JPS62205161A - Production of molded article - Google Patents
Production of molded articleInfo
- Publication number
- JPS62205161A JPS62205161A JP61045776A JP4577686A JPS62205161A JP S62205161 A JPS62205161 A JP S62205161A JP 61045776 A JP61045776 A JP 61045776A JP 4577686 A JP4577686 A JP 4577686A JP S62205161 A JPS62205161 A JP S62205161A
- Authority
- JP
- Japan
- Prior art keywords
- liquid crystal
- reaction
- high polymer
- rigid
- 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
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- 238000010107 reaction injection moulding Methods 0.000 claims abstract description 22
- 239000000203 mixture Substances 0.000 claims abstract description 11
- 239000000843 powder Substances 0.000 claims abstract description 6
- 229920003002 synthetic resin Polymers 0.000 claims abstract description 5
- 239000000057 synthetic resin Substances 0.000 claims abstract description 5
- 229920000106 Liquid crystal polymer Polymers 0.000 claims description 19
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 claims description 19
- 239000012295 chemical reaction liquid Substances 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 abstract description 20
- 239000000243 solution Substances 0.000 abstract description 19
- 229920000642 polymer Polymers 0.000 abstract description 17
- 239000004973 liquid crystal related substance Substances 0.000 abstract description 7
- 239000004974 Thermotropic liquid crystal Substances 0.000 abstract description 5
- 238000002156 mixing Methods 0.000 abstract description 2
- 239000004976 Lyotropic liquid crystal Substances 0.000 abstract 2
- 239000003054 catalyst Substances 0.000 description 11
- 238000000034 method Methods 0.000 description 10
- -1 alkylaluminum halide Chemical class 0.000 description 7
- 239000000178 monomer Substances 0.000 description 7
- 238000000465 moulding Methods 0.000 description 5
- 239000004677 Nylon Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 229920001778 nylon Polymers 0.000 description 4
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 3
- 235000018660 ammonium molybdate Nutrition 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 230000002535 lyotropic effect Effects 0.000 description 3
- 238000005649 metathesis reaction Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000002685 polymerization catalyst Substances 0.000 description 3
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 3
- 229910052721 tungsten Inorganic materials 0.000 description 3
- 239000010937 tungsten Substances 0.000 description 3
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 229940010552 ammonium molybdate Drugs 0.000 description 2
- 239000011609 ammonium molybdate Substances 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- LPIQUOYDBNQMRZ-UHFFFAOYSA-N cyclopentene Chemical compound C1CC=CC1 LPIQUOYDBNQMRZ-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 2
- 239000004088 foaming agent Substances 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 2
- 125000003518 norbornenyl group Chemical group C12(C=CC(CC1)C2)* 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920005862 polyol Polymers 0.000 description 2
- 150000003077 polyols Chemical class 0.000 description 2
- 238000007142 ring opening reaction Methods 0.000 description 2
- SWZDQOUHBYYPJD-UHFFFAOYSA-N tridodecylamine Chemical compound CCCCCCCCCCCCN(CCCCCCCCCCCC)CCCCCCCCCCCC SWZDQOUHBYYPJD-UHFFFAOYSA-N 0.000 description 2
- CGTZMJIMMUNLQD-STYNFMPRSA-N (2r)-2-[(r)-(2-ethoxyphenoxy)-phenylmethyl]morpholine;methanesulfonic acid Chemical compound CS(O)(=O)=O.CCOC1=CC=CC=C1O[C@H](C=1C=CC=CC=1)[C@@H]1OCCNC1 CGTZMJIMMUNLQD-STYNFMPRSA-N 0.000 description 1
- YWYIHWJAVXCTFB-UHFFFAOYSA-N 1-methylcyclododecene Chemical compound CC1=CCCCCCCCCCC1 YWYIHWJAVXCTFB-UHFFFAOYSA-N 0.000 description 1
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
- SGTNSNPWRIOYBX-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-{[2-(3,4-dimethoxyphenyl)ethyl](methyl)amino}-2-(propan-2-yl)pentanenitrile Chemical compound C1=C(OC)C(OC)=CC=C1CCN(C)CCCC(C#N)(C(C)C)C1=CC=C(OC)C(OC)=C1 SGTNSNPWRIOYBX-UHFFFAOYSA-N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 1
- QHJIJNGGGLNBNJ-UHFFFAOYSA-N 5-ethylbicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(CC)CC1C=C2 QHJIJNGGGLNBNJ-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- 239000004970 Chain extender Substances 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 241001408050 Oxydia Species 0.000 description 1
- 241000269851 Sarda sarda Species 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-N benzene-dicarboxylic acid Natural products OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 229940088033 calan Drugs 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- DRFGMUMDUXDALH-UHFFFAOYSA-N cyclobutyne Chemical compound C1CC#C1 DRFGMUMDUXDALH-UHFFFAOYSA-N 0.000 description 1
- HYPABJGVBDSCIT-UPHRSURJSA-N cyclododecene Chemical compound C1CCCCC\C=C/CCCC1 HYPABJGVBDSCIT-UPHRSURJSA-N 0.000 description 1
- URYYVOIYTNXXBN-UPHRSURJSA-N cyclooctene Chemical compound C1CCC\C=C/CC1 URYYVOIYTNXXBN-UPHRSURJSA-N 0.000 description 1
- 239000004913 cyclooctene Substances 0.000 description 1
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 description 1
- POULHZVOKOAJMA-UHFFFAOYSA-M dodecanoate Chemical compound CCCCCCCCCCCC([O-])=O POULHZVOKOAJMA-UHFFFAOYSA-M 0.000 description 1
- UAIZDWNSWGTKFZ-UHFFFAOYSA-L ethylaluminum(2+);dichloride Chemical compound CC[Al](Cl)Cl UAIZDWNSWGTKFZ-UHFFFAOYSA-L 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 150000003951 lactams Chemical class 0.000 description 1
- 229940070765 laurate Drugs 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- ANRQGKOBLBYXFM-UHFFFAOYSA-M phenylmagnesium bromide Chemical compound Br[Mg]C1=CC=CC=C1 ANRQGKOBLBYXFM-UHFFFAOYSA-M 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920003190 poly( p-benzamide) Polymers 0.000 description 1
- 229920003366 poly(p-phenylene terephthalamide) Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 1
- 150000003623 transition metal compounds Chemical class 0.000 description 1
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 description 1
- KPGXUAIFQMJJFB-UHFFFAOYSA-H tungsten hexachloride Chemical compound Cl[W](Cl)(Cl)(Cl)(Cl)Cl KPGXUAIFQMJJFB-UHFFFAOYSA-H 0.000 description 1
- 229920006305 unsaturated polyester Polymers 0.000 description 1
Landscapes
- Casting Or Compression Moulding Of Plastics Or The Like (AREA)
- Injection Moulding Of Plastics Or The Like (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は耐熱性が改善された成形体の製造方法に関する
ものである。DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a method for manufacturing a molded article with improved heat resistance.
（従来の技術）
近年、よシ耐熱性に優れるポリマーをよシ容易な成形方
法で得ようとする要求が年々高まり、各方面での研究が
活発に行なわれている。(Prior Art) In recent years, the demand for obtaining polymers with excellent heat resistance by easy molding methods has been increasing year by year, and research in various fields has been actively conducted.
こうし友中で、容易な成形法として、反応射出成形方式
（通常ＲＩＭと称される）が挙げられ、ウレタンをはじ
めナイロン、エポキシ、不飽和ポリエステルなどに加え
、ノルメルネン型単重体の反応射出成形（以下ではノル
？ルネンｉ ＲＩＭと称する）などが検討されている。At Koushi Tomonaka, reaction injection molding (usually referred to as RIM) is an easy molding method that can be used for reaction injection molding of urethane, nylon, epoxy, unsaturated polyester, etc., as well as normernene type monomers. (hereinafter referred to as Nor?runen i RIM), etc. are being considered.
しかしながら、共通して耐熱性が不充分であるという重
大な欠点を有していた。However, they had a common serious drawback of insufficient heat resistance.
（発明が解決しようとする問題点）
本発明者らは前記欠点を解決すべく鋭意研究の結果、合
成樹脂形成反応液中に液晶高分子粉末を配合し、反応射
出成形することにより耐熱性の改良された成形体が得ら
れることを見い出し、この知見に基づいて本発明を完成
するに到り几。(Problems to be Solved by the Invention) As a result of intensive research to solve the above-mentioned drawbacks, the present inventors have found that heat-resistant It was discovered that an improved molded article could be obtained, and based on this knowledge, the present invention was completed.
（問題点を解決するｔめの手段）
かくして本発明によれば、合成樹脂形成用反応液７０〜
９７重量％と液晶高分子粉末３〜３０重量％から成る混
合物を反応射出成形する成形体の製造方法が提供される
。(Tth Means for Solving the Problem) Thus, according to the present invention, the synthetic resin forming reaction solution 70-
A method for producing a molded article is provided, in which a mixture of 97% by weight and 3 to 30% by weight of liquid crystal polymer powder is reaction injection molded.
本発明で使用される合成樹脂形成用反応液は通常のポリ
ウレタンＩＩＩＭ 、ナイロンＲＩＭ％エポキシＩｔＩ
Ｍ％ポリエステルＲＩＭ 、フェノール樹脂ＲＩＭ 、
ノル♂ルネンｆｉＲＩＭ等で使用される公知の反応液か
ら選ばれる。The reaction solution for forming a synthetic resin used in the present invention is ordinary polyurethane IIIM, nylon RIM% epoxy ItI.
M% polyester RIM, phenolic resin RIM,
It is selected from known reaction solutions used in nor-♂runene fiRIM, etc.
ウレタンＲＩＭに使用される反応液はポリオール、触媒
から成る反応液と？リイノシアネートから成る反応液を
使用するが、各反応液を構成する成分は特開昭５３−３
６５９８号公報や特開昭５９−１５６７３７号公報など
に開示されているものが使用できる。The reaction liquid used for urethane RIM is a reaction liquid consisting of polyol and catalyst? A reaction solution consisting of linocyanate is used, and the components constituting each reaction solution are
Those disclosed in Japanese Patent Application Laid-open No. 6598, Japanese Patent Application Laid-open No. 156737/1984, etc. can be used.
工／キシＲＩＭに使用される反応液はポリエポキシ化合
物及び触媒から成る反応液と硬化剤から成る反応液であ
るが、これらの各成分は特開昭５８−９４４４３．１６
７１４４号公報、米国特許第４．３９７，９９８号明細
書などに開示されているものが使用できる。The reaction liquid used in the Polyepoxy RIM is a reaction liquid consisting of a polyepoxy compound and a catalyst, and a reaction liquid consisting of a curing agent.
Those disclosed in Japanese Patent No. 7144, US Pat. No. 4,397,998, etc. can be used.
ナイロンＲＩＭでは例えば特開昭５１−１８７９７゜４
８６２８号公報、特公昭５４−４０１２０号公報等に記
載されているカプロラクタムと重合触媒より成る反応液
が使用できる。For nylon RIM, for example, JP-A-51-18797゜4
A reaction solution comprising caprolactam and a polymerization catalyst described in Japanese Patent Publication No. 8628, Japanese Patent Publication No. 54-40120, etc. can be used.
いずれのＲＩＭにおいても使用できる反応液は樹脂状高
分子成形体が得られる反応液であれば上記の例に限定さ
れない。The reaction liquid that can be used in any RIM is not limited to the above examples as long as it can yield a resinous polymer molded article.
ノルボルネン型ＲＩＭはノル？ルネン単位含有モ／ −
ｒ −ｆメタセシス触媒を用いてＲＩＭ方式によシ開環
重合と成形とを同時に行うものである。Norbornene-type RIM is norbornene? Rune unit content / −
Ring-opening polymerization and molding are simultaneously performed by the RIM method using an r-f metathesis catalyst.
ノルぎルネン型ＲＩＭで用いられるノルボルネン単位含
有単量体は一般式（１）又は（２ンで示されるモノマー
である。The norbornene unit-containing monomer used in the norbornene type RIM is a monomer represented by the general formula (1) or (2).
（式中Ｒ１〜Ｒ４は水素又は置換基を表わし、Ｒ１とＲ
２，Ｒ，とＲ４は飽和又は不飽和の環を形成してもよい
。）
具体的には２−ノ／Ｌ／？ルネン、５−メチル−２−ノ
ルゴルネン、５，６−シメチルー２−ノル〆ルネン、５
−エチル−２−ノルボルネン、ジシクロペンタジェン、
メチルシクロドデセン、ノヒドロジシクロペンタジエン
、メチルテトラシクロドデセンなど及びこれらの混合物
が挙げられる。又これらの七ツマ−の１ｆ！以上と共に
開環共重合し得るシクロブチン、シクロペンテン、シク
ロオクテン、シクロドデセンなどのモノ及びノルクロオ
レフィンなどを併用することができる。(In the formula, R1 to R4 represent hydrogen or a substituent, and R1 and R
2, R, and R4 may form a saturated or unsaturated ring. ) Specifically, 2-ノ/L/? Runene, 5-methyl-2-norgorene, 5,6-dimethyl-2-nor〆runene, 5
-ethyl-2-norbornene, dicyclopentadiene,
Examples include methylcyclododecene, nohydrodicyclopentadiene, methyltetracyclododecene, and mixtures thereof. Also, 1f of these seven horses! Mono- and nor-chloroolefins such as cyclobutyne, cyclopentene, cyclooctene, and cyclododecene, which can be ring-opening copolymerized with the above, can be used in combination.
これらの単量体は公知の開環重合により重合体に転化さ
れるが、開環重合に使用される触媒としては公知のメタ
セシス重合触媒が用いられ、代表的な例としては、特開
昭５８−１２９０１３号公報開示の六塩化タングステン
、オキシ四塩化夕／ゲステンなどのタングステン含有化
合物と塩化ノエチルアルミニウム、二塩化エチルアルミ
ニウムナトのハロダン化アルキルアルミニウムから成る
触媒系、特開昭５８−１２７７２８号公報開示の前記同
様のへ〇グン化アルキルアルミニウムとトリドデシルア
ンモニウムモリブデン酸塩、同タングステン酸塩などの
有機アンモニウムモリブデン酸塩あるいは同タングステ
ン酸塩から成る触媒系、特開昭５９−５１９１１号公報
開示のＮ上の有機アンモニウムモリブデン酸塩あるいは
タングステン酸塩とアルコキシアルキルアルミニウムハ
ライドあるいはアリールオキジアルミニウムハライドか
ら成る触媒系などの遷移金属化合物と有機金属化合物あ
るいはルイス酸などの共触媒から成るメタセシス重合触
媒が挙げられる。These monomers are converted into polymers by known ring-opening polymerization, and known metathesis polymerization catalysts are used as catalysts for ring-opening polymerization. Catalyst system consisting of a tungsten-containing compound such as tungsten hexachloride, oxytetrachloride/gesten, etc. and alkylaluminum halide such as noethylaluminum chloride and ethylaluminum dichloride disclosed in Japanese Patent Application Laid-open No. 127728/1983 Catalyst system consisting of an alkylaluminide and an organic ammonium molybdate such as tridodecyl ammonium molybdate, tridodecylammonium molybdate, or tungstate as disclosed in JP-A-59-51911 Examples include metathesis polymerization catalysts consisting of transition metal compounds such as catalyst systems consisting of organic ammonium molybdates or tungstates on N and alkoxyalkyl aluminum halides or aryl oxydia aluminum halides and cocatalysts such as organometallic compounds or Lewis acids. It will be done.
ノルボルネンｆｉ ＲＩＭにおける反応液は上記の二成
分の触媒を別々にノルがルネン単位含有単量体く混合し
、二液の反応液として使用する。例えば。The reaction solution in norbornene fi RIM is prepared by separately mixing the above-mentioned two-component catalyst with the nornene unit-containing monomer and using it as a two-part reaction solution. for example.
モリブデン又はタングステン含有触媒の使用量は、モリ
ブデン又はタングステンとして通常全単量体１モル当り
０．０１〜５０ミリモルの範囲である。The amount of molybdenum or tungsten-containing catalyst used is usually in the range of 0.01 to 50 mmol per mole of total monomers.
ハロゲン化アルキルアルミニウム触媒の使用量はアルミ
ニウムとして通常モリブデン又はタングステンに対して
モル比で２００：１〜１：１０の範囲である。The amount of the alkylaluminium halide catalyst used is usually in a molar ratio of 200:1 to 1:10 relative to molybdenum or tungsten.
本発明で使用される液晶高分子としては、サーモトロピ
ック液晶全形成する剛直鎖高分子及びリオトロピック液
晶を形成する剛直鎖高分子あるいは側鎖に剛直原子団（
メソダン）を有するサーモトロピック液晶及びリオトロ
ピック液晶を形成する剛直側鎖を有する高分子が挙げら
れる。The liquid crystal polymers used in the present invention include rigid linear chain polymers that form thermotropic liquid crystals, rigid linear polymers that form lyotropic liquid crystals, or rigid atomic groups in side chains.
Examples include polymers with rigid side chains that form thermotropic liquid crystals and lyotropic liquid crystals (methodane).
サーモトロピック液晶を形成する高分子の例としてはヒ
ドロキシ安息香酸を共重合し次ポリエチレンテレフタレ
ー） （Ｅａｓｔｍａｎ Ｋｏｄａｘ社のＸ７Ｇ）、ビ
スフェノールとフタル酸の共重合体（ＣａｒｂｏｒＸｉ
ｎｄｕｍ社のＥｋｋｃ＋ｅＸ、 Ｄａｒｔｅｏ社のＸｙ
ｄａｒなと）、ヒドロキシ安息香酸／ソヒドロキシナフ
タレ／／テレフタル酸共重合体などの芳香族ポリエステ
ルなどが例示される。また、リオトロピック液晶を形成
する剛直鎖高分子としてはポリ（ｐ−フェニレンテレフ
タルアミド）、ポリ（ｐ−ベンズアミド）などの芳香族
ポリアミドなどが挙げられる。Examples of polymers that form thermotropic liquid crystals include polyethylene terephthalate copolymerized with hydroxybenzoic acid (X7G from Eastman Kodax), and a copolymer of bisphenol and phthalic acid (CarborXi).
ndum's Ekkc+eX, Darteo's Xy
Examples include aromatic polyesters such as hydroxybenzoic acid/sohydroxynaphthalene/terephthalic acid copolymers. Furthermore, examples of rigid linear polymers forming lyotropic liquid crystals include aromatic polyamides such as poly(p-phenylene terephthalamide) and poly(p-benzamide).
これらの液晶高分子は単独であるいは二種以上で該反応
液に添加されるが、添加量は該反応液との混合物中３〜
３０重ｔチである。３ｔｉ：％未満では耐熱性改良効果
は少なく、３０重量％を越えると該混合物の粘度が高く
なり、注入操作が困難となる。好ましくは５〜２５重量
％、さらに好゛ましくｒｉ、ｌＯ〜２０！ｔ％である。These liquid crystal polymers may be added alone or in combination of two or more to the reaction solution, but the amount added is 3 to 3 in the mixture with the reaction solution.
It's 30 weights. If it is less than 3ti:%, the effect of improving heat resistance will be small, and if it exceeds 30% by weight, the viscosity of the mixture will increase, making injection operations difficult. Preferably 5 to 25% by weight, more preferably ri, lO to 20! t%.
本発明においては液晶高分子は粉末状で使用することが
耐熱性改良のために必要であり、好ましい平均粒径は１
ｔｉ以丁、さらに好ましくは０．５ ｗ以下である。In the present invention, it is necessary to use the liquid crystal polymer in powder form to improve heat resistance, and the preferred average particle size is 1.
It is less than ti, more preferably 0.5 w or less.
本発明においては粉末は液晶高分子を該高分子ｉＲ造時
ｋＣ粉末状で回収したものでも、又該高分子の塊りを機
械的に粉砕し友もの、繊維状の該高分子を１鱈以下に切
断あるいは低温で破砕したものなどいずれの方法による
ものでも差しつかえない。In the present invention, the powder may be obtained by recovering the liquid crystal polymer in the form of kC powder during production of the polymer iR, or by mechanically crushing agglomerates of the polymer, or by pulverizing the polymer in the form of fibers. The following methods may be used, such as cutting or crushing at low temperatures.
樹脂形成用反応液と液晶高分子の混合物をＲＩＭ方式で
成形することによシ耐熱性の改良された成形体が得られ
る。A molded article with improved heat resistance can be obtained by molding a mixture of a resin-forming reaction liquid and a liquid crystal polymer using the RIM method.
本発明に用いられる反応射出成形（ＲＩＭ）方式は従来
公知のＲＩＭ方式でよく５個々には反応しない反応液を
２液以上に分割し、この反応液を常圧〜２００１（ｆ／
ｃ１Ｒ”の圧力下で混合１７、金型内に注入する。より
低圧で注入を行うことが好ましく、通常反応液および金
型の温度は反応速度を考慮し、各々２０〜１５０℃の範
囲に選定される。まｔ、必要に応じ後硬化することも出
来る。The reaction injection molding (RIM) method used in the present invention may be the conventionally known RIM method.5 A reaction liquid that does not react individually is divided into two or more liquids, and this reaction liquid is mixed at normal pressure to 2001 (f/f/2).
The mixture is mixed under a pressure of c1R'' and injected into the mold.It is preferable to perform the injection at a lower pressure, and the temperatures of the reaction solution and the mold are usually selected in the range of 20 to 150°C, taking into account the reaction rate. However, it can also be post-cured if necessary.
成形体を発泡体とする場合には反応液中に発泡剤を含ま
せればよく、従来よりＲＩＭ分野で使用される発泡剤が
使用できる。When the molded product is a foam, a foaming agent may be included in the reaction solution, and any foaming agent conventionally used in the RIM field can be used.
まえ、本発明においては、必要に応じて可塑剤や耐衝撃
付与剤、フィラー・類、Ｂ燃剤、接着性改質材および酸
化防止剤などを反応酸中に混合させることが出来る。First, in the present invention, a plasticizer, an impact-resistant agent, a filler, a B reagent, an adhesive modifier, an antioxidant, etc. can be mixed into the reaction acid as necessary.
（発明の効果）
かくして本発明によれば従来技術に比較して耐熱性に優
れる成形体が容易に製造される。(Effects of the Invention) Thus, according to the present invention, a molded article having superior heat resistance compared to the prior art can be easily produced.
以下に実施例を挙げて本発明をさらに具体的に説明する
。なお、実施例、比較例中の部及びチはとくに断りのな
いかぎり重重基準である。The present invention will be explained in more detail with reference to Examples below. Note that parts and parts in Examples and Comparative Examples are based on weight unless otherwise specified.
実施例Ｉ
Ａ液にポリオール成分としてポリオキシグロピレントリ
オール（Ｕｎｉｏｎ Ｃａｒｂｉｄｅ社製Ｎ１ａｘ ３
１−２８゜水酸基当量２００３）を３５．３ｆｉｔＳ、
鎖長延長剤（Ｕｎｉｏｎ、 Ｃａｒｂｉｄｅ社製ＮＬｈ
ｘ ５０−１１８０−水酸基当量４７゜６）を１５．１
部平均粒径０，５箇以下とじ九液晶高分子（Ｃａｌａｎ
ｅｉ社製Ｖｅｓｔｒａ Ｃ−１３）を５．６部及びジプ
チル錫ラウレートを０．０１２部の割合で混合し。Example I Polyoxyglopyrene triol (N1ax 3 manufactured by Union Carbide) was added to Solution A as a polyol component.
1-28° hydroxyl group equivalent 2003) is 35.3fitS,
Chain extender (Union, NLh manufactured by Carbide)
x 50-1180-hydroxyl group equivalent 47゜6) to 15.1
Liquid crystal polymer (Calan) with a part average particle diameter of 0.5 or less
5.6 parts of Vestra C-13) manufactured by Ei Corporation and 0.012 parts of diptyltin laurate were mixed.
一方のＢ液にクルードＭＤＩ（Ｕｐｊｏｈｎ社製Ｉｍｏ
ｎａｔｅ１９１、 ＮＣＯ当量１３８．９）を４９．５
部及びＡ液と同じ液晶高分子を５．５部をとり、Ａ液７
０部に対しＢ液３０部の割合で混合し、１００℃に加温
しｔ金型内に注入し５分間反応を行い、液晶高分子含有
［１０チの成形品を得た。このものの熱変形温度（ＪＩ
ＳＫ−７２０７人法）を測定した結果１３０℃であつた
。Crude MDI (Imo manufactured by Upjohn) was added to one B solution.
nate191, NCO equivalent 138.9) to 49.5
Take 5.5 parts of the same liquid crystal polymer as liquid A and 7 parts of liquid A.
The mixture was mixed at a ratio of 0 parts to 30 parts of liquid B, heated to 100°C, poured into a T mold, and reacted for 5 minutes to obtain a molded product containing liquid crystal polymer [10 parts]. The heat distortion temperature of this material (JI
SK-7207 (manual method), the temperature was 130°C.
ｔた比較のｔめ、液晶高分子を配合しない上記ウレタン
成形品及び液晶高分子単独の熱変形温度を測定し几結果
、各々９５℃、２４０℃であつＴ：、。For comparison, the heat distortion temperatures of the urethane molded product without the liquid crystal polymer and the liquid crystal polymer alone were measured, and the results were 95°C and 240°C, respectively.
実施例２
一方の容器に５０部の６−カグロラクタムと平均粒径を
０．５−以下とした高分子液晶（Ｄａｒｔｃ。Example 2 In one container, 50 parts of 6-caglolactam and a polymeric liquid crystal (Dartc) having an average particle size of 0.5- or less were mixed.
ＭＦＧ社製５ＲＴ−５００） ６．０部、３モル濃度の
臭化フェニルマグネシウム触媒３．６鰹、他方の容器に
５０部のＣ−カグロラクタムと同じ液晶高分子ｔ＝６゜
０部及びテレフタロイルビス力！ラクタム４６３部をと
り、いずれの反応液も８０″Ｃに加温した。5RT-500 manufactured by MFG Co.) 6.0 parts, 3 molar phenylmagnesium bromide catalyst 3.6 bonito, 50 parts of C-caglolactam in the other container, the same liquid crystal polymer t = 6°0 parts, and terephthalate. Roylvis power! 463 parts of lactam was taken, and both reaction solutions were heated to 80''C.
前記の２液の反応液を１：１の割合で混合し、１４０℃
の金型中に注入し、２分間重合反応金行い・、液晶高分
子含量１０チの成形品を得た。このものの熱変形温度を
測定し几結果１２０℃であつ几。The above two reaction solutions were mixed at a ratio of 1:1 and heated to 140°C.
The mixture was poured into a mold, and a polymerization reaction was carried out for 2 minutes to obtain a molded product having a liquid crystal polymer content of 10 cm. The heat distortion temperature of this product was measured and the result was 120℃.
ま九比較のため液晶ｙＪｆ ＋７マーを配合しない上記
ナイロン成形品及び液晶ポリマー単独の熱変形温度を測
定し几結果各々７３℃、３５０１Ｃであっ友。For comparison, the heat deformation temperatures of the above nylon molded product without liquid crystal yJf+7mer and the liquid crystal polymer alone were measured, and the results were 73°C and 3501°C, respectively.
実施例３
所望量のメチルテトラシクロドデセンを２つの容器に入
れ各々の容器に平均粒径０．５駕以下の液晶高分子（Ｃ
＊１ａｎｅｓｓ社製Ｖ＠ｃｔｒａ Ａ３１５ ）を１０
優になるように配合した。一方の容器にはジエチルアル
ミニウムクロライドを該単量体１モルに対し０．０４８
モルの濃度になるように調整し次。他方の容器には同様
に０．００７モル濃度となるようＫＷｃｔ６を添加した
。このようにして調整し友前記の２液の反応液を１＝１
の割合で混合し、５０℃に加温した金型中に注入し成形
品を得た。また同じ液晶高分子の配合量を２０％とし、
同様の操作で成形品を得、熱変形温度を測定し友。Example 3 A desired amount of methyltetracyclododecene was placed in two containers, and a liquid crystal polymer (C
*1Aness V@ctra A315) 10
It was blended so that it was good. In one container, 0.048% of diethylaluminum chloride was added per mole of the monomer.
Next, adjust the concentration to be molar. KWct6 was similarly added to the other container at a concentration of 0.007 molar. In this way, the above two reaction solutions were adjusted to 1=1.
The mixture was mixed in the following proportions and poured into a mold heated to 50°C to obtain a molded product. In addition, the amount of the same liquid crystal polymer was set to 20%,
A molded product was obtained using the same procedure, and the heat distortion temperature was measured.
ま之、比較のｔめに液晶高分子を入れないで成形し九メ
チルテトラシクロドデセン開環重合体及び液晶高分子の
熱変形温度を測定し比。For comparison, the heat deformation temperatures of the 9-methyltetracyclododecene ring-opening polymer and the liquid crystal polymer were measured and compared by molding without adding the liquid crystal polymer.
これらの結果を第１表に示す。These results are shown in Table 1.
第 １ 表Table 1
Claims (1)
末３〜３０重量％から成る混合物を反応射出成形するこ
とを特徴とする成形体の製造方法。1. A method for producing a molded article, which comprises reaction injection molding a mixture comprising 70 to 97% by weight of a reaction liquid for forming a synthetic resin and 3 to 30% by weight of liquid crystal polymer powder.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61045776A JPS62205161A (en) | 1986-03-03 | 1986-03-03 | Production of molded article |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61045776A JPS62205161A (en) | 1986-03-03 | 1986-03-03 | Production of molded article |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS62205161A true JPS62205161A (en) | 1987-09-09 |
Family
ID=12728694
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61045776A Pending JPS62205161A (en) | 1986-03-03 | 1986-03-03 | Production of molded article |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62205161A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02185559A (en) * | 1989-01-12 | 1990-07-19 | Agency Of Ind Science & Technol | Highly rigid polyester resin composition |
| WO2017150336A1 (en) * | 2016-02-29 | 2017-09-08 | ポリプラスチックス株式会社 | Resin composition including liquid-crystal polymer particles, molded object obtained using same, and production processes therefor |
-
1986
- 1986-03-03 JP JP61045776A patent/JPS62205161A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02185559A (en) * | 1989-01-12 | 1990-07-19 | Agency Of Ind Science & Technol | Highly rigid polyester resin composition |
| WO2017150336A1 (en) * | 2016-02-29 | 2017-09-08 | ポリプラスチックス株式会社 | Resin composition including liquid-crystal polymer particles, molded object obtained using same, and production processes therefor |
| JPWO2017150336A1 (en) * | 2016-02-29 | 2018-03-15 | ポリプラスチックス株式会社 | Resin composition containing liquid crystal polymer particles, molded product using the same, and production method thereof |
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