JP2015028155A5 - - Google Patents
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- JP2015028155A5 JP2015028155A5 JP2014128729A JP2014128729A JP2015028155A5 JP 2015028155 A5 JP2015028155 A5 JP 2015028155A5 JP 2014128729 A JP2014128729 A JP 2014128729A JP 2014128729 A JP2014128729 A JP 2014128729A JP 2015028155 A5 JP2015028155 A5 JP 2015028155A5
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- polyamide resin
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- 239000004952 Polyamide Substances 0.000 claims description 40
- 229920002647 polyamide Polymers 0.000 claims description 40
- 239000011528 polyamide (building material) Substances 0.000 claims description 40
- 239000011342 resin composition Substances 0.000 claims description 34
- 229920001225 Polyester resin Polymers 0.000 claims description 12
- 239000004645 polyester resin Substances 0.000 claims description 12
- 239000003381 stabilizer Substances 0.000 claims description 9
- 150000008065 acid anhydrides Chemical class 0.000 claims description 8
- 150000001412 amines Chemical class 0.000 claims description 8
- 239000003063 flame retardant Substances 0.000 claims description 7
- 229920005989 resin Polymers 0.000 claims description 6
- 239000011347 resin Substances 0.000 claims description 6
- 239000006096 absorbing agent Substances 0.000 claims description 5
- 229920001651 Cyanoacrylate Polymers 0.000 claims description 4
- 241000790917 Dioxys <bee> Species 0.000 claims description 4
- MWCLLHOVUTZFKS-UHFFFAOYSA-N Methyl 2-cyanoacrylate Chemical compound COC(=O)C(=C)C#N MWCLLHOVUTZFKS-UHFFFAOYSA-N 0.000 claims description 4
- 210000002356 Skeleton Anatomy 0.000 claims description 4
- 125000001931 aliphatic group Chemical group 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000003277 amino group Chemical group 0.000 claims description 2
- 150000001491 aromatic compounds Chemical class 0.000 claims description 2
- 235000021384 green leafy vegetables Nutrition 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 2
- 125000004435 hydrogen atoms Chemical group [H]* 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 238000000465 moulding Methods 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 229920000728 polyester Polymers 0.000 claims description 2
- 230000001747 exhibiting Effects 0.000 claims 1
- 230000000052 comparative effect Effects 0.000 description 7
- 239000000203 mixture Substances 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
Description
本発明者らは、上記課題を解決すべく鋭意研究した結果、本発明に到達した。すなわち本発明は、
（１）ポリアミド樹脂（ａ）１００重量部に対して、難燃剤（ｂ）１〜１００重量部、分子量が２６００以上であるヒンダードアミン系安定剤（ｃ）０．１〜５重量部およびシアノアクリレート系紫外線吸収剤（ｄ）０．１〜５重量部を配合してなり、
前記ヒンダードアミン系安定剤（ｃ）が末端アミノ基を封止されたものである、ポリアミド樹脂組成物。
（２）前記難燃剤（ｂ）が窒素系難燃剤である（１）記載のポリアミド樹脂組成物。
（３）ポリアミド樹脂（ａ）１００重量部に対して、さらに、芳香族オキシカルボニル単位（Ｓ）、芳香族および／または脂肪族ジオキシ単位（Ｔ）、および、芳香族ジカルボニル単位（Ｕ）から選ばれる少なくとも１種の構造単位と３官能以上の有機残基（Ｄ）とを含み、かつ、Ｄの含有量が樹状ポリエステルを構成する全単量体に対して７．５〜５０モル％の範囲にある溶融液晶性を示す樹状ポリエステル樹脂（ｅ）０．０１〜１０重量部および酸無水物（ｆ）０．０１〜１０重量部を配合してなる（１）または（２）記載のポリアミド樹脂組成物。
（４）前記樹状ポリエステル樹脂（ｅ）において、芳香族オキシカルボニル単位（Ｓ）、芳香族および／または脂肪族ジオキシ単位（Ｔ）、および、芳香族ジカルボニル単位（Ｕ）が、それぞれ下式（１）で表される構造単位から選ばれる少なくとも１種の構造単位であり、かつ、Ｄの含有量を１モルとした場合にＳ、ＴおよびＵそれぞれの含有量ｐ、ｑおよびｒがｐ＋ｑ＋ｒ＝１〜１０モルの範囲にある（３）記載のポリアミド樹脂組成物。
The inventors of the present invention have arrived at the present invention as a result of intensive studies to solve the above problems. That is, the present invention
(1) 1 to 100 parts by weight of a flame retardant (b), hindered amine stabilizer (c) having a molecular weight of 2600 or more and 0.1 to 5 parts by weight of a cyanoacrylate based on 100 parts by weight of a polyamide resin (a) ultraviolet absorber (d) Ri greens by blending 0.1 to 5 parts by weight,
A polyamide resin composition , wherein the hindered amine stabilizer (c) has a terminal amino group sealed .
(2) the flame retardant (b) is a nitrogen-based flame retardant (1) Symbol placement of the polyamide resin composition.
( 3 ) From 100 parts by weight of the polyamide resin ( a ), further from the aromatic oxycarbonyl unit (S), the aromatic and / or aliphatic dioxy unit (T), and the aromatic dicarbonyl unit (U) It contains at least one selected structural unit and a tri- or higher functional organic residue (D), and the D content is 7.5 to 50 mol% based on the total monomers constituting the dendritic polyester. (1) or (2), which is obtained by blending 0.01 to 10 parts by weight of a dendritic polyester resin (e) having a melt liquid crystallinity in the range of 0.01 to 10 parts by weight and an acid anhydride (f). Polyamide resin composition.
( 4 ) In the dendritic polyester resin (e), the aromatic oxycarbonyl unit (S), the aromatic and / or aliphatic dioxy unit (T), and the aromatic dicarbonyl unit (U) are each represented by the following formulae: When at least one structural unit selected from the structural units represented by (1) and the D content is 1 mol, the contents p, q and r of S, T and U are p + q + r. The polyamide resin composition as described in (3) which exists in the range of = 1-10 mol.
（ただし、式中Ｙは、水素原子、ハロゲン原子およびアルキル基から選ばれる少なくとも１種である。式中ｎは２〜８の整数である。）
（５）前記樹状ポリエステル樹脂（ｅ）が、式（２）で示される基本骨格を含有する（３）または（４）記載のポリアミド樹脂組成物。
(Wherein, Y is at least one selected from a hydrogen atom, a halogen atom and an alkyl group. In the formula, n is an integer of 2 to 8.)
( 5 ) The polyamide resin composition according to ( 3 ) or ( 4 ), wherein the dendritic polyester resin (e) contains a basic skeleton represented by the formula (2).
（ここで、Ｄは３官能化合物の有機残基であり、Ｄ−Ｄ間はエステル結合および／またはアミド結合により直接、あるいは、前記Ｓ、ＴおよびＵから選ばれる構造単位を介して結合している。）
（６）前記樹状ポリエステル樹脂（ｅ）が式（３）で示される基本骨格を含有する（３）または（４）記載のポリアミド樹脂組成物。
(Here, D is an organic residue of a trifunctional compound, and DD is bonded directly by an ester bond and / or an amide bond, or bonded via a structural unit selected from S, T and U. Yes.)
( 6 ) The polyamide resin composition according to ( 3 ) or ( 4 ), wherein the dendritic polyester resin (e) contains a basic skeleton represented by the formula (3).
（ここで、Ｄは４官能化合物の有機残基であり、Ｄ−Ｄ間はエステル結合および／またはアミド結合により直接、あるいは、前記Ｓ、ＴおよびＵから選ばれる構造単位を介して結合している。）
（７）前記樹状ポリエステル樹脂（ｅ）のＤで表される有機残基が芳香族化合物由来の有機残基である（３）〜（６）のいずれか１項に記載のポリアミド樹脂組成物。
（８）前記樹状ポリエステル樹脂（ｅ）のＤで表される有機残基が式（５）または（６）で表される有機残基である（７）記載のポリアミド樹脂組成物。
(Here, D is an organic residue of a tetrafunctional compound, and DD is bonded directly by an ester bond and / or an amide bond or via a structural unit selected from S, T and U. Yes.)
( 7 ) The polyamide resin composition according to any one of ( 3 ) to ( 6 ), wherein the organic residue represented by D of the dendritic polyester resin (e) is an organic residue derived from an aromatic compound. .
( 8 ) The polyamide resin composition according to ( 7 ), wherein the organic residue represented by D of the dendritic polyester resin (e) is an organic residue represented by the formula (5) or (6).
（９）前記酸無水物（ｆ）が不飽和炭化水素基を有しない（３）〜（８）のいずれか１項に記載のポリアミド樹脂組成物。
（１０）前記（１）〜（９）のいずれか１項に記載のポリアミド樹脂組成物を成形してなる成形品。
（１１）成形品の最薄肉部が０．５ｍｍ以下である（１０）に記載の成形品。
( 9 ) The polyamide resin composition according to any one of ( 3 ) to ( 8 ), wherein the acid anhydride (f) does not have an unsaturated hydrocarbon group.
( 10 ) A molded product obtained by molding the polyamide resin composition according to any one of (1) to ( 9 ).
( 11 ) The molded product according to ( 10 ), wherein the thinnest portion of the molded product is 0.5 mm or less.
［実施例２、４〜１６、比較例１〜１１］
表１〜４に示す各原料、熱安定剤（ＢＡＳＦ社製“ＩＲＧＡＮＯＸ”１０９８）０．３重量部および二酸化チタン（石原産業（株）製“タイペーク”（登録商標）ＣＲ−６０（平均粒径０．２μｍ））３．０重量部をドライブレンドし、得られた混合物を２軸押出機（スクリュー径：３０ｍｍ、Ｌ／Ｄ：２８、シリンダー温度：２６０℃、回転数：１５０ｒｐｍ）のホッパーからフィードして溶融混練し、ストランド状に押出した後、ペレタイザにより切断してペレット状のポリアミド樹脂組成物を得た。その後、８０℃で１２時間減圧乾燥して得られたポリアミド樹脂組成物を使用して、前記した方法に従って所定形状の試験片を作製し、各種物性を評価した。結果を表１〜４に示す。
[Examples 2 , 4 to 16, Comparative Examples 1 to 11 ]
Each raw material shown in Tables 1 to 4, 0.3 parts by weight of heat stabilizer ("IRGANOX" 1098 manufactured by BASF) and titanium dioxide ("Typaque" (registered trademark) CR-60 manufactured by Ishihara Sangyo Co., Ltd.) 0.2 μm)) 3.0 parts by weight of the mixture was dry blended, and the resulting mixture was fed from a hopper of a twin screw extruder (screw diameter: 30 mm, L / D: 28, cylinder temperature: 260 ° C., rotation speed: 150 rpm). After feeding, melt-kneading and extruding into a strand shape, it was cut by a pelletizer to obtain a pellet-shaped polyamide resin composition. Then, using the polyamide resin composition obtained by drying under reduced pressure at 80 ° C. for 12 hours, a test piece having a predetermined shape was prepared according to the method described above, and various physical properties were evaluated. The results are shown in Tables 1-4.
実施例２のポリアミド樹脂組成物を用いた成形品は、ヒンダードアミン系安定剤（ｃ）および紫外線吸収剤（ｄ）の両方を配合していない比較例１のポリアミド樹脂組成物を用いた成形品に比べ良好な耐候性を有していた。また、実施例４のポリアミド樹脂組成物を用いた成形品は、ヒンダードアミン系安定剤（ｃ）または紫外線吸収剤（ｄ）を配合していない比較例３および４のポリアミド樹脂組成物を用いた成形品に比べ良好な耐候性を有していた。実施例４のポリアミド樹脂組成物を用いた成形品は、ポリアミド樹脂１００重量部に対して、５重量部を越える分子量が２６００以上であるヒンダードアミン系安定剤および５重量部を越えるシアノアクリレート系紫外線吸収剤を配合した比較例５のポリアミド樹脂組成物を用いた成形品に対し良好な機械特性を有していた。また、実施例４のポリアミド樹脂組成物を用いた成形品は、ポリアミド樹脂１００重量部に対して、１００重量部を超える難燃剤を配合した比較例６のポリアミド樹脂組成物を用いた成形品に対し良好な機械特性を有していた。実施例４のポリアミド樹脂組成物を用いた成形品は、分子量が２６００未満であるヒンダードアミン系安定剤を配合した比較例７のポリアミド樹脂組成物を用いた成形品に対し、耐候性および機械特性を有していた。また、実施例４のポリアミド樹脂組成物を用いた成形品は、シアノアクリレート系でない紫外線吸収剤を配合した比較例８のポリアミド樹脂組成物を用いた成形品に対し良好な耐候性を有していた。 The molded article using the polyamide resin composition of Example 2 is a molded article using the polyamide resin composition of Comparative Example 1 in which both the hindered amine stabilizer (c) and the ultraviolet absorber (d) are not blended. It had better weather resistance. Moreover, the molded article using the polyamide resin composition of Example 4 was molded using the polyamide resin composition of Comparative Examples 3 and 4 in which no hindered amine stabilizer (c) or ultraviolet absorber (d) was blended. It had better weather resistance than the product. The molded article using the polyamide resin composition of Example 4 is a hindered amine stabilizer having a molecular weight of more than 2600 and a cyanoacrylate ultraviolet absorption of more than 5 parts by weight based on 100 parts by weight of the polyamide resin. The molded article using the polyamide resin composition of Comparative Example 5 containing the agent had good mechanical properties. Further, a molded article using the polyamide resin composition of Example 4 is a molded article using the polyamide resin composition of Comparative Example 6 in which a flame retardant exceeding 100 parts by weight is blended with 100 parts by weight of the polyamide resin. On the other hand, it had good mechanical properties. The molded article using the polyamide resin composition of Example 4 has weather resistance and mechanical properties compared to the molded article using the polyamide resin composition of Comparative Example 7 containing a hindered amine stabilizer having a molecular weight of less than 2600. Had. In addition, the molded article using the polyamide resin composition of Example 4 has better weather resistance than the molded article using the polyamide resin composition of Comparative Example 8 in which an ultraviolet absorber that is not cyanoacrylate is blended. It was.
Claims (11)
前記ヒンダードアミン系安定剤（ｃ）が末端アミノ基を封止されたものである、ポリアミド樹脂組成物。 1-100 parts by weight of a flame retardant (b), 0.1-5 parts by weight of a hindered amine stabilizer (c) having a molecular weight of 2600 or more, and a cyanoacrylate ultraviolet absorber with respect to 100 parts by weight of the polyamide resin (a) (d) Ri greens by blending 0.1 to 5 parts by weight,
A polyamide resin composition , wherein the hindered amine stabilizer (c) has a terminal amino group sealed .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2014128729A JP6354379B2 (en) | 2013-06-28 | 2014-06-24 | Polyamide resin composition |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2013136270 | 2013-06-28 | ||
| JP2013136270 | 2013-06-28 | ||
| JP2014128729A JP6354379B2 (en) | 2013-06-28 | 2014-06-24 | Polyamide resin composition |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| JP2015028155A JP2015028155A (en) | 2015-02-12 |
| JP2015028155A5 true JP2015028155A5 (en) | 2017-07-13 |
| JP6354379B2 JP6354379B2 (en) | 2018-07-11 |
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| Application Number | Title | Priority Date | Filing Date |
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| JP2014128729A Active JP6354379B2 (en) | 2013-06-28 | 2014-06-24 | Polyamide resin composition |
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3543292A4 (en) | 2016-11-15 | 2020-06-03 | Toray Industries, Inc. | Polyamide resin composition and molded article containing same |
| KR102218060B1 (en) * | 2016-12-28 | 2021-02-19 | 주식회사 엘지화학 | Polyamide-based resin molded article |
| WO2018181995A1 (en) | 2017-03-30 | 2018-10-04 | 旭化成株式会社 | Polyamide composition and molded article |
| KR20200062336A (en) | 2017-10-17 | 2020-06-03 | 셀라니즈 세일즈 저머니 게엠베하 | Flame retardant polyamide composition |
| JP7014633B2 (en) * | 2018-02-21 | 2022-02-01 | 旭化成株式会社 | Polyamide composition and molded products |
| CN112679919A (en) * | 2020-12-18 | 2021-04-20 | 南阳金牛电气有限公司 | Solidified core group injection molding material for lightning arrester |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0675160A3 (en) * | 1994-03-29 | 1995-11-29 | Gen Electric | Ultraviolet light stabilized polyamide compositions. |
| MY139230A (en) * | 2002-10-17 | 2009-08-28 | Ciba Holding Inc | Flame retardant polymeric electrical parts |
| PL2379643T3 (en) * | 2008-12-17 | 2013-04-30 | Basf Se | Layered silicate flame retardant compositions |
| JP5790005B2 (en) * | 2010-02-26 | 2015-10-07 | 東レ株式会社 | Polyamide resin composition and method for producing the same |
| JP2013043975A (en) * | 2011-08-26 | 2013-03-04 | Unitika Ltd | White polyamide film with excellent weather resistance |
| JP2013076001A (en) * | 2011-09-30 | 2013-04-25 | Toray Ind Inc | Polyamide resin composition |
| US20140316032A1 (en) * | 2011-11-11 | 2014-10-23 | Basf Se | P-n-compounds as flame retardants |
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2014
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