JP3233174B2 - Method for producing carbon fiber reinforced polyamide resin composition - Google Patents
Method for producing carbon fiber reinforced polyamide resin compositionInfo
- Publication number
- JP3233174B2 JP3233174B2 JP32965592A JP32965592A JP3233174B2 JP 3233174 B2 JP3233174 B2 JP 3233174B2 JP 32965592 A JP32965592 A JP 32965592A JP 32965592 A JP32965592 A JP 32965592A JP 3233174 B2 JP3233174 B2 JP 3233174B2
- Authority
- JP
- Japan
- Prior art keywords
- carbon fiber
- resin composition
- reinforced polyamide
- fiber reinforced
- epoxy 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.)
- Expired - Fee Related
Links
- 229920000049 Carbon (fiber) Polymers 0.000 title claims description 39
- 239000004917 carbon fiber Substances 0.000 title claims description 39
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims description 33
- 239000011342 resin composition Substances 0.000 title claims description 14
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- 229920006122 polyamide resin Polymers 0.000 title claims description 8
- 150000003951 lactams Chemical class 0.000 claims description 22
- 239000003822 epoxy resin Substances 0.000 claims description 17
- 229920000647 polyepoxide Polymers 0.000 claims description 17
- 238000010539 anionic addition polymerization reaction Methods 0.000 claims description 13
- 239000000835 fiber Substances 0.000 claims description 13
- 238000005470 impregnation Methods 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 11
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 10
- 239000012783 reinforcing fiber Substances 0.000 claims description 10
- 239000007822 coupling agent Substances 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 9
- 238000006116 polymerization reaction Methods 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 239000012190 activator Substances 0.000 claims description 6
- 238000004513 sizing Methods 0.000 claims description 6
- 210000002445 nipple Anatomy 0.000 claims description 5
- 239000002685 polymerization catalyst Substances 0.000 claims description 5
- 239000011248 coating agent Substances 0.000 claims description 4
- 238000000576 coating method Methods 0.000 claims description 4
- 239000000155 melt Substances 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 239000004952 Polyamide Substances 0.000 claims 1
- 239000000088 plastic resin Substances 0.000 claims 1
- 229920002647 polyamide Polymers 0.000 claims 1
- 125000002924 primary amino group Chemical class [H]N([H])* 0.000 claims 1
- 125000000467 secondary amino group Chemical class [H]N([*:1])[*:2] 0.000 claims 1
- 239000000203 mixture Substances 0.000 description 10
- 239000000178 monomer Substances 0.000 description 8
- 229920005992 thermoplastic resin Polymers 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 239000012295 chemical reaction liquid Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 239000011247 coating layer Substances 0.000 description 4
- 229920002292 Nylon 6 Polymers 0.000 description 3
- 239000006087 Silane Coupling Agent Substances 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- QPJCYJIZFCJYIR-UHFFFAOYSA-N 4-propylazetidin-2-one Chemical compound CCCC1CC(=O)N1 QPJCYJIZFCJYIR-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 2
- 239000004433 Thermoplastic polyurethane Substances 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 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 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical group C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- DGTNSSLYPYDJGL-UHFFFAOYSA-N phenyl isocyanate Chemical compound O=C=NC1=CC=CC=C1 DGTNSSLYPYDJGL-UHFFFAOYSA-N 0.000 description 2
- 150000003141 primary amines Chemical class 0.000 description 2
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 2
- 150000003335 secondary amines Chemical class 0.000 description 2
- 229910000104 sodium hydride Inorganic materials 0.000 description 2
- 239000012312 sodium hydride Substances 0.000 description 2
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- -1 Σ-valerolactam Chemical compound 0.000 description 2
- BDQNKCYCTYYMAA-UHFFFAOYSA-N 1-isocyanatonaphthalene Chemical compound C1=CC=C2C(N=C=O)=CC=CC2=C1 BDQNKCYCTYYMAA-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 235000010627 Phaseolus vulgaris Nutrition 0.000 description 1
- 244000046052 Phaseolus vulgaris Species 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 238000000944 Soxhlet extraction Methods 0.000 description 1
- 241001147388 Uncia Species 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- CJYXCQLOZNIMFP-UHFFFAOYSA-N azocan-2-one Chemical compound O=C1CCCCCCN1 CJYXCQLOZNIMFP-UHFFFAOYSA-N 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- KQWGXHWJMSMDJJ-UHFFFAOYSA-N cyclohexyl isocyanate Chemical compound O=C=NC1CCCCC1 KQWGXHWJMSMDJJ-UHFFFAOYSA-N 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000007765 extrusion coating Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000011253 protective coating Substances 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Landscapes
- Reinforced Plastic Materials (AREA)
- Polyamides (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
【0001】[0001]
【産業上の利用分野】本発明は炭素繊維強化ポリアミド
樹脂組成物の製造方法において、炭素繊維との接着が強
固で優れた機械的強度の成形品の原材料となる組成物を
生産性良く製造する方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a carbon fiber reinforced polyamide resin composition, in which a composition as a raw material of a molded article having a strong adhesion to carbon fibers and excellent mechanical strength is produced with high productivity. About the method.
【0002】[0002]
【従来の技術】熱可塑性樹脂と補強繊維からなる繊維強
化熱可塑性樹脂ペレットについてはこれまで種々検討さ
れている。本出願人は装置上、取扱上容易に繊維強化ポ
リアミド樹脂組成物を得る方法を研究し、例えば特願平
2−179064号公報などの出願をした。2. Description of the Related Art Various studies have been made on fiber-reinforced thermoplastic resin pellets comprising a thermoplastic resin and reinforcing fibers. The present applicant has researched a method for obtaining a fiber-reinforced polyamide resin composition easily in terms of equipment and handling, and has filed an application such as Japanese Patent Application No. 2-17964.
【0003】この方法は、アニオン重合触媒、活性化剤
を添加したラクタム類を連続的に混合しながら長繊維状
の補強繊維に含浸し、直ちにこれの外周を溶融熱可塑性
樹脂により被覆し冷却した後加熱槽に供給し、内部のラ
クタム類を前記触媒および活性化剤によりアニオン重合
させ、次いで所定の長さに切断してペレットとする方法
である。In this method, a long fiber reinforcing fiber is impregnated with a lactam added with an anionic polymerization catalyst and an activator while being continuously mixed, and the periphery thereof is immediately coated with a molten thermoplastic resin and cooled. In this method, the lactam is supplied to a post-heating tank, and the lactam inside is anionically polymerized by the catalyst and the activator, and then cut into a predetermined length to form a pellet.
【0004】この方法において、長繊維状の補強繊維と
して炭素繊維を選択した場合には、サイズ剤による処理
が施されていない炭素繊維ロービングに熱可塑性ポリウ
レタンをサイズ処理して用いる方法は、このサイズ剤が
ラクタム類のアニオン重合を阻害することがないので、
重合後の残存モノマーが少なく炭素繊維と重合樹脂との
接着も良好である。In this method, when carbon fiber is selected as the long-fiber reinforcing fiber, the method of sizing a thermoplastic polyurethane to a carbon fiber roving that has not been treated with a sizing agent uses this size. Since the agent does not inhibit the anionic polymerization of lactams,
There are few residual monomers after the polymerization, and the adhesion between the carbon fiber and the polymerized resin is also good.
【0005】[0005]
【発明が解決しようとする課題】しかし、無サイズ状態
の炭素繊維を取り扱う際には単糸切れが発生し、その後
ポリウレタンエマルジョンで処理した後でも炭素繊維の
毛羽立ちが起こりこれにより含浸室内に切断した単糸が
堆積して連続操業時のトラブルの原因となっていた。However, when handling carbon fibers in a non-sized state, single yarn breaks occur, and after that, the fibers are fluffed even after being treated with a polyurethane emulsion, thereby cutting into the impregnation chamber. Single yarns accumulated and caused problems during continuous operation.
【0006】これに対して予め未硬化エポキシ樹脂によ
りサイズ処理された市販の長繊維状の炭素繊維を用いる
と、このようなトラブルの発生がない。On the other hand, when a commercially available long-fiber carbon fiber pre-sized with an uncured epoxy resin is used, such a trouble does not occur.
【0007】しかし、未硬化エポキシ樹脂にはラクタム
類のアニオン重合を阻害する反応性基が含まれるため、
重合反応後の樹脂中に残存するモノマーの量が増加して
実用化できなかった。However, since the uncured epoxy resin contains a reactive group that inhibits anionic polymerization of lactams,
The amount of monomer remaining in the resin after the polymerization reaction increased, and the resin could not be put to practical use.
【0008】本発明は以上の問題を解決するものであっ
て、その目的は、市販の未硬化エポキシ樹脂サイズ処理
炭素繊維を用いて未硬化エポキシ樹脂中にある重合阻害
反応性基を封鎖する処理を施すことにより、連続操業時
に毛羽立ちによるトラブル発生なく、ラクタム類のアニ
オン重合を完結することにある。The present invention solves the above-mentioned problems, and an object of the present invention is to use a commercially available uncured epoxy resin-sized carbon fiber to block a polymerization-inhibiting reactive group in the uncured epoxy resin. Is to complete the anionic polymerization of lactams without causing trouble due to fluffing during continuous operation.
【0009】[0009]
【課題を解決するための手段】前記目的を達成するた
め、この発明は、アニオン重合触媒を添加した液状のラ
クタム類と、活性化剤を添加した液状のラクタム類とを
所定比率で混合しながら含浸室に供給し、該含浸室中で
連続的に供給される長繊維状の炭素繊維束を前記混合液
に含浸し、次いでこれをニップルを介して溶融押出機の
被覆ヘッド部に導き、この含浸補強繊維の外周に軟化点
が少なくとも120℃以上の熱可塑性樹脂を被覆して継
ぎ目なく被覆層を形成した後、加熱された重合室中に導
いて前記被覆層内部のラクタム類をアニオン重合させた
後、所定長さに切断する炭素長繊維強化ポリアミド樹脂
組成物の製造方法において、前記炭素繊維束は未硬化エ
ポキシ樹脂のサイズ剤で処理された市販の長繊維状の炭
素繊維束を一般式:R1 O−Ti−(OR2 )3 (但
し、R1 O−は加水分解性基あり、R2 O−は非加水分
解性基で一級アミン(−NH2 −)或いは二級アミン
(−NH−)、もしくはその両方を含む)で示されるチ
タネートカップリング剤の稀薄溶液に予め浸漬後乾燥し
たものを用いることを特徴とするものである。In order to achieve the above object, the present invention provides a liquid lactam to which an anionic polymerization catalyst has been added and a liquid lactam to which an activator has been added at a predetermined ratio. The mixed solution is impregnated with a long fiber carbon fiber bundle which is supplied to the impregnation chamber and continuously supplied in the impregnation chamber, and then guided to the coating head portion of the melt extruder via a nipple. After coating the outer periphery of the impregnated reinforcing fiber with a thermoplastic resin having a softening point of at least 120 ° C. or more to form a coating layer seamlessly, it is led into a heated polymerization chamber to anionically polymerize the lactams inside the coating layer. Then, in a method for producing a carbon long fiber reinforced polyamide resin composition which is cut to a predetermined length, the carbon fiber bundle is obtained by converting a commercially available long fiber carbon fiber bundle treated with an uncured epoxy resin sizing agent according to a general formula. : 1 O-Ti- (OR 2) 3 ( where, R 1 O-is a hydrolyzable group, R 2 O-are primary amines in non-hydrolyzable groups (-NH 2 -) or secondary amine (-NH -) Or both) are immersed in a dilute solution of a titanate coupling agent and then dried.
【0010】次に以上の各成分についてさらに詳しく説
明する。Next, each of the above components will be described in more detail.
【0011】本発明で用いられる未硬化エポキシ樹脂
は、ビスフェノールA型エポキシ樹脂、ウレタン変性エ
ポキシ樹脂、ノボラック型エポキシ樹脂およびこれらの
混合樹脂が掲げられる。またこれらの炭素繊維への付着
量は1〜3重量%である。The uncured epoxy resin used in the present invention includes bisphenol A type epoxy resin, urethane modified epoxy resin, novolak type epoxy resin, and a mixed resin thereof. The amount of these carbon fibers attached is 1 to 3% by weight.
【0012】この限定理由としては、1重量%を下回る
と炭素繊維の集束性が悪くなり、毛羽が発生し易くな
り、逆に3重量%を越えると炭素長繊維強化ポリアミド
樹脂組成物より得られる成形品の強度が低下するからで
ある。したがって、以上の数値範囲とすることが望まし
い。[0012] The reason for this limitation is that if it is less than 1% by weight, the convergence of the carbon fibers is deteriorated and fluff is liable to occur. Conversely, if it exceeds 3% by weight, it is obtained from a long carbon fiber reinforced polyamide resin composition. This is because the strength of the molded article decreases. Therefore, it is desirable to set the above numerical range.
【0013】本発明で用いられるチタネートカップリン
グ剤は、前述のごとく一般式:R1O−Ti−(O
R2 )3 で示されるものであるが、その代表例としてイ
ソプロピル−トリ(n−アミノエチル−アミノエチル)
チタネート(i−C3 H7 O−Ti−(O−C2 H4 N
HC2 H4 NH2 )3 )が掲げられる。これらの炭素繊
維への付着量は0.5〜2重量%である。The titanate coupling agent used in the present invention has the general formula: R 1 O—Ti— (O
R 2 ) 3 , a typical example of which is isopropyl-tri (n-aminoethyl-aminoethyl)
Titanate (i-C 3 H 7 O -Ti- (O-C 2 H 4 N
HC 2 H 4 NH 2 ) 3 ). The amount of adhesion to these carbon fibers is 0.5 to 2% by weight.
【0014】この限定理由としては、0.5重量%を下
回った場合にはラクタム類のアニオン重合が阻害され、
逆に2重量%を越えると未硬化エポキシ樹脂の架橋が進
行して炭素繊維の柔軟性が失われて取扱時に毛羽が発生
し易くなり、また液状ラクタム類が含浸し難くなるから
である。したがって以上の数値の範囲とすることが望ま
しい。The reason for this limitation is that if the amount is less than 0.5% by weight, anionic polymerization of lactams is inhibited,
Conversely, if the content exceeds 2% by weight, the crosslinking of the uncured epoxy resin proceeds, and the flexibility of the carbon fiber is lost, so that fluff is likely to be generated during handling, and it is difficult to impregnate the liquid lactam. Therefore, it is desirable to set the range of the above numerical values.
【0015】なお、前記チタネートカップリング剤と類
似の働きをするものにシランカップリング剤(一般式:
(R3 O)3 −Si−R4 、但しR3 Oは−加水分解性
基であり、R4 −は非加水分解性基で一級アミンおよび
二級アミンを含む)がある。しかしながら、シランカッ
プリング剤を未硬化エポキシ樹脂に対する処理剤として
用いると炭素繊維ロービングの柔軟性が失われて取扱時
に毛羽が発生し易くなり、また液状ラクタム類が含浸し
難くなる。これはシランカップリング剤は加水分解性基
が多く、エポキシ樹脂の架橋反応が進行し過ぎて硬くな
り過ぎることによる。[0015] A silane coupling agent (general formula:
(R 3 O) 3 —Si—R 4 , wherein R 3 O is a —hydrolyzable group, and R 4 — is a non-hydrolyzable group and includes a primary amine and a secondary amine. However, when a silane coupling agent is used as a treating agent for an uncured epoxy resin, the flexibility of the carbon fiber roving is lost, and fluff is easily generated during handling, and it is difficult to impregnate liquid lactams. This is because the silane coupling agent has many hydrolyzable groups, and the crosslinking reaction of the epoxy resin proceeds too much and becomes too hard.
【0016】本発明で用いられるラクタム類は、γ−ブ
チロラクタム,Σ−バレロラクタム,β−カプロラクタ
ム,ω−エナントラクタム,ω−カプリルラクタム,ω
−ウンデカノラクタムおよびこれらの混合物が掲げられ
る。The lactams used in the present invention include γ-butyrolactam, Σ-valerolactam, β-caprolactam, ω-enantholactam, ω-caprylactam, ω
-Undecanolactam and mixtures thereof.
【0017】本発明で用いられるアニオン重合触媒は、
水素化ナトリウムを加熱して液状としたラクタム類に対
して0.1〜3mol %添加して混合する。The anionic polymerization catalyst used in the present invention comprises:
Sodium hydride is heated and added to the liquid lactam in an amount of 0.1 to 3 mol% and mixed.
【0018】本発明で用いられる活性化剤は、一官能
性,二官能性有機イソシアネートおよびこれらの混合物
を加熱して液状としたラクタム類に対して0.2〜3mo
l %添加して混合する。The activator used in the present invention may be a monofunctional or bifunctional organic isocyanate or a lactam obtained by heating a mixture thereof to a liquid state in an amount of 0.2 to 3 mol.
Add 1% and mix.
【0019】一官能性イソシアネートとしては、フェニ
ルイソシアネート,シクロヘキシルイソシアネート,ナ
フチルイソシアネートが掲げられる。二官能性イソシア
ネートとしては、ヘキサメチレンジイソシアネート,
4,4−ジフェニルメタンジイソシアネート,2,4−
トルエンジイソシアネートが掲げられる。Examples of the monofunctional isocyanate include phenyl isocyanate, cyclohexyl isocyanate and naphthyl isocyanate. Hexamethylene diisocyanate,
4,4-diphenylmethane diisocyanate, 2,4-
Toluene diisocyanate is listed.
【0020】本発明で用いられる被覆層熱可塑性樹脂
は、重合成生物と相溶性のあるポリアミド樹脂,ポリア
ミド−ポリプロピレン,ポリアミド−PPO,ポリアミ
ド−ABS等のアロイ樹脂が掲げられる。As the thermoplastic resin for the coating layer used in the present invention, alloy resins such as polyamide resin, polyamide-polypropylene, polyamide-PPO and polyamide-ABS which are compatible with heavy synthetic organisms are listed.
【0021】[0021]
【作用】以上の構成において、炭素繊維のサイズ剤とし
て用いられる未硬化エポキシ樹脂中にあるアニオン重合
阻害反応性基として水酸基およびグリシジルエーテル基
が考えられる。In the above constitution, a hydroxyl group and a glycidyl ether group are considered as anionic polymerization inhibition reactive groups in an uncured epoxy resin used as a carbon fiber sizing agent.
【0022】これに対して予めこの繊維をチタネートカ
ップリング剤により処理することにより、チタネートカ
ップリング剤中の加水分解性基(i−C3 H7 O−)が
前記水酸基と反応すること、および非加水分解性基(−
OC2 H4 NHC2 H4 NH2 )のアミノ基がグリシジ
ルエーテル基と開環反応することによってアニオン重合
阻害物質が除去されると考えられる。[0022] By pre-treating the fibers by titanate coupling agent contrast, the hydrolyzable groups in the titanate coupling agent (i-C 3 H 7 O- ) reacts with the hydroxyl group, and Non-hydrolyzable group (-
It is considered that the anion polymerization inhibitor is removed by the ring opening reaction of the amino group of OC 2 H 4 NHC 2 H 4 NH 2 ) with the glycidyl ether group.
【0023】したがって、重合後に得られる炭素長繊維
強化ポリアミド樹脂組成物中の残存モノマー量は減少
し、機械強度に優れた組成物を得られることになる。Therefore, the amount of residual monomers in the carbon long fiber reinforced polyamide resin composition obtained after the polymerization is reduced, and a composition having excellent mechanical strength can be obtained.
【0024】[0024]
【実施例】次に本発明の好適な実施例を説明する。但し
本発明は以下の実施例にのみ限定されるものではない。Next, preferred embodiments of the present invention will be described. However, the present invention is not limited only to the following examples.
【0025】<実施例>図1,2は本発明に係る製造方
法による製造工程の全体と一部拡大した状態を示してい
る。<Embodiment> FIGS. 1 and 2 show the whole and partially enlarged state of the manufacturing process according to the manufacturing method according to the present invention.
【0026】[前処理]まず、未硬化エポキシ樹脂によ
りサイズ処理が施された市販の炭素繊維ロービング(商
品名:東レ社製トレカT300−12K、エポキシ樹脂
付着量1.5%)に、イソプロピルトリ(N−アミノエ
チル−アミノエチル)チタネート(商品名:味の素社製
プレンアクトKR−44)0.5重量部をメタノール4
9.5重量部および蒸溜水50重量部に溶解したものを
付着させ、熱風乾燥機中に通して、チタネーチカップリ
ング剤が0.7%付着した炭素繊維材料を得た。これを
補強繊維5として使用することにした。[Pretreatment] First, a commercially available carbon fiber roving (trade name: Torayca T300-12K manufactured by Toray Industries Inc., epoxy resin adhering amount 1.5%) sized with an uncured epoxy resin was added to isopropyl tribe. 0.5 parts by weight of (N-aminoethyl-aminoethyl) titanate (trade name: Plenact KR-44 manufactured by Ajinomoto Co.) was added to methanol 4
A solution dissolved in 9.5 parts by weight and 50 parts by weight of distilled water was adhered and passed through a hot air drier to obtain a carbon fiber material to which 0.7% of a titanium coupling agent had adhered. This was used as the reinforcing fiber 5.
【0027】[成形工程]次に図に示すように、80℃
に加熱され、モノマーしてのε−カプロラクタムに対し
てアニオン重合触媒として1mol %の水素化ナトリウム
を添加して混合したA液が入ったタンク1と、同じく8
0℃に加温され、活性化剤として0.5mol %のヘキサ
メチレンジイソシアネートと0.5mol %のフェニルイ
ソシアネートを添加したB液が入ったタンク2とを準備
した。[Molding step] Next, as shown in FIG.
And a tank 1 containing a solution A prepared by adding 1 mol% of sodium hydride as an anionic polymerization catalyst to ε-caprolactam as a monomer and mixing the same.
A tank 2 was prepared which was heated to 0 ° C. and contained Liquid B to which 0.5 mol% of hexamethylene diisocyanate and 0.5 mol% of phenyl isocyanate were added as activators.
【0028】タンク1,2の下部に混合部3を設け、混
合部3でA液およびB液を1:1で混合して反応液を作
製した。混合部3の下部に接続された含浸室4に作製さ
れた反応液を連続的に供給し、この含浸室4中に乾燥処
理された前記補強繊維5を導いて混合された反応液を含
浸した後ダイヘッド30に導く。A mixing section 3 was provided at the lower portion of the tanks 1 and 2, and the mixing section 3 mixed the solution A and the solution B at a ratio of 1: 1 to prepare a reaction solution. The prepared reaction liquid was continuously supplied to the impregnation chamber 4 connected to the lower part of the mixing section 3, and the reinforcing fiber 5 dried was introduced into the impregnation chamber 4 to impregnate the mixed reaction liquid. After that, it is led to the die head 30.
【0029】含浸室4の周囲は80℃に保持し、窒素ガ
ス雰囲気とし、含浸室4の入口には、図2に示すよう
に、内径2mmの繊維案内孔6を設け、溶液の含浸部7に
は長さ500mm,内径10〜3mmに絞られた円錘状と
し、さらに反応液の逆流や滞留がないように曲管構造の
ものを用いた。前記繊維5へ含浸させるときの反応液の
粘度は、10.5センチポイズであった。The periphery of the impregnation chamber 4 is maintained at 80 ° C. and a nitrogen gas atmosphere is provided. At the entrance of the impregnation chamber 4, a fiber guide hole 6 having an inner diameter of 2 mm is provided as shown in FIG. Used had a conical shape narrowed to a length of 500 mm and an inner diameter of 10 to 3 mm, and had a curved tube structure so that the reaction solution did not flow backward or stayed. The viscosity of the reaction liquid when impregnating the fiber 5 was 10.5 centipoise.
【0030】この含浸部7の出口側は、内径3mmの案内
部9を有し、パイプ10に接続された温水によって80
℃に保持された前記ダイヘッド30のニップル11に接
続されている。The outlet side of the impregnating section 7 has a guide section 9 having an inner diameter of 3 mm.
It is connected to the nipple 11 of the die head 30 maintained at a temperature of ° C.
【0031】前記ニップル11に導かれた反応液が含浸
された繊維の外周をニップル11の先端部に近接した外
径6mm,内径4mmの円管状ダイ13から溶融吐出したナ
イロン6樹脂で3m/分の速度で押出被覆した。The outer periphery of the fiber impregnated with the reaction liquid led to the nipple 11 is 3 m / min with a nylon 6 resin melt-discharged from a cylindrical die 13 having an outer diameter of 6 mm and an inner diameter of 4 mm close to the tip of the nipple 11. Extrusion coating at a speed of.
【0032】以上の押出し工程で得られた熱可塑性樹脂
被覆物は、直ちに冷却槽17に導いて表面の熱可塑性樹
脂被覆層14を冷却した後、170〜200℃に制御さ
れた、長さ30mの重合槽18中で反応液を連続的に硬
化させ、冷却水槽19中で水冷した後、引取り機20で
引取り、その後カッター21により長さ約10mmにカッ
トし、ペレット化した組成物を得られた。The thermoplastic resin coating obtained in the above extrusion step is immediately introduced into a cooling tank 17 to cool the thermoplastic resin coating layer 14 on the surface, and then controlled at 170 to 200 ° C., a length of 30 m. The reaction solution was continuously cured in a polymerization tank 18 and cooled with water in a cooling water tank 19, taken up by a take-up machine 20, and then cut into a length of about 10 mm by a cutter 21 to obtain a pelletized composition. Obtained.
【0033】このペレット化された組成物は、メタノー
ルを溶媒としてソックレー抽出を行って残存モノマーを
除去した。残存モノマー量は、最初のラクタム原料量に
対するこの抽出前後の重量減少量の割合から算出した。
残存モノマー除去後の組成物は、スクリュ径16mm,L
/Dが28の射出成形機に供給して13.5×120m
m,厚さ3.2mmの曲げ試験片を成形して、曲げ試験お
よびアイゾット衝撃強度を測定した。これらの結果は別
掲の表に以下の比較例1〜3ととも掲載した。The pelletized composition was subjected to Soxhlet extraction using methanol as a solvent to remove residual monomers. The residual monomer amount was calculated from the ratio of the weight loss before and after the extraction to the initial lactam raw material amount.
The composition after removing the residual monomer has a screw diameter of 16 mm, L
/ D is supplied to the injection molding machine of 28 and 13.5 × 120m
A bending test piece having a thickness of 3.2 mm and a thickness of 3.2 mm was formed, and a bending test and an Izod impact strength were measured. These results are shown in the separate table together with the following Comparative Examples 1 to 3.
【0034】<比較例1>実施例の炭素繊維に代えて補
強繊維5として、チタネートカップリング剤処理がなさ
れず、エポキシ樹脂のみでサイズ処理された炭素繊維ロ
ービング(商品名:東レ社製トレカT300−12K)
を使用して、実施例と同様にして炭素繊維強化ナイロン
6樹脂組成物を得て残存モノマーおよび機械的物性を測
定した。<Comparative Example 1> Carbon fiber roving (trade name: Torayca T300 manufactured by Toray Industries Co., Ltd.) which was not treated with a titanate coupling agent but was sized only with an epoxy resin as reinforcing fiber 5 instead of the carbon fiber of the example. -12K)
Was used to obtain a carbon fiber reinforced nylon 6 resin composition in the same manner as in the example, and the residual monomer and mechanical properties were measured.
【0035】<比較例2>実施例のチタネートカップリ
ング剤に代えて、N−β−アミノエチル−γ−アミノプ
ロピル−トリメトキシシラン(NH2 CH2 CH2 NH
CH2 CH2 CH2 Si(OCH3 )3 、商品名:日本
ユニカ社製A−1120)カップリング剤を用いたこと
以外は実施例と同様に樹脂組成物を得ようとした。Comparative Example 2 Instead of the titanate coupling agent of the example, N-β-aminoethyl-γ-aminopropyl-trimethoxysilane (NH 2 CH 2 CH 2 NH
CH 2 CH 2 CH 2 Si (OCH 3 ) 3 (trade name: A-1120 manufactured by Nihon Unica) A resin composition was obtained in the same manner as in the example except that a coupling agent was used.
【0036】しかし、このもので処理された炭素繊維ロ
ービングは、非常に硬くなり、ラクタム反応液がほとん
ど含浸しない状態で、機械的強度を測定するための成形
品を得ることはできなかった。However, the carbon fiber roving treated with this material became very hard, and a molded product for measuring mechanical strength could not be obtained in a state where the lactam reaction liquid was hardly impregnated.
【0037】<比較例3>実施例の炭素繊維に代えて補
強繊維5としてサイズ剤による処理が施されていない炭
素繊維ロービーング(商品名:住化ハーキュレス社製マ
グナマイトAS4−12K)に前処理として熱可塑性ポ
リウレタンエマルジョン(商品名:大日本インキ化学工
業社製ボンディック1310F)を0.5%付着させた
炭素繊維ロービングを使用して、実施例と同様にして炭
素繊維強化ナイロン6樹脂組成物を得た。<Comparative Example 3> Carbon fiber raw bean (trade name: Magnumite AS4-12K manufactured by Sumika Hercules Co., Ltd.) not treated with a sizing agent as the reinforcing fiber 5 in place of the carbon fiber of the example was used as a pretreatment. Using a carbon fiber roving to which 0.5% of a thermoplastic polyurethane emulsion (trade name: Bondic 1310F manufactured by Dainippon Ink and Chemicals, Inc.) was adhered, a carbon fiber reinforced nylon 6 resin composition was prepared in the same manner as in the example. Obtained.
【0038】この炭素繊維ロービングは、β−カプロラ
クタムのアニオン重合を阻害することはなかったが、無
サイズの炭素繊維ロービングの単糸切れの多い部分によ
り、毛羽詰まりが発生し、カプロラクタムの含浸量が大
巾に変動し、最終的にロービングが破断してしまった。Although this carbon fiber roving did not inhibit the anionic polymerization of β-caprolactam, the portion of the non-sized carbon fiber roving that had many single yarn breaks caused fluff clogging, and the impregnation amount of caprolactam was reduced. It fluctuated widely, and the roving eventually broke.
【0039】ラクタム反応液の含浸が正常であった部分
の樹脂組成部は、実施例と同様に成形品物性を測定し
た。但しこの組成物をペレット化する際縦割れが多く発
生し、成形品の充填不良の原因となった。The physical properties of the molded product of the resin composition portion where the impregnation of the lactam reaction solution was normal were measured in the same manner as in the examples. However, when this composition was pelletized, many vertical cracks were generated, which caused poor filling of the molded product.
【0040】次に前記実施例および比較例1〜3により
得られた結果を以下の表に一括して掲載する。Next, the results obtained in the above Examples and Comparative Examples 1 to 3 are collectively shown in the following table.
【0041】[0041]
【表1】 [Table 1]
【0042】[0042]
【発明の効果】以上の表に示す結果から明らかなよう
に、本発明の製造方法によれば、未硬化エポキシ樹脂に
よりサイズ処理された炭素繊維ロービングでもカプロラ
クタムのアニオン重合を阻害することがなくなり、さら
に炭素繊維を取り扱う際に発生する単糸切れおよび毛羽
詰まり等の連続操業上に装置に対するトラブルが発生す
ることがなくなり、製品品質の安定した樹脂組成物を得
ることができる。As is apparent from the results shown in the above table, according to the production method of the present invention, even if the carbon fiber roving sized by the uncured epoxy resin, the anion polymerization of caprolactam is not inhibited, Further, troubles in the apparatus do not occur in continuous operation such as breakage of single yarn and clogging of fluff generated when handling carbon fibers, and a resin composition with stable product quality can be obtained.
【0043】また、得られた樹脂組成物のラクタム反応
液の含浸性が良好となるため、ペレットの縦割れがなく
なり、成形性,および機械的強度の優れた成形品の原材
料となる組成物を生産性良く製造できる。Further, since the impregnating property of the obtained resin composition with the lactam reaction solution is improved, the longitudinal cracking of the pellets is eliminated, and the composition which becomes a raw material of a molded article having excellent moldability and mechanical strength is used. Can be manufactured with high productivity.
【図1】本発明にかかる製造方法の工程を示す全体説明
図である。FIG. 1 is an overall explanatory view showing steps of a manufacturing method according to the present invention.
【図2】図1の要部詳細図である。FIG. 2 is a detailed view of a main part of FIG. 1;
3 混合室 4 含浸室 5 補強繊維(炭素繊維) 14 保護用被覆層 18 重合槽 20 引取り機 21 カッター 30 ダイヘッド Reference Signs List 3 mixing chamber 4 impregnation chamber 5 reinforcing fiber (carbon fiber) 14 protective coating layer 18 polymerization tank 20 take-off machine 21 cutter 30 die head
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 平4−249538(JP,A) 特開 平3−130112(JP,A) (58)調査した分野(Int.Cl.7,DB名) C08G 69/00 - 69/44 C08L 77/00 - 77/12 ────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-4-249538 (JP, A) JP-A-3-130112 (JP, A) (58) Fields investigated (Int. Cl. 7 , DB name) C08G 69/00-69/44 C08L 77/00-77/12
Claims (1)
タム類と、活性化剤を添加した液状のラクタム類とを所
定比率で混合しながら含浸室に供給し、該含浸室中で連
続的に供給される長繊維状の炭素繊維束を前記混合液に
含浸し、次いでこれをニップルを介して溶融押出機の被
覆ヘッド部に導き、この含浸補強繊維の外周に軟化点が
少なくとも120℃以上の熱可塑性樹脂を被覆して継ぎ
目なく被複層を形成した後、加熱された重合室中に導い
て前記被複層内部のラクタム類をアニオン重合させた
後、所定長さに切断する炭素繊維強化ポリアミド樹脂組
成物の製造方法において:前記炭素繊維束は、未硬化エ
ポキシ樹脂のサイズ剤で処理された長繊維状の炭素繊維
束を一般式: R1 O−Ti−(OR2 )3 (但し、R1 O−は加水分解性基であり、R2 O−は非
加水分解性基で一級アミン(−NH2 −)或いは二級ア
ミン(−NH−)、もしくはその両方を含む)で示され
るチタネートカップリング剤の稀薄溶液に予め浸漬後乾
燥したものを用いることを特徴とする炭素繊維強化ポリ
アミド樹脂組成物の製造方法。1. A liquid lactam to which an anionic polymerization catalyst has been added and a liquid lactam to which an activator has been added are mixed at a predetermined ratio and supplied to an impregnation chamber, and continuously supplied in the impregnation chamber. The mixed solution is impregnated with the long-fibrous carbon fiber bundle to be introduced into a coating head of a melt extruder through a nipple, and the outer periphery of the impregnated reinforcing fiber has a softening point of at least 120 ° C. or higher. A carbon fiber reinforced polyamide that is coated with a plastic resin to form a multi-layer seamlessly, then guided into a heated polymerization chamber to anionically polymerize the lactams in the multi-layer, and then cut to a predetermined length. In the method for producing a resin composition, the carbon fiber bundle is obtained by converting a long fiber carbon fiber bundle treated with an uncured epoxy resin sizing agent to a general formula: R 1 O—Ti— (OR 2 ) 3 (where, R1 O- is a hydrolyzable group R 2 O— is a non-hydrolyzable group and is pre-soaked in a dilute solution of a titanate coupling agent represented by a primary amine (—NH 2 —) or a secondary amine (—NH—) or both) A method for producing a carbon fiber reinforced polyamide resin composition, comprising using a post-dried product.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP32965592A JP3233174B2 (en) | 1992-12-09 | 1992-12-09 | Method for producing carbon fiber reinforced polyamide resin composition |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP32965592A JP3233174B2 (en) | 1992-12-09 | 1992-12-09 | Method for producing carbon fiber reinforced polyamide resin composition |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH06172515A JPH06172515A (en) | 1994-06-21 |
JP3233174B2 true JP3233174B2 (en) | 2001-11-26 |
Family
ID=18223778
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JP32965592A Expired - Fee Related JP3233174B2 (en) | 1992-12-09 | 1992-12-09 | Method for producing carbon fiber reinforced polyamide resin composition |
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JP (1) | JP3233174B2 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102729450A (en) * | 2012-07-18 | 2012-10-17 | 常州大学 | Preparation device and method of macrofiber-reinforced thermoplastic resin composite board/sheet |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2852322B1 (en) * | 2003-03-11 | 2006-07-07 | Rhodia Eng Plastics Srl | POLYAMIDE ARTICLE REINFORCED WITH LONG FIBERS |
KR101969613B1 (en) * | 2011-11-29 | 2019-04-16 | 도레이 카부시키가이샤 | Carbon fiber-reinforced thermoplastic resin composition, and pellets and molded article thereof |
CN107614784B (en) * | 2015-06-23 | 2020-03-17 | 松本油脂制药株式会社 | Sizing agent for reinforcing fiber and use thereof |
JP2017155172A (en) * | 2016-03-03 | 2017-09-07 | 国立大学法人信州大学 | Carbon fiber-reinforced plastic, method for producing the same, and carbon fiber |
WO2018036885A1 (en) * | 2016-08-23 | 2018-03-01 | Basf Se | Process for the preparation of a reinforced polyamide by extrusion |
JP7194536B2 (en) * | 2018-08-31 | 2022-12-22 | 宇部エクシモ株式会社 | Method for producing fiber-reinforced thermoplastic resin prepreg, and method for producing fiber-reinforced thermoplastic resin |
-
1992
- 1992-12-09 JP JP32965592A patent/JP3233174B2/en not_active Expired - Fee Related
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102729450A (en) * | 2012-07-18 | 2012-10-17 | 常州大学 | Preparation device and method of macrofiber-reinforced thermoplastic resin composite board/sheet |
CN102729450B (en) * | 2012-07-18 | 2015-08-05 | 常州大学 | The preparation facilities of fiber reinforced thermoplastic resin composite board/sheet material and method |
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JPH06172515A (en) | 1994-06-21 |
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