JP2015143339A5

JP2015143339A5 -

Info

Publication number: JP2015143339A5
Application number: JP2014247561A
Authority: JP
Filing date: 2014-12-08
Publication date: 2017-12-21
Anticipated expiration: 2034-12-08

Description

上記の課題を解決するため、本発明の繊維強化熱可塑性樹脂成形材料は、主として以下の構成からなる。
（１）炭素繊維（Ａ）、引張破断伸度が１０〜５０％である有機繊維（Ｂ）、熱可塑性樹脂（Ｃ）および難燃剤（Ｄ）の合計１００重量部に対して、炭素繊維（Ａ）を５〜４５重量部、引張破断伸度が１０〜５０％である有機繊維（Ｂ）を１〜４５重量部、熱可塑性樹脂（Ｃ）を２０〜９３重量部、難燃剤（Ｄ）を１〜２０重量部含み、
前記引張破断伸度が１０〜５０％である有機繊維（Ｂ）のＬＯＩ値（限界酸素指数）が２６％以上である、繊維強化熱可塑性樹脂成形材料。
（２）前記引張破断伸度が１０〜５０％である有機繊維（Ｂ）がポリアリーレンスルフィド繊維、ポリアクリロニトリル系耐炎化糸、フッ素樹脂繊維および液晶ポリマー繊維からなる群より選択される少なくとも１種である（１）に記載の繊維強化熱可塑性樹脂成形材料。
（３）さらに、２００℃における溶融粘度が熱可塑性樹脂（Ｃ）より低い化合物（Ｅ）を、炭素繊維（Ａ）、引張破断伸度が１０〜５０％である有機繊維（Ｂ）、熱可塑性樹脂（Ｃ）および難燃剤（Ｄ）の合計１００重量部に対して１〜２０重量部含む（１）または（２）に記載の繊維強化熱可塑性樹脂成形材料。
（４）炭素繊維（Ａ）と引張破断伸度が１０〜５０％である有機繊維（Ｂ）を含む繊維束（Ｆ）の外側に熱可塑性樹脂（Ｃ）を含み、繊維束（Ｆ）内および／またはその外側に難燃剤（Ｄ）を含み、繊維束（Ｆ）断面において炭素繊維（Ａ）と引張破断伸度が１０〜５０％である有機繊維（Ｂ）が偏在し、繊維束（Ｆ）の長さと繊維強化熱可塑性樹脂成形材料の長さが実質的に同じである（１）または（２）に記載の繊維強化熱可塑性樹脂成形材料。
（５）炭素繊維（Ａ）と引張破断伸度が１０〜５０％である有機繊維（Ｂ）を含む繊維束（Ｆ）に、２００℃における溶融粘度が熱可塑性樹脂（Ｃ）より低い化合物（Ｅ）を含浸させてなる複合体（Ｇ）の外側に熱可塑性樹脂（Ｃ）および難燃剤（Ｄ）を含み、繊維束（Ｆ）断面において炭素繊維（Ａ）と引張破断伸度が１０〜５０％である有機繊維（Ｂ）が偏在し、繊維束（Ｆ）の長さと繊維強化熱可塑性樹脂成形材料の長さが実質的に同じである（３）に記載の繊維強化熱可塑性樹脂成形材料。
（６）前記炭素繊維（Ａ）の表面酸素濃度比［Ｏ／Ｃ］が０．０５〜０．５であり、かつ炭素繊維（Ａ）エポキシ樹脂で被覆されている（１）〜（５）のいずれかに記載の繊維強化熱可塑性樹脂成形材料。
（７）（１）〜（６）のいずれかに記載の繊維強化熱可塑性樹脂成形材料を成形して得られる繊維強化熱可塑性樹脂成形品であって、繊維強化熱可塑性樹脂成形品中における前記炭素繊維（Ａ）の平均繊維長（Ｌ_Ａ）が０．３〜１．５ｍｍであり、かつ、炭素繊維（Ａ）の始点から終点までの平均繊維端部間距離（Ｄ_Ａ）と平均繊維長（Ｌ_Ａ）が下記式［１］を満たし、繊維強化熱可塑性樹脂成形品中における前記引張破断伸度が１０〜５０％である有機繊維（Ｂ）の平均繊維長（Ｌ_Ｂ）が１．５〜４ｍｍであり、かつ、引張破断伸度が１０〜５０％である有機繊維（Ｂ）の始点から終点までの平均繊維端部間距離（Ｄ_Ｂ）と平均繊維長（Ｌ_Ｂ）が下記式［２］を満たす繊維強化熱可塑性樹脂成形品。
０．９×Ｌ_Ａ≦Ｄ_Ａ≦Ｌ_Ａ［１］
０．１×Ｌ_Ｂ≦Ｄ_Ｂ≦０．９×Ｌ_Ｂ［２］ In order to solve the above problems, the fiber-reinforced thermoplastic resin molding material of the present invention mainly comprises the following constitution.
(1) Carbon fiber (A), carbon fiber (B), organic fiber (B) having a tensile elongation at break of 10 to 50%, thermoplastic resin (C) and flame retardant (D) 5) to 45 parts by weight of A), 1 to 45 parts by weight of organic fiber (B) having a tensile elongation at break of 10 to 50%, 20 to 93 parts by weight of thermoplastic resin (C), flame retardant (D) 1 to 20 parts by weight of only including,
A fiber reinforced thermoplastic resin molding material, wherein the organic fiber (B) having a tensile elongation at break of 10 to 50% has a LOI value (limit oxygen index) of 26% or more.
( 2 ) The organic fiber (B) having a tensile elongation at break of 10 to 50% is at least one selected from the group consisting of polyarylene sulfide fibers, polyacrylonitrile-based flameproof yarns, fluororesin fibers and liquid crystal polymer fibers. The fiber-reinforced thermoplastic resin molding material according to (1) .
( 3 ) Further, a compound (E) having a melt viscosity at 200 ° C. lower than that of the thermoplastic resin (C) is obtained from carbon fiber (A), organic fiber (B) having a tensile elongation at break of 10 to 50%, and thermoplastic. The fiber-reinforced thermoplastic resin molding material according to (1) or (2) , comprising 1 to 20 parts by weight with respect to 100 parts by weight as a total of the resin (C) and the flame retardant (D).
( 4 ) The thermoplastic resin (C) is included outside the fiber bundle (F) containing the carbon fiber (A) and the organic fiber (B) having a tensile elongation at break of 10 to 50%, and the fiber bundle (F) And / or carbon fiber (A) containing the flame retardant (D) on the outside thereof, and the carbon fiber (A) and the organic fiber (B) having a tensile elongation at break of 10 to 50% in the cross section of the fiber bundle (F). The fiber-reinforced thermoplastic resin molding material according to (1) or (2) , wherein the length of F) and the length of the fiber-reinforced thermoplastic resin molding material are substantially the same.
( 5 ) A compound (C) having a melt viscosity at 200 ° C. lower than that of the thermoplastic resin (C) in the fiber bundle (F) containing the carbon fiber (A) and the organic fiber (B) having a tensile elongation at break of 10 to 50%. E) containing a thermoplastic resin (C) and a flame retardant (D) outside the composite (G) impregnated with carbon fiber (A) and a tensile elongation at break of 10 to 10 in the cross section of the fiber bundle (F) 50% organic fiber (B) is unevenly distributed, and the length of the fiber bundle (F) and the length of the fiber-reinforced thermoplastic resin molding material are substantially the same ( 3 ). material.
( 6 ) The surface oxygen concentration ratio [O / C] of the carbon fiber (A) is 0.05 to 0.5, and the carbon fiber (A) is coated with an epoxy resin (1) to ( 5 ) The fiber-reinforced thermoplastic resin molding material according to any one of the above.
( 7 ) A fiber reinforced thermoplastic resin molded article obtained by molding the fiber reinforced thermoplastic resin molding material according to any one of (1) to ( 6 ), wherein the fiber reinforced thermoplastic resin molded article is The average fiber length (L _A ) of the carbon fiber (A) is 0.3 to 1.5 mm, and the average fiber end-to-end distance (D _A ) from the start point to the end point of the carbon fiber ( _A ) and the average fiber the length _{(L a)} satisfies the following formula [1], the average fiber length of the organic fiber the tensile elongation at break in the fiber-reinforced thermoplastic resin molded article in is _{10~50% (B) (L B} ) is 1 The average fiber end-to-end distance (D _B ) and the average fiber length (L _B ) from the start point to the end point of the organic fiber (B) that is 5 to 4 mm and the tensile elongation at break is 10 to 50% A fiber-reinforced thermoplastic resin molded product satisfying the following formula [2].
_{_{0.9 × L A ≦ D A ≦}} L A [1]
0.1 × L _B ≦ D _B ≦ 0.9 × L _B [2]

（参考例１）
有機繊維（Ｂ）を（Ｂ−４）に変更した以外は、実施例１と同様にして成形品を作製し、評価を行った。評価結果はまとめて表１に示した。 ( Reference Example 1 )
Except for changing the organic fiber (B) to (B-4), a molded product was produced and evaluated in the same manner as in Example 1. The evaluation results are collectively shown in Table 1.

実施例１〜２、４〜７いずれの材料も、有機繊維（Ｂ）と難燃剤（Ｄ）が成形品内に存在しており、高い衝撃強度と高い難燃性を示した。 In any of Examples 1 to 2, 4 to 7, the organic fiber (B) and the flame retardant (D) were present in the molded product, and exhibited high impact strength and high flame retardancy.

Claims

炭素繊維（Ａ）、引張破断伸度が１０〜５０％である有機繊維（Ｂ）、熱可塑性樹脂（Ｃ）および難燃剤（Ｄ）の合計１００重量部に対して、炭素繊維（Ａ）を５〜４５重量部、引張破断伸度が１０〜５０％である有機繊維（Ｂ）を１〜４５重量部、熱可塑性樹脂（Ｃ）を２０〜９３重量部、難燃剤（Ｄ）を１〜２０重量部含み、
前記引張破断伸度が１０〜５０％である有機繊維（Ｂ）のＬＯＩ値（限界酸素指数）が２６％以上である、繊維強化熱可塑性樹脂成形材料。 Carbon fiber (A) is added to 100 parts by weight of carbon fiber (A), organic fiber (B) having a tensile elongation at break of 10 to 50%, thermoplastic resin (C) and flame retardant (D). 5 to 45 parts by weight, 1 to 45 parts by weight of organic fiber (B) having a tensile elongation at break of 10 to 50%, 20 to 93 parts by weight of thermoplastic resin (C), and 1 to 1 of flame retardant (D) 20 parts by weight of only including,
A fiber reinforced thermoplastic resin molding material, wherein the organic fiber (B) having a tensile elongation at break of 10 to 50% has a LOI value (limit oxygen index) of 26% or more .

前記引張破断伸度が１０〜５０％である有機繊維（Ｂ）がポリアリーレンスルフィド繊維、ポリアクリロニトリル系耐炎化糸、フッ素樹脂繊維および液晶ポリマー繊維からなる群より選択される少なくとも１種である請求項１に記載の繊維強化熱可塑性樹脂成形材料。 The organic fiber (B) having a tensile elongation at break of 10 to 50% is at least one selected from the group consisting of polyarylene sulfide fibers, polyacrylonitrile-based flameproofing yarns, fluororesin fibers and liquid crystal polymer fibers. Item 2. A fiber-reinforced thermoplastic resin molding material according to Item 1 .

さらに、２００℃における溶融粘度が熱可塑性樹脂（Ｃ）より低い化合物（Ｅ）を、炭素繊維（Ａ）、引張破断伸度が１０〜５０％である有機繊維（Ｂ）、熱可塑性樹脂（Ｃ）および難燃剤（Ｄ）の合計１００重量部に対して１〜２０重量部含む請求項１または２に記載の繊維強化熱可塑性樹脂成形材料。 Further, a compound (E) having a melt viscosity at 200 ° C. lower than that of the thermoplastic resin (C) is obtained from carbon fibers (A), organic fibers (B) having a tensile elongation at break of 10 to 50%, and thermoplastic resins (C ) And the flame retardant (D), the fiber-reinforced thermoplastic resin molding material according to claim 1 or 2 , comprising 1 to 20 parts by weight relative to 100 parts by weight in total.

炭素繊維（Ａ）と引張破断伸度が１０〜５０％である有機繊維（Ｂ）を含む繊維束（Ｆ）の外側に熱可塑性樹脂（Ｃ）を含み、繊維束（Ｆ）内および／またはその外側に難燃剤（Ｄ）を含み、繊維束（Ｆ）断面において炭素繊維（Ａ）と引張破断伸度が１０〜５０％である有機繊維（Ｂ）が偏在し、繊維束（Ｆ）の長さと繊維強化熱可塑性樹脂成形材料の長さが実質的に同じである請求項１または２に記載の繊維強化熱可塑性樹脂成形材料。 The thermoplastic resin (C) is included outside the fiber bundle (F) including the carbon fiber (A) and the organic fiber (B) having a tensile elongation at break of 10 to 50%, and the fiber bundle (F) and / or The outer side of the fiber bundle (F) contains a flame retardant (D), and the carbon fiber (A) and the organic fiber (B) having a tensile elongation at break of 10 to 50% are unevenly distributed in the cross section of the fiber bundle (F). The fiber-reinforced thermoplastic resin molding material according to claim 1 or 2 , wherein the length and the length of the fiber-reinforced thermoplastic resin molding material are substantially the same.

炭素繊維（Ａ）と引張破断伸度が１０〜５０％である有機繊維（Ｂ）を含む繊維束（Ｆ）に、２００℃における溶融粘度が熱可塑性樹脂（Ｃ）より低い化合物（Ｅ）を含浸させてなる複合体（Ｇ）の外側に熱可塑性樹脂（Ｃ）を含み、複合体（Ｇ）内および／またはその外側に難燃剤（Ｄ）を含み、繊維束（Ｆ）断面において炭素繊維（Ａ）と引張破断伸度が１０〜５０％である有機繊維（Ｂ）が偏在し、繊維束（Ｆ）の長さと繊維強化熱可塑性樹脂成形材料の長さが実質的に同じである請求項３に記載の繊維強化熱可塑性樹脂成形材料。 A compound (E) having a melt viscosity at 200 ° C. lower than that of the thermoplastic resin (C) is added to the fiber bundle (F) containing the carbon fiber (A) and the organic fiber (B) having a tensile elongation at break of 10 to 50%. Carbon fiber in the fiber bundle (F) cross section including the thermoplastic resin (C) outside the composite (G) impregnated, the flame retardant (D) inside and / or outside the composite (G) (A) and the organic fiber (B) having a tensile elongation at break of 10 to 50% are unevenly distributed, and the length of the fiber bundle (F) and the length of the fiber-reinforced thermoplastic resin molding material are substantially the same. Item 4. The fiber-reinforced thermoplastic resin molding material according to Item 3 .

前記炭素繊維（Ａ）の表面酸素濃度比［Ｏ／Ｃ］が０．０５〜０．５であり、かつ炭素繊維（Ａ）がエポキシ樹脂で被覆されている請求項１〜５のいずれかに記載の繊維強化熱可塑性樹脂成形材料。 The surface oxygen concentration ratio of carbon fibers (A) [O / C] is from 0.05 to 0.5, and to any one of claims 1 to 5 carbon fibers (A) is coated with epoxy resin The fiber-reinforced thermoplastic resin molding material as described.

請求項１〜６のいずれかに記載の繊維強化熱可塑性樹脂成形材料を成形して得られる繊維強化熱可塑性樹脂成形品であって、繊維強化熱可塑性樹脂成形品中における前記炭素繊維（Ａ）の平均繊維長（Ｌ_Ａ）が０．３〜１．５ｍｍであり、かつ、炭素繊維（Ａ）の始点から終点までの平均繊維端部間距離（Ｄ_Ａ）と平均繊維長（Ｌ_Ａ）が下記式［１］を満たし、繊維強化熱可塑性樹脂成形品中における前記引張破断伸度が１０〜５０％である有機繊維（Ｂ）の平均繊維長（Ｌ_Ｂ）が１．５〜４ｍｍであり、かつ、有機繊維（Ｂ）の始点から終点までの平均繊維端部間距離（Ｄ_Ｂ）と平均繊維長（Ｌ_Ｂ）が下記式［２］を満たす繊維強化熱可塑性樹脂成形品。
０．９×Ｌ_Ａ≦Ｄ_Ａ≦Ｌ_Ａ［１］
０．１×Ｌ_Ｂ≦Ｄ_Ｂ≦０．９×Ｌ_Ｂ［２］ A fiber reinforced thermoplastic resin molded product obtained by molding the fiber reinforced thermoplastic resin molding material according to any one of claims 1 to 6 , wherein the carbon fiber (A) in the fiber reinforced thermoplastic resin molded product. the average fiber length of _{(L a)} is 0.3 to 1.5 mm, and an average fiber end distance _{(D a)} and the average fiber length from the start point to the end point of the carbon fiber _{(a) (L} a) Satisfies the following formula [1], and the average fiber length (L _B ) of the organic fiber (B) having a tensile elongation at break of 10 to 50% in the fiber-reinforced thermoplastic resin molded product is 1.5 to 4 mm: A fiber reinforced thermoplastic resin molded article having an average fiber end-to-end distance (D _B ) and an average fiber length (L _B ) from the start point to the end point of the organic fiber (B) and satisfying the following formula [2].
_{_{0.9 × L A ≦ D A ≦}} L A [1]
0.1 × L _B ≦ D _B ≦ 0.9 × L _B [2]