JPH0222336A - Production of fiber-reinforced thermoplastic polyamide-imide resin prepreg - Google Patents
Production of fiber-reinforced thermoplastic polyamide-imide resin prepregInfo
- Publication number
- JPH0222336A JPH0222336A JP17314788A JP17314788A JPH0222336A JP H0222336 A JPH0222336 A JP H0222336A JP 17314788 A JP17314788 A JP 17314788A JP 17314788 A JP17314788 A JP 17314788A JP H0222336 A JPH0222336 A JP H0222336A
- Authority
- JP
- Japan
- Prior art keywords
- prepreg
- solvent
- fiber
- thermoplastic polyamide
- imide resin
- 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 47
- 239000011347 resin Substances 0.000 title claims abstract description 47
- 239000004962 Polyamide-imide Substances 0.000 title claims abstract description 36
- 229920002312 polyamide-imide Polymers 0.000 title claims abstract description 36
- 229920001169 thermoplastic Polymers 0.000 title claims abstract description 33
- 239000004416 thermosoftening plastic Substances 0.000 title claims abstract description 33
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 57
- 239000002904 solvent Substances 0.000 claims abstract description 45
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000001035 drying Methods 0.000 claims abstract description 9
- 239000012783 reinforcing fiber Substances 0.000 claims abstract description 9
- 239000011342 resin composition Substances 0.000 claims abstract description 8
- 238000005406 washing Methods 0.000 claims abstract description 7
- 230000000704 physical effect Effects 0.000 abstract description 8
- 239000013557 residual solvent Substances 0.000 abstract description 4
- 230000002542 deteriorative effect Effects 0.000 abstract 1
- 239000000835 fiber Substances 0.000 description 27
- 238000000034 method Methods 0.000 description 24
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 19
- 239000000243 solution Substances 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 8
- 238000000465 moulding Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 6
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 5
- 229920000049 Carbon (fiber) Polymers 0.000 description 4
- 239000004917 carbon fiber Substances 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000004804 winding Methods 0.000 description 4
- -1 aromatic tricarboxylic acid Chemical class 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 230000002411 adverse Effects 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
- 239000012535 impurity Substances 0.000 description 2
- 230000014759 maintenance of location Effects 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
- 238000005507 spraying Methods 0.000 description 2
- 239000004753 textile Substances 0.000 description 2
- 229920005992 thermoplastic resin Polymers 0.000 description 2
- 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
- SUAKHGWARZSWIH-UHFFFAOYSA-N N,N‐diethylformamide Chemical compound CCN(CC)C=O SUAKHGWARZSWIH-UHFFFAOYSA-N 0.000 description 1
- 239000004697 Polyetherimide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000011157 advanced composite material Substances 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
- 238000009835 boiling Methods 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
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000004807 desolvation Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000007598 dipping method 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
- 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
- 238000005470 impregnation Methods 0.000 description 1
- 239000008235 industrial water Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000012784 inorganic fiber Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229920001778 nylon Polymers 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
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 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
- 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
- 229920001187 thermosetting polymer Polymers 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望性ポリアミドイミド樹脂中間プ
リプレグ中に残留する溶媒を容易に除去し、繊維強化熱
可塑性ポリアミドイミド樹脂プリプレグを製造する方法
に関するものである。[Detailed Description of the Invention] [Industrial Field of Application] The present invention enables easy removal of the solvent remaining in the fiber-reinforced thermoplastic polyamide-imide resin intermediate prepreg, and manufactures the fiber-reinforced thermoplastic polyamide-imide resin prepreg. It is about the method.
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、この熱可塑性ポリアミドイミド樹脂と強化繊維か
らなる繊維強化熱可塑性ポリアミドイミド樹脂プリプレ
グの製造方法は、ポリアミドイミド樹脂の溶融粘度が極
めて高いため、フィルムスタッキング法あるいはホント
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
用いなければならないのが現状である。すなわち湿式法
による繊維強化熱可塑性ポリアミドイミド樹脂プリプレ
グは、熱可塑性ポリアミドイミド樹脂を親和性のある適
当な良溶媒に約１０〜３０重■％の割合で溶解させ、こ
の粘度を低くした溶液を繊維織物に塗布し、あるいは繊
維織物を該溶液中へ浸漬し、かかる後加熱により溶媒を
除去して製造されてきた。Conventionally, methods for producing fiber-reinforced thermoplastic polyamide-imide resin prepregs made of thermoplastic polyamide-imide resin and reinforcing fibers have been difficult to produce, such as by film stacking or real-melt methods, because the melt viscosity of polyamide-imide resin is extremely high. At present, it is difficult to use the so-called dry method, in which the resin is molten and impregnated into reinforcing fiber bundles under pressure, and a complicated wet method must be used. In other words, the fiber-reinforced thermoplastic polyamide-imide resin prepreg produced by the wet method is produced by dissolving the thermoplastic polyamide-imide resin in a suitable and compatible solvent at a ratio of about 10 to 30% by weight, and then adding this solution with a lower viscosity to the fibers. It has been produced by applying the solution to textiles or by dipping the textile into the solution and subsequently heating to remove the solvent.
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.
しかしながら特開昭５９−２０２８１９号公報では、従
来に比べ溶媒量が少ないというものの溶媒を除去する方
法として、大気中での加熱あるいは減圧下での加熱をし
ているため、脱溶媒の工程に多大の時間と費用を要し、
また低粘度の溶液を含浸した繊維織物あるいは一方向引
揃え繊維束は、極めて柔軟なため形態保持性に乏しく、
脱溶媒の工程中に繊維の目ずれや乱れが生じ十分な複合
効果が発現しないという課題がある。また特開昭６１−
６９８４１号公報では多量の溶媒を使用するので特開昭
５９−２０２８１９号公報と同様の課題がある。However, in JP-A No. 59-202819, although the amount of solvent is small compared to the conventional method, heating in the air or under reduced pressure is used as a method for removing the solvent, which requires a large amount of time in the desolvation process. It takes time and money,
In addition, fiber fabrics or unidirectionally aligned fiber bundles impregnated with a low viscosity solution are extremely flexible and have poor shape retention.
There is a problem that fibers are misaligned or disordered during the solvent removal process, and a sufficient composite effect is not achieved. Also, JP-A-61-
Since JP-A-69841 uses a large amount of solvent, it has the same problem as JP-A-59-202819.
さらに、これらの技術では熱可塑性ポリアミドイミド樹
脂に対して良溶媒を用いており、また加熱により該溶媒
を除去しているが、該良溶媒は熱可塑性ポリアミドイミ
ド樹脂との親和性が強いため、必要以上に樹脂中に残留
している。したがって、これらを用いて成形した場合に
は、ボイドが発生したりあるいは高温時の物性が低下し
たりする課題を有する。Furthermore, in these techniques, a good solvent is used for the thermoplastic polyamide-imide resin, and the solvent is removed by heating, but since the good solvent has a strong affinity with the thermoplastic polyamide-imide resin, Remains in the resin longer than necessary. Therefore, when molded using these materials, there are problems such as generation of voids or deterioration of physical properties at high temperatures.
本発明の目的はこれらの課題を解決する繊維強化熱可望
性ポリアミドイミド樹脂プリプレグ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 prepreg that solves these problems.
また本発明の別の目的は成形した時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繊維強化熱可塑
性ポリアミドイミド樹脂プリプレグを提供することにあ
る。Another object of the present invention is to provide a fiber-reinforced thermoplastic polyamide-imide resin prepreg that does not generate voids when molded and does not deteriorate its physical properties at high temperatures.
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、取り扱い易い水または／およびメタノー
ルを用い、かつ簡単な操作で中間プリプレグから残留溶
媒を除去し、プリプレグを製造す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 conducted intensive studies on the above-mentioned problems, and have discovered that a prepreg can be produced by removing the residual solvent from an intermediate prepreg using easy-to-handle water and/or methanol and with a simple operation. The invention was completed.
すなわち、本発明は熱可塑性ポリアミドイミド樹脂及び
溶媒からなる樹脂組成物を強化繊維に含浸して作製され
た中間プリプレグから溶媒を除去し、プリプレグを製造
する方法において、該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プリプレグの製造方
法を提供するものである。That is, the present invention provides a method for producing a prepreg by removing the solvent from an intermediate prepreg produced by impregnating reinforcing fibers with a resin composition consisting of a thermoplastic polyamide-imide resin and a solvent. The present invention provides a method for producing a fiber-reinforced thermoplastic polyamide-imide resin prepreg, which comprises washing with methanol and drying.
以下、本発明の詳細な説明する。The present invention will be explained in detail below.
本発明における中間プリプレグとは、熱可塑性ポリアミ
ドイミド樹脂及び溶媒からなる樹脂組成物を強化ＭＩｉ
Ｍ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。一方、プリプレグとは中間プリプレグ中に
残留する不要な溶媒を除去した状態のものをいい、該プ
リプレグが成形に供されるものである。すなわち本発明
における繊維強化熱可塑性ポリアミドイミド樹脂プリプ
レグは中間プリプレグから不要な溶媒を除去することに
より製造される。The intermediate prepreg in the present invention refers to a resin composition consisting of a thermoplastic polyamideimide resin and a solvent reinforced with MIi.
It refers to the product impregnated with M, and the solvent has not been removed. On the other hand, prepreg refers to intermediate prepreg from which unnecessary solvent remaining is removed, and this prepreg is used for molding. That is, the fiber-reinforced thermoplastic polyamideimide resin prepreg in the present invention is produced by removing unnecessary solvent from an intermediate prepreg.
本発明に用いる熱可塑性ポリアミドイミド樹脂は、−ａ
弐（１）で表わされる繰り返し単位を主上記一般式（１
）及び（Ｉｆ）において、Ａｒ。The thermoplastic polyamideimide resin used in the present invention is -a
The repeating unit represented by 2 (1) is mainly represented by the above general formula (1
) and (If), 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％有し、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（ｎ）で表わされる繰り返し
単位を有する。30 to 100 mol% as essential structure, preferably 50-1
00 mol%, remaining less than 70 mol%, preferably 5
It has less than 0 mol% of repeating units represented by the following general formula (n).
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５８−１
８０５３２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 Japanese Patent No. 80532, 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.
本発明に用いる溶媒とは、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をいい、本発明に
用いる溶媒は良溶媒であれぼ特に限定されるものではな
い、良溶媒として具体的にはＮ−メチル−２−ピロリド
ン、Ｎ、トジメチルホルムアミド、Ｎ、トジメチルアセ
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−−クレゾールな
どが挙げられる。The solvent used in the present invention refers to a good organic solvent that has good affinity with the thermoplastic polyamide-imide resin, and the solvent used in the present invention is not particularly limited as long as it is a good solvent. Examples include N-methyl-2-pyrrolidone, N, todimethylformamide, N, todimethylacetamide, N, N-diethylformamide, dimethyl sulfoxide, tetramethylurea, and --cresol.
より好ましくはＮ、Ｎ−ジメチルホルムアミド及びＮ。More preferably N,N-dimethylformamide and N.
Ｎ−ジメチルアセトアミドである。N-dimethylacetamide.
本発明に用いる溶媒の量は、熱可塑性ポリアミドイミド
樹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重量％、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 solvent used in the present invention is not particularly limited as long as a uniform solution state of the thermoplastic polyamideimide resin is obtained, and can be appropriately selected depending on the resin content in the prepreg, but is preferably 50% by weight to 97% by weight. % by weight, more preferably 65% to 85% by weight. If it is less than 50% by weight, it is difficult to obtain a uniform solution state;
If it is used in excess of this weight percent, the resin concentration will be too low to be of practical use, which is not preferable.
したがって、本発明に用いる熱可塑性ポリアミドイミド
樹脂の量は３重量％〜５０重量％であり、より好ましく
は１５重量％〜３５重量％である。Therefore, the amount of thermoplastic polyamideimide resin used in the present invention is 3% to 50% by weight, more preferably 15% to 35% by weight.
本発明に用いる溶媒の効果は、親和性の強い良溶媒によ
り熱可塑性ポリアミドイミド樹脂を溶解し、低粘度の均
一な溶液状態を作り、強化繊維への含浸性を向上させる
ことである。The effect of the solvent used in the present invention is to dissolve the thermoplastic polyamide-imide resin with a good solvent with strong affinity, create a uniform solution state with low viscosity, and improve impregnation into reinforcing fibers.
本発明において溶媒の除去に水、メタノールまたはその
混合物を用いる。水は純水を用いる必要はなく、プリプ
レグに悪影響を及ぼさない不純物を含んでいてもよい。In the present invention, water, methanol, or a mixture thereof is used to remove the solvent. It is not necessary to use pure water, and the water may contain impurities that do not adversely affect the prepreg.
またはメタノールも同様に純粋なメタノールを用いる必
要はなく、プリプレグに悪影響を及ぼさない不純物を含
んでいてもよい。さらにその混合物も同様である。Similarly, methanol does not need to be pure methanol, and may contain impurities that do not adversely affect the prepreg. Furthermore, the same applies to mixtures thereof.
水または／およびメタノールの使用量は溶媒量に対して
十分多ければ制限はなく、約３０〜５０倍の量があれば
十分である。The amount of water and/or methanol to be used is not limited as long as it is sufficiently larger than the amount of solvent, and it is sufficient if the amount is about 30 to 50 times the amount of solvent.
中間プリプレグを水または／およびメタノールで洗浄す
ることにより、プリプレグ中の溶媒の残留分が容易にｌ
Ｏ０重量％未満なり、続いて通常の乾燥方法、たとえば
加熱方法、減圧方法などによりさらに不要な溶媒が従来
より短時間で除去される。また具体的な乾燥温度は用い
た溶媒の沸点以上の温度であればよい、乾燥設備はオー
プン、熱風乾燥機、遠赤外線炉等がギげられ、中でもオ
ーブンが簡便であるため好ましい。By washing the intermediate prepreg with water and/or methanol, residual solvent in the prepreg can be easily removed.
0% by weight, and then the unnecessary solvent is removed in a shorter time than conventionally by a conventional drying method, such as a heating method or a vacuum method. Further, the specific drying temperature may be any temperature higher than the boiling point of the solvent used, and the drying equipment may be an open air dryer, a hot air dryer, a far-infrared oven, etc. Among them, an oven is preferable because it is simple.
中間プリプレグは水または／およびメタノールで洗浄さ
れると均一な熱可塑性ポリアミドイミド樹脂の多孔質膜
が該プリプレグ中に形成され、次の乾燥工程で該膜から
不要の溶媒が容易に除去されるものと推察される。When the intermediate prepreg is washed with water or/and methanol, a uniform porous film of thermoplastic polyamideimide resin is formed in the prepreg, and unnecessary solvent is easily removed from the film in the next drying process. It is presumed that.
水または／およびメタノールで洗浄する方法は中間プリ
プレグを水または／およびメタノール中に浸漬させるこ
とにより洗浄する方法あるいは中間プリプレグに水また
は／およびメタノールでスプレーすることにより洗浄す
る方法が挙げられる。Examples of the method of cleaning with water and/or methanol include a method of cleaning the intermediate prepreg by immersing it in water or/and methanol, and a method of cleaning by spraying the intermediate prepreg with water and/or methanol.
またプリプレグ中の溶媒の残留分のコントロールは、水
または／およびメタノールによる洗浄の程度あるいは乾
燥温度及び時間により適宜調整できる。さらにプリプレ
グ中の溶媒の残留分は３重量％未満が好ましく、より好
ましくは１重量％未満である。溶媒の残留分が３重量％
を超えると成形したときにボイドが発生し好ましくない
。Further, the amount of residual solvent in the prepreg can be appropriately adjusted by adjusting the degree of washing with water and/or methanol, and the drying temperature and time. Furthermore, the residual content of the solvent in the prepreg is preferably less than 3% by weight, more preferably less than 1% by weight. Solvent residual content is 3% by weight
If it exceeds this value, voids will occur during molding, which is undesirable.
溶媒と熱可塑性ポリアミドイミド樹脂との混合方法は、
均一な溶液状態が得られる方法であれば特に限定されな
い、混合方法の具体例としてマグネチソクスクーラー、
撹拌機、ミキサーなどが例示されるが、中でも撹拌機は
溶液粘度の幅広い領域において適用できるので好ましい
。The method of mixing the solvent and thermoplastic polyamideimide resin is as follows:
Specific examples of the mixing method include a magnetic cooler,
Examples include a stirrer and a mixer, and among them, a stirrer is preferred because it can be applied in a wide range of solution viscosities.
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ｌ”繊維、芳香族ポリエステル繊
維、ナイロン繊維、ポリエチレン繊維などの有機繊維、
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、さらに平織、朱子織または綾蟻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, and organic fibers such as aramid fibers, aromatic polyester fibers, nylon fibers, and polyethylene fibers. ,
Further examples include those used as reinforcing fibers for FRP, such as metal fibers. In addition, the form of the fiber is preferably a long fiber form in order to fully express the effects of the present invention.
Specific examples include continuous fiber rovings or tows, and further include fiber fabrics such as plain weave, satin weave, and twill weave.
熱可塑性ポリアミドイミド樹脂及び溶媒からなる樹脂組
成物の繊維束への含浸状態は、樹脂組成物が繊維束中へ
均一に含浸されていることが重要である。かかる状態の
均一なプリプレグは、成形後のボイドの発生が起こりに
くく好ましい。本発明によれば、繊維束を一連のバーあ
るいはローラーで代表される通常の開繊手段を用いて開
繊し、かかる状態下で熱可塑性ポリアミドイミド樹脂及
び溶媒からなる樹脂組成物を含浸させることにより樹脂
組成物が繊維束中に均一に含浸したプリプレグが得られ
る。It is important that the fiber bundle is impregnated with the resin composition consisting of a thermoplastic polyamide-imide resin and a solvent such that the resin composition is uniformly impregnated into the fiber bundle. A uniform prepreg in such a state is preferable because voids are less likely to occur after molding. According to the present invention, the fiber bundle is opened using a conventional opening means such as a series of bars or rollers, and is impregnated with a resin composition consisting of a thermoplastic polyamide-imide resin and a solvent under such conditions. A prepreg in which the fiber bundle is uniformly impregnated with the resin composition can be obtained.
以上詳述したように、本発明は中間プリプレグを水また
は／およびメタノールで洗浄することにより、容易に溶
媒を除去することができ、さらに短時間の乾燥で中間プ
リプレグ中の溶媒の残留分をコントロールすることがで
きるので、プリプレグを製造するうえで有用な方法であ
る。As detailed above, the present invention allows the solvent to be easily removed by washing the intermediate prepreg with water and/or methanol, and furthermore, the residual amount of solvent in the intermediate prepreg can be controlled by drying in a short time. Therefore, it is a useful method for manufacturing prepreg.
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
ド樹脂プリプレグは、成形した時に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 resin prepreg obtained by the present invention does not generate voids when molded and its physical properties at high temperatures do not deteriorate, 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射出成形グレード）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 molding 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。A uniform solution state was obtained by mixing the resin and N,N-dimethylformamide using a stirrer.
強化繊維として炭素繊維トウ（住化バーキュレス■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 ■, 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。ドラム上に巻き取った状態の中間プリプレグ
に３で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
強固に結合した極めて形態保持性のよい状態を示し、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。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. As a result of spraying industrial water on the intermediate prepreg wound on a drum to remove the solvent, the intermediate prepreg showed a state in which the thermoplastic polyamide-imide resin and the fibers were strongly bonded and had extremely 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該中間プリプレグを切り開き、
２００°Ｃの温度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％である該樹脂を均一に含浸したプリプレグが得
られた。Subsequently, the intermediate prepreg is cut in the axial direction of the drum,
As a result of heating for 1 hour in an oven set at a temperature of 200°C, there was no residual amount of N,N-dimethylformamide.
A prepreg uniformly impregnated with 5% by weight of the resin was obtained.
該プリプレグ１６枚を、１００■Ｘ１００ｍサイズの金
型へ積層し、３８０″Ｃ１６０ｋｇ／ｃｄの成形条件に
てホットプレス成形した。その結果、ボイドのない１０
０ ｍＸ１００ ｍｍＸ ２ｍ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。The 16 sheets of prepreg were laminated into a mold of 100 x 100 m size and hot press molded under the molding conditions of 380"C 160 kg/cd. As a result, 10 sheets with no voids were formed.
A good laminate measuring 0 m x 100 mm x 2 m thick 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
中間プリプレグの脱溶媒にメタノールを用いた以外は実
施例１と同様にして、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。Example 2 A unidirectionally aligned intermediate prepreg was produced by the drum winding method in the same manner as in Example 1 except that methanol was used to remove the solvent from the intermediate prepreg.
メタノール３ｉＶ、で洗浄後、中間プリプレグ中のＮ、
Ｎ−ジメチルホルムアミドの残留分は６．２重世％を示
した。After cleaning with methanol 3 iV, N in the intermediate prepreg,
The residual content of N-dimethylformamide was 6.2% by weight.
続いて中間プリプレグをドラムの軸方向に切り開き１．
２００°Ｃの温度に設定したオーブン中で１時間加熱し
た結果、Ｎ、 Ｎ−ジメチルアセトアミドの残留分が０
．６重量％である該樹脂を均一に含浸したプリプレグが
得られた。Next, cut the intermediate prepreg in the axial direction of the drum.1.
As a result of heating for 1 hour in an oven set at a temperature of 200°C, there was no residual N,N-dimethylacetamide.
．． A prepreg uniformly impregnated with 6% by weight of the resin was obtained.
該プリプレグを実施例１と同様にして成形した結果、ボ
イドのない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 of molding the prepreg in the same manner as in Example 1, a good laminate without 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.
実施例３
ン容媒としてＮ、Ｎ−ジメチルアセトアミドを用いた以
外は実施例１と同様にして、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。Example 3 A unidirectionally aligned intermediate prepreg was produced by the drum winding method in the same manner as in Example 1 except that N,N-dimethylacetamide was used as the medium.
水３！で洗浄後、中間プリプレグ中のＮ、Ｎ−ジメチル
アセトアミドの残留分は３．６重量％を示した。Water 3! After washing, the residual amount of N,N-dimethylacetamide in the intermediate prepreg was 3.6% by weight.
続いて中間プリプレグをドラムの軸方向に切り開き、２
００°Ｃの温度に設定したオープン中で１時間加熱した
結果、Ｎ、Ｎ−ジメチルアセトアミドの残留分が０．２
重量％である該樹脂を均一に含浸したプリプレグが得ら
れた。Next, cut the intermediate prepreg in the axial direction of the drum, and
As a result of heating for 1 hour in an open air set at a temperature of 00°C, the residual amount of N,N-dimethylacetamide was 0.2
A prepreg was obtained which was uniformly impregnated with the resin in the same amount by weight.
該プリプレグを実施例１と同様にして成形した結果、ボ
イドのない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 of molding the prepreg in the same manner as in Example 1, a good laminate without 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.
比較例１
実施例１と同様にして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。Comparative Example 1 A unidirectionally aligned intermediate prepreg was produced in the same manner as in Example 1 by the drum winding method.
中間プリプレグをドラム上に巻き取った状態で、２００
°Ｃに設定したオープン中で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３．８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 in an open air set at °C,
The residual content of N,N-dimethylformamide is 3.8% by weight.
A prepreg was obtained.
該プリプレグを実施例１と同様にして成形した結果、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 of molding the prepreg in the same manner as in Example 1, a laminate with many voids was obtained. The fiber volume content in the laminate was 60% by volume.
該ａ層板の物性を第１表に示す。The physical properties of the A-layer plate are shown in Table 1.
Claims (1)
成物を強化繊維に含浸して作製された中間プリプレグか
ら溶媒を除去し、プリプレグを製造する方法において、
該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
ミドイミド樹脂プリプレグの製造方法In a method for producing a prepreg by removing the solvent from an intermediate prepreg produced by impregnating reinforcing fibers with a resin composition consisting of a thermoplastic polyamide-imide resin and a solvent,
A method for producing a fiber-reinforced thermoplastic polyamide-imide resin prepreg, which comprises washing the intermediate prepreg with water or/and methanol and drying it.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17314788A JPH0222336A (en) | 1988-07-11 | 1988-07-11 | Production of fiber-reinforced thermoplastic polyamide-imide resin prepreg |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17314788A JPH0222336A (en) | 1988-07-11 | 1988-07-11 | Production of fiber-reinforced thermoplastic polyamide-imide resin prepreg |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0222336A true JPH0222336A (en) | 1990-01-25 |
Family
ID=15954977
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP17314788A Pending JPH0222336A (en) | 1988-07-11 | 1988-07-11 | Production of fiber-reinforced thermoplastic polyamide-imide resin prepreg |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0222336A (en) |
-
1988
- 1988-07-11 JP JP17314788A patent/JPH0222336A/en active Pending
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