JP3899263B2 - Manufacturing method of long glass fiber reinforced thermoplastic resin molding material - Google Patents
Manufacturing method of long glass fiber reinforced thermoplastic resin molding material Download PDFInfo
- Publication number
- JP3899263B2 JP3899263B2 JP2001396957A JP2001396957A JP3899263B2 JP 3899263 B2 JP3899263 B2 JP 3899263B2 JP 2001396957 A JP2001396957 A JP 2001396957A JP 2001396957 A JP2001396957 A JP 2001396957A JP 3899263 B2 JP3899263 B2 JP 3899263B2
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- Prior art keywords
- glass
- glass fiber
- thermoplastic resin
- molding material
- reinforced thermoplastic
- 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.)
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Links
- 239000003365 glass fiber Substances 0.000 title claims description 115
- 229920005992 thermoplastic resin Polymers 0.000 title claims description 50
- 239000012778 molding material Substances 0.000 title claims description 49
- 238000004519 manufacturing process Methods 0.000 title claims description 19
- 239000011521 glass Substances 0.000 claims description 95
- 229920005989 resin Polymers 0.000 claims description 32
- 239000011347 resin Substances 0.000 claims description 32
- 229920001431 Long-fiber-reinforced thermoplastic Polymers 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 16
- 239000008188 pellet Substances 0.000 claims description 8
- 238000009987 spinning Methods 0.000 description 20
- 238000005470 impregnation Methods 0.000 description 17
- 238000005520 cutting process Methods 0.000 description 11
- -1 for example Substances 0.000 description 11
- 238000000465 moulding Methods 0.000 description 11
- 239000011230 binding agent Substances 0.000 description 9
- 238000001816 cooling Methods 0.000 description 8
- 239000004743 Polypropylene Substances 0.000 description 7
- 239000011159 matrix material Substances 0.000 description 7
- 229920001155 polypropylene Polymers 0.000 description 7
- 238000004804 winding Methods 0.000 description 7
- 239000006185 dispersion Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000007822 coupling agent Substances 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 230000007547 defect Effects 0.000 description 4
- 239000002612 dispersion medium Substances 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 238000001746 injection moulding Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 239000001993 wax Substances 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 229930182556 Polyacetal Natural products 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004697 Polyetherimide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004734 Polyphenylene sulfide Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229910001260 Pt alloy Inorganic materials 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 229920010524 Syndiotactic polystyrene Polymers 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000008378 aryl ethers Chemical class 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 239000006059 cover glass Substances 0.000 description 1
- HBGGXOJOCNVPFY-UHFFFAOYSA-N diisononyl phthalate Chemical compound CC(C)CCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCC(C)C HBGGXOJOCNVPFY-UHFFFAOYSA-N 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000006060 molten glass Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229920006287 phenoxy resin Polymers 0.000 description 1
- 239000013034 phenoxy resin Substances 0.000 description 1
- 239000000088 plastic resin Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920002285 poly(styrene-co-acrylonitrile) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920001601 polyetherimide Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
Images
Landscapes
- Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Reinforced Plastic Materials (AREA)
Description
【0001】
【発明の属する技術分野】
本発明は、熱可塑性樹脂からなるマトリックス中に複数のガラスフィラメントが実質的に同一長さでかつ同一方向に並列して配列された、ペレット状又はロッド状の形態を有するガラス長繊維強化熱可塑性樹脂成形材料の製造方法に関するものである。
【0002】
【従来の技術】
従来より、ガラス繊維で強化された熱可塑性樹脂成形品の機械的物性、特に耐衝撃性や耐熱性を向上させることを目的とした、ガラス長繊維強化熱可塑性樹脂成形材料が提案されている。これらは一般的に、例えば特公昭52−10140号公報、特開平6−114830号公報等に開示されている方法に従い、例えば図1に概略を示した製造装置によって製造することができる。
【0003】
図1の製造装置においては、まず、連続したガラスフィラメントの複数を集束してなるガラス繊維を巻き取って得た回巻体1から、連続したガラス繊維11が引き出され、引き出されたガラス繊維11が、ガイド2に従ってそれぞれ別個に又は数本を引きそろえつつ含浸ダイ(溶融樹脂槽)4に導入される。含浸ダイ4は、押出機3から供給され溶融した熱可塑性樹脂で満たされており、該溶融した熱可塑性樹脂の中をガラス繊維11が通過する際に、ガラス繊維11へ熱可塑性樹脂が塗布又は含浸される。
【0004】
次いで、熱可塑性樹脂を塗布又は含浸されたガラス繊維11が、含浸ダイ4の出口に設けられた所定の口径のノズル(ダイス)5を通して引き出され、それによって余分な熱可塑性樹脂が除去されて所定のガラス繊維含有率とされると共に、所定の断面形状に賦形されて、連続した線状物6となる。続いて、この線状物6が、冷却槽7で冷水に浸漬されて冷却された後、切断装置(ペレタイザー)9で所定の長さに切断されて、ペレット状又はロッド状のガラス長繊維強化熱可塑性樹脂成形材料10となる。
【0005】
なお、回巻体1から含浸ダイ4及び冷却槽7を経て切断装置9に至る、ガラス繊維11及び線状物6の一連の流れは、引き取り機8の上下一対のコンベアで線状物6を挟圧しつつ引き取ることによって行われる。また、実際の製造装置においては、数十個の回巻体が用いられて、これらから引き出された数十本のガラス繊維がそれぞれ別個に並列して含浸ダイに導入されて、含浸ダイの出口に設けられた数十個のノズルから、数十本の線状物がそれぞれ別個に並列して引き出されている。
【0006】
こうして得られたガラス長繊維強化熱可塑性樹脂成形材料は、ペレット状又はロッド状の形態を有し、熱可塑性樹脂からなるマトリックス中に複数のガラスフィラメントが実質的に同一長さでかつ同一方向に並列して配列されたものである。
【0007】
このガラス長繊維強化熱可塑性樹脂成形材料は、その成形法や得られる成形品の用途により、そのまま単独で、あるいは所望のガラス繊維含有率になるようにガラス繊維を含有しない熱可塑性樹脂と混合し、必要に応じて着色剤やその他の添加剤等を添加した後、射出成形等の方法により所望の形状に成形して成形品とされる。なお、成形時におけるガラス長繊維強化熱可塑性樹脂成形材料を含む成形材料の移送には、空気流等による搬送手段(空気輸送等)が用いられる場合がある。
【0008】
【発明が解決しようとする課題】
ガラス長繊維強化熱可塑性樹脂成形材料の製造に用いられるガラス繊維は、連続したガラスフィラメントの数百本〜数千本を集束してなるもので、ガラス繊維を構成するガラスフィラメントの平均直径は一般的に3〜30μmであり、求められる性能やコスト等によって、ガラスフィラメントの平均直径や集束本数を特定の値とされたガラス繊維が適宜選択されて用いられる。このガラス繊維は、白金製又は白金合金製の紡糸炉(ブッシング)の底部に設けられた数百個〜数千個のノズル(チップ)から、溶融したガラスを高速で引き出しつつ冷却することによって繊維化したガラスフィラメントを集束して得られるものであり、紡糸炉の下側に配置された巻き取り装置(ワインダー)によってガラス繊維が巻き取られて回巻体とされる。
【0009】
上記のようにして得られるガラス繊維においては、それを構成する個々のガラスフィラメントの直径が全て同じであるわけではなく、直径はある範囲内に分布しており、すなわち、ガラスフィラメントの直径にはばらつきがあるのが実際であるが、このばらつきが大きい場合においては、次のような問題が発生する。
【0010】
まず、構成するガラスフィラメントの直径のばらつきが大きいガラス繊維を巻き取った回巻体においては、直径の比較的小さいガラスフィラメントが、直径の比較的大きいガラスフィラメントに比べて高い張力で巻き取られている傾向にある。単一のガラス繊維を構成するガラスフィラメントのそれぞれに巻き取り張力の差があると、ガラス繊維を構成する一部のガラスフィラメントが弛んでしまっていたり、回巻体からガラス繊維を引き出す際に一部のガラスフィラメントが追従し難かったりする。
【0011】
そして、上記のようなガラス繊維を用い、図1のような装置によってガラス長繊維強化熱可塑性樹脂成形材料を製造すると、一部のガラスフィラメントが切断してしまい、これが毛羽となってガイド2やノズル5に蓄積し、毛羽の蓄積が顕著になると、ガラス繊維11又は線状物6が切断してしまい、この場合、含浸ダイ4から並列して引き出される線状物6の数十本の内の一部を欠損したままで稼動させなければならず、生産効率の低下を招いてしまうのである。
【0012】
また、構成するガラスフィラメントの直径のばらつきが大きいガラス繊維を用い、図1のような装置によってガラス長繊維強化熱可塑性樹脂成形材料を製造した場合、切断装置9における線状物6の切断条件がガラスフィラメントの平均直径を要因の一つとして考慮して設定されるために、直径の比較的小さいガラスフィラメントは直径の比較的大きいガラスフィラメントに比べて切断し難くなり、その結果、得られたガラス長繊維強化熱可塑性樹脂成形材料の端面から直径の比較的小さいガラスフィラメントの一端が突出して見える状態となる。
【0013】
上記のようなガラス長繊維強化熱可塑性樹脂成形材料を用いて成形品を製造した場合は、端面から突出しているガラスフィラメントが脱落して毛羽になりやすく、この毛羽が原因となって、成形材料の移送の際の空気輸送や成形に支障をきたしたり、成形品の外観上の欠点となったりするという問題が発生してしまう。
【0014】
更に、ガラス長繊維強化熱可塑性樹脂成形材料の中に配列されるガラスフィラメントの直径のばらつきが大きいということは、直径が極端に小さいガラスフィラメントも多く含まれているということになり、このようなガラス長繊維強化熱可塑性樹脂成形材料を射出成形法によって成形すると、その成形条件がガラスフィラメントの平均直径を要因の一つとして考慮して設定されているために、直径が極端に小さいガラスフィラメントが熱可塑性樹脂の中に均一に分散し難くなり、ガラスフィラメントの分散が不十分な部分が欠点となって、得られる成形品の表面の外観が悪くなってしまうという問題もある。
【0015】
本発明は上記のような従来技術の問題点に鑑みてなされたもので、その目的は、製造時、空気輸送時及び成形時に発生する毛羽に起因する問題が発生せず、成形時にガラスフィラメントが十分に分散するために成形品の外観欠点が発生することがないガラス長繊維強化熱可塑性樹脂成形材料の製造方法を提供することにある。
【0016】
【課題を解決するための手段】
上記目的を達成するために本発明が採用したガラス長繊維強化熱可塑性樹脂成形材料の製造方法の構成は、連続したガラスフィラメントの複数を集束してなるガラス繊維に溶融した熱可塑性樹脂を塗布又は含浸させ、冷却した後に所定長さに切断してペレット状又はロッド状のガラス長繊維強化熱可塑性樹脂成形材料とする製造方法において、前記ガラス繊維として、該ガラス繊維を構成するガラスフィラメントの直径の変動係数が13%以下であるものを使用することを特徴とする。
【0017】
本発明で製造されるガラス長繊維強化熱可塑性樹脂成形材料(以下、単に本発明のガラス長繊維強化熱可塑性樹脂成形材料という。)は、上記のように、すでに知られているガラス長繊維強化熱可塑性樹脂成形材料において、そのマトリックス中に含有されるガラスフィラメントの直径の変動係数が所定の範囲内であることを特徴とするものであるが、本発明におけるガラスフィラメントの直径の変動係数(いわゆる「CV」)とは、ペレット状又はロッド状のガラス長繊維強化熱可塑性樹脂成形材料に含有されるガラスフィラメントの直径のばらつきの大きさを表す指標であり、ガラスフィラメントの直径を測定した測定値から標準偏差及び平均値を算出し、この標準偏差を平均値で除した値を百分率で表示したものである。また、ガラスフィラメントの直径とは、ガラスフィラメントの長さ方向と直交する断面の円における直径を意味する。
【0018】
本発明のガラス長繊維強化熱可塑性樹脂成形材料は、含有されるガラスフィラメントの直径の変動係数を13%以下とする、すなわち、ガラスフィラメントの直径のばらつきを小さくすることによって、製造時、空気輸送時及び成形時に毛羽が発生し難くなってこれに起因する問題がなくなり、かつ、得られるガラス繊維強化熱可塑性樹脂成形品の中のガラスフィラメントの分散が良好となって成形品の外観が向上するようにしたものである。
【0019】
【発明の実施の形態】
以下、本発明の具体的態様について更に詳細に説明する。
【0020】
本発明において用いられるガラス繊維としては、ガラス長繊維強化熱可塑性樹脂成形材料の原料として従来から用いられていたものと同様のものを用いることができるが、ガラス繊維を構成するガラスフィラメントの直径の変動係数が13%以下であることが必須であり、該変動係数が10%以下であることが本発明の効果を顕著に得られる点で好ましい。このようなガラス繊維を用いることによって、得られるガラス長繊維強化熱可塑性樹脂成形材料に含有されるガラスフィラメントの直径の変動係数を13%以下、好ましくは10%以下にすることができる。
【0021】
上記ガラス繊維としては、例えば、ガラスフィラメントの平均直径が3〜30μmのものが好ましく用いられ、その集束本数は100〜10000本程度であることが、熱可塑性樹脂をガラス繊維に塗布又は含浸させ易いので好ましい。
【0022】
また、紡糸炉のノズルが設けられた面における温度の分布やその付近の冷却状態が不均一になる、すなわち場所によって温度に大きな差があったり、稼働時間の経過に伴う紡糸炉の底部の変形(撓み)が大きくなったりすることによって、ガラス繊維を構成するガラスフィラメントの直径のばらつきが大きくなる。したがって、ガラスフィラメントの直径のばらつきを小さくしてその変動係数を13%以下にするには、紡糸炉の底部のノズルが設けられた面の温度分布を調整して均一にすること、稼働時間の経過に伴う紡糸炉の底部の変形を抑えること、又は、紡糸炉の底部が変形した場合に速やかに修正すること等が必要となる。
【0023】
なお、紡糸炉の稼働時間が長期にわたると、上記のような対策を実施しても、ガラスフィラメントの直径のばらつきが大きくなり過ぎたり、番手(単位長さ当りの質量)等のガラス繊維の品質が所定の規格範囲内に治められなかったり、紡糸炉での繊維化に支障を生じたりするようになるので、このような場合においては、紡糸炉を新しいものと交換することになる。この紡糸炉の稼動開始から交換までの期間は、概ね十数ヶ月である。
【0024】
上記のようなガラス繊維の回巻体としては、紡糸炉のノズルから引き出された数千本のガラスフィラメントを1本にまとめて集束したガラス繊維を、巻き取り装置にて円筒状に巻き取ったシングルエンドロービング(ダイレクトワインドロービング)であっても、紡糸炉のノズルから引き出された数千本のガラスフィラメントを数本に分けて集束したガラス繊維を、巻き取り装置にて太鼓状に巻き取ったもの(いわゆる「ケーキ」)であってもよい。また、複数の回巻体から引き出された複数のガラス繊維を引き揃えつつ、1本のガラス繊維として取り扱うこともできる。
【0025】
一般的に、ガラス繊維には、使用時の毛羽や静電気の発生を抑えてハンドリング性を改善するためや、マトリックスである熱可塑性樹脂へのガラス繊維の接着性を改善するために、種々のバインダーが付与されているが、本発明においても、これらのバインダーの種類はマトリックスである熱可塑性樹脂の種類に応じて選択すればよい。また、そのガラス繊維への付与量は、付与後のガラス繊維の質量を基準にして固形分として0.1〜3.0質量%が好ましく、付与量が0.1質量%より少ないと前記のハンドリング性及び接着性を十分に改善することが難しく、3.0質量%より多いとバインダーが熱可塑性樹脂のガラスフィラメントの間への含浸を妨げることになる。
【0026】
このバインダーは一般的に、例えば、アミノシラン、エポキシシラン、アクリルシラン等のシラン系カップリング剤に代表されるカップリング剤、及び、酢酸ビニル樹脂、ウレタン樹脂、アクリル樹脂、ポリエステル樹脂、ポリエーテル樹脂、フェノキシ樹脂、ポリアミド樹脂、エポキシ樹脂、ポリオレフィン樹脂等のポリマー又はその変性物、あるいは、ポリオレフィン系ワックスに代表されるワックス類等のオリゴマーを含むものである。なお、上記のポリマーやオリゴマーは、通常、界面活性剤による水分散化によって得られた水分散体、あるいは、ポリマーやオリゴマーの骨格中に存在するカルボキシル基やアミド基の中和や水和による水溶化によって得られる水溶液という形態で使用されるのが一般的である。
【0027】
更に、上記バインダーは、上記の成分以外に、塩化リチウム、ヨウ化カリウム等の無機塩や、アンモニウムクロライド型やアンモニウムエトサルフェート型等の4級アンモニウム塩に代表される帯電防止剤、あるいは、脂肪族エステル系、脂肪族エーテル系、芳香族エステル系、芳香族エーテル系の界面活性剤に代表される潤滑剤などを含んでいてもよい。
【0028】
一方、本発明においてマトリックスとなる熱可塑性樹脂としては、特に限定されないが、例えば、ポリエチレン、ポリプロピレン、ポリアミド、ポリエチレンテレフタレート、ポリブチレンテレフタレート、ポリスチレン、シンジオタクチックポリスチレン、スチレン−アクリロニトリル共重合体、アクリロニトリル−ブタジエン−スチレン共重合体、ポリアセタール、ポリエーテルイミド、ポリカーボネート、ポリフェニレンサルファイド、熱可塑性ポリウレタン樹脂等を挙げることができる。
【0029】
本発明では上記のような樹脂を単独で用いてもよく、また、2種以上の混合物、あるいは予め2種以上を共重合させた共重合体を用いてもよいし、熱可塑性樹脂には、用途や成形条件に応じて、着色剤、改質剤、ガラス繊維以外の充填剤等、公知の添加剤を適宜配合させることができ、これらは常法に従い樹脂と混練して、使用することができる。
【0030】
本発明のガラス長繊維強化熱可塑性樹脂成形材料は、ペレット状又はロッド状の形態を有し、熱可塑性樹脂からなるマトリックス中に複数のガラスフィラメントが実質的に同一長さでかつ同一方向に並列して配列されたものである。この場合、「実質的に同一長さでかつ同一方向に並列して配列された」とは、ガラスフィラメントの大部分が同一方向に並列してほぼ平行に配列されているが、一部のガラスフィラメントは部分的に湾曲していたり、お互いに絡み合っていたりしてもよい状態を意味する。また、ガラスフィラメントが実質的に同一長さであるために、ガラス長繊維強化熱可塑性樹脂成形材料のガラスフィラメントの配列方向における端面に、ガラスフィラメントの切断された断面がほぼ揃えられて、すなわち成形材料の端面とガラスフィラメントの断面とがほぼ同一面にあるように、ガラスフィラメントが配列されるようになっている。
【0031】
本発明のガラス長繊維強化熱可塑性樹脂成形材料において、ガラス繊維含有率は特に限定されないが、30〜80質量%とすることが好ましく、ガラス繊維含有率が30%未満の場合は、従来技術と同様の方法で成形材料を成形して所望のガラス繊維含有率の成型品を得る際に、ガラス繊維含有率を選択できる範囲が低い側に狭くなるのであまり好ましくなく、ガラス繊維含有率が80%を超えると、熱可塑性樹脂に対するガラス繊維の比率が多くなり過ぎて、成形材料の製造工程で支障を生じやすい。
【0032】
また、本発明のガラス長繊維強化熱可塑性樹脂成形材料の長さも特に限定されないが、3〜100mmであることが好ましく、長さが3mm未満の場合は、ガラス長繊維強化熱可塑性樹脂成形材料の製造時に毛羽が発生しやすくなる場合があり、長さが100mmを超える場合には、ホッパー内で成形材料がブリッジングをおこして、射出成形法、押出成形法又は押出圧縮成形法等による成形機への供給に支障を来たす場合がある。なお、本発明のガラス長繊維強化熱可塑性樹脂成形材料においては、長さが50mm未満のものをペレット状と称し、長さが50mm以上のものをロッド状と称する。
【0033】
本発明の長繊維強化熱可塑性樹脂成形材料は、上記のようなガラス繊維、熱可塑性樹脂及び図1と同様の装置を用いて、上述の従来技術と同様の方法によって製造することができる。また、含浸ダイ4に供給する溶融した熱可塑性樹脂に代えて、熱可塑性樹脂のエマルジョン、熱可塑性樹脂粉末を水又はその他の分散媒の中に分散させた懸濁液、あるいは熱可塑性樹脂を溶媒に溶解させた樹脂溶液を供給し、かつ、冷却槽7に代えて溶媒又は分散媒を除去する乾燥装置を用いる方法であってもよい。但し、溶媒又は分散媒の除去が不要であることや生産性やコストの面からは、溶融含浸法、すなわち、連続したガラスフィラメントの複数を集束してなるガラス繊維に、溶融した熱可塑性樹脂を塗布又は含浸させ、冷却した後に所定長さに切断してペレット状又はロッド状のガラス長繊維強化熱可塑性樹脂成形材料とする方法を採用することが好ましい。
【0034】
【実施例】
以下に本発明を実施例により更に詳細に説明する。
【0035】
実施例1
図1に示した製造装置を用いる前述した方法にしたがって、ガラス長繊維強化熱可塑性樹脂成形材料を製造した。すなわち、呼び径が16μmであるEガラスのフィラメントの4000本を集束させたガラス繊維に、アミノシランカップリング剤と変性ポリプロピレンとを主成分としたバインダーを、付与後のガラス繊維の質量を基準にして固形分として0.5質量%となるように付与し、円筒状に巻き取った後、乾燥させて得たシングルエンドロービングをガラス繊維の回巻体1とし、これから引き出した一本のガラス繊維をガラス繊維11として用いて、溶融したポリプロピレン樹脂で満たされた含浸ダイ4に導入した。冷却槽7、引き取り機8、切断装置9は、従来から用いられている通常のものを用いて、含浸ダイ4の出口のダイス5の口径は2.2mm、引き取り機8による引き取り速度は30m/分とし、線状物6を切断装置9で切断する長さは10mmとして、ガラス繊維含有率が50質量%である本発明のペレット状のガラス長繊維強化熱可塑性樹脂成形材料10を得た。なお、フィラメントの直径の変動係数の目標を9%にして、紡糸炉底部の温度分布の調節等を行い、また、含浸ダイ4に導入するガラス繊維11(含浸ダイ4から引き出す線状物6)は、1本だけではなく複数本を同時に並列させて図1の製造装置を稼動させた。
【0036】
実施例2
呼び径が16μmであるEガラスのフィラメントの4000本を集束させたガラス繊維に、アミノシランカップリング剤と変性ポリプロピレンとを主成分としたバインダーを、付与後のガラス繊維の質量の基準にして固形分として0.5質量%となるように付与し、円筒状に巻き取った後、乾燥させて得たシングルエンドロービングをガラス繊維の回巻体1とし、これらから引き出した一本のガラス繊維をガラス繊維11として用いた以外は、実施例1と同じ装置、方法及び条件で、ガラス繊維含有率が50質量%である本発明のペレット状のガラス長繊維強化熱可塑性樹脂成形材料10を得た。なお、フィラメントの直径の変動係数の目標を12%にして、紡糸炉底部の温度分布の調節等を行った。
【0037】
実施例3
呼び径が16μmであるEガラスのフィラメントの600本を集束させたガラス繊維に、アミノシランカップリング剤と変性ポリプロピレンとを主成分としたバインダーを、付与後のガラス繊維の質量を基準にして固形分として0.5質量%となるように付与し、太鼓状に巻き取った後、乾燥させて得たケーキの7個をガラス繊維の回巻体1とし、これらから引き出したガラス繊維7本を引き揃えたものをガラス繊維11として用いた以外は、実施例1と同じ装置、方法及び条件で、ガラス繊維含有率が50質量%である本発明のペレット状のガラス長繊維強化熱可塑性樹脂成形材料10を得た。なお、フィラメントの直径の変動係数の目標を9%にして、紡糸炉底部の温度分布の調節等を行った。また、上記7個のケーキは、同じ紡糸炉で製造されたもの用いた。
【0038】
比較例
呼び径が16μmであるEガラスのフィラメントの4000本を集束させたガラス繊維に、アミノシランカップリング剤と変性ポリプロピレンとを主成分としたバインダーを、付与後のガラス繊維の質量を基準にして固形分として0.5質量%となるように付与し、円筒状に巻き取った後、乾燥させて得たシングルエンドロービングをガラス繊維の回巻体1とし、これから引き出した一本のガラス繊維をガラス繊維11として用いた以外は、実施例1と同じ装置、方法及び条件で、ガラス繊維含有率が50質量%のペレット状のガラス長繊維強化熱可塑性樹脂成形材料10を得た。なお、この比較例に用いたガラス繊維は、約10ヶ月稼働させたために新しい紡糸炉との交換時期が近付いている紡糸炉によって製造されたものを用いた。
【0039】
評価
実施例1〜3及び比較例によって得られたガラス長繊維強化熱可塑性樹脂成形材料のそれぞれを次の方法によって評価した。その結果を表1に示す。
【0040】
ガラスフィラメントの直径の平均値及び変動係数
実施例1〜3及び比較例によって得られたガラス長繊維強化熱可塑性樹脂成形材料のペレット1個を磁製皿の上に載せ、これを625℃の電気炉の中に入れて1時間加熱することにより樹脂を主とする有機質部分を焼却除去して、ペレット中のガラスフィラメントのみを取り出した。これを、乳鉢を用いて砕いて個々のガラスフィラメントに分散させてスライドグラスの上に散布し、そこへ数滴のアニソールを滴下してからカバーグラスを被せて試験体とした。顕微鏡及びそのレンズに設置したスケールを用いて、この試験体の中の無作為に選択した1000本のガラスフィラメントの直径を測定した(円柱状のガラスフィラメントは顕微鏡の視野では長方形に見えるので、その幅を測定して直径とした)。この測定値から、平均値及び標準偏差を算出し、更に変動係数を算出した。このガラスフィラメントの直径の測定及び算出を別の2個のペレットについても行い、合計3個のペレットでの平均値及び変動係数を平均して、各例でのガラスフィラメントの直径の平均値及び変動係数とした。
【0041】
成形品の外観
実施例1〜3及び比較例によって得られたガラス長繊維強化熱可塑性樹脂成形材料のペレットのそれぞれと、ガラス繊維を含有しないポリプロピレンのペレットとを、得られる試験片におけるガラス繊維含有率が40質量%となる比率で混合した後、これを射出成形して長さ12cm、幅12cm、厚さ3mmの試験片を得た。この試験片の両面を目視によって観察し、ガラスフィラメントが束状又は塊状に見える部分を分散が不十分な部分、すなわち外観欠点として計数して、試験片の大きさから100cm2当りの数に換算した。
【0042】
ガラス繊維又は線状物の切断本数
図1の製造装置を約5時間連続して稼動させる間に、同時に並列させて含浸ダイ4に導入した複数本のガラス繊維11(含浸ダイ4から引き出した線状物6)の内の何本が、毛羽が原因でダイス5において切断してしまったかを計数し、これを全本数に対する百分率で表して、切断のし難さの指標とした。
【0043】
【表1】
【0044】
【発明の効果】
以上説明したように、本発明によれば、ガラス長繊維強化熱可塑性樹脂成形材料に含有されるガラスフィラメントの直径の変動係数を13%以下とする、すなわち、ガラスフィラメントの直径のばらつきを小さくすることによって、製造時、空気輸送時及び成形時に毛羽が発生し難くなってこれに起因する問題がなくなり、かつ、得られるガラス繊維強化熱可塑性樹脂成形品の中のガラスフィラメントの分散が良好となって成形品の外観が向上する。
【0045】
また、本発明のガラス長繊維強化熱可塑性樹脂成形材料では、ガラスフィラメントの直径のばらつきを小さくしたことによって、直径の比較的大きいガラスフィラメントも少なくなるので、ペレットの取り扱い時にチクチクとした刺激を感じることがなくなる。
【図面の簡単な説明】
【図1】 ガラス繊維で強化された熱可塑性樹脂成形品の製造装置の概略図である。
【符号の説明】
1 回巻体
11 連続したガラス繊維
3 押出機
4 含浸ダイ(溶融樹脂槽)
5 ノズル(ダイス)
6 線状物
7 冷却槽
8 引き取り機
9 切断装置(ペレタイザー)
10 ガラス長繊維強化熱可塑性樹脂成形材料[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a glass long fiber reinforced thermoplastic having a pellet-like or rod-like form in which a plurality of glass filaments are arranged in parallel in the same direction in a matrix made of a thermoplastic resin. Resin molding material of It relates to a manufacturing method.
[0002]
[Prior art]
Conventionally, a long glass fiber reinforced thermoplastic resin molding material has been proposed for the purpose of improving mechanical properties, particularly impact resistance and heat resistance, of a thermoplastic resin molded product reinforced with glass fiber. In general, these can be produced by, for example, a production apparatus schematically shown in FIG. 1 according to the methods disclosed in, for example, Japanese Patent Publication No. 52-10140 and Japanese Patent Laid-Open No. 6-114830.
[0003]
In the manufacturing apparatus of FIG. 1, first, continuous glass fibers 11 are drawn from a wound body 1 obtained by winding a glass fiber formed by converging a plurality of continuous glass filaments, and the drawn glass fibers 11 are drawn. Are introduced into the impregnation die (molten resin tank) 4 separately or in accordance with the
[0004]
Next, the glass fiber 11 coated or impregnated with the thermoplastic resin is drawn out through a nozzle (die) 5 having a predetermined diameter provided at the outlet of the impregnation die 4, thereby removing the excess thermoplastic resin and determining the predetermined value. In addition to the glass fiber content, the continuous linear product 6 is formed into a predetermined cross-sectional shape. Subsequently, the linear object 6 is immersed in cold water in a cooling bath 7 and cooled, and then cut into a predetermined length by a cutting device (pelletizer) 9 to reinforce a pellet-like or rod-like glass long fiber. The thermoplastic resin molding material 10 is obtained.
[0005]
A series of flow of the glass fiber 11 and the linear object 6 from the wound body 1 through the impregnation die 4 and the cooling tank 7 to the cutting device 9 is carried out by the pair of upper and lower conveyors of the take-up machine 8. It is carried out by pulling out while pinching. Further, in an actual manufacturing apparatus, dozens of wound bodies are used, and dozens of glass fibers drawn from these are separately introduced in parallel to the impregnation die, and the exit of the impregnation die Several tens of linear objects are drawn out separately in parallel from tens of nozzles provided in the nozzle.
[0006]
The glass long fiber reinforced thermoplastic resin molding material thus obtained has a pellet-like or rod-like form, and a plurality of glass filaments are substantially the same length and in the same direction in a matrix made of a thermoplastic resin. They are arranged in parallel.
[0007]
This long glass fiber reinforced thermoplastic resin molding material can be used alone or mixed with a thermoplastic resin containing no glass fiber so as to have a desired glass fiber content, depending on the molding method and use of the resulting molded product. After adding a colorant or other additives as necessary, the molded product is formed into a desired shape by a method such as injection molding. In addition, the conveyance means (air conveyance etc.) by an airflow etc. may be used for the transfer of the molding material containing the long glass fiber reinforced thermoplastic resin molding material at the time of shaping | molding.
[0008]
[Problems to be solved by the invention]
Glass fibers used for the production of long glass fiber reinforced thermoplastic resin molding materials are formed by concentrating hundreds to thousands of continuous glass filaments, and the average diameter of the glass filaments constituting the glass fibers is generally The glass fiber having a specific value for the average diameter and the number of converging glass filaments is appropriately selected and used depending on the required performance and cost. This glass fiber is cooled by drawing molten glass at a high speed from hundreds to thousands of nozzles (chips) provided at the bottom of a spinning furnace (bushing) made of platinum or platinum alloy. The glass fiber is obtained by converging, and the glass fiber is wound up by a winding device (winder) disposed on the lower side of the spinning furnace to form a wound body.
[0009]
In the glass fiber obtained as described above, the diameters of the individual glass filaments constituting the glass fiber are not all the same, and the diameters are distributed within a certain range. Actually, there is a variation, but when this variation is large, the following problem occurs.
[0010]
First, in a wound body in which a glass fiber having a large variation in the diameter of the glass filament is wound, a glass filament having a relatively small diameter is wound with a higher tension than a glass filament having a relatively large diameter. Tend to be. If there is a difference in winding tension between the glass filaments that make up a single glass fiber, some of the glass filaments that make up the glass fiber may be loosened, or it may be difficult to pull out the glass fiber from the wound body. Some glass filaments are difficult to follow.
[0011]
And when a glass long fiber reinforced thermoplastic resin molding material is manufactured by the apparatus as shown in FIG. 1 using the glass fiber as described above, a part of the glass filament is cut, and this becomes fluff to become the
[0012]
Moreover, when the glass fiber reinforced thermoplastic resin molding material is manufactured by the apparatus as shown in FIG. 1 using the glass fiber having a large variation in the diameter of the glass filament constituting the cutting condition of the linear object 6 in the cutting apparatus 9. Since the average diameter of the glass filament is set as one of the factors, the glass filament having a relatively small diameter is harder to cut than the glass filament having a relatively large diameter. One end of the glass filament having a relatively small diameter appears to protrude from the end face of the long fiber reinforced thermoplastic resin molding material.
[0013]
When a molded product is manufactured using the glass long fiber reinforced thermoplastic resin molding material as described above, the glass filament protruding from the end face is likely to fall off and become fluffy. This causes problems such as troubles in pneumatic transportation and molding during the transfer of the resin, and defects in the appearance of the molded product.
[0014]
Furthermore, the large variation in the diameter of the glass filaments arranged in the glass fiber reinforced thermoplastic resin molding material means that many glass filaments having extremely small diameters are included. When a long glass fiber reinforced thermoplastic resin molding material is molded by the injection molding method, the molding conditions are set taking into consideration the average diameter of the glass filament as one of the factors. There is also a problem that it becomes difficult to uniformly disperse in the thermoplastic resin, and the portion where the dispersion of the glass filament is insufficient becomes a defect, and the appearance of the surface of the obtained molded product is deteriorated.
[0015]
The present invention has been made in view of the problems of the prior art as described above, and its purpose is to prevent problems caused by fuzz generated during production, pneumatic transportation and molding, and glass filaments during molding. Long glass fiber reinforced thermoplastic resin molding material that does not cause appearance defects of molded products due to sufficient dispersion of It is to provide a manufacturing method.
[0016]
[Means for Solving the Problems]
The present invention has been adopted to achieve the above object. Manufacturing method of long glass fiber reinforced thermoplastic resin molding material The composition is made by applying or impregnating a molten thermoplastic resin to a glass fiber formed by converging a plurality of continuous glass filaments, cooling, cutting to a predetermined length, and pellet- or rod-shaped glass long fiber reinforced heat. In the manufacturing method using the plastic resin molding material, a glass fiber having a variation coefficient of a diameter of a glass filament constituting the glass fiber of 13% or less is used as the glass fiber.
[0017]
The present invention Manufactured in Long glass fiber reinforced thermoplastic resin molding material (Hereinafter, simply referred to as the glass long fiber reinforced thermoplastic resin molding material of the present invention.) As described above, in the known long glass fiber reinforced thermoplastic resin molding material, the coefficient of variation of the diameter of the glass filament contained in the matrix is within a predetermined range. However, the coefficient of variation (so-called “CV”) of the diameter of the glass filament in the present invention is a large variation in the diameter of the glass filament contained in the pellet-like or rod-like glass long fiber reinforced thermoplastic resin molding material. A standard deviation and an average value are calculated from measured values obtained by measuring the diameter of the glass filament, and a value obtained by dividing the standard deviation by the average value is displayed as a percentage. Moreover, the diameter of a glass filament means the diameter in the circle | round | yen of the cross section orthogonal to the length direction of a glass filament.
[0018]
The glass long fiber reinforced thermoplastic resin molding material of the present invention has a coefficient of variation of the diameter of the glass filament to be contained of 13% or less, that is, by reducing the variation in the diameter of the glass filament, thereby producing pneumatic transportation during production. Fluff is less likely to occur at the time of molding and molding, and there are no problems caused by this, and the dispersion of glass filaments in the obtained glass fiber reinforced thermoplastic resin molded product is improved, and the appearance of the molded product is improved. It is what I did.
[0019]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, specific embodiments of the present invention will be described in more detail.
[0020]
As the glass fiber used in the present invention, the same glass fiber that has been conventionally used as a raw material for the long glass fiber reinforced thermoplastic resin molding material can be used. It is essential that the coefficient of variation is 13% or less, and it is preferable that the coefficient of variation is 10% or less from the viewpoint that the effects of the present invention can be remarkably obtained. By using such a glass fiber, the variation coefficient of the diameter of the glass filament contained in the obtained long glass fiber reinforced thermoplastic resin molding material can be 13% or less, preferably 10% or less.
[0021]
As the glass fiber, for example, glass filaments having an average diameter of 3 to 30 μm are preferably used, and the number of bundles is about 100 to 10,000, which makes it easy to apply or impregnate the glass fiber with a thermoplastic resin. Therefore, it is preferable.
[0022]
Also, the temperature distribution on the surface where the nozzle of the spinning furnace is provided and the cooling state in the vicinity thereof are non-uniform, that is, there is a large difference in temperature depending on the location, or deformation of the bottom of the spinning furnace with the passage of operating time When (flexure) becomes large, the variation of the diameter of the glass filament which comprises glass fiber becomes large. Therefore, in order to reduce the variation in the diameter of the glass filament and reduce its coefficient of variation to 13% or less, the temperature distribution on the surface of the spinning furnace provided with the nozzle at the bottom is adjusted to be uniform. It is necessary to suppress the deformation of the bottom of the spinning furnace with the progress, or to correct quickly when the bottom of the spinning furnace is deformed.
[0023]
If the spinning furnace is operating for a long period of time, even if the measures described above are implemented, the glass filament diameter will vary too much, and the quality of the glass fiber such as the count (mass per unit length). In such a case, the spinning furnace is replaced with a new one. In this case, the spinning furnace is not controlled within a predetermined standard range or the fiberization in the spinning furnace is hindered. The period from the start of operation of the spinning furnace to the replacement is approximately ten and several months.
[0024]
As a glass fiber winding body as described above, a glass fiber in which thousands of glass filaments drawn from a spinning furnace nozzle are bundled into one is wound into a cylindrical shape by a winding device. Even with single-end roving (direct wind roving), thousands of glass filaments drawn from the spinning furnace nozzles were divided into several pieces and wound into a drum shape with a winder. It may be a thing (so-called “cake”). Moreover, it can also handle as one glass fiber, aligning several glass fiber pulled out from the several winding body.
[0025]
Generally, various binders are used for glass fibers in order to improve the handling properties by suppressing the generation of fuzz and static electricity during use, and to improve the adhesion of the glass fibers to the thermoplastic resin as a matrix. However, in the present invention, the kind of these binders may be selected according to the kind of the thermoplastic resin as the matrix. Further, the amount applied to the glass fiber is preferably 0.1 to 3.0% by mass as the solid content based on the mass of the glass fiber after the application, and when the applied amount is less than 0.1% by mass, It is difficult to sufficiently improve the handleability and adhesion, and if it exceeds 3.0% by mass, the binder prevents impregnation of the thermoplastic resin between the glass filaments.
[0026]
In general, this binder is, for example, a coupling agent typified by a silane coupling agent such as amino silane, epoxy silane, or acrylic silane, and vinyl acetate resin, urethane resin, acrylic resin, polyester resin, polyether resin, It contains polymers such as phenoxy resin, polyamide resin, epoxy resin, polyolefin resin or modified products thereof, or oligomers such as waxes represented by polyolefin wax. The above-mentioned polymer or oligomer is usually an aqueous dispersion obtained by water dispersion with a surfactant, or water-soluble by neutralization or hydration of carboxyl groups or amide groups present in the skeleton of the polymer or oligomer. In general, it is used in the form of an aqueous solution obtained by chemical conversion.
[0027]
In addition to the above components, the binder may be an antistatic agent typified by an inorganic salt such as lithium chloride or potassium iodide, a quaternary ammonium salt such as an ammonium chloride type or an ammonium ethosulphate type, or an aliphatic group. A lubricant typified by an ester-based, aliphatic ether-based, aromatic ester-based, or aromatic ether-based surfactant may be included.
[0028]
On the other hand, the thermoplastic resin used as a matrix in the present invention is not particularly limited. For example, polyethylene, polypropylene, polyamide, polyethylene terephthalate, polybutylene terephthalate, polystyrene, syndiotactic polystyrene, styrene-acrylonitrile copolymer, acrylonitrile- Examples thereof include a butadiene-styrene copolymer, polyacetal, polyetherimide, polycarbonate, polyphenylene sulfide, and thermoplastic polyurethane resin.
[0029]
In the present invention, the above-mentioned resins may be used alone, or a mixture of two or more kinds, or a copolymer obtained by copolymerizing two or more kinds in advance may be used. Depending on the application and molding conditions, known additives such as colorants, modifiers, fillers other than glass fibers, and the like can be appropriately blended, and these can be used by kneading with a resin according to a conventional method. it can.
[0030]
The glass long fiber reinforced thermoplastic resin molding material of the present invention has a pellet-like or rod-like form, and a plurality of glass filaments are substantially the same length in parallel in the same direction in a matrix made of thermoplastic resin. Are arranged. In this case, “substantially the same length and arranged in parallel in the same direction” means that most of the glass filaments are arranged in parallel in the same direction in parallel. The filament means a state where it may be partially curved or entangled with each other. In addition, since the glass filaments are substantially the same length, the cut sections of the glass filaments are almost aligned with the end faces in the glass filament arrangement direction of the long glass fiber reinforced thermoplastic resin molding material, that is, molded. The glass filaments are arranged so that the end face of the material and the cross section of the glass filament are substantially in the same plane.
[0031]
In the glass long fiber reinforced thermoplastic resin molding material of the present invention, the glass fiber content is not particularly limited, but is preferably 30 to 80% by mass, and when the glass fiber content is less than 30%, When a molding material is molded by the same method to obtain a molded product having a desired glass fiber content, the range in which the glass fiber content can be selected is narrowed to the lower side, which is not so preferable, and the glass fiber content is 80%. If the ratio exceeds 50, the ratio of the glass fiber to the thermoplastic resin is excessively increased, which tends to cause trouble in the manufacturing process of the molding material.
[0032]
Further, the length of the glass long fiber reinforced thermoplastic resin molding material of the present invention is not particularly limited, but is preferably 3 to 100 mm. When the length is less than 3 mm, the glass long fiber reinforced thermoplastic resin molding material Fluff may easily occur during production, and when the length exceeds 100 mm, the molding material causes bridging in the hopper, and a molding machine using an injection molding method, an extrusion molding method, an extrusion compression molding method, or the like. May interfere with the supply to In the long glass fiber reinforced thermoplastic resin molding material of the present invention, those having a length of less than 50 mm are referred to as pellets, and those having a length of 50 mm or more are referred to as rods.
[0033]
The long fiber reinforced thermoplastic resin molding material of the present invention can be produced by the same method as in the above-described conventional technique using the glass fiber, the thermoplastic resin and the apparatus similar to FIG. Further, instead of the molten thermoplastic resin supplied to the impregnation die 4, a thermoplastic resin emulsion, a suspension in which a thermoplastic resin powder is dispersed in water or other dispersion medium, or a thermoplastic resin as a solvent. Alternatively, a method may be used in which a resin solution dissolved in is supplied and a drying apparatus that removes the solvent or the dispersion medium in place of the cooling bath 7 is used. However, from the standpoints of eliminating the solvent or dispersion medium, and productivity and cost, a melt impregnation method, that is, a glass fiber formed by bundling a plurality of continuous glass filaments with a molten thermoplastic resin. It is preferable to employ a method of applying or impregnating, cooling, and cutting into a predetermined length to form a pellet-shaped or rod-shaped glass long fiber reinforced thermoplastic resin molding material.
[0034]
【Example】
Hereinafter, the present invention will be described in more detail with reference to examples.
[0035]
Example 1
A glass long fiber reinforced thermoplastic resin molding material was manufactured according to the method described above using the manufacturing apparatus shown in FIG. That is, on the basis of the mass of the glass fiber after the application of a binder mainly composed of an aminosilane coupling agent and a modified polypropylene to a glass fiber obtained by focusing 4000 filaments of E glass having a nominal diameter of 16 μm. A single-end roving obtained by giving a solid content of 0.5% by mass, winding up into a cylindrical shape, and drying the resultant is used as a glass fiber wound body 1, and a single glass fiber drawn from this is used. Used as glass fiber 11 and introduced into impregnation die 4 filled with molten polypropylene resin. The cooling tank 7, the take-up machine 8, and the cutting device 9 are conventional ones that are conventionally used, the diameter of the die 5 at the exit of the impregnation die 4 is 2.2 mm, and the take-up speed by the take-up machine 8 is 30 m / The length of cutting the linear object 6 with the cutting device 9 was 10 mm, and the pellet-shaped glass long fiber reinforced thermoplastic resin molding material 10 of the present invention having a glass fiber content of 50% by mass was obtained. The target of the coefficient of variation of the filament diameter is set to 9%, the temperature distribution at the bottom of the spinning furnace is adjusted, and the glass fiber 11 to be introduced into the impregnation die 4 (linear object 6 drawn from the impregnation die 4). 1 operated the manufacturing apparatus of FIG. 1 with not only one but also a plurality of them arranged in parallel.
[0036]
Example 2
Solid content based on the mass of the glass fiber after the application of a binder mainly composed of an aminosilane coupling agent and a modified polypropylene to a glass fiber obtained by focusing 4000 filaments of E glass having a nominal diameter of 16 μm. The single-ended roving obtained by drying the glass fiber after being wound into a cylindrical shape and then dried is used as a glass fiber wound body 1, and a single glass fiber drawn from these is used as glass. Except having used as the fiber 11, the same apparatus, method, and conditions as Example 1 obtained the pellet-like long glass fiber reinforced thermoplastic resin molding material 10 of the present invention having a glass fiber content of 50% by mass. The temperature distribution at the bottom of the spinning furnace was adjusted by setting the target for the coefficient of variation of the filament diameter to 12%.
[0037]
Example 3
Solid content based on the mass of the glass fiber after applying a binder mainly composed of an aminosilane coupling agent and a modified polypropylene to a glass fiber obtained by converging 600 filaments of E glass having a nominal diameter of 16 μm. As a result, 7 pieces of cake obtained by drying the cake after being wound in a drum shape are used as a glass fiber wound body 1, and 7 glass fibers drawn from these are drawn. Except that the prepared glass fiber 11 was used, the pelletized glass long fiber reinforced thermoplastic resin molding material of the present invention having a glass fiber content of 50% by mass was used in the same apparatus, method and conditions as in Example 1. 10 was obtained. The temperature distribution at the bottom of the spinning furnace was adjusted by setting the target of the coefficient of variation of the filament diameter to 9%. In addition, the seven cakes produced in the same spinning furnace were used.
[0038]
Comparative example
Solid content based on the mass of the glass fiber after the application of a binder mainly composed of an aminosilane coupling agent and a modified polypropylene to a glass fiber in which 4000 filaments of E glass having a nominal diameter of 16 μm are focused. The single-ended roving obtained by drying the glass fiber after being wound into a cylindrical shape and then dried is used as a glass fiber wound body 1, and a single glass fiber drawn from the glass fiber is used as a glass fiber. Except that it was used as 11, a pellet-like long glass fiber reinforced thermoplastic resin molding material 10 having a glass fiber content of 50% by mass was obtained using the same apparatus, method and conditions as in Example 1. In addition, the glass fiber used for this comparative example used what was manufactured by the spinning furnace which is operating for about 10 months and the time for replacement | exchange with a new spinning furnace is approaching.
[0039]
Evaluation
Each of the glass long fiber reinforced thermoplastic resin molding materials obtained in Examples 1 to 3 and Comparative Example was evaluated by the following method. The results are shown in Table 1.
[0040]
Mean value and coefficient of variation of glass filament diameter
One pellet of the long glass fiber reinforced thermoplastic resin molding material obtained in Examples 1 to 3 and Comparative Example was placed on a porcelain dish, and this was placed in an electric furnace at 625 ° C. and heated for 1 hour. Thus, the organic part mainly composed of resin was removed by incineration, and only the glass filament in the pellet was taken out. This was crushed using a mortar, dispersed into individual glass filaments, sprayed onto a slide glass, a few drops of anisole were dropped on it, and a cover glass was then applied to give a test specimen. Using a microscope and a scale placed on its lens, the diameter of 1000 randomly selected glass filaments in this specimen was measured (the cylindrical glass filament appears to be rectangular in the field of view of the microscope. The width was measured and used as the diameter). From this measured value, an average value and a standard deviation were calculated, and a coefficient of variation was further calculated. The measurement and calculation of the diameter of the glass filament was also performed for two other pellets, and the average value and variation coefficient of the total of three pellets were averaged, and the average value and variation of the glass filament diameter in each example Coefficient.
[0041]
Appearance of molded product
Each of the glass long fiber reinforced thermoplastic resin molding material pellets obtained in Examples 1 to 3 and the comparative example and a polypropylene pellet not containing glass fibers have a glass fiber content of 40 mass in the obtained test piece. After mixing at a ratio of%, this was injection molded to obtain a test piece having a length of 12 cm, a width of 12 cm, and a thickness of 3 mm. Both sides of the test piece are visually observed, and the part where the glass filaments appear to be bundles or lumps is counted as an insufficiently dispersed part, that is, the appearance defect, and 100 cm from the size of the test piece. 2 Converted to per number.
[0042]
Number of cut glass fibers or linear objects
While the manufacturing apparatus of FIG. 1 is continuously operated for about 5 hours, how many of the plurality of glass fibers 11 (the linear objects 6 drawn from the impregnation die 4) introduced into the impregnation die 4 in parallel at the same time. However, it was counted whether or not the die 5 had been cut due to fluff, and this was expressed as a percentage of the total number and used as an index of difficulty in cutting.
[0043]
[Table 1]
[0044]
【The invention's effect】
As described above, according to the present invention, the variation coefficient of the diameter of the glass filament contained in the long glass fiber reinforced thermoplastic resin molding material is set to 13% or less, that is, the variation in the diameter of the glass filament is reduced. As a result, fluff is less likely to occur during production, pneumatic transportation, and molding, and there are no problems caused by this, and dispersion of glass filaments in the obtained glass fiber reinforced thermoplastic resin molded article is improved. This improves the appearance of the molded product.
[0045]
In addition, in the glass long fiber reinforced thermoplastic resin molding material of the present invention, since the variation in the diameter of the glass filament is reduced, the number of glass filaments having a relatively large diameter is also reduced. Nothing will happen.
[Brief description of the drawings]
FIG. 1 is a schematic view of an apparatus for producing a thermoplastic resin molded article reinforced with glass fibers.
[Explanation of symbols]
1 roll
11 Continuous glass fiber
3 Extruder
4 Impregnation die (molten resin tank)
5 Nozzles (dies)
6 linear objects
7 Cooling tank
8 Picker
9 Cutting device (pelletizer)
10 Long glass fiber reinforced thermoplastic resin molding material
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| JP2001396957A JP3899263B2 (en) | 2001-12-27 | 2001-12-27 | Manufacturing method of long glass fiber reinforced thermoplastic resin molding material |
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| JP4876377B2 (en) * | 2004-08-05 | 2012-02-15 | 日東紡績株式会社 | Method for producing flat glass fiber-containing pellets |
| ES2376076T3 (en) * | 2007-12-21 | 2012-03-08 | Saudi Basic Industries Corporation | PROCEDURE TO PRODUCE THERMOPLED COMPOSITIONS REINFORCED STICES WITH LONG GLASS FIBER. |
| CN105848851B (en) * | 2013-12-18 | 2019-06-18 | Dic株式会社 | Resin composition for hollow blow-molded article, hollow blow-molded article, and production method |
| EP3101057B1 (en) | 2014-01-29 | 2019-08-28 | Sumitomo Bakelite Co., Ltd. | Method for producing a molded article |
| JP6497088B2 (en) * | 2014-01-29 | 2019-04-10 | 住友ベークライト株式会社 | Manufacturing method of back plate, back plate and brake pad |
| KR102017178B1 (en) * | 2015-03-10 | 2019-09-02 | 화이바 레인포스드 써모플라스틱스 비.브이. | Spreader member for making unidirectional fiber-reinforced tape |
| EP3546167B1 (en) | 2015-06-24 | 2021-01-13 | Mitsubishi Chemical Corporation | Method for manufacturing fiber-reinforced resin material, and fiber bundle group inspection device |
| CN115339013B (en) * | 2022-09-02 | 2024-12-13 | 苏州博安图工程塑料技术有限公司 | Multi-point coating multifunctional composite polymer material enhanced production process and system |
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| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
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| LAPS | Cancellation because of no payment of annual fees |