JP7284930B2 - 繊維強化熱可塑性樹脂フィラメントおよびその成形品 - Google Patents
繊維強化熱可塑性樹脂フィラメントおよびその成形品 Download PDFInfo
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- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
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- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
- D01F6/60—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyamides
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- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
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- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
- D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
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- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/39—Aldehyde resins; Ketone resins; Polyacetals
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- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
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- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
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- D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain
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- B29B15/00—Pretreatment of the material to be shaped, not covered by groups B29B7/00 - B29B13/00
- B29B15/08—Pretreatment of the material to be shaped, not covered by groups B29B7/00 - B29B13/00 of reinforcements or fillers
- B29B15/10—Coating or impregnating independently of the moulding or shaping step
- B29B15/12—Coating or impregnating independently of the moulding or shaping step of reinforcements of indefinite length
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B15/00—Pretreatment of the material to be shaped, not covered by groups B29B7/00 - B29B13/00
- B29B15/08—Pretreatment of the material to be shaped, not covered by groups B29B7/00 - B29B13/00 of reinforcements or fillers
- B29B15/10—Coating or impregnating independently of the moulding or shaping step
- B29B15/12—Coating or impregnating independently of the moulding or shaping step of reinforcements of indefinite length
- B29B15/122—Coating or impregnating independently of the moulding or shaping step of reinforcements of indefinite length with a matrix in liquid form, e.g. as melt, solution or latex
- B29B15/125—Coating or impregnating independently of the moulding or shaping step of reinforcements of indefinite length with a matrix in liquid form, e.g. as melt, solution or latex by dipping
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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- B29B15/00—Pretreatment of the material to be shaped, not covered by groups B29B7/00 - B29B13/00
- B29B15/08—Pretreatment of the material to be shaped, not covered by groups B29B7/00 - B29B13/00 of reinforcements or fillers
- B29B15/10—Coating or impregnating independently of the moulding or shaping step
- B29B15/12—Coating or impregnating independently of the moulding or shaping step of reinforcements of indefinite length
- B29B15/14—Coating or impregnating independently of the moulding or shaping step of reinforcements of indefinite length of filaments or wires
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- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
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- C08J2381/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen, or carbon only; Polysulfones; Derivatives of such polymers
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Description
(a)繊維強化熱可塑性樹脂フィラメント中の強化繊維の体積割合が30~80%であり、熱可塑性樹脂の体積割合が70~20%である。
(b)厚みが0.01~3mmである。
(c)フィラメント長が1m以上である。
[2]ボイド率が5%以下である[1]に記載の繊維強化熱可塑性樹脂フィラメント。
[3]曲げ剛性が1N・m2以下である[1]または[2]に記載の繊維強化熱可塑性樹脂フィラメント。
[4]前記強化繊維が炭素繊維、ガラス繊維、アラミド繊維から選ばれる少なくとも1種である[1]~[3]のいずれかに記載の繊維強化熱可塑性樹脂フィラメント。
[5]前記熱可塑性樹脂がポリフェニレンスルフィド樹脂(PPS)、ポリアリーレンエーテルケトン樹脂(PAEK)、ポリエーテルイミド樹脂(PEI)、ポリエーテルスルホン樹脂(PES)、液晶ポリマー樹脂(LCP)から選ばれる少なくとも1種である[1]~[4]のいずれかに記載の繊維強化熱可塑性樹脂フィラメント。
[6]下記手順(i)~(iv)の方法によって算出される強化繊維の分散パラメータdの平均値Dが90%以上である[1]~[5]に記載の繊維強化熱可塑性樹脂フィラメント。
(i)前記繊維強化熱可塑性樹脂フィラメントの配向方向に垂直な横断面の写真を撮影する。
(ii)前記横断面の写真を下記式(1)で規定される一辺の長さtを有する正方形ユニットに分割する。
(iii)下記式(2)で定義される分散パラメータdを算出する。
(iv)上記手順(i)~(iii)を複数回繰り返し、分散パラメータdの平均値Dを算出する。
式(1) 1.5a≦t≦2.5a
a: 繊維平均直径
t: ユニットの一辺の長さ
式(2) 分散パラメータd=100×区画内に強化繊維が含まれるユニットの個数/ユニット全体の個数
[7]前記分散パラメータdの平均値Dの変動係数が4%以下である[1]~[6]に記載の繊維強化熱可塑性樹脂フィラメント。
[8]断面形状が円形、四角形、楕円形、長円形、星形のいずれかの形状である[1]~[7]のいずれかに記載の繊維強化熱可塑性樹脂フィラメント。
[9]最外層に熱可塑性樹脂層が被覆されてなる[1]~[8]のいずれかに記載の繊維強化熱可塑性樹脂フィラメント。
[10][1]~[9]のいずれかに記載の繊維強化熱可塑性樹脂フィラメントからなる成形品。
ρf:強化繊維の密度(g/cm3)
ρr:熱可塑性樹脂の密度(g/cm3)
(i)繊維強化熱可塑性樹脂フィラメントの配向方向とほぼ垂直な横断面を撮影する。
(ii)該横断面写真を式(1)で規定された一辺の長さを有する正方形ユニットに分割する。
(iii)式(2)で定義する分散パラメータdを算出する。
(iv)(i)~(iii)の手順を繰り返し、分散パラメータdの平均値Dを算出する。
a:繊維平均直径
t:ユニットの1辺の長さ
試料である繊維強化熱可塑性樹脂フィラメントを、ビューラー社製エポキシ樹脂「エポクイック(登録商標)」に埋め込み、室温で24時間硬化させた後、繊維強化熱可塑性樹脂フィラメントにおける強化繊維の配向方向にほぼ垂直な横断面を研磨し、次いで研磨面を超深度カラー3D形状測定顕微鏡VHX-950F(コントローラー部)/VH-Z100R(測定部)((株)キーエンス製)で、位置を変えながら撮影する。
各実施例および比較例により得られた繊維強化熱可塑性樹脂フィラメントの体積含有率Vfは、繊維強化熱可塑性樹脂フィラメントの質量W0を測定したのち、該繊維強化熱可塑性樹脂フィラメントを空気中500℃で30分間加熱して熱可塑性樹脂成分を焼き飛ばし、残った強化繊維の質量W1を測定し、式(3)により算出した。
ρf:強化繊維の密度(g/cm3)
ρr:熱可塑性樹脂の密度(g/cm3)
各実施例および比較例により得られた繊維強化熱可塑性樹脂フィラメントの厚み方向断面を以下のように観察した。繊維強化熱可塑性樹脂フィラメントをエポキシ樹脂で包埋したサンプルを用意し、繊維強化熱可塑性樹脂フィラメントの厚み方向断面が良好に観察できるようになるまで、前記サンプルを研磨した。研磨したサンプルを、超深度カラー3D形状測定顕微鏡VHX-950F(コントローラー部)/VH-Z100R(測定部)((株)キーエンス製)を使用して、拡大倍率400倍で撮影した。撮影範囲は、繊維強化熱可塑性樹脂フィラメントの厚み×幅500μmの範囲とした。撮影画像において、繊維強化熱可塑性樹脂フィラメントの面積および空隙(ボイド)となっている部位の面積を求め、式(4)により含浸率を算出した。
(i)繊維強化熱可塑性樹脂フィラメントの配向方向とほぼ垂直な横断面を撮影する。
(ii)該横断面写真を式(1-1)で規定された一辺の長さを有する正方形ユニットに分割する。
(iii)式(2)で定義する分散パラメータdを算出する。
(iv)(i)~(iii)の手順を繰り返し、分散パラメータdの平均値Dを算出する。
a:繊維平均直径
t:ユニットの1辺の長さ
試料である繊維強化熱可塑性樹脂フィラメントを、エポキシ樹脂に埋め込み、室温で24時間硬化させた後、繊維強化熱可塑性樹脂フィラメントにおける強化繊維の配向方向にほぼ垂直な横断面を研磨し、次いで該研磨面を超深度カラー3D形状測定顕微鏡VHX-950F(コントローラー部)/VH-Z100R(測定部)((株)キーエンス製)で撮影した。
各実施例および比較例により得られた繊維強化熱可塑性樹脂フィラメントの曲げ剛性は下記式(6)により算出した。
E:繊維強化熱可塑性樹脂フィラメントの曲げ弾性率
I:断面二次モーメント
各実施例および比較例により得られた繊維強化熱可塑性樹脂フィラメントの取り扱い性は繊維強化熱可塑性樹脂フィラメントを内径150mmのロールに巻き付け、巻き付けた繊維強化熱可塑性樹脂フィラメントの折れやたわみを判断基準とし、以下の2段階で評価し、〇を合格とした。
〇(良):折れ、たわみなし
×(不良):折れ、たわみあり
実施例および比較例において、原料は以下に示すものを用いた。
・東レ(株)製 PAN系炭素繊維(CF)“トレカ(登録商標)”
・東レ(株)製 ポリフェニレンスルフィド樹脂(PPS)“トレリナ(登録商標)”
・ビクトレックス・ジャパン(株)製 ポリエーテルエーテルケトン樹脂(PEEK)“VICTREX(登録商標)”
・アルケマ(株)製 ポリエーテルケトンケトン(PEKK)“KEPSTAN(登録商標)”
・サビック(株)製 ポリエーテルイミド(PEI)“ULTEM(登録商標)”
Claims (5)
- 連続した強化繊維にポリフェニレンスルフィド樹脂(PPS)からなる熱可塑性樹脂が含浸されてなる断面形状が円形の繊維強化熱可塑性樹脂フィラメントであって、下記条件(a)~(e)のすべてを満たすことを特徴とする繊維強化熱可塑性樹脂フィラメント。
(a)強化繊維の体積割合が30~80%であり、熱可塑性樹脂の体積割合が70~20%である。
(b)厚みが0.01~3mmである。
(c)フィラメント長が1m以上である。
(d)曲げ剛性が1N・m2以下である。
(e)下記手順(i)~(iv)の方法によって算出される強化繊維の分散パラメータdの平均値Dが90%以上であり、前記平均値Dの変動係数が4%以下である。
(i)前記繊維強化熱可塑性樹脂フィラメントの配向方向に垂直な横断面の写真を撮影する。
(ii)前記横断面の写真を下記式(1-1)で規定される一辺の長さtを有する正方形ユニットに分割する。
(iii)下記式(2)で定義される分散パラメータdを算出する。
(iv)上記手順(i)~(iii)を複数回繰り返し、分散パラメータdの平均値Dを算出する。
式(1-1) t=1.5a
a: 繊維平均直径
t: ユニットの一辺の長さ
式(2) 分散パラメータd=100×区画内に強化繊維が含まれるユニットの個数/ユニット全体の個数 - ボイド率が5%以下である請求項1に記載の繊維強化熱可塑性樹脂フィラメント。
- 前記強化繊維が炭素繊維、ガラス繊維、アラミド繊維から選ばれる少なくとも1種である請求項1または2に記載の繊維強化熱可塑性樹脂フィラメント。
- 最外層に熱可塑性樹脂層が被覆されてなる請求項1~3のいずれかに記載の繊維強化熱可塑性樹脂フィラメント。
- 請求項1~4のいずれかに記載の繊維強化熱可塑性樹脂フィラメントからなる成形品。
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US10967585B2 (en) | 2017-03-16 | 2021-04-06 | Guerrilla Industries LLC | Composite structures and methods of forming composite structures |
CA3108462A1 (en) * | 2018-08-22 | 2020-02-27 | Toray Industries, Inc. | Fiber-reinforced thermoplastic resin substrate and laminate using same |
WO2020241615A1 (ja) * | 2019-05-30 | 2020-12-03 | リンテック株式会社 | 3dプリンタ用造形材料及び造形物 |
CN112662070A (zh) * | 2020-12-31 | 2021-04-16 | 广州金发碳纤维新材料发展有限公司 | 一种连续金属丝增强热塑性复合材料带材 |
WO2022192355A1 (en) | 2021-03-09 | 2022-09-15 | Guerrilla Industries LLC | Composite structures and methods of forming composite structures |
EP4286455A1 (de) | 2022-06-03 | 2023-12-06 | Evonik Operations GmbH | Endlosfaserverstärktes filament aus thermoplastischem kunststoff zum einsatz in additiven fertigungsprozessen und verfahren dazu |
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