JPH0512377B2 - - Google Patents
Info
- Publication number
- JPH0512377B2 JPH0512377B2 JP1288986A JP1288986A JPH0512377B2 JP H0512377 B2 JPH0512377 B2 JP H0512377B2 JP 1288986 A JP1288986 A JP 1288986A JP 1288986 A JP1288986 A JP 1288986A JP H0512377 B2 JPH0512377 B2 JP H0512377B2
- Authority
- JP
- Japan
- Prior art keywords
- resin
- polyarylene
- temperature
- molded product
- thioether
- 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
- 229920005989 resin Polymers 0.000 claims description 35
- 239000011347 resin Substances 0.000 claims description 35
- 229920000412 polyarylene Polymers 0.000 claims description 31
- 150000003568 thioethers Chemical class 0.000 claims description 31
- 239000000126 substance Substances 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 23
- 238000004519 manufacturing process Methods 0.000 claims description 16
- -1 polyphenylene Polymers 0.000 claims description 12
- 238000002844 melting Methods 0.000 claims description 10
- 230000008018 melting Effects 0.000 claims description 10
- 230000007704 transition Effects 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 6
- 229920000265 Polyparaphenylene Polymers 0.000 claims description 5
- 230000008014 freezing Effects 0.000 claims description 4
- 238000007710 freezing Methods 0.000 claims description 4
- 125000000732 arylene group Chemical group 0.000 claims description 3
- 150000001408 amides Chemical class 0.000 claims description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 150000002170 ethers Chemical class 0.000 claims description 2
- 150000002576 ketones Chemical class 0.000 claims description 2
- 238000002425 crystallisation Methods 0.000 description 19
- 230000008025 crystallization Effects 0.000 description 19
- 229920000642 polymer Polymers 0.000 description 19
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 11
- 229920001400 block copolymer Polymers 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- 238000000465 moulding Methods 0.000 description 6
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 5
- 229920001577 copolymer Polymers 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- 238000009998 heat setting Methods 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- 239000008188 pellet Substances 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 229910052979 sodium sulfide Inorganic materials 0.000 description 4
- 238000011282 treatment Methods 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000005684 electric field Effects 0.000 description 3
- 239000003365 glass fiber Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 230000001737 promoting effect Effects 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 3
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 3
- ZPQOPVIELGIULI-UHFFFAOYSA-N 1,3-dichlorobenzene Chemical compound ClC1=CC=CC(Cl)=C1 ZPQOPVIELGIULI-UHFFFAOYSA-N 0.000 description 2
- QPUYECUOLPXSFR-UHFFFAOYSA-N 1-methylnaphthalene Chemical compound C1=CC=C2C(C)=CC=CC2=C1 QPUYECUOLPXSFR-UHFFFAOYSA-N 0.000 description 2
- ODPYDILFQYARBK-UHFFFAOYSA-N 7-thiabicyclo[4.1.0]hepta-1,3,5-triene Chemical compound C1=CC=C2SC2=C1 ODPYDILFQYARBK-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 150000004686 pentahydrates Chemical class 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- XWUCFAJNVTZRLE-UHFFFAOYSA-N 7-thiabicyclo[2.2.1]hepta-1,3,5-triene Chemical compound C1=C(S2)C=CC2=C1 XWUCFAJNVTZRLE-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical group ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910052977 alkali metal sulfide Inorganic materials 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000003484 crystal nucleating agent Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Natural products C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 1
- LTYMSROWYAPPGB-UHFFFAOYSA-N diphenyl sulfide Chemical compound C=1C=CC=CC=1SC1=CC=CC=C1 LTYMSROWYAPPGB-UHFFFAOYSA-N 0.000 description 1
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000008393 encapsulating agent Substances 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 235000012438 extruded product Nutrition 0.000 description 1
- 239000012765 fibrous filler Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000010128 melt processing Methods 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000003495 polar organic solvent Substances 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 229950011008 tetrachloroethylene Drugs 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- PXXNTAGJWPJAGM-UHFFFAOYSA-N vertaline Natural products C1C2C=3C=C(OC)C(OC)=CC=3OC(C=C3)=CC=C3CCC(=O)OC1CC1N2CCCC1 PXXNTAGJWPJAGM-UHFFFAOYSA-N 0.000 description 1
- 229910052882 wollastonite Inorganic materials 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Treatments Of Macromolecular Shaped Articles (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Description
〔発明の背景〕
産業上の利用分野
本発明は、結晶化度を高めたポリアリーレンチ
オエーテル成形物の製造法に関するものである。
さらに詳しくは、本発明は、ポリアリーレンチ
オエーテルの結晶化度をその成形物中において高
める方法の改良に関するものである。
従来技術
ポリアリーレンチオエーテルは、耐熱性、耐薬
品性等の物性が優れ、モールド品をはじめとし
て、フイルム、シート、繊維、パイプ、ボルト等
各種の成形物に加工することができる。
これ等の成形物に、ポリアリーレンチオエーテ
ル生得の高い耐熱性や高い機械的強度を付与する
ためには、溶融加工後に結晶化度を高める処理を
行う必要があつた。
低い結晶化度のまま用いると、本来目的とする
性質である耐熱性、耐薬品性等の物性を、いちじ
るしく損なつてしまうことがあり、また適正な比
重が出ないことや成形品表面の艶が悪くなる等ポ
リアリーレンチオエーテル由来の性能を十分に発
揮させることができない等の問題が起ることがあ
るからである。
その目的のためには、通常は金型のまま加熱し
たり加熱された成形物を緊張下、制限変形下、も
しくはフリーな状態で、使用樹脂の二次転移温度
（通常は70〜90℃）以上、融点以下の温度で加熱
すること（即ち、アニーリングまたは熱固定）を
行つていた。
しかし、この加熱による方法は、熱変形し易い
成形物や加熱が難かしい成形物ではできるだけ低
温度で結晶化させたいところ、低温ほど結晶化に
時間がかかるという問題点があつた。
〔発明の概要〕
要 旨
従来、樹脂の結晶化は樹脂分子が熱運動するこ
とによつて、配列して起こることから、ポリアリ
ーレンチオエーテル樹脂は、その二次転移温度
（通常70〜90℃）以上の温度でなければ、結晶化
はほとんど進行しないものと考えられていた。す
なわち、少なくとも70℃以上までは加熱しなけれ
ば実質的に結晶化を高めることができないと考え
られていた。
そこで、発明者は樹脂の二次転移温度以上に加
熱しないで、結晶化を高める方法がないものかど
うか探索してきた。その結果、おどろくべきこと
に、常温のような低い温度でも、ポリアリーレン
チオエーテル樹脂に対する有機液体または蒸気と
の接触下であれば当該成形物の結晶化度を高める
ことができることが判つた。
本発明は、この発見を基に完成したものであ
る。すなわち、本発明による結晶化度を高めた、
ポリアリーレンチオエーテル成形物の製造法は、
繰返し単位（―Ar−Ｓ）―、（Arはアリーレン基を
示す）を50モル％以上含むポリアリーレンチオエ
ーテルの有意量からなる樹脂の成形物を、当該樹
脂との親和性の高い有機物の液体または蒸気に、
当該有機物の凝固点以上であつて当該樹脂の融解
温度以下の温度で接触させること、を特徴とする
ものである。
効 果
本発明の結晶化度を上げた、ポリアリーレンチ
オエーテル成形物の製造法は熱変形し易い成形物
や、加熱が難かしい成形物では或る程度性能を犠
牲にして、低結晶化度のまま用いざるを得なかつ
たのに対して、常温もしくは樹脂の二次転移温度
以下で結晶化度を上げることができるようになつ
たことから、耐熱性、耐薬品性等の物性は、樹脂
の二次転移温度以上で加熱して結晶化度高めたも
のと同等に優れたものとなる。また、二次転移温
度以上で本法を用いた結晶化では、結晶化時間が
短時間ですむので、省エネルギーになり、さらに
は設備もより小型になるという効果も期待でき
る。
樹脂の結晶化は樹脂分子が熱運動することによ
つて生じることを考慮すれば、そのための下記温
度すなわち二次転移温度附近以下の温度で結晶化
が行ないえたということは思いがけなかつたこと
というべきである。
〔発明の具体的説明〕
素材樹脂
本発明で対象とする素材樹脂は、ポリアリーレ
ンチオエーテルの有意量からなるものである
（「有意量」の定義は後記）。
ポリアリーレンチオエーテル
本発明に用いられるポリアリーレンチオエーテ
ルは、式（―Ar−Ｓ）―の繰り返し単位を主要構成
単位とするホモポリマーまたはコポリマーであ
る。Arは、アリーレン基を示す。この繰り返し
単位を主要構成単位とする限り（―Ar′Ｓ
Ｓ）＝等で
あらわされる少量の分枝結合または架橋結合を含
むこともできる。
Arとしては、
[Background of the Invention] Industrial Application Field The present invention relates to a method for producing a polyarylene thioether molded product with increased crystallinity. More particularly, the present invention relates to an improved method for increasing the crystallinity of polyarylene thioethers in molded articles thereof. Prior Art Polyarylene lentioether has excellent physical properties such as heat resistance and chemical resistance, and can be processed into various molded products such as films, sheets, fibers, pipes, and bolts. In order to provide these molded products with the high heat resistance and high mechanical strength inherent to polyarylene thioether, it was necessary to perform a treatment to increase the degree of crystallinity after melt processing. If used with a low crystallinity, the intended physical properties such as heat resistance and chemical resistance may be significantly impaired, and the proper specific gravity may not be obtained or the surface of the molded product may become glossy. This is because problems may occur, such as the performance derived from polyarylene thioether being unable to be fully exhibited, such as poor performance. For this purpose, it is usually necessary to heat the mold while it is still in use, or to heat the heated molded product under tension, limited deformation, or in a free state, to the secondary transition temperature of the resin used (usually 70 to 90°C). In the above, heating at a temperature below the melting point (ie, annealing or heat setting) was performed. However, this heating method has the problem that it is desirable to crystallize molded products that are easily thermally deformed or difficult to heat at as low a temperature as possible, but that the lower the temperature, the longer it takes for crystallization. [Summary of the Invention] Abstract Conventionally, crystallization of resin occurs in alignment due to thermal movement of resin molecules, so polyarylene thioether resin has a high secondary transition temperature (usually 70 to 90°C). It was thought that crystallization would hardly proceed unless the temperature was higher than that. In other words, it was thought that crystallization could not be substantially enhanced unless heated to at least 70°C. Therefore, the inventor has been searching for a way to increase crystallization without heating the resin above its secondary transition temperature. As a result, it was surprisingly found that even at a low temperature such as room temperature, the crystallinity of the molded product can be increased if the polyarylene thioether resin is brought into contact with an organic liquid or vapor. The present invention was completed based on this discovery. That is, the crystallinity according to the present invention is increased,
The manufacturing method for polyarylene lentioether molded products is as follows:
A resin molded product consisting of a significant amount of polyarylene thioether containing 50 mol% or more of repeating units (-Ar-S)-, (Ar represents an arylene group) is heated with an organic liquid or an organic material that has a high affinity with the resin. to steam,
It is characterized in that the contact is carried out at a temperature above the freezing point of the organic substance and below the melting temperature of the resin. Effects The method for producing polyarylene thioether molded products with increased crystallinity according to the present invention can be used for molded products that are easily deformed by heat or that are difficult to heat, by sacrificing performance to some extent. In contrast, it has become possible to increase the degree of crystallinity at room temperature or below the secondary transition temperature of the resin, so physical properties such as heat resistance and chemical resistance have improved. It is as good as that obtained by heating above the second-order transition temperature to increase the degree of crystallinity. In addition, in crystallization using this method at a temperature above the second-order transition temperature, the crystallization time is short, so it can be expected to save energy and further reduce the size of equipment. Considering that crystallization of resin occurs due to thermal movement of resin molecules, it should be said that it was unexpected that crystallization could be carried out at the following temperature, that is, a temperature around the second-order transition temperature or lower. It is. [Specific Description of the Invention] Material Resin The material resin targeted by the present invention consists of a significant amount of polyarylene thioether (the definition of "significant amount" will be described later). Polyarylenethioether The polyarylenethioether used in the present invention is a homopolymer or copolymer whose main constituent unit is a repeating unit of the formula (-Ar-S). Ar represents an arylene group. As long as this repeating unit is the main constituent unit, a small amount of branched bond or crosslinked bond expressed as (--Ar'S S)= etc. may be included. As Ar,
【式】【formula】
【式】【formula】
【式】【formula】
【式】【formula】
【式】【formula】
【式】【formula】
【式】【formula】
【式】
（Ｒ：アルキル基またはアルコキシ基。特に
C1〜C4程度。）などがあり、A′rとしては
[Formula] (R: alkyl group or alkoxy group, especially
About C1 to C4 . ) etc., and as A′r
【式】などがある。[Formula] etc.
【式】は、【ceremony,
【式】が好ましい。
特に好ましく用いられるポリアリーレンチオエ
ーテルとしては、ポリマーの主構成単位としてｐ
−フエニレンチオエーテル単位
[Formula] is preferred. Particularly preferably used polyarylene thioethers include p as the main structural unit of the polymer.
-Phenyl lentioether unit
【式】を50モル％以上含有するポ
リパラフエニレンチオエーテル及びフエニレンチ
オエーテルコポリマーがあげられる。
コポリマーとしては、耐熱性、加工性の点から
特にブロツクコポリマーが好ましい。コポリマー
は共重合体単位としてはメタフエニレンチオエー
テル単位Examples include polyparaphenylenethioether and phenylenethioether copolymers containing 50 mol% or more of the formula. As the copolymer, block copolymers are particularly preferred from the viewpoint of heat resistance and processability. The copolymer has a metaphenylenethioether unit as a copolymer unit.
【式】ジフエニルケトンチ オエーテル単位[Formula] Diphenyl ketone Oether unit
【式】ジフエニルエ
ーテルチオエーテル単位
[Formula] Diphenyl ether thioether unit
【式】ビフエニルチ オエーテル単位[Formula] Biphenylchi Oether unit
【式】 ２，６−ナフタレンチオエーテル単位【formula】 2,6-naphthalene thioether unit
【式】三官能単位[Formula] Trifunctional unit
【式】などがあげられる。ただ
し、三官能単位は１モル％以下が望ましい。
このようなポリアリーレンチオエーテルとして
は、公知の方法によつて合成されたものを用いる
ことができる。合成法としては、例えば、米国特
許3354129号明細書に開示されている方法がある。
この方法は、例えば、ポリフエニレンチオエーテ
ルを生成させる為にＮ−メチルピロリドン
（NMP）中でｐ−ジクロルベンゼンと硫化ソー
ダとを反応させる方法である。特公昭52−12240
号公報に記載されているように、NMP中でのジ
クロルベンゼンと硫化ソーダとの反応時に酢酸リ
チウムや酢酸ナトリウムのような有機酸のアルカ
リ金属塩を共存させることによる、より高分子量
のポリフエニレンチオエーテルを得る方法も好適
である。より高分子量のポリフエニレンチオエー
テルを得る為に用いられる他の方法、例えば
NMP中での重合反応時に炭酸リチウムや水酸化
カルシウムなどのような無機塩を共存させる方法
あるいは共存H2O量、重合温度のコントロール
による方法（特願昭59−126725号）等も用いられ
る。また、重合仕上りのポリマーを粉末状態で酸
素共存下（好ましくは空気中）で融点以下の温度
で加熱して溶融粘度を増加させたものも用いるこ
とができる。
フエニレンチオエーテルブロツクコポリマーと
しては、パラフエニレンチオエーテルとメタフエ
ニレンチオエーテルとのブロツクコポリマーが好
適である。
このブロツクコポリマーは、繰り返し単位
Examples include [Formula]. However, the content of the trifunctional unit is preferably 1 mol% or less. As such a polyarylene thioether, one synthesized by a known method can be used. Examples of the synthesis method include the method disclosed in US Pat. No. 3,354,129.
This method is, for example, a method in which p-dichlorobenzene and sodium sulfide are reacted in N-methylpyrrolidone (NMP) to produce polyphenylene thioether. Tokuko Showa 52-12240
As described in the publication, higher molecular weight polyphenylene is produced by coexisting an alkali metal salt of an organic acid such as lithium acetate or sodium acetate during the reaction between dichlorobenzene and sodium sulfide in NMP. Also suitable are methods for obtaining nilentioether. Other methods used to obtain higher molecular weight polyphenylene thioethers, e.g.
A method in which an inorganic salt such as lithium carbonate or calcium hydroxide is allowed to coexist during the polymerization reaction in NMP, or a method in which the amount of coexisting H 2 O and the polymerization temperature are controlled (Japanese Patent Application No. 126725/1982), etc., are also used. It is also possible to use a polymer prepared by heating the finished polymer in powder form at a temperature below the melting point in the presence of oxygen (preferably in air) to increase the melt viscosity. As the phenylene thioether block copolymer, a block copolymer of paraphenylene thioether and metaphenylene thioether is suitable. This block copolymer has repeating units
【式】と繰り返し単位[Formula] and repeating unit
【式】とのブロツクからなる限り、
各ブロツクの形成および両ブロツクの結合が可能
な限り任意の方法によつて製造することができ
る。例えば、特願昭59−134633号明細書に示され
た方法が用いられる。具体的な製造法としては、
一方のブロツクを形成させてからそこで他方のブ
ロツクを形成させて両ブロツクの結合を同時に実
現する方法、および両ブロツクをそれぞれ形成さ
せておいてから結合させる方法、を挙げることが
できる。このようにブロツクの形成および結合な
らびにフエニレンスルフイド繰返し単位の種類に
配慮することを除けば、また必要に応じて行なう
べき改変を除けば、本発明に用いるブロツクコポ
リマーの製造法は従来のフエニレンチオエーテル
ポリマーの製造法と本質的には異ならないという
ことができる。すなわち、本発明ブロツクポリマ
ーの製造法は、アルカリ金属硫化物とジハロ芳香
族化合物（主としてｐ−およびｍ−ジハロベンゼ
ンからなる）とを非プロトン性極性有機溶媒（た
とえばNMP）中での加熱による縮合（脱アルカ
リ金属ハロゲン化物）からなるものである。な
お、このブロツクコポリマーは、310℃／剪断速
度200（秒）-1の条件で測定した溶融粘度が50〜
100000ボイズの範囲にあることが望ましい。
ポリアリーレンチオエーテル樹脂
本発明で対象とする成形物を構成すべき樹脂
は、ポリアリーレンチオエーテルの有意量からな
るものである。ここで「有意量からなる」という
ことは、本発明による処理が有意に実現しうる量
以上にポリアリーレンチオエーテルを含むという
ことである。
このようなところから、ポリアリーレンチオエ
ーテルはそのまま用いることが好ましいが、成形
加工に支障を来たさない限度において、又、後述
の有機物と反応もしくは相溶しない無機フイラー
（シリカ粉末、アルミナ粉末、シリカアルミナ粉
末、マイカ、カオリン、炭酸カルシウム粉末、珪
酸カルシウム粉末、タルク、カーボン黒、ウオラ
ストナイト、チタン酸カリウイスカーなど）、繊
維状フイラー（ガラス繊維、炭素繊維など）、結
晶核剤、結晶化調整剤、顔料、安定剤、滑剤、離
型剤などを添加して用いることも可能である。
また成形加工に支障を来たさない限度におい
て、又、後述の有機物と反応もしくは相溶しな
い、他のポリアリーレンチオエーテルや他の熱可
塑性樹脂をブレンドして用いることも可能であ
る。この樹脂ブレンドの場合はポリアリーレンチ
オエーテルはその優位量を占めるべきである。
高結晶化
有機物
本発明の結晶化ポリアリーレンチオエーテル又
はその組成物の成形物の製造法に使用する有機物
としては、ポリアリーレンチオエーテルに対して
親和性の優れたものが好ましい。これらは、液体
として、あるいはその蒸気として、用いられる。
有機重合物と溶剤との親和性に関しては、一般
にSP値（溶解度パラメーター）が有効な尺度と
なる。
ポリアリーレンチオエーテルのSP値は、未だ
明確でないが、SP値の小さな脂肪族炭化水素や、
SP値の大きすぎるものあるいは水素結合力の大
きな、水、アルコール類、アミン類などは好まし
くない。
従つて、本発明で使用する有機物としては、
SP値が８〜12、好ましくは8.4〜11、の間の水素
結合力の弱い有機物が好ましい。
本発明の結晶化度を上げたポリアリーレンチオ
エーテル成形物の製造法に適用する有機物として
は、二硫化炭素（本発明では、二硫化炭素を有機
物として考えるものとする）、ハロゲン化炭化水
素（クロロホルム、トリクレン、パークロロエチ
レン、エチレンジクロライド、ブロムベンゼンな
ど）、エーテル類（テトラヒドロフランなど）、チ
オエーテル類（ジフエニールチオエーテルなど）、
ケトン類（アセトン、メチルエチルケトン、シク
ロヘキサノンなど）、アミド類（ジメチルアセト
アミド、ジメチルホルムアミド、Ｎ−メチル−２
−ピロリドン）、エステル類（酢酸エチルなど
（芳香族炭化水素（ベンゼン、トルエン、キシレ
ン、メチルナフタレン、デカリン、テトラリン、
エチルベンゼン、スチレン）などが挙げられる。
これらの有機物は、単独でも、あるいは２種以上
混合しても用いることができる。
これらの有機物の中で、CS2、クロロホルム、
トリクレンなどは結晶化効果が顕著に大きいので
特に好ましい。
結晶化成形物の製造
本発明の結晶化成形物を製造するには、ポリア
リーレンチオエーテルの有意量からなる樹脂を、
あらかじめ溶融成形しておくことが必要である。
この溶融成形物を当該樹脂と親和性の高い有機
物の液体または蒸気に接触させることによつて、
有機物分子を成形物内部へ分子拡散させ、当該樹
脂の結晶化を高めることができる。樹脂内部に拡
散した低分子有機物分子が一種のコロのような働
きをして、樹脂内重合物分子の運動を促進して高
分子の結晶化を促進するものと考えられる。たと
え二次転移点以下の温度であつてもこのコロの作
用は働くので、低分子量有機物分子の高分子成形
物内部への分子拡散が、結晶化の速度を律するも
のと考えられる。
従つて、この拡散を促進する手段としては、高
分子と親和性の高い有機物を選ぶこと及び温度を
高めて分子運動を高めてやる方法がある。
接触温度は、有機物分子が拡散できる凝固点以
上であれば、本質的には結晶化を起こさせること
ができる。しかし、温度はやはり高い方が、結晶
化を速めることができて都合がよい。ただし、ボ
リフエニレンチオエーテル樹脂の融解温度より高
い温度は樹脂の結晶構造が破壊されるので不適当
である。本発明は融解温度未満ならばいずれも実
施可能であるが、当該樹脂の二次転移温度以下が
好ましい。
結晶化に必要な接触時間は、接触温度との相関
で変動するが、低温ほど長時間を要し、高温ほど
短時間でよい。通常は、１秒〜100時間程度の範
囲、好ましくは３秒〜24時間の範囲、が用いられ
る。１未満では結晶化が不充分であり、100時間
超過では経済的見地から実用性がない。フイルム
或いはシート状のものでは短く、成形物では長い
時間が必要である。
本発明が樹脂の融解温度未満の温度で実施しう
ることは前記したところであり、従つて本発明の
方法を従来の糸やフイルムの融解温度以下の高温
度での熱固定処理に適用して、その際にこの低分
子有機物を併用すれば、熱固定温度を大巾に下げ
たり、あるいは熱固定時間を大巾に短縮すること
ができる。
低分子有機物と樹脂成形物との接触方法は、成
形物を低分子有機物中に浸漬する方法、成形物に
低分子有機物を塗布する方法、あるいは低分子有
機物の蒸気に曝す方法（蒸気曝露法）などが好ま
しい。この際、成形物が変形し易いもの、例えば
延伸フイルム、延伸シート、延伸糸などは緊張下
もしくは制限変形下で実施することが好ましい。
成形物がフイルム、シート、糸などのような場合
には、応力を加えて延伸させながら結晶化を同時
に行うこともできる。
結晶化ポリアリーレンチオエーテル樹脂成形物
本発明により得られる結晶化ポリアリーレンチ
オエーテル樹脂成形物はその耐熱性、耐薬品性、
難燃性などの特徴を活かして、種々の分野に利用
することができる。
例えば、種々の成形物品、シート、フイルム、
パイプ、繊維等に好ましく用いられる。
フイルムないしシートは、例えば電子・電気分
野ではプリント基板、磁気テープ（塗布タイプ、
蒸着タイプなど）、絶縁テープ、フロツピーデイ
スクなどとして有用である。押出成形物の結晶化
物（プレート、パイプ、プロフイルムなど）は例
えば電子・電気分野ではプリント基板、集合配線
用保護管など、化学工業分野では、各種耐食耐熱
配管などとして有用である。この樹脂成物を被覆
し結晶化させた電線は、耐熱・耐食電線として有
用である。射出成形物の結晶化物としては例えば
電子・電気分野ではプリント基板IC封止材、コ
ネクター、マイクロ波機器部品などとして、化学
工業分野では大型ポンプ、大型バルブ、シール
材、ライニング材などとして有用である。
実験例
ポリマーの合成
(A) 20リツトルオートクレーブにＮ−メチル−２
−ピロリドン（以下NMPと略記する）11.0Kg
と46.02重量％のNa2Sを含むNa2S五水塩結晶
（長尾ソーダ社製）4.239℃（Na2Sとして25.0モ
ル）を仕込み、窒素雰囲気下に約２時間かけて
撹拌しながら徐々に200℃まで昇温して、水を
留出させた。
130℃まで冷却したのち、パラジクロルベン
ゼン（以下ｐ−DCBと略記する）3.6Kgと
NMP3.2Kgとを加え、220℃で４時間加熱して
重合させた。次いで、水1.3Kgを添加し、窒素
雰囲気下に265℃に昇温して、４時間重合させ
た。冷却後、得られたポリマーをオリゴマー等
から篩別し、次いで脱イオン水でくり返し洗浄
したのち、100℃で減圧乾燥した。
得られたポリマーＡは、ｐ−フエニレンスル
フイドストレートポリマーであつて、溶融粘度
η*＝5000ポイズ（310℃、剪断速度200（秒）-1）、
結晶融点Tm＝282℃の高結晶性のものであつ
た。このポリマーＡを330℃で溶融押出しして
ペレツトＡとした。
(B) 20リツトルオートクレーブにNMP11.0Kg、
46.02重量％のNa2Sを含むNa2S五水塩結晶
4.239Kgを仕込み、窒素雰囲気下に約２時間か
けて撹拌しながら徐々に200℃まで昇温して、
水を留出させた。これに、メタ−ジクロルベン
ゼン3.6KgとNMP3.0Kgとを加えて、220℃で８
時間重合させて、ポリ（メタフエニレンスルフ
イド）含有スラリーを得た。メタジクロルベン
ゼンはほぼ完全に重合した。得られたポリメタ
フエニレンスルフイドの重合度はほぼ20であつ
た（螢光Ｘ線により両末端Clの量を測定し、計
算により決定）。
別に、20リツトルオートクレーブにNMP9.0
KgおよびNa2S五水塩結晶3.604Kgを仕込み、窒
素雰囲気下約２時間かけて撹拌しながら徐々に
200℃まで昇温して、水を留出させた。これに、
パラジクロルベンゼン3.4KgとNMP3.0Kgおよ
び前記ポリ（メタフエニレンスルフイド）含有
スラリー2.8Kgとを仕込み、220℃に昇温して９
時間反応させた。次いで、水1.5Kgを添加し、
265℃に昇温して４時間反応させた。(A)と同様
の後処理をして、ポリマー(B)を回収した。
得られたポリマー(B)はAs long as it consists of a block with the formula, each block can be formed and the two blocks can be combined by any method possible. For example, the method disclosed in Japanese Patent Application No. 59-134633 is used. The specific manufacturing method is
Examples of methods include a method in which one block is formed and then the other block is formed to simultaneously realize the combination of both blocks, and a method in which both blocks are respectively formed and then combined. Apart from consideration of the formation and bonding of blocks and the type of phenylene sulfide repeating units as described above, and other than modifications to be made as necessary, the method for producing the block copolymer used in the present invention is conventional. It can be said that this method is not essentially different from the method for producing phenylene thiolether polymer. That is, the method for producing the block polymer of the present invention involves condensing an alkali metal sulfide and a dihaloaromatic compound (mainly consisting of p- and m-dihalobenzene) by heating in an aprotic polar organic solvent (for example, NMP). It consists of a dealkali metal halide). In addition, this block copolymer has a melt viscosity of 50 to 1, measured at 310°C/shear rate of 200 (seconds) -1 .
It is desirable to be in the range of 100,000 boise. Polyarylene lentioether resin The resin that constitutes the molded product targeted by the present invention consists of a significant amount of polyarylene lentioether. Here, "consisting of a significant amount" means that the polyarylene thioether is contained in an amount greater than that which can be significantly realized by the treatment according to the present invention. For these reasons, it is preferable to use polyarylene thioether as it is, but as long as it does not interfere with molding, it is also advisable to use inorganic fillers (silica powder, alumina powder, silica powder, silica powder, alumina powder, mica, kaolin, calcium carbonate powder, calcium silicate powder, talc, carbon black, wollastonite, potassium titanate whisker, etc.), fibrous filler (glass fiber, carbon fiber, etc.), crystal nucleating agent, crystallization adjustment It is also possible to add agents, pigments, stabilizers, lubricants, mold release agents, and the like. It is also possible to blend other polyarylene thioethers or other thermoplastic resins that do not react with or be compatible with the organic substances described below, as long as they do not interfere with the molding process. The polyarylene thioether should predominate in this resin blend. Highly Crystallized Organic Substance The organic substance used in the method for producing a molded product of the crystallized polyarylene thioether or its composition of the present invention is preferably one that has excellent affinity for polyarylene thioether. These are used as liquids or their vapors. Regarding the affinity between organic polymers and solvents, the SP value (solubility parameter) is generally an effective measure. The SP value of polyarylene lentioether is not yet clear, but aliphatic hydrocarbons with small SP values,
Water, alcohols, amines, etc. that have an excessively large SP value or a large hydrogen bonding force are not preferred. Therefore, the organic substances used in the present invention include:
Organic substances with a weak hydrogen bonding strength and an SP value of 8 to 12, preferably 8.4 to 11 are preferred. Examples of organic substances that can be applied to the method of manufacturing polyarylene thioether molded products with increased crystallinity of the present invention include carbon disulfide (in the present invention, carbon disulfide is considered as an organic substance), halogenated hydrocarbons (chloroform , tricrene, perchlorethylene, ethylene dichloride, bromobenzene, etc.), ethers (tetrahydrofuran, etc.), thioethers (diphenylthioether, etc.),
Ketones (acetone, methyl ethyl ketone, cyclohexanone, etc.), amides (dimethylacetamide, dimethylformamide, N-methyl-2
-pyrrolidone), esters (ethyl acetate, etc.), aromatic hydrocarbons (benzene, toluene, xylene, methylnaphthalene, decalin, tetralin,
Examples include ethylbenzene, styrene), etc.
These organic substances can be used alone or in combination of two or more. Among these organic substances, CS 2 , chloroform,
Trichlene and the like are particularly preferred since they have a significantly large crystallization effect. Production of crystallized molded product In order to produce the crystallized molded product of the present invention, a resin consisting of a significant amount of polyarylene thioether,
It is necessary to melt and mold it in advance. By bringing this melt-molded product into contact with an organic liquid or vapor that has a high affinity with the resin,
The organic molecules can be diffused into the molded article to enhance the crystallization of the resin. It is thought that the low-molecular organic molecules diffused inside the resin act like a kind of roller, promoting the movement of the polymer molecules within the resin and promoting the crystallization of the polymer. Since the effect of this roller works even if the temperature is below the second-order transition point, it is thought that the molecular diffusion of low molecular weight organic molecules into the interior of the polymer molding controls the rate of crystallization. Therefore, methods for promoting this diffusion include selecting an organic substance with high affinity for polymers and increasing temperature to increase molecular motion. As long as the contact temperature is above the freezing point at which organic molecules can diffuse, crystallization can essentially occur. However, it is advantageous to have a higher temperature because crystallization can be accelerated. However, temperatures higher than the melting temperature of the polyphenylene thioether resin are unsuitable because the crystal structure of the resin will be destroyed. Although the present invention can be carried out at any temperature below the melting temperature, it is preferably below the secondary transition temperature of the resin. The contact time required for crystallization varies depending on the contact temperature, but the lower the temperature, the longer the time required, and the higher the temperature, the shorter the time required. Usually, a range of 1 second to about 100 hours, preferably a range of 3 seconds to 24 hours is used. If it is less than 1, crystallization is insufficient, and if it exceeds 100 hours, it is not practical from an economic standpoint. A short time is required for a film or sheet, but a long time is required for a molded product. It has been mentioned above that the present invention can be carried out at temperatures below the melting temperature of the resin, and therefore the method of the present invention can be applied to conventional heat setting treatments at high temperatures below the melting temperature of yarns and films. If this low-molecular-weight organic substance is used in combination at that time, the heat-setting temperature can be significantly lowered or the heat-setting time can be significantly shortened. The method of contacting the low-molecular-weight organic substance with the resin molded article is to immerse the molded article in the low-molecular-weight organic substance, to apply the low-molecular-weight organic substance to the molded article, or to expose it to the vapor of the low-molecular-weight organic substance (steam exposure method). etc. are preferable. At this time, it is preferable to carry out moldings that are easily deformed, such as stretched films, stretched sheets, stretched threads, etc., under tension or limited deformation.
When the molded product is a film, sheet, thread, etc., crystallization can be performed simultaneously while applying stress and stretching. Crystallized Polyarylenethioether Resin Molded Article The crystallized polyarylene lentioether resin molded article obtained by the present invention has excellent heat resistance, chemical resistance,
It can be used in various fields by taking advantage of its flame retardant properties. For example, various molded articles, sheets, films,
Preferably used for pipes, fibers, etc. Films or sheets are used, for example, in the electronic and electrical fields, such as printed circuit boards, magnetic tape (coated type,
It is useful as evaporation type), insulating tape, floppy disk, etc. Crystallized products of extruded products (plates, pipes, profiles, etc.) are useful, for example, in the electronic and electrical fields as printed circuit boards and protection tubes for collective wiring, and in the chemical industry as various corrosion-resistant and heat-resistant piping. An electric wire coated with this resin composition and crystallized is useful as a heat-resistant and corrosion-resistant electric wire. As a crystallized product of injection molding, it is useful, for example, in the electronics and electrical fields as printed circuit board IC encapsulant, connectors, microwave equipment parts, etc., and in the chemical industry as large pumps, large valves, sealing materials, lining materials, etc. . Experimental example Polymer synthesis (A) N-methyl-2 in a 20 liter autoclave
-Pyrrolidone (hereinafter abbreviated as NMP) 11.0Kg
and Na 2 S pentahydrate crystals (manufactured by Nagao Soda Co., Ltd.) containing 46.02% by weight of Na 2 S at 4.239°C (25.0 mol as Na 2 S) were charged, and the mixture was gradually heated under nitrogen atmosphere for about 2 hours while stirring. The temperature was raised to 200°C and water was distilled off. After cooling to 130℃, 3.6 kg of paradichlorobenzene (hereinafter abbreviated as p-DCB) and
3.2 kg of NMP was added and polymerized by heating at 220°C for 4 hours. Next, 1.3 kg of water was added, the temperature was raised to 265° C. under a nitrogen atmosphere, and polymerization was carried out for 4 hours. After cooling, the obtained polymer was sieved from oligomers and the like, washed repeatedly with deionized water, and then dried under reduced pressure at 100°C. The obtained polymer A is a p-phenylene sulfide straight polymer with a melt viscosity η * =5000 poise (310°C, shear rate 200 (sec) -1 ),
It was highly crystalline with a crystal melting point Tm = 282°C. This polymer A was melt-extruded at 330°C to form pellets A. (B) NMP11.0Kg in a 20 liter autoclave,
Na2S pentahydrate crystals containing 46.02 wt% Na2S
4.239Kg was charged, and the temperature was gradually raised to 200℃ while stirring under a nitrogen atmosphere for about 2 hours.
Water was distilled out. Add 3.6 kg of meta-dichlorobenzene and 3.0 kg of NMP to this, and
Polymerization was carried out for a period of time to obtain a slurry containing poly(metaphenylene sulfide). Metadichlorobenzene was almost completely polymerized. The degree of polymerization of the obtained polymetaphenylene sulfide was approximately 20 (determined by calculation by measuring the amount of Cl at both terminals using fluorescent X-rays). Separately, NMP9.0 into 20 liters autoclave
Kg and 3.604 Kg of Na 2 S pentahydrate crystals were charged and gradually stirred for about 2 hours under a nitrogen atmosphere.
The temperature was raised to 200°C and water was distilled off. to this,
3.4 kg of paradichlorobenzene, 3.0 kg of NMP, and 2.8 kg of the poly(metaphenylene sulfide)-containing slurry were charged, and the temperature was raised to 220°C.
Allowed time to react. Then add 1.5Kg of water,
The temperature was raised to 265°C and the reaction was carried out for 4 hours. Polymer (B) was recovered by the same post-treatment as in (A). The obtained polymer (B) is
【式】ユ ニツトと[Formula] Yu With Nittu
【式】ユニツトとのブロツ
ク共重合体であり、溶融粘度η*＝4200ボイズ、
結晶融点＝272℃の高結晶性のものであつた。な
お、このブロツク共重合体の組成はFT−IRによ
り測定の結果、メタ／パラ＝15／85（モル比）で
あつた。このポリマー(B)も320℃で溶融押出を行
つて、ペレツト(B)とした。
ポリマーの成形
ペレツト(A)及び(B)について、310〜320℃で溶融
押出し、急冷して、厚さ0.2mmのＴダイシート(A)
及び(B)を調製した。
結晶化物の製造
Ｔダイシート(A)及び(B)の、短冊形サンプルをそ
れぞれ各種低分子有機物液体に浸漬し、30℃で24
時間保持した。
結晶化度の測定
溶媒処理したサンプルを恒量に達するまで減圧
乾燥した後、密度勾配管を用いて密度を測定し、
その値から結晶化度を算出した（但し、結晶部密
度＝1.43、非結晶部密度＝1.32として計算した）。
得られた結果は下記表１に示す通りであつた。[Formula] Block copolymer with unit, melt viscosity η * = 4200 voids,
It was highly crystalline with a crystal melting point of 272°C. The composition of this block copolymer was determined by FT-IR to be meta/para=15/85 (molar ratio). This polymer (B) was also melt-extruded at 320°C to form pellets (B). Polymer molding Pellet (A) and (B) are melt extruded at 310-320℃, rapidly cooled, and a T-die sheet (A) with a thickness of 0.2 mm is produced.
and (B) were prepared. Production of crystallized products: Immerse rectangular samples of T-die sheets (A) and (B) in various low-molecular-weight organic liquids, and heat them at 30℃ for 24 hours.
Holds time. Measurement of crystallinity After drying the solvent-treated sample under reduced pressure until it reached a constant weight, the density was measured using a density gradient tube.
The degree of crystallinity was calculated from the value (however, it was calculated assuming that the density of the crystalline part was 1.43 and the density of the amorphous part was 1.32). The results obtained were as shown in Table 1 below.
【表】【table】
【表】
組成物の成形及び結晶化物の製造
ポリマー(B)90重量部にガラス繊維チヨツプ（日
東紡(株)製CS3PE−471S）10重量部を添加し、320
℃で溶融押出してペレツトとし、これを310〜320
でホツトプレスし、急冷して、厚さ0.25mmのシー
トを調製した。これをCS2に25℃／24時間浸漬
し、それから恒量に達するまで減圧乾燥したの
ち、密度勾配管を用いて密度を測定し、その値か
ら結晶化度を算出した（但し、ガラス繊維密度＝
2.54）。その結果、結晶化度は28（％）であつた。[Table] Molding of composition and production of crystallized product 10 parts by weight of glass fiber chops (CS3PE-471S manufactured by Nittobo Co., Ltd.) were added to 90 parts by weight of polymer (B), and 320
Melt extrude at 310-320℃ to make pellets.
A sheet with a thickness of 0.25 mm was prepared by hot pressing and quenching. This was immersed in CS 2 at 25°C for 24 hours, and then dried under reduced pressure until it reached a constant weight.The density was then measured using a density gradient tube, and the degree of crystallinity was calculated from that value (however, glass fiber density =
2.54). As a result, the crystallinity was 28 (%).
Claims (1)
を示す）を50モル％以上含むポリアリーレンチオ
エーテルの有意量からなる樹脂の成形物を、当該
樹脂との親和性の高い有機物の液体または蒸気
に、当該有機物の凝固点以上であつて当該樹脂の
融解温度以下の温度で接触させることを特徴とす
る、結晶化度を高めたポリアリーレンチオエーテ
ル成形物の製造法。 ２ ポリアリーレンチオエーテルがポリフエニレ
ンチオエーテルである、特許請求の範囲第１項記
載のポリアリーレンチオエーテル成形物の製造
法。 ３ ポリアリーレンチオエーテルの有意量からな
る樹脂の成形物と、当該樹脂と親和性の高い有機
物との接触温度が、当該有機物の凝固点以上であ
つて、当該樹脂の二次転移温度以下である、特許
請求の範囲第１項もしくは第２項記載のポリアリ
ーレンチオエーテル成形物の製造法。 ４ 樹脂との親和性の高い有機物が、二硫化炭
素、ハロゲン化炭化水素、エーテル類、チオエー
テル類、ケトン類、アミド類、エステル類および
芳香族炭化水素の中から選らばれた、少なくとも
１種である、特許請求の範囲第１項乃至第３項の
いずれか１項に記載のポリアリーレンチオエーテ
ル成形物の製造法。[Scope of Claims] 1. A molded article of a resin comprising a significant amount of polyarylene thioether containing 50 mol% or more of repeating units (-Ar-S)-(Ar represents an arylene group), A method for producing a polyarylene thioether molded product with an increased degree of crystallinity, the method comprising contacting a liquid or vapor of an organic substance with a high degree of crystallinity at a temperature above the freezing point of the organic substance and below the melting temperature of the resin. 2. The method for producing a polyarylene thioether molded product according to claim 1, wherein the polyarylenchioether is polyphenylene thioether. 3. A patent in which the contact temperature between a resin molded product made of a significant amount of polyarylene thioether and an organic substance with high affinity for the resin is above the freezing point of the organic substance and below the secondary transition temperature of the resin. A method for producing a polyarylene thiolether molded product according to claim 1 or 2. 4. The organic substance having high affinity with the resin is at least one selected from carbon disulfide, halogenated hydrocarbons, ethers, thioethers, ketones, amides, esters, and aromatic hydrocarbons. A method for producing a polyarylene thiolether molded product according to any one of claims 1 to 3.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1288986A JPS62172033A (en) | 1986-01-23 | 1986-01-23 | Production of molded polyarylene thioether article having enhanced crystallinity |
| EP87100743A EP0233494A3 (en) | 1986-01-23 | 1987-01-20 | Method for producing high-crystallinity polyarylene thioether formed products |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1288986A JPS62172033A (en) | 1986-01-23 | 1986-01-23 | Production of molded polyarylene thioether article having enhanced crystallinity |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62172033A JPS62172033A (en) | 1987-07-29 |
| JPH0512377B2 true JPH0512377B2 (en) | 1993-02-17 |
Family
ID=11817964
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1288986A Granted JPS62172033A (en) | 1986-01-23 | 1986-01-23 | Production of molded polyarylene thioether article having enhanced crystallinity |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62172033A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0747295B2 (en) * | 1986-11-20 | 1995-05-24 | 呉羽化学工業株式会社 | Slippery polyary lentithioether film and process for producing the same |
| ATE345786T1 (en) * | 1994-09-09 | 2006-12-15 | Shozo Koyama | AGENT FOR REDUCING MOLECULAR FUNCTIONS |
-
1986
- 1986-01-23 JP JP1288986A patent/JPS62172033A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS62172033A (en) | 1987-07-29 |
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