JP2017052903A5

JP2017052903A5 -

Info

Publication number: JP2017052903A5
Application number: JP2015179254A
Authority: JP
Filing date: 2015-09-11
Publication date: 2017-06-29
Anticipated expiration: 2035-09-11

Description

そこで、本発明の実施形態は、ＰＡＳ樹脂、ＰＡＳ樹脂１００質量部に対して６５〜３００質量部という高い濃度の充填剤、及びカーボンブラックを含む樹脂組成物であって、黒色色調を有し、かつ、曲げ破断ひずみ特性などの性能の低下が抑制された樹脂組成物を提供すること、及び、樹脂組成物の曲げ破断ひずみの低下を抑制する方法を提供することを課題とする。 Therefore, an embodiment of the present invention is a resin composition containing a PAS resin, a high concentration filler of 65 to 300 parts by mass with respect to 100 parts by mass of the PAS resin, and carbon black, and has a black color tone. And it makes it a subject to provide the resin composition in which the fall of performance, such as a bending fracture distortion characteristic, was suppressed, and the method of suppressing the fall of the bending fracture distortion of a resin composition.

本発明の実施形態によれば、ＰＡＳ樹脂、ＰＡＳ樹脂１００質量部に対して６５〜３００質量部という高い濃度の充填剤、及びカーボンブラックを含む樹脂組成物において、特定のカーボンブラックを選択したことにより、曲げ破断ひずみ特性などの性能の低下が抑制され、かつ、黒色色調を与えることができる。
また、本発明の別の実施形態によれば、樹脂組成物の曲げ破断ひずみの低下を抑制することができる。 According to an embodiment of the present invention, the PAS resin, filler concentrations as high as 65 to 300 parts by weight with respect to the PAS resin 100 parts by weight, and the resin composition containing carbon black, it selects a particular carbon black As a result, a decrease in performance such as bending fracture strain characteristics can be suppressed, and a black color tone can be provided.
Moreover, according to another embodiment of this invention, the fall of the bending fracture | rupture distortion | strain of a resin composition can be suppressed.

コポリマーとしては、上述したアリーレン基を含むアリーレンサルファイド基の中で、アリーレン基が相異なる２種以上のアリーレンサルファイド基の組み合わせを使用することができる。これらの中では、ｐ−フェニレンサルファイド基とｍ−フェニレンサルファイド基を含む組み合わせが、耐熱性、成形性、機械的物性等の物性上の点から好ましい。また、ｐ−フェニレンサルファイド基を７０ｍｏｌ％以上の割合で含むポリマーがより好ましく、８０ｍｏｌ％以上の割合で含むポリマーがさらに好ましい。なお、フェニレンサルファイド基を有するＰＡＳ樹脂は、ＰＰＳ樹脂である。 As the copolymer, among the above-mentioned arylene sulfide groups containing an arylene group, a combination of two or more arylene sulfide groups having different arylene groups can be used. Among these, a combination containing a p-phenylene sulfide group and an m-phenylene sulfide group is preferable from the viewpoint of physical properties such as heat resistance, moldability, and mechanical properties . Further, a polymer containing a p-phenylene sulfide group in a proportion of 70 mol% or more is more preferable, and a polymer containing a proportion of 80 mol% or more is more preferable. The PAS resin having a phenylene sulfide group is a PPS resin.

［実施例１〜９、比較例１〜５、参考例１〜４］
≪材料≫
［（Ａ）ＰＡＳ樹脂］
ＰＡＳ樹脂：ＰＰＳ樹脂（重量平均分子量Ｍｗ：２００００）、（株）クレハ製「フォートロンＫＰＳ」 [Examples 1 to 9, Comparative Examples 1 to 5, Reference Examples 1 to 4]
≪Material≫
[(A) PAS resin]
PAS resin: PPS resin ( weight average molecular weight Mw: 20000), “Fortron KPS” manufactured by Kureha Corporation

（ＰＡＳ樹脂の合成方法）
上述のＰＡＳ樹脂の合成方法を以下に示す。すなわち、先ず、２０ＬのオートクレーブにＮＭＰ（Ｎ−メチル−２−ピロリドン）５７００ｇを仕込み、オートクレーブ内の空気を窒素ガスで置換後、約１時間かけて撹拌機の回転数２５０ｒｐｍで撹拌しながら、１００℃まで昇温した。１００℃に到達後、濃度７４．７質量％のＮａＯＨ水溶液１１７０ｇ、硫黄源水溶液１９９０ｇ（ＮａＳＨ＝２１．８モル及びＮａ_２Ｓ＝０．５０モルを含む）、及びＮＭＰ１０００ｇを加え、約２時間かけて徐々に２００℃まで昇温し、水９４５ｇ、ＮＭＰ１５９０ｇ、及び０．３１モルの硫化水素を系外に排出した。 (Synthesis method of PAS resin)
A method for synthesizing the above PAS resin is shown below. That is, first, 5700 g of NMP (N-methyl-2-pyrrolidone) was charged into a 20 L autoclave, the air in the autoclave was replaced with nitrogen gas, and then stirred for about 1 hour at a rotational speed of 250 rpm while stirring. The temperature was raised to ° C. After reaching 100 ° C., 1170 g of NaOH aqueous solution having a concentration of 74.7% by mass, 1990 g of sulfur source aqueous solution (including NaSH = 21.8 mol and Na ₂ S = 0.50 mol), and NMP 1000 g were added, and it took about 2 hours. The temperature was gradually raised to 200 ° C., and 945 g of water, 1590 g of NMP, and 0.31 mol of hydrogen sulfide were discharged out of the system.

［（Ｃ）カーボンブラック］
（Ｃ−１）ウィルバー・エリス（株）製「Ｒａｖｅｎ２５００Ｕｌｔｒａ」、算術平均粒子径：１３ｎｍ、比表面積（ＮＳＡ）：２７０ｍ^２/ｇ、ＤＢＰ吸収量：６５ｃｍ^３/１００ｇ
（Ｃ−２）ウィルバー・エリス（株）製「Ｒａｖｅｎ３５００」、算術平均粒子径：１３ｎｍ、比表面積（ＮＳＡ）：３７５ｍ^２/ｇ、ＤＢＰ吸収量：１０５ｃｍ^３/１００ｇ、揮発分：５質量％
（Ｃ−３）三菱化学（株）製「＃２６００」、算術平均粒子径：１３ｎｍ、比表面積（ＮＳＡ）：３７０ｍ^２/ｇ、ＤＢＰ吸収量：７７ｃｍ^３/１００ｇ、揮発分：１．８質量％
（Ｃ−４）三菱化学（株）製「＃２３００Ｂ」、算術平均粒子径：１５ｎｍ、比表面積（ＮＳＡ）：３２０ｍ^２/ｇ、ＤＢＰ吸収量：４８ｃｍ^３/１００ｇ、揮発分：２質量％
（Ｃ−５）ウィルバー・エリス（株）製「Ｒａｖｅｎ２３５０Ｕｌｔｒａ」、算術平均粒子径：１５ｎｍ、比表面積（ＮＳＡ）：１９５ｍ^２/ｇ、ＤＢＰ吸収量：６０ｃｍ^３/１００ｇ
（Ｃ−６）三菱化学（株）製「＃９８０」、算術平均粒子径：１６ｎｍ、比表面積（ＮＳＡ）：２６０ｍ^２/ｇ、ＤＢＰ吸収量：６６ｃｍ^３/１００ｇ、揮発分：１．５質量％
（Ｃ−７）三菱化学（株）製「＃９６０Ｂ」、算術平均粒子径：１６ｎｍ、比表面積（ＮＳＡ）：２６０ｍ^２/ｇ、ＤＢＰ吸収量：６４ｃｍ^３/１００ｇ、揮発分：１．５質量％
（Ｃ−８）三菱化学（株）製「＃７５０Ｂ」、算術平均粒子径：２２ｎｍ、比表面積（ＮＳＡ）：１２４ｍ^２/ｇ、ＤＢＰ吸収量：１１６ｃｍ^３/１００ｇ、揮発分：１質量％
（Ｃ−９）ウィルバー・エリス（株）製「Ｒａｖｅｎ５０００Ｕｌｔｒａ」、算術平均粒子径：８ｎｍ、比表面積（ＮＳＡ）：５８３ｍ^２/ｇ、ＤＢＰ吸収量：９５ｃｍ^３/１００ｇ、揮発分：１０．５質量％
なお、上記のカーボンブラックの算術平均粒子径、比表面積（ＮＳＡ）、ＤＢＰ吸収量、及び揮発分は、カーボンブラックの項で述べた方法で測定された値である。 [(C) Carbon black]
(C-1) Wilbur Ellis Co. "Raven 2500 Ultra", the arithmetic mean particle diameter: 13 nm, specific surface area ^{(NSA): 270m 2 / g} , DBP absorption amount: 65cm ³ / 100g
(C-2) Wilbur Ellis Co. "Raven 3500", the arithmetic mean particle diameter: 13 nm, specific surface area ^{(NSA): 375m 2 / g} , DBP absorption amount: 105 cm ^3/100 g, volatile content: 5 wt%
(C-3) Mitsubishi Chemical Corp. "# 2600", the arithmetic mean particle diameter: 13 nm, specific surface area ^{(NSA): 370m 2 / g} , DBP absorption amount: 77cm ^3/100 g, volatile content: 1.8 mass %
(C-4) manufactured by Mitsubishi Chemical Co., Ltd. "# 2300B", the arithmetic mean particle diameter: 15 nm, specific surface area (NSA): 320 m ² / g, DBP absorption amount: 48cm ^3/100 g, volatile content: 2 wt%
(C-5) Wilbur Ellis Co. "Raven 2350 Ultra", the arithmetic mean particle diameter: 15 nm, specific surface area ^{(NSA): 195m 2 / g} , DBP absorption amount: 60cm ³ / 100g
(C-6) manufactured by Mitsubishi Chemical Co., Ltd. "# 980", the arithmetic mean particle diameter: 16 nm, specific surface area ^{(NSA): 260m 2 / g} , DBP absorption amount: 66cm ^3/100 g, volatile content: 1.5 mass %
(C-7) manufactured by Mitsubishi Chemical Co., Ltd. "# 960B", the arithmetic mean particle diameter: 16 nm, specific surface area ^{(NSA): 260m 2 / g} , DBP absorption amount: 64cm ^3/100 g, volatile content: 1.5 mass %
(C-8) manufactured by Mitsubishi Chemical Co., Ltd. "# 750B", the arithmetic mean particle diameter: 22 nm, specific surface area ^{(NSA): 124m 2 / g} , DBP absorption amount: 116cm ^3/100 g, volatile content: 1 wt%
(C-9) Wilbur Ellis Co. "R aven 5000 Ultra", the arithmetic average particle diameter: 8 nm, specific surface area ^{(NSA): 583m 2 / g} , DBP absorption amount: 95cm ^3/100 g, volatile matter: 10 .5% by mass
The arithmetic average particle diameter, specific surface area (NSA), DBP absorption amount, and volatile content of the above carbon black are values measured by the method described in the section of carbon black.

（３）曲げ強さ（ＦＳ）及び曲げ弾性率（ＦＭ）
実施例及び比較例の樹脂組成物ペレットを１４０℃で３時間乾燥後、射出成形により、成形シリンダー温度３２０℃、金型温度１５０℃で、ＩＳＯ３１６７に準じた試験片（幅１０ｍｍ、厚み４ｍｍｔ）を作製した。この試験片を用い、ＩＳＯ１７８に準じて曲げ強さ（ＭＰａ）と曲げ弾性率（ＧＰａ）を測定した。 (3) Flexural strength (FS) and flexural modulus ( FM )
After 3 hours drying the resin composition pellets of Examples and Comparative Examples at 140 ° C., by injection molding, molding cylinder temperature 320 ° C., a mold temperature of 150 ℃, ISO316 7 in accordance specimens (width 10 mm, thickness 4Mmt) Was made. Using this test piece, bending strength (MPa) and bending elastic modulus (GPa) were measured according to ISO178.

（４）シャルピー衝撃強さ
実施例及び比較例の樹脂組成物ペレットを１４０℃で３時間乾燥後、射出成形により、成形シリンダー温度３２０℃、金型温度１５０℃で、ＩＳＯ３１６７に準じた試験片（幅１０ｍｍ、厚み４ｍｍｔ）を作製した。この試験片を用いて、ＩＳＯ１７９／１ｅＡに準じてシャルピー衝撃強さ（ノッチ付き）（ｋＪ／ｍ^２）を測定した。 (4) after 3 hours drying Charpy impact strength examples and comparative examples of the resin composition pellets at 140 ° C., by injection molding, molding cylinder temperature 320 ° C., a mold temperature of 0.99 ° C., the test piece according to ISO316 7 (Width 10 mm, thickness 4 mmt) was produced. Using this test piece, Charpy impact strength (notched) (kJ / m ² ) was measured according to ISO 179 / 1eA.

Claims

(A) polyarylene sulfide resin;
65 to 300 parts by weight of (B) filler with respect to 100 parts by weight of the (A) polyarylene sulfide resin;
The observed free 0.2 part by weight, the arithmetic mean particle diameter of 10 to 15 nm (C) carbon black, with respect to (A) polyarylene sulfide resin 100 parts by weight,
The filler (B) is made of glass fiber or calcium carbonate, or a combination thereof .
Resin composition.

The resin composition according to claim 1, wherein the (A) polyarylene sulfide resin contains a polyphenylene sulfide resin.

The resin composition according to claim 1 or 2, wherein the (C) carbon black has an arithmetic average particle size of 13 to 15 nm.

The resin composition according to any one of claims 1 to 3, wherein a content of the (C) carbon black is 0.2 to 6 parts by mass with respect to 100 parts by mass of the (A) polyarylene sulfide resin. object.

The content of the front Kiga Las fibers, wherein (B) is at least 50% by weight, based on the total amount of filler, the resin composition according to any one of claims 1 to 4.

Wherein (C) the volatile component of the carbon black is not more than 7 wt%, the resin composition according to any one of claims 1-5.

Furthermore, the resin composition of any one of Claims 1-6 containing 3-35 mass parts (D) elastomer with respect to 100 mass parts of said (A) polyarylene sulfide resin.

(A) and polyarylene sulfide resin contains said (A) a polyarylene sulfide relative to the resin 100 parts by weight from 65 to 300 parts by weight (B) a filler, and a (C) carbon black, wherein (B ) In a resin composition in which the filler is glass fiber or calcium carbonate, or a combination thereof, (C) carbon black having an arithmetic average particle size of 10 to 15 nm is used as the carbon black, and (A) polyarylene sulfide resin is used. The method of suppressing the fall of the bending fracture strain of the said resin composition by using 0.2 mass part or more with respect to 100 mass parts.

The method according to claim 8 , wherein the (A) polyarylene sulfide resin comprises a polyphenylene sulfide resin.

The method according to claim 8 or 9 , wherein the (C) carbon black has an arithmetic average particle size of 13 to 15 nm.

The method according to any one of claims 9 to 10 , wherein a content of the (C) carbon black is 0.2 to 6 parts by mass with respect to 100 parts by mass of the (A) polyarylene sulfide resin.

Before the content of outs Las fibers, it is said (B) at least 50 mass% against the total amount filler The method of claim 11.

The method according to any one of claims 8 to 12 , wherein a volatile component of the (C) carbon black is 7% by mass or less.

The method according to any one of claims 8 to 13 , wherein the resin composition further comprises 3 to 35 parts by mass of (D) an elastomer with respect to 100 parts by mass of the (A) polyarylene sulfide resin.