−ジアミ
ノベンズアニリド、テレフタルアミド、ポリバラフェニ
レン−２，６−ナツタリンクアミド、コポリパラフェニ
レン／４．４’ （３゜３−ジメチルビフェニレン）
−テレフタルアミド、コポリバラフェニレン／２．５−
ピリジレンーテレフタルアミド、ポリオルソフェニレン
フタルアミド、ポリメタフェニレンフタルアミド、ポリ
バ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
、ポリバラフェニレンイソツクルアミド、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−１５−ナフタレンフタルアミド、ポ
リ−４，４ジフェニレン−オルソ−フタルアミド、ポリ
−４゜４−ジフェニレンイソフタルアミド、ポリ−１４
−ナフタレンフタルアミド、ポリ−１４−ナフタレンイ
ソフタルアミド、ポリ−１，５−ナフタレンイソフタル
アミド等、及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ーン核の一部をピペラジン、２
．５−ジメチルピペラジン、２．５−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３３′−オ
キシジフェニレンジアミン、３４オキシジフエニレンジ
アミン等のエール基、アルキル基、−Ｓ−−ＳＯ。Specific examples thereof include polyparabenzamide, polyparaphenylene terephthalamide, poly-4゜4゛-diaminobenzanilide, terephthalamide, polyparaphenylene-2,6-natutalinkamide, and copolyparaphenylene/4.4' (3゜3-dimethylbiphenylene)
-Terephthalamide, copolyvaraphenylene/2.5-
Pyridylene terephthalamide, polyorthophenylene phthalamide, polymethaphenylene phthalamide, polyparaphenylene phthalamide, polyorthophenylene isophthalamide, polymethaphenylene isophthalamide, polyparaphenylene isotucramide, polyorthophenylene terephthalamide, poly Metaphenylene terephthalamide, poly-15-naphthalene phthalamide, poly-4,4 diphenylene-ortho-phthalamide, poly-4゜4-diphenylene isophthalamide, poly-14
- Naphthalene phthalamide, poly-14-naphthalene isophthalamide, poly-1,5-naphthalene isophthalamide, etc., and compounds in which a part of the benzene nucleus of these aromatic diamines is replaced with halogen, and furthermore, these aromatic diamines A part of the benzene nucleus of the diamine is converted into piperazine, 2
．． Aromatic polyamides containing alicyclic amines, such as compounds substituted with 5-dimethylpiperazine and 2,5-diethylpiperazine; or aromatic diamines such as 33'-oxydiphenylenediamine, 34oxydiphenylenediamine, etc. ale group, alkyl group, -S--SO.
Ｃ−−ＮＨ−等の基により結合された２個の＾
フェニル基を含む芳香族ポリアミド；または上述の芳香
族ポリアミドのコポリマー、たとえば、ボ１Ｊ−３，３
−オキシジフェニレンテレフタルアミド／ポリバラフェ
ニレンテレフタルアミド共重合体、ポリ−３，４′−オ
キシジフェニレンテレフタルアミド／ポリバラフェニレ
ンテレフタルアミド共重合体等を挙げることができる。Aromatic polyamides containing two phenyl groups linked by groups such as C--NH-; or copolymers of the aromatic polyamides described above, e.g.
-oxydiphenylene terephthalamide/polyvara phenylene terephthalamide copolymer, poly-3,4'-oxydiphenylene terephthalamide/polyvara phenylene terephthalamide copolymer, and the like.
本発明に用いられる全芳香族ポリアミド成形物とは、上
述の全芳香族ポリアミドを例えば溶液状、繊維状、フィ
ルム状で押出す等して成形された繊維、フィルム、ある
いは粒子等をいう。これらは、種々の形態のものが可能
であり、特に制限はなく、例えば、繊維（マルチフィラ
メント、スフ、チョンプドストランド、モノフィラメン
トなど）、ファイブリッド、フィルム、織布、不織布、
シート、紙、粉体などが挙げられる。The wholly aromatic polyamide molded product used in the present invention refers to fibers, films, or particles formed by extruding the above-mentioned wholly aromatic polyamide in the form of a solution, fiber, or film. These can be in various forms, and there are no particular limitations, such as fibers (multifilament, staple fiber, chopped strand, monofilament, etc.), fibrid, film, woven fabric, non-woven fabric,
Examples include sheets, paper, and powder.
本発明において用いられる全芳香族ポリアミドは、特に
乾燥して使用される必要はなく、未乾燥の膨潤、湿潤状
態の成形物も使用することが出来る。特に、高い接着性
を得ようとする場合には、膨潤、湿潤状態の全芳香族ポ
リアミド成形物を用いた方が良好な結果を得る場合が多
い。The wholly aromatic polyamide used in the present invention is not particularly required to be used in a dry state, and undried, swollen or wet molded products can also be used. In particular, when high adhesion is desired, better results are often obtained by using a wholly aromatic polyamide molded product in a swollen, wet state.
また、該全芳香族ポリアミド成形物は、オキサゾリン基
含有物質で処理される前に、アミド結合のメタル化やＮ
−アルキル化、薬品処理、プラズマやコロナ放電処理等
の物理処理など公知の技術によって前処理することもで
きる。これらの前処理は、該全芳香族ポリアミド成形物
の機械強度の低下や、高次構造の破棄等がない限りにお
いて使用できる。In addition, before the wholly aromatic polyamide molded product is treated with an oxazoline group-containing substance, the amide bond is metalized and N
- Pretreatment can also be carried out by known techniques such as alkylation, chemical treatment, physical treatment such as plasma or corona discharge treatment. These pretreatments can be used as long as they do not reduce the mechanical strength of the wholly aromatic polyamide molded product or destroy the higher-order structure.
本発明において、オキサゾリン基含有物質とは、−ａの
有機化合物または有機ポリマー、オリゴマーを主骨格と
した物質の末端または側鎖にオキサプリン基（好ましく
は２−オキサゾリン基）を含む物質をいう。In the present invention, the oxazoline group-containing substance refers to a substance containing an oxapurine group (preferably a 2-oxazoline group) at the terminal or side chain of the organic compound, organic polymer, or oligomer-based substance of -a.
オキサゾリン基は、その骨格に１つまたは２つ以上持つ
ことが出来るが、接着性能の向上のためには反応性官能
基であるオキサゾリン基を多く持つ方がより好ましい。Although the skeleton can have one or more oxazoline groups, it is more preferable to have as many oxazoline groups as reactive functional groups in order to improve adhesive performance.
オキサゾリン基含有物質の主鎖の骨格としては、炭化水
素鎖、エチレングリコール鎖、ビスフェノール−Ａ等の
ビスフェノール類やフェノール樹脂、ノボラック樹脂、
レゾール樹脂等の初期重合物等が用いられ、それらの分
子骨格中には芳香環や複素環を含む物質も使用される。The main chain skeleton of the oxazoline group-containing substance includes hydrocarbon chains, ethylene glycol chains, bisphenols such as bisphenol-A, phenolic resins, novolac resins,
Initial polymers such as resol resins are used, and substances containing aromatic rings or heterocycles in their molecular skeletons are also used.
耐熱性を考えた場合は、かえって芳香環や複素環をその
分子中に持った方がよい。When considering heat resistance, it is better to have an aromatic ring or a heterocycle in the molecule.
さらに、主成分モノマー及び／またはそれらからなるポ
リマーやオリゴマーの、末端や側鎖にオキサゾリン基を
持つオキサプリン基含有物質も有用である。Furthermore, oxapurine group-containing substances having oxazoline groups at the terminals or side chains of main monomers and/or polymers and oligomers made of them are also useful.
これらの七ツマ−としては、スチレン、スチレン誘導体
、アクリロニトリル、メタクリル酸エステル、メタクリ
ル酸、塩化ビニル、塩化ビニリデン、酢酸ビニル、ビニ
ルピリジン、ビニルエーテル、エチレン、ブタジェン、
アクリルアミド、ビニルカルバゾール、インデン、アセ
ナフテン、無水マレイン酸等が用いられ、これらは単独
のポリマー及び／またはオリゴマーとして、さらに共重
合物質としても使用される。また、さらにこれらの混合
物としても使用できる。These seven polymers include styrene, styrene derivatives, acrylonitrile, methacrylic acid ester, methacrylic acid, vinyl chloride, vinylidene chloride, vinyl acetate, vinylpyridine, vinyl ether, ethylene, butadiene,
Acrylamide, vinylcarbazole, indene, acenaphthene, maleic anhydride, etc. are used, and these are used as individual polymers and/or oligomers, and also as copolymerized substances. Furthermore, it can also be used as a mixture of these.
また、−ａの熱可塑性樹脂末端にオキサゾリン基を持つ
物質も使用される。Moreover, a substance having an oxazoline group at the thermoplastic resin terminal of -a is also used.
オキサゾリン基含有物質の形態としては、液状、溶融状
、固体またはこれらを熔解しうる水や有機溶媒中での溶
液状、さらに水等に分散した懸濁液状（エマルジョン粒
子、ラテックス粒子状等）で使用される。The oxazoline group-containing substance can be in the form of a liquid, a melt, a solid, a solution in water or an organic solvent that can dissolve these, or a suspension dispersed in water (emulsion particles, latex particles, etc.). used.
オキサゾリン基含有物質を全芳香族ポリアミド成形物に
接触させる方法は、本発明において特に限定されない、
具体的には、液体状、溶液状、懸濁液状、溶融状のオキ
サゾリン基含有物質中に全芳香族ポリアミド成形物を浸
漬する方法、噴霧する方法、あるいは塗布する方法、ま
たは、オキサゾリン基含有物質のフィルムやマット状の
成形物を該全芳香族ポリアミド成形物に積層する方法等
いずれであってもよい、接触させる温度も特に限定され
るものではなく、オキサゾリン基含有物質の性状や種類
によってそれぞれ異なる。−船釣には、室温〜９０’Ｃ
の範囲で行われる。The method of bringing the oxazoline group-containing substance into contact with the wholly aromatic polyamide molded article is not particularly limited in the present invention.
Specifically, a method of immersing a wholly aromatic polyamide molded article in a liquid, solution, suspension, or molten oxazoline group-containing substance, a method of spraying, or a method of coating the oxazoline group-containing substance; Any method may be used, such as laminating a film or mat-like molded product on the wholly aromatic polyamide molded product.The contact temperature is not particularly limited, and may vary depending on the properties and type of the oxazoline group-containing substance. different. -For boat fishing, room temperature - 90'C
It is carried out within the range of
オキサゾリン基含有物質で処理された変性全芳香族ポリ
アミド成形物は、後で熱処理及び／またはプレス処理す
ることも可能である。これらの後処理をすることは、全
芳香族ポリアミド成形物とオキサゾリン基含有物質との
よりよい含浸性または化学結合の促進につながるため、
かえって良好な態様であるといえる。The modified wholly aromatic polyamide molded article treated with the oxazoline group-containing substance can also be subsequently subjected to heat treatment and/or press treatment. These post-treatments lead to better impregnation or promotion of chemical bonding between the wholly aromatic polyamide molded product and the oxazoline group-containing substance.
On the contrary, it can be said that this is a good aspect.
以上の操作によって得られた変性全芳香族ポリアミド成
形物は、（イ）全芳香族ポリアミドの末端残基である一
ＣＯＯＨや−Ｎ ＋（、と化学反応によって結合してい
てもよく、及び／または、（ロ）化学反応せずにオキサ
ゾリン基を残したままの状態でオキサゾリン基含有物質
が全芳香族ポリアミド成形物中に含浸されたままの状態
でもよい。The modified wholly aromatic polyamide molded article obtained by the above operation may be bonded (a) to -COOH or -N + (, which is the terminal residue of the wholly aromatic polyamide) by a chemical reaction, and/ Alternatively, (b) the oxazoline group-containing substance may be impregnated into the wholly aromatic polyamide molded article with the oxazoline group remaining without any chemical reaction.
（イ）の場合には、オキサプリン基と全芳香族ポリアミ
ドとの結合を高める上で好ましい。この場合、変性全芳
香族ポリアミド成形物と異種及び／または同種の複合化
される素材との接着は、オキサゾリン基含有物質の主鎖
の構造に由来する。In the case of (a), it is preferable in terms of increasing the bond between the oxapurine group and the wholly aromatic polyamide. In this case, the adhesion between the modified wholly aromatic polyamide molded article and the different and/or the same type of composite material originates from the structure of the main chain of the oxazoline group-containing substance.
（ロ）の場合には、変性全芳香族ポリアミド酸成形物と
他素材及び／または同種の素材との接着では、含浸され
ているオキサゾリン基と複合化される他素材の持つ官能
基とが反応してより強固な異種の素材同志の界面結合力
を達成しうる。In the case of (b), when adhering the modified wholly aromatic polyamic acid molded product to other materials and/or the same type of material, the impregnated oxazoline groups react with the functional groups of the other materials to be composited. By doing so, it is possible to achieve stronger interfacial bonding force between different materials.
こういった意味におい゛６本発明に使用されるオキサゾ
リン基含有物質は、その物質中にオキサゾリン基を２つ
もしくはそれ以上持つことが望ましいＬ！ｉ様であり、
このオキサゾリン基含有物質を介して、全芳香族ポリア
ミド成形物は他素材及び／または同種の素材同志とより
強固に複合化、接着される。In this sense, it is desirable that the oxazoline group-containing substance used in the present invention has two or more oxazoline groups in the substance. Mr. i,
Through this oxazoline group-containing substance, the wholly aromatic polyamide molded product is more strongly composited and bonded to other materials and/or materials of the same type.
これは、オキサゾリン基が全芳香族ポリアミド成形物の
末端官能基（−ＣＯＯＨｌ−ＮＨｚ ）と化学結合し、
及び／または、変性ポリアミド成形物中のオキサゾリン
基が複合化する相手の素材分子や樹脂分子の持つ官能基
と化学結合するためである。This is because the oxazoline group chemically bonds with the terminal functional group (-COOHl-NHz) of the wholly aromatic polyamide molded product.
And/or this is because the oxazoline group in the modified polyamide molded product chemically bonds with the functional group of the material molecule or resin molecule to be composited.
オキサゾリン基と化学反応を行う官能基としては、例え
ば−Ｃ○０Ｈ１−ＯＨ１−ＮＨ２、−３Ｉ］等の活性水
素を持つものである。例えば、オキサゾリン基はカルボ
ン酸基と以下のような結合を作る。Examples of functional groups that chemically react with the oxazoline group include those having active hydrogen such as -C0H1-OH1-NH2, -3I]. For example, an oxazoline group forms the following bond with a carboxylic acid group.
いかなるオキサゾリン基含有物質で全芳香族ポリアミド
成形物を処理するかは、その変性全芳香族ポリアミド成
形物の使用用途によって異なる。Which oxazoline group-containing substance is used to treat the wholly aromatic polyamide molded article depends on the intended use of the modified wholly aromatic polyamide molded article.
例えば、該成形物と他素材との複合化の場合には、相手
のマトリックス樹脂の種類によって、また他素材と接着
・積層する場合には、それらの材質の違いによって選ば
れるべきである。For example, in the case of compositing the molded product with other materials, the choice should be made depending on the type of matrix resin to be used, and in the case of adhesion or lamination with other materials, the choice should be made depending on the differences in the materials.
具体的には、成形物が繊維であって樹脂補強やゴム補強
する目的で用いたり、成形物がフィルムであってその表
面に樹脂層を形成したり、他の接着剤で接着を行ったり
等の、各種の使用形態の違いにより、オキサゾリンで変
性した全芳香族ポリアミド成形物とそこで使用される樹
脂や素材との組合せは、それら相互間の親和性・反応性
を勘案して選ばれるべきであり、これは当業者に容易に
選択でるものである。Specifically, the molded product is a fiber and is used for the purpose of reinforcing resin or rubber, the molded product is a film and a resin layer is formed on its surface, or it is bonded with another adhesive, etc. Due to the differences in the various usage forms, the combination of fully aromatic polyamide molded products modified with oxazoline and the resins and materials used therein should be selected by taking into consideration their mutual affinity and reactivity. This can be easily selected by those skilled in the art.
全芳香族ポリアミド成形物表面に含浸及び／または結合
されたオキサゾリン基含有物質は、赤外吸収スペクトル
法で確認できる（１６３０ｃｍ−’にオキサゾリン基の
吸収ピークがある）。他に、化学分析電子分光法（ＥＳ
ＣＡ）等の方法によっても検出できる。The oxazoline group-containing substance impregnated and/or bonded to the surface of the wholly aromatic polyamide molded article can be confirmed by infrared absorption spectroscopy (there is an absorption peak of the oxazoline group at 1630 cm-'). In addition, chemical analytical electron spectroscopy (ES)
It can also be detected by methods such as CA).
（作用）
本発明のオキサプリン基含有物質で変性された全芳香族
ポリアミド成形物は、該ポリアミド表面層にオキサゾリ
ン基を持つ化合物を有するために、他素材もしくは同素
材と良好な複合化・接着化した新しい素材を得ることが
出来る。(Function) The wholly aromatic polyamide molded product modified with the oxapurine group-containing substance of the present invention has a compound having an oxazoline group in the surface layer of the polyamide, and therefore has good compositing and adhesion with other materials or the same material. You can obtain new materials.
また、ゴムや熱硬化性樹脂、熱可塑性樹脂を補強する目
的で複合化された該成形物が繊維である場合には、該ポ
リアミド繊維表面とマ］・リックス樹脂との親和性が高
まるため、該繊維の凝集を引き起こすことなくマトリッ
クス中に均一に分散することが出来る。この結果、繊維
強化の効果も大きくなる。In addition, when the composite molded product for the purpose of reinforcing rubber, thermosetting resin, or thermoplastic resin is a fiber, the affinity between the surface of the polyamide fiber and the matrix resin increases. The fibers can be uniformly dispersed in the matrix without causing agglomeration. As a result, the effect of fiber reinforcement also increases.
（実施例）
以下に本発明をさらに詳し〈実施例を挙げて説明するが
、本発明の範囲は決してこれらの実施例によって限られ
るものではない。(Examples) The present invention will be described in more detail below with reference to Examples, but the scope of the present invention is by no means limited to these Examples.
実施例１
長さ１５ｃａ＋、幅１０ｃｍのポリバラフェニレンテレ
フタルアミド（以下ＰＰＴＡと略称する）繊維（ケブラ
ー４９．デュポン社商標）の１１４０デニールのヤーン
を、樅、横共に１７本／１５ｍｍの織密度として平織り
構造の織布を作成した。Example 1 A 1140 denier yarn of polybara phenylene terephthalamide (hereinafter abbreviated as PPTA) fiber (Kevlar 49, trademark of DuPont) with a length of 15 ca+ and a width of 10 cm was fabricated with a weave density of 17 threads/15 mm for both fir and width. A woven fabric with a plain weave structure was created.
この織布を主成分モノマーがスチレン−アクリロニトリ
ルとしたオキサゾリン基台ｆ１５％の物質（日本触媒化
学工業（ｌ＠製； ＣＸ−ＲＡＳ Ｉ ＯＯ５）の水／
Ｎ−メチルピロリドン（以下、ＮＭＰと称す） ＝５０
１５０のｉ８液に１時間浸漬後、水洗し、乾燥（減圧下
、６０°Ｃ）させた、この織布をＦＴ−ＩＲ；ＡＴＲ法
で調べたところ、１６３０Ｃ「１にオキサゾール環の吸
収ピークを確認した。This woven fabric was made of a 15% oxazoline-based material whose main monomer was styrene-acrylonitrile (manufactured by Nippon Shokubai Chemical Co., Ltd. (l@; CX-RAS I OO5), water/
N-methylpyrrolidone (hereinafter referred to as NMP) = 50
After soaking in i8 liquid of 150 for 1 hour, washing with water and drying (under reduced pressure, 60°C), this woven fabric was examined by FT-IR; ATR method, and an absorption peak of oxazole ring was found at 1630C. confirmed.
（以下、オキサゾリン基含有物質で処理された試料を処
理物という。）
上記で得られた織布にビスフェノール型エポキシ樹脂（
ＤＥＲ３８３，ダウケミカル製）１００ｇとトリエチル
テトラミン１３．５ｇから成る樹脂組成物を塗布し、２
枚張り合わせ、減圧上室温で３時間プレスし、次いで常
圧１００″Ｃで２時間硬化させた。(Hereinafter, a sample treated with an oxazoline group-containing substance is referred to as a treated product.) The woven fabric obtained above is coated with a bisphenol-type epoxy resin (
A resin composition consisting of 100 g of DER383 (manufactured by Dow Chemical) and 13.5 g of triethyltetramine was applied.
The sheets were laminated together, pressed under reduced pressure at room temperature for 3 hours, and then cured at normal pressure of 100''C for 2 hours.
この硬化物を幅１５順、長さ１５０ｒｍに切断し、万能
引張試験機（ＡＵＴＯＧＲＡＰＨ； ＤＳＳ５００、島
津社製）によりＴ−剥離試験（ヘッドスピード１００
ｍ ／ｗｉｎ、 ）を行ったところ、Ｔ−剥離強度は、
２． １５ｋｇ／１５ｍｎ＋ （測定数１０回の平均値
）であった。This cured product was cut into pieces with a width of 15 and a length of 150 rm, and a T-peel test (head speed of 100
m/win, ), the T-peel strength was
2. It was 15 kg/15 mn+ (average value of 10 measurements).
実施例２
実施例１と同じ織布をエマルジョン型のオキサプリン基
含有物質（日本触媒化学工業株式会社製、 ＣＸ−Ｋ
１０２０ Ｅ）の水懸？ＩＡｉにｉ時間浸漬後（６０°
Ｃ）、水洗し、乾燥（減圧下、６０’Ｃ）させた。この
織布をＦＴ−ＩＲ；ＡＴＲ法で調べたところ、１６３０
ｃｍ−’にオキサゾール環の吸収ピークを確認した。Example 2 The same woven fabric as in Example 1 was coated with an emulsion type oxapurine group-containing substance (manufactured by Nippon Shokubai Kagaku Kogyo Co., Ltd., CX-K).
1020 E) water stake? After i hours of immersion in IAi (60°
C), washed with water and dried (under reduced pressure, 60'C). When this woven fabric was examined by FT-IR; ATR method, it was found that 1630
An absorption peak of the oxazole ring was confirmed at cm-'.
上記で得られた処理織布について、実施例１と同様の方
法で成形し、同様の方法でＴ−剥離試験した結果、Ｔ−
剥離強度は１． ９３ｋｇ／ ］ ５ｏ＊（測定数１０
回の平均値）であった。The treated woven fabric obtained above was molded in the same manner as in Example 1 and subjected to a T-peel test in the same manner.
Peel strength is 1. 93kg/] 5o* (number of measurements: 10
was the average value of the times).
比較例１
実施例１と同し織布をそのままで（処理無し）、実施例
１と同様の方法で成形し、同様の方法でＴ剥離試験した
結果、この未処理織布のＴ−剥離強度は０． ９１ｋｇ
／ １５１１＋＋ｏ （測定数１０回の平均（直）であ
った。Comparative Example 1 The same woven fabric as in Example 1 was molded as it was (no treatment) in the same manner as in Example 1, and the T-peel test was conducted in the same manner. As a result, the T-peel strength of this untreated woven fabric was determined. is 0. 91kg
/ 1511++o (average (direct) of 10 measurements.
実施例３
実施例１で得られた処理布と同様の織布をビスフェノー
ルＡ型エポキシ末端をメタクリル酸エステル化した樹脂
（昭和高分子■製；リポキシＲ８０２）にメチルエチル
ケトンパーオキシド１．５％とナフテン酸コバルト０．
５％を添加したちのを塗布し、４枚を積層してプレス下
に６０゛Ｃで硬化した。得られた積層板から試験片を切
り出し、曲げ応力歪み特性を測定（ｊ ｉ ｓ−に−６
９１１）したところ、曲げ強度１４．’ ９ｋｇ／＋１
１１ｔ、曲げモジュラス１８２０ ｋｇ／ ｔｍ”を示
した。Example 3 A woven fabric similar to the treated fabric obtained in Example 1 was mixed with 1.5% methyl ethyl ketone peroxide and naphthene in a resin (manufactured by Showa Kobunshi ■; Lipoxy R802) in which the ends of bisphenol A type epoxy were esterified with methacrylic acid. Cobalt acid 0.
A 5% additive was applied, four sheets were laminated, and the sheets were cured at 60°C under a press. A test piece was cut out from the obtained laminate and the bending stress strain characteristics were measured (j i s- to -6
911), the bending strength was 14. '9kg/+1
11t and a bending modulus of 1820 kg/tm.
比較例２
実施例１と同じ織布をそのままで（処理無し）、実施例
３と同様の方法で成形し、同様の方法で曲げ応力歪み特
性試験をした結果、この未処理礒布仮の曲げ強度は１０
． ０ｋｇ／＋ｏ＋ａ” 、曲げモジュラス１１００
ｋｇ／ｎｏ”を示した。Comparative Example 2 The same woven fabric as in Example 1 was molded as it was (no treatment) in the same manner as in Example 3, and a bending stress strain characteristic test was conducted in the same manner. Strength is 10
．． 0kg/+o+a”, bending modulus 1100
kg/no”.
実施例４
実施例１と同じ織布を、従来法と同様にエポキシ処理（
処方は以下に説明）し、処理織布を酸液に浸漬後、２４
０ ’Ｃ１３Ｈｒで熱処理した。Example 4 The same woven fabric as in Example 1 was treated with epoxy (
The recipe is explained below), and after immersing the treated fabric in the acid solution,
Heat treatment was performed at 0'C13Hr.
（エポキシ処理処方）
樹脂；キャラ１１スト９５（帝国化学製品）２．０％Ｎ
ａＯＨ０，１％
ベレンクスｏＴＰ（５％）２．０％
５９
合計 １００％次いで、レゾル
シンーホルマリンーラテンクス（ＲＦＬ）処理液に浸漬
（処方は以下に説明）し、マングルで液を絞りだした後
、１５０°Ｃで３分間乾燥し、次いで１８０ ’Ｃで２
分間、２３０°Ｃで２分間キエアリングした。このとき
ＲＦＬ重合体組成物の付着量は、対繊維８．１％であっ
た。(Epoxy treatment prescription) Resin; Chara 11 Stroke 95 (Teikoku Kagaku Products) 2.0%N
aOH 0.1% Berenx oTP (5%) 2.0% 59 Total 100% Next, immerse in a resorcinol-formalin-Latenx (RFL) treatment solution (the prescription is explained below), and squeeze out the solution with a mangle. , dried at 150°C for 3 minutes, then dried at 180'C for 2 minutes.
The mixture was heated for 2 minutes at 230°C. At this time, the amount of the RFL polymer composition adhered to the fiber was 8.1%.
（ＲＦＬ処理剤処方）
レゾルシン １１．０ｇ水
２３８． ４ｇホルマ
リン（３７％水溶液） １６．２ｇＮａＯＨ０，
３Ｇ
スチレン／ブタジエン／ビニルピリジンの共重合体
−・・クス ４１ ２４４０合計
５０９．９ｇ次いで、処理織物と厚さ約
０．７ｍｍの未加硫ゴムシートを合わせ、加圧プレスで
＋ ４０ ’ＣＩ ５時間加硫した。用いたゴムシート
の組成は次のごとくである。(RFL treatment agent formulation) Resorcinol 11.0g water
238. 4g formalin (37% aqueous solution) 16.2g NaOH0,
3G Styrene/butadiene/vinylpyridine copolymer--cus 41 2440 total
509.9 g The treated fabric was then combined with an unvulcanized rubber sheet approximately 0.7 mm thick and vulcanized in a pressure press at +40' CI for 5 hours. The composition of the rubber sheet used is as follows.
＃１ （天然ゴム） ７０ｇハイカー＃
１５０２ （ＳＢＲゴム）３０ｇカーボンＦＥＦ
５０ ｇステアリン酸
２，０ｇ芳香族柔軟剤 １
０ｇ亜鉛華 ５ｇ老化防止
剤ＡＴＶ １． ５ｇ加硫促進剤Ｄ
Ｍ ２ｇ５
合計 １７３ｇゴム／襟物間
の剥離強度は５．９ｋｇであり、剥離部分はＲＦＬ重合
体の暗褐色を呈し、実体顕微鏡による観察でも繊維の露
出は見られず、剥離はＲＦＬ重合体組成物とゴムとの間
で生じていることが分かった。#1 (Natural Rubber) 70g Hiker #
1502 (SBR rubber) 30g carbon FEF
50 g stearic acid
2.0g aromatic softener 1
0g zinc white 5g anti-aging agent ATV 1. 5g vulcanization accelerator D
M 2g5 total 173g The peel strength between the rubber and the collar was 5.9 kg, and the peeled part exhibited the dark brown color of RFL polymer, and no fibers were exposed even when observed with a stereomicroscope. It was found that this occurs between objects and rubber.
比較例３
実施例１と同じ織布をそのままで（処理無し）、実施例
４と同様の方法で成形した（エポキシ処理、ＲＦＬ処理
、ゴム複合）、このとき繊維に付着したＲＦＩ、重合体
組成物の星は対繊維６．１％であった。Comparative Example 3 The same woven fabric as in Example 1 was used as it was (no treatment) and molded in the same manner as in Example 4 (epoxy treatment, RFL treatment, rubber composite). At this time, RFI attached to the fibers and polymer composition The star of the article was 6.1% of fiber.
このことから、実施例４では、オキサゾリン基含有物質
で処理した全芳香族ポリアミド成形物は処理液との濡れ
が良いことが分かる。この未処理織布／ゴム複合物の剥
離強度は２．８ｋｇで実施例４の半分以下であった。ま
た、未処理成形物の剥離部分は所々にＰＰＴＡ繊維の黄
褐色を呈し、明らかな繊維の露呈が見られた。From this, it can be seen that in Example 4, the wholly aromatic polyamide molded product treated with the oxazoline group-containing substance has good wettability with the treatment liquid. The peel strength of this untreated woven fabric/rubber composite was 2.8 kg, less than half that of Example 4. In addition, the peeled portion of the untreated molded product exhibited a yellowish brown color of PPTA fibers in some places, and obvious fiber exposure was observed.
実施例５
特開昭４７−３９４５８号公報の記載に従って、ＰＰＴ
Ａフィルムを製膜した。得られたフィルムは、厚さ４０
μｍ、幅５０ｍ、長さ１５０胴であった。Example 5 According to the description in Japanese Patent Application Laid-open No. 47-39458, PPT
A film was formed. The resulting film has a thickness of 40
It had a diameter of 50 m, a width of 50 m, and a length of 150 m.
このフィルムを、主成分モノマーがスチレン−アクリロ
ニトリルとしたオキサゾリン基含有量５％の物質（日本
触媒化学工業株式会社製、ＣＸ−ＲＡＳ１００５）の水
／Ｎ−メチルピロリドン（以下ＮＭＰと称す）＝５０１
５０の？８液に１時間浸漬後、水洗し、乾燥（減圧下、
６０°Ｃ）させた。この織布をＦＴ−Ｉ Ｒ、ＡＴＲ法
で調べたところ、１６３０ｃｍ−’にオキサゾール環野
吸収ピークを確認した。（以下、オキサゾリン基含有物
質で処理された試料を処理物という、）
得られた処理フィルムに接着剤（東し社製；５９００）
を塗布し、ホットプレス（２，５ｋｇ／ｃ＋Ｊ、１５０
°Ｃ）した後、８０゛Ｃで２４時間、１６０°Ｃで４時
間硬化させた。This film was prepared using a material (CX-RAS1005, manufactured by Nippon Shokubai Kagaku Kogyo Co., Ltd.) with a 5% oxazoline group content whose main monomer is styrene-acrylonitrile, water/N-methylpyrrolidone (hereinafter referred to as NMP) = 501.
50? After soaking in liquid 8 for 1 hour, washing with water and drying (under reduced pressure,
60°C). When this woven fabric was examined by FT-IR and ATR methods, an oxazole ring field absorption peak was confirmed at 1630 cm-'. (Hereinafter, a sample treated with an oxazoline group-containing substance is referred to as a treated product.) An adhesive (manufactured by Toshisha Co., Ltd.; 5900) was applied to the obtained treated film.
and hot press (2.5kg/c+J, 150
°C) and then cured at 80°C for 24 hours and at 160°C for 4 hours.
この硬化物を幅１５ｍ、長さ１５０ｍａ＋に切断し、万
能引張試験機（ＡＵＴＯＧＲＡＰＨ； ＤＳＳ５００、
島津社製）により１８０°−剥離試験（ヘッドスピード
１００ｍｍ／ｍｉｎ、）を行ったところ、１８０°−剥
離強度は、１． ８７ｋｇ／ １５ｎｕｎ （測定数１
０回の平均値）であった。This cured product was cut into pieces of 15 m wide and 150 m long, and tested using a universal tensile tester (AUTOGRAPH; DSS500,
When a 180° peel test (head speed 100 mm/min) was carried out using a 180° peel strength (manufactured by Shimadzu Corporation), the 180° peel strength was 1. 87kg/ 15nun (Number of measurements: 1
(average value of 0 times).
実施例６
実施例５と同じフィルムをエマルジョン型のオキサゾリ
ン基含有物質（日本触媒化学工業株式会社製、ＣＸ−Ｋ
１０２０Ｅ）の水懸濁液に１時間浸漬後（６０°Ｃ）、
水洗し、乾燥（減圧下、６０’Ｃ）させた。この処理フ
ィルムをＦＴ−ＩＲ，ＡＴＲ法で調べたところ、１６３
０ｃｍ−’にオキサプール環の吸収ピークを６奮認した
。Example 6 The same film as in Example 5 was coated with an emulsion type oxazoline group-containing substance (manufactured by Nippon Shokubai Kagaku Kogyo Co., Ltd., CX-K).
After immersion in a water suspension of 1020E for 1 hour (60°C),
It was washed with water and dried (under reduced pressure, 60'C). When this treated film was examined using FT-IR and ATR methods, it was found that 163
Six absorption peaks of the oxapool ring were observed at 0 cm-'.
この処理フィルムを実施例５と同様な方法で接着し、１
８０°剥離試験を実施例５と同し方法で行ったとコロ、
１８０°？、ｌＩ Ｍ強度＋、ｔｌ、９５ｋｇ／１５ｍ
ｍ（測定数１０回の平均値）であった。This treated film was adhered in the same manner as in Example 5, and
An 80° peel test was conducted in the same manner as in Example 5.
180°? , lI M strength +, tl, 95kg/15m
m (average value of 10 measurements).
比較例４
実施例５と同じフィルムをそのまま（処理無し）で実施
例５と同し方法で接着処理した。この未処理フィルムの
１８０°剥離強度は、０．３１ｋｇ／１５薗であった。Comparative Example 4 The same film as in Example 5 was subjected to adhesive treatment in the same manner as in Example 5 without any treatment. The 180° peel strength of this untreated film was 0.31 kg/15 mm.
以上のような実施例と比較例から、全芳香族ポリアミド
成形物をオキサゾリン基含有物質で処理した繊維、織物
、フィルム等は同種の及び／または異種の物質との接着
性能等が非常に良くなったことが分かる。From the above Examples and Comparative Examples, fibers, fabrics, films, etc. made of fully aromatic polyamide molded products treated with oxazoline group-containing substances have very good adhesion performance with the same and/or different types of substances. I understand that
（発明の効果）
本発明によれば、全芳香族ポリアミド成形物は、オキサ
ゾリン基含有物質で処理することによって、他素材もし
くは同素材と良好な複合化・接着化することができる。(Effects of the Invention) According to the present invention, a wholly aromatic polyamide molded product can be successfully composited and bonded with other materials or the same material by being treated with an oxazoline group-containing substance.
このために、得られた変性成形物から複合化された成形
物は、全芳香族ポリアミド成形物が本来持つ高強度・高
弾性率を生かした力学性能を持つ成形物となる。For this reason, a molded product composited from the obtained modified molded product has mechanical performance that takes advantage of the high strength and high elastic modulus inherent to the wholly aromatic polyamide molded product.
また、その処理方法は、容易でしがも安価であるため、
工業生産に適した方法である。In addition, the treatment method is easy and inexpensive, so
This method is suitable for industrial production.
（ほか１名）(1 other person)
Claims (1)
で処理した、新規な成形物。A new molded product made by treating a wholly aromatic polyamide molded product with an oxazoline group-containing substance.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1252217A JPH03115443A (en) | 1989-09-29 | 1989-09-29 | Molded article of wholly aromatic polyamide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1252217A JPH03115443A (en) | 1989-09-29 | 1989-09-29 | Molded article of wholly aromatic polyamide |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH03115443A true JPH03115443A (en) | 1991-05-16 |
Family
ID=17234138
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1252217A Pending JPH03115443A (en) | 1989-09-29 | 1989-09-29 | Molded article of wholly aromatic polyamide |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03115443A (en) |
-
1989
- 1989-09-29 JP JP1252217A patent/JPH03115443A/en active Pending
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