JPH0264137A - Production of molded fiber-reinforced thermoplastic polyamide-imide resin body - Google Patents
Production of molded fiber-reinforced thermoplastic polyamide-imide resin bodyInfo
- Publication number
- JPH0264137A JPH0264137A JP21598488A JP21598488A JPH0264137A JP H0264137 A JPH0264137 A JP H0264137A JP 21598488 A JP21598488 A JP 21598488A JP 21598488 A JP21598488 A JP 21598488A JP H0264137 A JPH0264137 A JP H0264137A
- Authority
- JP
- Japan
- Prior art keywords
- prepreg
- imide resin
- fiber
- resin
- pressure
- 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
- 229920005989 resin Polymers 0.000 title claims abstract description 61
- 239000011347 resin Substances 0.000 title claims abstract description 61
- 239000004962 Polyamide-imide Substances 0.000 title claims abstract description 45
- 229920002312 polyamide-imide Polymers 0.000 title claims abstract description 44
- 229920001169 thermoplastic Polymers 0.000 title claims abstract description 39
- 239000004416 thermosoftening plastic Substances 0.000 title claims abstract description 39
- 238000004519 manufacturing process Methods 0.000 title claims description 11
- 239000003960 organic solvent Substances 0.000 claims abstract description 11
- 238000000748 compression moulding Methods 0.000 claims description 2
- 230000000704 physical effect Effects 0.000 abstract description 8
- 239000011157 advanced composite material Substances 0.000 abstract description 2
- 230000002542 deteriorative effect Effects 0.000 abstract 1
- 239000002904 solvent Substances 0.000 description 29
- 239000000835 fiber Substances 0.000 description 22
- 238000000034 method Methods 0.000 description 21
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 17
- 239000012783 reinforcing fiber Substances 0.000 description 13
- 238000000465 moulding Methods 0.000 description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 7
- 239000013557 residual solvent Substances 0.000 description 7
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 229920000049 Carbon (fiber) Polymers 0.000 description 5
- 239000004917 carbon fiber Substances 0.000 description 5
- 239000011342 resin composition Substances 0.000 description 5
- 238000004804 winding Methods 0.000 description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- UBOXGVDOUJQMTN-UHFFFAOYSA-N 1,1,2-trichloroethane Chemical compound ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 229920001187 thermosetting polymer Polymers 0.000 description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-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
- -1 aromatic tricarboxylic acid Chemical class 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 229920005992 thermoplastic resin Polymers 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- MYDJEUINZIFHKK-UHFFFAOYSA-N 1,1,2-trichloroethane-1,2-diol Chemical class OC(Cl)C(O)(Cl)Cl MYDJEUINZIFHKK-UHFFFAOYSA-N 0.000 description 1
- AVQQQNCBBIEMEU-UHFFFAOYSA-N 1,1,3,3-tetramethylurea Chemical compound CN(C)C(=O)N(C)C AVQQQNCBBIEMEU-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920002430 Fibre-reinforced plastic Polymers 0.000 description 1
- 239000004697 Polyetherimide Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000005336 allyloxy group Chemical group 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920006231 aramid fiber Polymers 0.000 description 1
- 150000004984 aromatic diamines Chemical class 0.000 description 1
- 238000011074 autoclave method Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000004918 carbon fiber reinforced polymer Substances 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 description 1
- 239000000805 composite resin Substances 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000011151 fibre-reinforced plastic Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910052736 halogen Chemical group 0.000 description 1
- 150000002367 halogens Chemical group 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 239000008235 industrial water Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000012784 inorganic fiber Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001601 polyetherimide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 230000001568 sexual effect Effects 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 229920006345 thermoplastic polyamide Polymers 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は繊維強化熱可塑性ポリアミドイミド樹脂成形体
を低圧力下で容易に製造する方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for easily producing a fiber-reinforced thermoplastic polyamideimide resin molded article under low pressure.
近年、炭素繊維強化プラスチックに代表される繊維強化
プラスチック（以下ＦＲＰと称する。）は先進複合材料
として、その高比強度及び高比弾性率の優れた特性を生
かして、航空・宇宙分野、スポーツ・レジャー分野、自
動車及び一般産業分野において実用化されている。In recent years, fiber-reinforced plastics (hereinafter referred to as FRP), represented by carbon fiber-reinforced plastics, have been used as advanced composite materials, taking advantage of their excellent properties of high specific strength and high specific modulus. It has been put into practical use in the leisure field, automobiles, and general industrial fields.
従来、ＦＲＰに用いられるマトリックス樹脂は、エポキ
シ樹脂に代表される熱硬化性樹脂が一般的であるが、脆
性、耐衝撃性に劣り、さらに硬化時間が長いなどの欠点
を有する。このため近年熱可塑性樹脂が、その高靭性、
成形サイクルが短い、さらに修復性などの利点を有する
ため、ＦＲＰのマトリックス樹脂として注目されている
。Conventionally, matrix resins used in FRP are generally thermosetting resins such as epoxy resins, but they have drawbacks such as brittleness, poor impact resistance, and long curing time. For this reason, in recent years thermoplastic resins have become popular due to their high toughness and
It is attracting attention as a matrix resin for FRP because it has advantages such as a short molding cycle and repairability.
特に耐熱性及び高靭性の要求される航空・宇宙分野の用
途において、いわゆるスーパーエンジニアリングプラス
チックと称される耐熱性熱可塑性樹脂が用いられている
。なかでも熱可塑性ポリアミドイミド樹脂はその優れた
耐熱性、耐薬品性、機械特性などの点で重要なマトリッ
クス樹脂として注目されている。Heat-resistant thermoplastic resins, so-called super engineering plastics, are used particularly in applications in the aerospace field that require heat resistance and high toughness. Among these, thermoplastic polyamide-imide resin is attracting attention as an important matrix resin due to its excellent heat resistance, chemical resistance, mechanical properties, etc.
従来、この繊維強化熱可塑性ポリアミドイミド樹脂成形
体の製造方法は、熱可塑性ポリアミドイミド樹脂の溶融
粘度が極めて高いため、高温度かつ高圧力の条件下で、
プリプレグをホットプレス法またはオートクレーブ法な
どで例示されるＦＲＰの通常の成形方法にて製造されて
いる。Conventionally, the manufacturing method of this fiber-reinforced thermoplastic polyamide-imide resin molded article has been carried out under conditions of high temperature and high pressure because the melt viscosity of the thermoplastic polyamide-imide resin is extremely high.
The prepreg is manufactured by a normal FRP molding method such as a hot press method or an autoclave method.
例えば、特開昭５９−２０２８１９号公報には熱可塑性
ポリアミドイミド樹脂５０〜９７重量％と有機溶媒５０
〜３重量％からなる組成物と繊維織物を積層し、これを
加熱、加圧してシート状にする第１工程、第１工程で得
たシート状積層物から有機溶媒を３重量％未満まで脱溶
媒する第２工程、第２工程で得た脱溶媒シート状物を所
望の形状に賦形する第３工程からなる繊維補強熱可塑性
ポリアミドイミド樹脂成形品の製造方法が記載されてい
る。また別の方法として特開昭６１−６９８４１号公報
にはアミドイミドポリマーの溶液で含浸した熱安定性連
続繊維、たとえばガラス、アルミナ、スチール、グラフ
ァイトまたは炭素繊維からなるラミネートが記載されて
おり、さらに該繊維がアミドイミドコポリマーあるいは
アミドイミドコポリマー／アミドイミド・フタルアミド
コポリマーのブレンド系あるいはポリアミドイミド／ポ
リエーテルイミドのブレンド系のサイズ組成物で被覆さ
れたものであり、これによりポリアミドイミド樹脂の流
動性を向上した旨記載されている。For example, JP-A-59-202819 discloses that 50 to 97% by weight of thermoplastic polyamideimide resin and 50% by weight of organic solvent are used.
A first step in which a composition consisting of ~3% by weight and a fiber fabric are laminated and heated and pressurized to form a sheet.The organic solvent is removed from the sheet-like laminate obtained in the first step to less than 3% by weight. A method for manufacturing a fiber-reinforced thermoplastic polyamide-imide resin molded article is described, which comprises a second step of applying a solvent and a third step of shaping the desolventized sheet material obtained in the second step into a desired shape. Alternatively, JP-A-61-69841 describes laminates of thermally stable continuous fibers, such as glass, alumina, steel, graphite or carbon fibers, impregnated with a solution of an amide-imide polymer; The fibers are coated with a size composition of an amide-imide copolymer, an amide-imide copolymer/amide-imide-phthalamide copolymer blend, or a polyamide-imide/polyetherimide blend, thereby improving the fluidity of the polyamide-imide resin. It is stated that it has improved.
〔発明が解決しようとする課題］
しかしながら、特開昭５９−２０２８１９号公報ではプ
リプレグ中に有機溶媒を残留させることにより熱可塑性
ポリアミドイミド樹脂の流動性を向上させているが、成
形圧力は７０〜８０ｋｇ／ｃＩＩＩ２という高圧力を必
要としている。また特開昭６１−６９８４１号公報には
、熱可塑性ポリアミドイミド樹脂の十分に凝結したラミ
ネートを得るために７０＝１０５ ｋｇ／ｃｍ２という
高圧力が必要である旨記載されている。[Problems to be Solved by the Invention] However, in JP-A-59-202819, the fluidity of thermoplastic polyamide-imide resin is improved by leaving an organic solvent in the prepreg, but the molding pressure is 70~202819. A high pressure of 80 kg/cIII2 is required. Further, JP-A No. 61-69841 describes that a high pressure of 70=105 kg/cm2 is necessary to obtain a sufficiently solidified laminate of thermoplastic polyamideimide resin.
一般に熱硬化性樹脂と強化繊維からなる複合材料は６０
ｋｇ／ｃ麟２以下の圧力にて成形されている。したがっ
て、熱硬化性樹脂と強化繊維からなる複合材料のように
、より低圧力下で成形できる繊維強化熱可塑性ポリアミ
ドイミド樹脂複合材料の出現が望まれている。Composite materials made of thermosetting resin and reinforcing fibers generally have a
Molded at a pressure of less than 2 kg/cm. Therefore, there is a desire for a fiber-reinforced thermoplastic polyamide-imide resin composite material that can be molded under lower pressure, such as a composite material made of a thermosetting resin and reinforced fibers.
本発明の目的はこれらの課題を解決する繊維強化熱可塑
性ポリアミドイミド樹脂成形体の製造方法を提供するこ
とにある。An object of the present invention is to provide a method for producing a fiber-reinforced thermoplastic polyamide-imide resin molding that solves these problems.
また本発明の別の目的は成形体中にボイドの発生がなく
、高温時の物性が低下することのない４繊維強化熱可塑
性ポリアミドイミド樹脂成形体を提供することにある。Another object of the present invention is to provide a 4-fiber-reinforced thermoplastic polyamide-imide resin molded product in which no voids are generated in the molded product and the physical properties at high temperatures do not deteriorate.
かかる事情に鑑み、本発明者らは上記課題について鋭意
検討した結果、有機溶媒を０．１〜３重量％残留させた
繊維強化熱可塑性ポリアミドイミド樹脂プリプレグを昇
温し、特定の温度頭載において熱可塑性ポリアミドイミ
ド樹脂の流動性が向上し、その際であれば低圧力下でも
成形できることを見出し、本発明を完成するに至った。In view of these circumstances, the inventors of the present invention have intensively studied the above-mentioned problems, and as a result, the temperature of a fiber-reinforced thermoplastic polyamide-imide resin prepreg containing 0.1 to 3% by weight of an organic solvent is increased, and at a specific temperature initialization. The present inventors have discovered that the fluidity of thermoplastic polyamide-imide resin is improved and that it can be molded even under low pressure, leading to the completion of the present invention.
すなわち、本発明は繊維強化熱可塑性ポリアミドイミド
樹脂プリプレグを圧縮成形して成形体を製造する方法に
おいて、有機溶媒を０．１〜３重量％以下残留させた該
プリプレグを昇温し２１０〜３１０℃のとき６０ ｋｇ
／ｃ４以下の圧力を加え、該圧力下で３４０〜３９０’
Ｃまで昇温することを特徴とする繊維強化熱可塑性ポリ
アミドイミド樹脂成形体の製造方法を提供するものであ
る。That is, the present invention provides a method for producing a molded article by compression molding a fiber-reinforced thermoplastic polyamideimide resin prepreg, in which the prepreg in which 0.1 to 3% by weight or less of an organic solvent remains is heated to 210 to 310°C. 60 kg when
Apply a pressure of /c4 or less, and under this pressure 340 to 390'
The present invention provides a method for producing a fiber-reinforced thermoplastic polyamide-imide resin molded article, which is characterized in that the temperature is raised to C.
以下、本発明の詳細な説明する。The present invention will be explained in detail below.
本発明におけるプリプレグとは、熱可塑性ポリアミドイ
ミド樹脂及び強化繊維からなる樹脂組成物をいう、熱可
塑性ポリアミドイミド樹脂は？ｆＩ融粘度が極めて高い
ため、該プリプレグはフィルムスクツキング法またはホ
ントメルト法などで例示されるように樹脂を溶融状態に
して、加圧下で強化繊維束中に含浸させる方法、いわゆ
る乾式法を用いることが困難であり、工程の煩雑な湿式
法を用いて製造されている。The prepreg in the present invention refers to a resin composition consisting of a thermoplastic polyamide-imide resin and reinforcing fibers.What is the thermoplastic polyamide-imide resin? Since the fI melt viscosity is extremely high, the prepreg uses a so-called dry method, in which the resin is molten and impregnated into reinforcing fiber bundles under pressure, as exemplified by the film-sucking method or the real-melt method. It is difficult to do so, and is manufactured using a complicated wet method.
本発明に用いるプリプレグは湿式法により製造されたも
のであれば特に限定されるものではない。The prepreg used in the present invention is not particularly limited as long as it is produced by a wet method.
例えば前記した特開昭５９−２０２８１９号公報または
特開昭６１−６９８４１号において得られたプリプレグ
でもよい。For example, the prepreg obtained in JP-A-59-202819 or JP-A-61-69841 mentioned above may be used.
また本発明者らが見出したプリプレグの別の製造方法の
ように、粉末状の熱可塑性ポリアミドイミド樹脂を貧溶
媒中で分散させて樹脂中の低分子成分のみを貧溶媒に溶
解し、バインダー的効果を発現させ、かかる状況下で繊
維織物または連続繊維束中へ含浸して得られたプリプレ
グでもよい。In addition, as in another prepreg manufacturing method discovered by the present inventors, powdered thermoplastic polyamideimide resin is dispersed in a poor solvent, and only the low molecular components in the resin are dissolved in the poor solvent. It may also be a prepreg obtained by developing the effect and impregnating it into a fiber fabric or continuous fiber bundle under such conditions.
さらに本発明者らが見出したプリプレグの別の製造方法
のように、熱可塑性ポリアミドイミド樹脂および良溶媒
からなる樹脂組成物を強化繊維に含浸した中間プリプレ
グを水または／およびメタノールで洗浄し、乾燥して得
られたプリプレグでもよい。Furthermore, as in another prepreg manufacturing method discovered by the present inventors, an intermediate prepreg in which reinforcing fibers are impregnated with a resin composition consisting of a thermoplastic polyamideimide resin and a good solvent is washed with water and/or methanol, and then dried. Prepreg obtained by
本発明に用いる熱可塑性ポリアミドイミド樹脂は、−最
式（Ｎで表わされる繰り返し単位を主上記一般式（１）
及び（ｎ）において、Ａｒ。The thermoplastic polyamide-imide resin used in the present invention has the repeating unit represented by the formula (N) as the main formula (1).
and (n), Ar.
はヘテロ環あるいはアルキル、アルコキシ、アリルオキ
シ、ハロゲンなどの不活性な置換基を導入していること
がある３価の芳香族残基であり、３つのカルボニル基の
うち２つとは相隣る炭素原子で結合している。is a heterocycle or a trivalent aromatic residue that may have an inert substituent such as alkyl, alkoxy, allyloxy, or halogen introduced, and two of the three carbonyl groups are adjacent carbon atoms. It is connected with.
Ａｒ、の具体例として次の基が挙げられる。Specific examples of Ar include the following groups.
要構造として３０〜１００モル％、好ましくは５０〜１
００モル％存し、残りの７０モル％未満、好ましくは５
０モル％未満を次の一般式ＣＩ＋３で表わされる繰り返
し単位を有する。The essential structure is 30 to 100 mol%, preferably 50 to 1
00 mol%, remaining less than 70 mol%, preferably 5
It has less than 0 mol% of repeating units represented by the following general formula CI+3.
またＡｒ、及びＡｒ、は互いに異なる２価の芳香族残基
であり、具体例として次の基が挙げられ本発明に用いる
熱可塑性ポリアミドイミド樹脂は例えば特開昭５８４８
０５３２号公報に記載のとおり芳香族トリカルボン酸お
よび／または芳香族トリカルボン酸無水物と芳香族ジア
ミンとを脱水触媒の存在下に加熱重縮合反応せしめる方
法において、溶媒としてスルホランを含有する溶媒を用
いて製造することができる。Further, Ar and Ar are divalent aromatic residues different from each other, and specific examples include the following groups.
As described in Publication No. 0532, in a method of subjecting an aromatic tricarboxylic acid and/or an aromatic tricarboxylic acid anhydride to an aromatic diamine in the presence of a dehydration catalyst through a heating polycondensation reaction, a solvent containing sulfolane is used as a solvent. can be manufactured.
本発明に用いるプリプレグは、熱可塑性ポリアミドイミ
ド樹脂と親和性の良い有機溶媒系の良溶媒からなる樹脂
組成物を強化繊維に含浸させたものでもよく、あるいは
熱可塑性ポリアミドイミド樹脂と親和性の悪い有機溶媒
系の貧溶媒からなる樹脂組成物を強化繊維に含浸させた
ものでもよい。The prepreg used in the present invention may be one in which reinforcing fibers are impregnated with a resin composition consisting of a good organic solvent that has good affinity with the thermoplastic polyamide-imide resin, or one that has a poor affinity with the thermoplastic polyamide-imide resin. The reinforcing fibers may be impregnated with a resin composition made of an organic solvent-based poor solvent.
したがって有機溶媒であれば良溶媒でも貧溶媒でもよい
、良溶媒として具体的にはＮ−メチル−２−ピロリドン
、 Ｎ、Ｎ−ジメチルホルムアミド、 Ｎ、Ｎ−ジメチ
ルアセトアミド、 Ｎ、Ｎ−ジエチルホルムアミドジメ
チルスルホキシド、テトラメチル尿°素及びｍクレゾー
ルなどが挙げられる。より好ましくはＮＮ−ジメチルホ
ルムアミド及びＮ、Ｎ−ジメチルアセトアミドである。Therefore, as long as it is an organic solvent, it may be a good solvent or a poor solvent. Specific examples of good solvents include N-methyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, and N,N-diethylformamide dimethyl. Examples include sulfoxide, tetramethylurea and m-cresol. More preferred are NN-dimethylformamide and N,N-dimethylacetamide.
また貧溶媒として具体的には塩化メチレン、四塩化炭素
、 １，１．２− トリクロロエタントリクロロエチレ
ンなどの塩素化炭化水素、メタノール、エタノールなど
のアルコール、１．４−ジオキサン テトラヒドロフラ
ンなどのエーテル、さらにはアセトン、メチルエチルケ
トンなどのケトンなどが挙げられ、これらの貧溶媒を単
独または２種以上混合して用いることができる。より好
ましくはトリクロロエチレン、１．４−ジオキサン、テ
トラヒドロフランなどの貧溶媒を単独または２種以上混
合して用いることができる。溶媒の混合比は特に限定さ
れるものではない。Specific examples of poor solvents include methylene chloride, carbon tetrachloride, chlorinated hydrocarbons such as 1,1,2-trichloroethane and trichloroethylene, alcohols such as methanol and ethanol, ethers such as 1,4-dioxane and tetrahydrofuran, and even acetone. , and ketones such as methyl ethyl ketone. These poor solvents can be used alone or in combination of two or more. More preferably, poor solvents such as trichloroethylene, 1,4-dioxane, and tetrahydrofuran can be used alone or in combination of two or more. The mixing ratio of the solvents is not particularly limited.
本発明に用いるプリプレグを製造する際の上記良溶媒の
量は、熱可塑性ポリアミドイミド樹５脂の均一な溶液状
態が得られれば特に限定されず、またプリプレグ中の樹
脂含有量によって適宜選ぶことができるが、好ましくは
５０重量％〜９７重景％、より好ましくは６５重量％〜
８５重量％である。 ５０重量％未満では均一な溶液状
態を得ることが困難であり、また９７重量％を越えて用
いると樹脂濃度が低すぎて実用に供しえないので好まし
くない。The amount of the above-mentioned good solvent when producing the prepreg used in the present invention is not particularly limited as long as a uniform solution state of the thermoplastic polyamideimide resin 5 is obtained, and can be appropriately selected depending on the resin content in the prepreg. Preferably from 50% to 97% by weight, more preferably from 65% by weight
It is 85% by weight. If it is less than 50% by weight, it is difficult to obtain a uniform solution state, and if it exceeds 97% by weight, the resin concentration will be too low to be of practical use, which is not preferred.
一方、貧溶媒を用いた場合の量は粉末状の熱可塑性ポリ
アミドイミド樹脂の良好な分散状態が得られれば特に限
定されず、またプリプレグ中の樹脂含有量によって適宜
選ぶことができるが、好ましくは７０重量％〜９７重量
％、より好ましくは８０重量％〜９０重量％である。７
０重量％未満では良好な分散状態を得るのが困難であり
、また９７重四％を超えて用いるとプリプレグ中の粉末
状の熱可塑性ポリアミドイミド樹脂の分散が不均一とな
り好ましくない。On the other hand, when a poor solvent is used, the amount is not particularly limited as long as a good dispersion state of the powdered thermoplastic polyamideimide resin is obtained, and it can be appropriately selected depending on the resin content in the prepreg, but is preferably It is 70% to 97% by weight, more preferably 80% to 90% by weight. 7
If it is less than 0% by weight, it is difficult to obtain a good dispersion state, and if it is more than 97% by weight, the powdery thermoplastic polyamide-imide resin in the prepreg will not be uniformly dispersed.
本発明に用いるプリプレグ中の残留溶媒の量は、良溶媒
または貧溶媒がプリプレグ中に均一に残留されていれば
特に限定されないが、好ましくは０゜１〜３重量％、よ
り好ましくは０．２〜２重量％である。残留溶媒が０．
１重量％未満のプリプレグでは本発明の効果を十分に発
現することが困難であり、また残留溶媒が３重量％を超
えたプリプレグでは成形体にしたとき成形体中にボイド
が発生し好ましくない。The amount of residual solvent in the prepreg used in the present invention is not particularly limited as long as the good solvent or poor solvent remains uniformly in the prepreg, but is preferably 0.1 to 3% by weight, more preferably 0.2% by weight. ~2% by weight. Residual solvent is 0.
If the prepreg contains less than 1% by weight, it is difficult to fully exhibit the effects of the present invention, and if the residual solvent exceeds 3% by weight, voids will occur in the molded product when it is made into a molded product, which is not preferable.
残留溶媒量の調整方法は、通常のプリプレグの乾燥方法
、例えば加熱方法、減圧方法および本発明者らが発明し
た水または／およびメタノールで洗浄し乾燥する方法な
どが挙げられる。加熱方法、減圧方法などにより溶媒を
除去するには、乾燥温度または／および乾燥時間を調整
すればよい。この際、乾燥設備はオープン、熱風乾燥機
、遠赤外線炉などが挙げられ、中でもオーブンが簡便で
あるため好ましい。The amount of residual solvent can be adjusted by conventional prepreg drying methods, such as a heating method, a reduced pressure method, and a method invented by the present inventors in which the prepreg is washed with water and/or methanol and then dried. In order to remove the solvent by a heating method, a pressure reduction method, etc., the drying temperature and/or drying time may be adjusted. In this case, the drying equipment includes an open dryer, a hot air dryer, a far-infrared oven, etc. Among them, an oven is preferable because it is simple.
本発明における成形体は残留溶媒をコントロールしたプ
リプレグを昇温し、２１０〜３１０℃のとき６０ ｋｇ
／ｃｄ以下の圧力を加え、該圧力下で３４０〜３９０℃
まで昇温し製造される。かかる条件下において、残留溶
媒の作用により熱可塑性ポリアミドイミド樹脂の流動性
が橿めて向上し、従来よりさらに低圧力下で成形できる
ものと推察される。The molded article in the present invention is produced by heating prepreg with controlled residual solvent, and weighs 60 kg at 210 to 310°C.
/cd or less and 340-390℃ under this pressure.
It is manufactured by raising the temperature to . It is presumed that under such conditions, the fluidity of the thermoplastic polyamide-imide resin is greatly improved by the action of the residual solvent, making it possible to mold it under even lower pressure than before.
成形時の条件は、残留溶媒の種類及び量により適宜選ぶ
ことができるが、好ましくはプリプレグの加熱温度が２
１０〜３１０℃のときに６０ ｋｇ／ｃｊ以下の圧力を
加え、より好ましくは２３０〜２９０℃のとき５〜５０
ｋｇ／ｃＪの圧力を加えればよい。加熱温度が２１０
℃未満または３１０℃を超える場合は、本発明の効果が
発現されず、６０ｋｊ／ａｆｌ以下の圧力では成形が困
難となり好ましくない。さらに６０ ｋｇ／ｃＩＩｌ以
下の圧力を加えた状態でプリプレグを３４０〜３９０℃
まで昇温する。２１０〜３１０℃の温度範囲からさらに
３４０〜３９０℃の温度範囲まで昇温するのは熱可塑性
ポリアミドイミド樹脂の重合度を高め、
また機械強度を向上せしめるためである。昇温する温度
範囲はより好ましくは３５０〜３８０℃である。Conditions during molding can be appropriately selected depending on the type and amount of residual solvent, but preferably the heating temperature of the prepreg is 2.
A pressure of 60 kg/cj or less is applied at a temperature of 10 to 310°C, more preferably a pressure of 5 to 50 kg/cj is applied at a temperature of 230 to 290°C.
A pressure of kg/cJ may be applied. Heating temperature is 210
If the temperature is less than 0.degree. C. or more than 310.degree. C., the effects of the present invention will not be achieved, and if the pressure is less than 60 kj/afl, molding will become difficult, which is not preferable. Furthermore, the prepreg is heated at 340 to 390℃ while applying a pressure of 60 kg/cIIl or less.
Increase the temperature to. The reason why the temperature is further increased from the temperature range of 210 to 310°C to the temperature range of 340 to 390°C is to increase the degree of polymerization of the thermoplastic polyamideimide resin and to improve the mechanical strength. The temperature range for increasing the temperature is more preferably 350 to 380°C.
３４０℃未満では機械強度が発現せず、３９０’Ｃを超
えると樹脂が熱分解してしまうので好ましくない。If the temperature is lower than 340°C, no mechanical strength will be developed, and if the temperature exceeds 390°C, the resin will thermally decompose, which is not preferable.
本発明に用いる強化繊維は特に制限されるものではなく
、ガラス繊維、炭素繊維、アルミナ繊維炭化珪素繊維な
どの無機繊維、アラミド繊維、芳香族ポリエステル繊維
などの有機織組、さらには金属繊維などＦＲＰの強化繊
維として使用しているものが挙げられる。また繊維の形
態は、本発明の効果を十分に発現させるために長繊維の
形態が好ましく、具体例として連続繊維のロービングま
たはトウが例示でき、さらに平犠、朱子織または綾織な
どの繊維織物が挙げられる。The reinforcing fibers used in the present invention are not particularly limited, and include inorganic fibers such as glass fibers, carbon fibers, alumina fibers and silicon carbide fibers, organic weave structures such as aramid fibers and aromatic polyester fibers, and FRP such as metal fibers. Examples include those used as reinforcing fibers. In addition, the form of the fibers is preferably in the form of long fibers in order to fully exhibit the effects of the present invention, and specific examples include continuous fiber rovings or tows, and furthermore, fiber fabrics such as flat sacrificial, satin weave, and twill weave. Can be mentioned.
以上詳述したように、本発明は溶媒を０．１〜３重量％
残留させた繊維強化熱可塑性ポリアミドイミド樹脂プリ
プレグを昇温し、特定の温度領域において熱可塑性ポリ
アミドイミド樹脂の流動性が向上し、その際であれば低
圧力下でも成形できるので、繊維強化熱可塑性ポリアミ
ドイミド樹脂成形体を製造するうえで有用な方法である
。As detailed above, the present invention uses 0.1 to 3% by weight of the solvent.
By raising the temperature of the remaining fiber-reinforced thermoplastic polyamide-imide resin prepreg, the fluidity of the thermoplastic polyamide-imide resin improves in a specific temperature range, and in that case, it can be molded even under low pressure, so fiber-reinforced thermoplastic This is a useful method for producing polyamide-imide resin moldings.
また本発明で得られる繊維強化熱可塑性ポリアミドイミ
１゛樹脂成形体は、ボイドの発生がなく、高温時の物性
が低下することがないのであるから、その工業的価値は
頗る大である。Furthermore, the fiber-reinforced thermoplastic polyamide imide 1 resin molded article obtained by the present invention does not generate voids and does not deteriorate in physical properties at high temperatures, so its industrial value is extremely large.
本発明をさらに実施例により説明するが、本発明はこれ
によって限定されるものではない。The present invention will be further explained by examples, but the present invention is not limited thereto.
実施例１
熱可塑性ポリアミドイミド樹脂（住人化学工業■製スミ
カＦＡＩ射出グレード）を２５重量％用い、溶媒として
Ｎ、Ｎ−ジメチルホルムアミドを７５重量％用いた。Example 1 25% by weight of thermoplastic polyamide-imide resin (Sumika FAI injection grade manufactured by Sumikagaku Kogyo ■) was used, and 75% by weight of N,N-dimethylformamide was used as a solvent.
該樹脂とＮ、Ｎ〜ジメチルホルムアミドは撹拌機で混合
することにより均一な溶液状態を得た。The resin and N,N-dimethylformamide were mixed using a stirrer to obtain a uniform solution state.
強化繊維として炭素繊維トウ（住化バーキュレス株製マ
グナマイト＠ＡＳ−４、フィラメント数＝１２ｋｆ）を
用いた。Carbon fiber tow (Magnamite@AS-4 manufactured by Sumika Vercules Co., Ltd., number of filaments = 12 kf) was used as the reinforcing fiber.
該炭素繊維トウを上記溶液中へ浸漬した２連のバーを通
過させることにより、繊維束へ溶液を含浸させ、ドラム
ワインディング法により一方向引揃え中間プリプレグを
作製した。なお、中間プリプレグとは、熱可塑性ポリア
ミドイミド樹脂および溶媒からなる樹脂組成物を強化繊
維に含浸した状態のものをいい、溶媒を除去していない
ものである。By passing the carbon fiber tow through two bars immersed in the solution, the fiber bundle was impregnated with the solution, and a unidirectionally aligned intermediate prepreg was produced by a drum winding method. Note that the intermediate prepreg is one in which reinforcing fibers are impregnated with a resin composition consisting of a thermoplastic polyamideimide resin and a solvent, and the solvent is not removed.
中間プリプレグをドラム上に巻き取った状態で、２００
’Ｃに設定したオーブン中で減圧下１２時間加熱したと
ころ、Ｎ、Ｎ−ジメチルホルムアミドの残留分が１．２
重量％であるプリプレグが得られた。With the intermediate prepreg wound on the drum, 200
When heated for 12 hours under reduced pressure in an oven set at
A prepreg was obtained that was % by weight.
該プリプレグ１６枚を１００ｗＸ １００＋ｎａサイズ
の金型へ積層して昇温し、２６０℃のとき２０ｋｇ／ｃ
ｄの圧力を加え、該圧力下で３８０℃まで昇温しホット
プレス成形した。16 sheets of prepreg were stacked in a 100w x 100+na size mold and heated to 20kg/c at 260°C.
A pressure of d was applied, and the temperature was raised to 380° C. under the pressure to perform hot press molding.
その結果、ボイドのない１００Ｍ Ｘ １００１！ＩＩ
Ｉ Ｘ ’Ｊ−厚さの良好な積層板が得られた。該積層
板中の繊維体積含有率は６０容量％であった。As a result, 100M x 1001 without voids! II
IX'J-A laminate with good thickness was obtained. The fiber volume content in the laminate was 60% by volume.
該積層板の物性を第１表に示す。The physical properties of the laminate are shown in Table 1.
実施例２
粉末状の熱可塑性ポリアミドイミド樹脂（住人化学工業
■製スミカＦＡＩ射出成形グレード、１２０メツシユ下
〜２００メソシユ上）を１５重量％用い、貧溶媒として
トリクロロエチレンを８５重量％用いた。Example 2 15% by weight of a powdered thermoplastic polyamide-imide resin (Sumika FAI injection molding grade manufactured by Sumikagaku Kogyo ■, below 120 mesh to above 200 mesh) was used, and 85% by weight of trichlorethylene was used as a poor solvent.
該樹脂とトリクロロエチレンは、マグネチノクスクーラ
ーで混合することにより良好な分散状態を得た。A good dispersion state was obtained by mixing the resin and trichlorethylene in a magnetinox cooler.
実施例Ｉと同様の炭素繊維および方法を用いて、ドラム
ワインディング法により一方向引揃えプリプレグを作製
した。ドラム上に巻き取った状態で、該プリプレグは熱
可塑性ポリアミドイミド樹脂の低分子成分がトリクロロ
エチレンにより溶解し、バインダー的効果を発現し、樹
脂と繊維の強固な結合が生成し、掻めて形態保持性の良
い状態を示した。続いて該プリプレグをドラムの軸方向
に切り開き、１３０℃に設定したオーブン中で１時間加
熱した結果、トリクロロエチレンの残留分が０．８重量
％であるプリプレグが得られた。Using the same carbon fibers and method as in Example I, a unidirectionally aligned prepreg was produced by the drum winding method. When wound on a drum, the low-molecular components of the thermoplastic polyamide-imide resin are dissolved in trichlorethylene, creating a binder-like effect, forming a strong bond between the resin and the fibers, and retaining its shape by scraping. showed good sexual condition. Subsequently, the prepreg was cut in the axial direction of the drum and heated in an oven set at 130° C. for 1 hour. As a result, a prepreg with a residual trichlorethylene content of 0.8% by weight was obtained.
該プリプレグを実施例１と同様にして金型へ積層して昇
温し、２５０″Ｃのとき２０ ｋｇ ／ ｃｔＡの圧力
を加え、該圧力下で３８０℃まで昇温しホントプレス成
形した。The prepreg was laminated into a mold in the same manner as in Example 1, the temperature was raised, a pressure of 20 kg/ctA was applied at 250''C, the temperature was raised to 380°C under this pressure, and true press molding was performed.
その結果、ボイドのない１００＋ｍｅＸ １００薗×２
ＩＩ１１厚さの良好な積層板が得られた。該積層板中の
繊維体積含有率は６０容量％であった。As a result, 100 + meX 100 Son x 2 without void
A good laminate with a thickness of II11 was obtained. The fiber volume content in the laminate was 60% by volume.
該積層板の物性を第１表に示す。The physical properties of the laminate are shown in Table 1.
実施例３
実施例１と同様の樹脂、溶媒および強化繊維を用い、同
様のドラムワインディング法により一方向引揃え中間プ
リプレグを作製した。ドラム上に巻き取った状態の中間
プリプレグに３Ｐの工業用水をスプレーし脱溶媒した結
果、該中間プリプレグは熱可塑性ポリアミドイミド樹脂
と繊維とが強固に結合した掻めて形態保持性の良い状態
を示し、さらにＮ、Ｎ−ジメチルホルムアミドの残留分
は５，６重量％であった。Example 3 Using the same resin, solvent, and reinforcing fiber as in Example 1, a unidirectionally aligned intermediate prepreg was produced by the same drum winding method. As a result of spraying 3P industrial water onto the intermediate prepreg wound on a drum to remove the solvent, the intermediate prepreg is in a state where the thermoplastic polyamide-imide resin and fibers are firmly bonded and have good shape retention. Furthermore, the residual content of N,N-dimethylformamide was 5.6% by weight.
続いて、ドラムの軸方向に中間プリプレグを切り開き、
２００℃に設定したオーブン中で１時間加熱した結果、
Ｎ、Ｎ−ジメチルホルムアミドの残留分が０．５重量％
であるプリプレグが得られた。Next, cut the intermediate prepreg in the axial direction of the drum,
As a result of heating in an oven set at 200℃ for 1 hour,
Residual content of N,N-dimethylformamide is 0.5% by weight
A prepreg was obtained.
該プリプレグを実施例１と同様に金型へ積層して昇温し
、２３０℃のとき３０ｋｇ／ｃｄの圧力を加え、該圧力
下で３８０℃まで昇温しホットプレス成形した。The prepreg was laminated into a mold in the same manner as in Example 1, the temperature was raised, a pressure of 30 kg/cd was applied when the temperature was 230°C, and the temperature was raised to 380°C under this pressure for hot press molding.
その結果、ボイドのない１ＯＯＩＩＩＩＩ×１００ＩＩ
ＩＩｌ×２１１ＩＩ１１厚さの良好な積層板が得られた
。該積層板中の繊維体積含有率は６０容量％であった。As a result, 1OOIII×100II without voids
A good laminate with a thickness of II1×211II11 was obtained. The fiber volume content in the laminate was 60% by volume.
該積層板の物性を第１表に示す。The physical properties of the laminate are shown in Table 1.
比較例１
実施例１と同様の樹脂、溶媒および強化繊維を用い、同
様のドラムワインディング法により一方向引揃え中間プ
リプレグを作製し、実施例１と同様に溶媒を除去し、Ｎ
、Ｎ−ジメチルホルムアミドの残留分が１．２重量％で
あるプリプレグを作製した。Comparative Example 1 Using the same resin, solvent and reinforcing fiber as in Example 1, a unidirectionally aligned intermediate prepreg was produced by the same drum winding method, the solvent was removed in the same manner as in Example 1, and N
, a prepreg with a residual N-dimethylformamide content of 1.2% by weight was produced.
該プリプレグを実施例１と同様にして金型へ積層して昇
温し、３５０℃のとき２０ｋｇ／ｃ４の圧力を加えてホ
ントプレス成形した。The prepreg was laminated into a mold in the same manner as in Example 1, heated, and press-molded by applying a pressure of 20 kg/c4 at 350°C.
その結果、ボイドの多数発生した積ＮＦｉ、が得られた
。該積層板中の繊維体積含有率は６０容量％であった。As a result, a product NFi in which many voids were generated was obtained. The fiber volume content in the laminate was 60% by volume.
該積層板の物性を第１表に示す。The physical properties of the laminate are shown in Table 1.
比較例２
実施例２と同様の樹脂、溶媒および強化繊維を用い、同
様のドラムワインディング法によりトリクロロエチレン
の残留分が０．８重量％であるプリプレグを作製した。Comparative Example 2 Using the same resin, solvent, and reinforcing fiber as in Example 2, a prepreg with a residual trichlorethylene content of 0.8% by weight was produced by the same drum winding method.
該プリプレグを実施例１と同様にして金型へ積層して昇
温し、３３０’Ｃのとき３０ｋｇ ／ ｃ４の圧力を加
え、該圧力下で３８０℃まで昇温しホットプレス成形し
た。The prepreg was laminated into a mold in the same manner as in Example 1, the temperature was raised, a pressure of 30 kg/c4 was applied at 330'C, the temperature was raised to 380°C under this pressure, and hot press molding was performed.
その結果、ボイドの多数発生した積層板が得られた。該
積層板中の繊維体積含有率は６０容量％であった。As a result, a laminate with many voids was obtained. The fiber volume content in the laminate was 60% by volume.
該積層板の物性を第１表に示す。The physical properties of the laminate are shown in Table 1.
第１表Table 1
Claims (1)
縮成形して成形体を製造する方法において、有機溶媒を
０．１〜３重量％以下残留させた該プリプレグを昇温し
、２１０〜３１０℃のとき６０ｋｇ／ｃｍ＾２以下の圧
力を加え、該圧力下で３４０〜３９０℃まで昇温するこ
とを特徴とする繊維強化熱可塑性ポリアミドイミド樹脂
成形体の製造方法In a method of manufacturing a molded article by compression molding a fiber-reinforced thermoplastic polyamide-imide resin prepreg, the prepreg in which 0.1 to 3% by weight or less of an organic solvent remains is heated, and when the temperature is 210 to 310°C, 60 kg/ A method for producing a fiber-reinforced thermoplastic polyamide-imide resin molded article, which comprises applying a pressure of cm^2 or less and raising the temperature to 340 to 390°C under the pressure.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21598488A JPH0264137A (en) | 1988-08-29 | 1988-08-29 | Production of molded fiber-reinforced thermoplastic polyamide-imide resin body |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21598488A JPH0264137A (en) | 1988-08-29 | 1988-08-29 | Production of molded fiber-reinforced thermoplastic polyamide-imide resin body |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0264137A true JPH0264137A (en) | 1990-03-05 |
Family
ID=16681485
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP21598488A Pending JPH0264137A (en) | 1988-08-29 | 1988-08-29 | Production of molded fiber-reinforced thermoplastic polyamide-imide resin body |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0264137A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0569808A1 (en) * | 1992-05-09 | 1993-11-18 | Btr Industries Limited | Heat exchanger |
| JP2005320495A (en) * | 2004-04-06 | 2005-11-17 | Hitachi Chem Co Ltd | Prepreg, metal foil clad laminate and printed circuit board obtained using the same |
-
1988
- 1988-08-29 JP JP21598488A patent/JPH0264137A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0569808A1 (en) * | 1992-05-09 | 1993-11-18 | Btr Industries Limited | Heat exchanger |
| JP2005320495A (en) * | 2004-04-06 | 2005-11-17 | Hitachi Chem Co Ltd | Prepreg, metal foil clad laminate and printed circuit board obtained using the same |
| JP4555985B2 (en) * | 2004-04-06 | 2010-10-06 | 日立化成工業株式会社 | Prepreg, and metal foil-clad laminate and printed circuit board obtained using the same |
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