JP6725265B2 - Polyamide resin composition - Google Patents
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- JP6725265B2 JP6725265B2 JP2016040844A JP2016040844A JP6725265B2 JP 6725265 B2 JP6725265 B2 JP 6725265B2 JP 2016040844 A JP2016040844 A JP 2016040844A JP 2016040844 A JP2016040844 A JP 2016040844A JP 6725265 B2 JP6725265 B2 JP 6725265B2
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- 229920006122 polyamide resin Polymers 0.000 title claims description 82
- 239000011342 resin composition Substances 0.000 title claims description 34
- 239000003365 glass fiber Substances 0.000 claims description 53
- 239000004952 Polyamide Substances 0.000 claims description 23
- 125000003277 amino group Chemical group 0.000 claims description 23
- 229920002647 polyamide Polymers 0.000 claims description 23
- 239000000835 fiber Substances 0.000 claims description 16
- 229920000299 Nylon 12 Polymers 0.000 claims description 11
- 229920002292 Nylon 6 Polymers 0.000 claims description 11
- 229920000571 Nylon 11 Polymers 0.000 claims description 9
- 229920000572 Nylon 6/12 Polymers 0.000 claims description 9
- 239000012783 reinforcing fiber Substances 0.000 claims description 7
- 230000002787 reinforcement Effects 0.000 claims 6
- 239000011521 glass Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000006087 Silane Coupling Agent Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 239000004953 Aliphatic polyamide Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000004677 Nylon Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229920003231 aliphatic polyamide Polymers 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 239000000806 elastomer Substances 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 229920001778 nylon Polymers 0.000 description 2
- 238000007493 shaping process Methods 0.000 description 2
- 238000004513 sizing Methods 0.000 description 2
- 239000012756 surface treatment agent Substances 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- 239000005749 Copper compound Substances 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 229920003189 Nylon 4,6 Polymers 0.000 description 1
- 229920000305 Nylon 6,10 Polymers 0.000 description 1
- 229920002302 Nylon 6,6 Polymers 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 150000001880 copper compounds Chemical class 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000002530 phenolic antioxidant Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
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Description
本発明は、耐衝撃性が良い成形品が得られるポリアミド樹脂組成物と、それから得られる成形品に関する。 TECHNICAL FIELD The present invention relates to a polyamide resin composition capable of obtaining a molded article having good impact resistance, and a molded article obtained from the polyamide resin composition.
軽量化の目的で金属代替品として樹脂成形品が使用されているが、その機械的強度を高めるため、繊維が配合された樹脂組成物が汎用されている。 A resin molded product is used as a metal substitute for the purpose of weight reduction, but a resin composition containing a fiber is widely used in order to increase its mechanical strength.
特許文献１には、脂肪族ポリアミド樹脂（Ａ）、ガラス繊維（Ｂ）、銅化合物（Ｃ）、分子中にアミノ基を持つシランカップリング剤（Ｄ）からなるポリアミド樹脂組成物（相対粘度１．８〜２．５）の発明が記載されている（特許請求の範囲）。
前記ポリアミド樹脂組成物は、機械特性、疲労特性、流動性が優れていると記載されている（段落番号０００８）。
脂肪族ポリアミド樹脂（Ａ）としては、ナイロン６６、ナイロン４６、ナイロン６１０が例示されており（段落番号００１１、００１２）、実施例（表２）では、１種類のポリアミド樹脂を使用している。
Patent Document 1 describes a polyamide resin composition comprising an aliphatic polyamide resin (A), a glass fiber (B), a copper compound (C), and a silane coupling agent (D) having an amino group in the molecule (relative viscosity 1 8 to 2.5) are described (Claims).
It is described that the polyamide resin composition has excellent mechanical properties, fatigue properties, and fluidity (paragraph number 0008).
As the aliphatic polyamide resin (A), nylon 66, nylon 46, and nylon 610 are exemplified (paragraph numbers 0011 and 0012), and one type of polyamide resin is used in the examples (Table 2).
特許文献２には、数平均分子量２０００以上のポリアミド（ａ−１）と、数平均分子量５００〜２０００未満のポリアミドオリゴマー（ａ−２）を含むポリアミド樹脂（Ａ）および重量平均繊維長が１〜１５ｍｍである強化繊維を含有するポリアミド樹脂組成物の発明が記載されている（特許請求の範囲）。
前記ポリアミド樹脂組成物は、耐熱性、低吸水性、剛性、流動性、耐衝撃性が優れていることが記載されている（段落番号００１０）。
Patent Document 2 discloses a polyamide resin (A) containing a polyamide (a-1) having a number average molecular weight of 2000 or more and a polyamide oligomer (a-2) having a number average molecular weight of 500 to less than 2000 and a weight average fiber length of 1 to 1. The invention of a polyamide resin composition containing reinforcing fibers of 15 mm is described (Claims).
It is described that the polyamide resin composition has excellent heat resistance, low water absorption, rigidity, fluidity, and impact resistance (paragraph number 0010).
特許文献３には、（Ａ）ポリアミド樹脂、（Ｂ）ＡＢＳ樹脂、（Ｃ）カルボン酸変性ＡＳ樹脂など、（Ｄ）ガラス繊維および／またはガラス繊維を含有する塗装成形品用の樹脂組成物の発明が記載されている（特許請求の範囲）。
前記樹脂組成物から得られた成形品は、機械的性質や物理的性質が良く、塗装後の塗膜の密着性も良いことが記載されている（段落番号０００８）。
（Ａ）ポリアミド樹脂としてポリアミド１２も例示されているが（段落番号００１１）、実施例（表１）では、ポリアミド６のみが使用されている。
Patent Document 3 discloses (A) a polyamide resin, (B) an ABS resin, (C) a carboxylic acid-modified AS resin, and the like (D) a glass fiber and/or a resin composition for a coated molded article containing a glass fiber. The invention has been described (claims).
It is described that a molded product obtained from the resin composition has good mechanical properties and physical properties, and also has good adhesion of a coating film after coating (paragraph number 0008).
Although polyamide 12 is also exemplified as the (A) polyamide resin (paragraph number 0011), only polyamide 6 is used in the examples (Table 1).
本発明は、耐衝撃性が良い成形品を得ることができるポリアミド樹脂組成物と、前記組成物から得られる成形品を提供することを課題とする。 An object of the present invention is to provide a polyamide resin composition capable of obtaining a molded article having good impact resistance, and a molded article obtained from the composition.
本発明は、（Ａ）ポリアミド樹脂と（Ｂ）ガラス繊維を含むポリアミド樹脂組成物であって、
前記（Ａ）成分のポリアミド樹脂が、相対粘度が１．４〜２．９であるポリアミド６、ポリアミド６１２、ポリアミド１１およびポリアミド１２から選ばれるものであり、
前記（Ａ）成分と前記（Ｂ）成分が、それらの合計量中の割合が、（Ａ）成分が４０〜９５質量％、（Ｂ）成分が５〜６０質量％であり、
前記（Ａ）成分のポリアミド樹脂が、アミノ基濃度が４０mmol／kg以上のものを２５質量％以上含有しており、
前記ポリアミド樹脂組成物が、前記（Ｂ）成分のガラス繊維が長さ方向に揃えて束ねられたものに、前記（Ａ）成分のポリアミド樹脂が付着一体化されたものが５〜２５ｍｍの長さに切断されたポリアミド樹脂付着ガラス繊維束を含むものである、ポリアミド樹脂組成物とその成形品を提供する。
The present invention is a polyamide resin composition containing (A) polyamide resin and (B) glass fiber,
The polyamide resin of the component (A) is selected from polyamide 6, polyamide 612, polyamide 11 and polyamide 12 having a relative viscosity of 1.4 to 2.9,
The ratio of the component (A) and the component (B) in the total amount thereof is 40 to 95% by mass for the component (A) and 5 to 60% by mass for the component (B),
The polyamide resin as the component (A) contains 25% by mass or more of one having an amino group concentration of 40 mmol/kg or more,
The polyamide resin composition having a glass fiber of the component (B) aligned in the lengthwise direction and bundled with the polyamide resin of the component (A) has a length of 5 to 25 mm. Provided are a polyamide resin composition and a molded article thereof, which comprises a polyamide resin-adhered glass fiber bundle cut into pieces.
本発明は、（Ａ）ポリアミド樹脂と（Ｂ）ガラス繊維を含むポリアミド樹脂組成物であって、
前記（Ａ）成分のポリアミド樹脂が、相対粘度が１．４〜２．９であるポリアミド６、ポリアミド６１２、ポリアミド１１およびポリアミド１２から選ばれるものであり、
前記（Ａ）成分と前記（Ｂ）成分が、それらの合計量中の割合が、（Ａ）成分が４０〜９５質量％、（Ｂ）成分が５〜６０質量％であり、
前記（Ａ）成分のポリアミド樹脂中のアミノ基の平均濃度が４０mmol／kg以上であり、
前記ポリアミド樹脂組成物が、前記（Ｂ）成分のガラス繊維が長さ方向に揃えて束ねられたものに、前記（Ａ）成分のポリアミド樹脂が付着一体化されたものが５〜２５ｍｍの長さに切断されたポリアミド樹脂付着ガラス繊維束を含むものである、ポリアミド樹脂組成物とその成形品を提供する。
The present invention is a polyamide resin composition containing (A) polyamide resin and (B) glass fiber,
The polyamide resin of the component (A) is selected from polyamide 6, polyamide 612, polyamide 11 and polyamide 12 having a relative viscosity of 1.4 to 2.9,
The ratio of the component (A) and the component (B) in the total amount thereof is 40 to 95% by mass for the component (A) and 5 to 60% by mass for the component (B),
The average concentration of amino groups in the polyamide resin of component (A) is 40 mmol/kg or more,
The polyamide resin composition having a glass fiber of the component (B) aligned in the lengthwise direction and bundled with the polyamide resin of the component (A) has a length of 5 to 25 mm. Provided are a polyamide resin composition and a molded article thereof, which comprises a polyamide resin-adhered glass fiber bundle cut into pieces.
本発明のポリアミド樹脂組成物は、耐衝撃強度の高い成形品を得ることができる。 With the polyamide resin composition of the present invention, a molded article having high impact strength can be obtained.
〔（Ａ）成分〕
（Ａ）成分のポリアミド樹脂は、相対粘度が１．４〜２．９、好ましくは１．８〜２．５であるポリアミド６、ポリアミド６１２、ポリアミド１１およびポリアミド１２から選ばれるものである。
[(A) component]
The polyamide resin as the component (A) is selected from polyamide 6, polyamide 612, polyamide 11 and polyamide 12 having a relative viscosity of 1.4 to 2.9, preferably 1.8 to 2.5.
（Ａ）成分のポリアミド樹脂は、ポリアミド樹脂の種類（ポリアミド６、ポリアミド６１２、ポリアミド１１およびポリアミド１２）によりアミノ基濃度が異なるが、本発明では、アミノ基濃度が下記のいずれかの要件を満たすようにする。
＜要件１＞
（Ａ）成分のポリアミド樹脂が、アミノ基濃度が４０mmol／kg以上のものを２５質量％以上含有していること。
ここで、アミノ基濃度が４０mmol／kg以上のもののみを使用してもよし、アミノ基濃度が４０mmol／kg以上のものとアミノ基濃度が４０mmol／kg未満のものとを組み合わせてもよい。
＜要件２＞
（Ａ）成分のポリアミド樹脂中のアミノ基の平均濃度が４０mmol／kg以上であること。
ここで、アミノ基濃度が４０mmol／kg以上のもののみを使用してもよいし、アミノ基濃度が４０mmol／kg以上のものとアミノ基濃度が４０mmol／kg未満のものとを組み合わせることで、アミノ基の平均濃度を４０mmol／kg以上にしたものでもよい。
アミノ基の平均濃度は、４０〜１００mmol／kgが好ましく、４０〜８０mmol／kgがより好ましい。
本発明では、要件１と要件２のいずれか一方を満たしていればよいが、両方を満たしていてもよい。
The polyamide resin as the component (A) has a different amino group concentration depending on the type of the polyamide resin (polyamide 6, polyamide 612, polyamide 11 and polyamide 12), but in the present invention, the amino group concentration satisfies one of the following requirements. To do so.
<Requirement 1>
The polyamide resin as the component (A) contains 25% by mass or more of one having an amino group concentration of 40 mmol/kg or more.
Here, only those having an amino group concentration of 40 mmol/kg or more may be used, or those having an amino group concentration of 40 mmol/kg or more and those having an amino group concentration of less than 40 mmol/kg may be combined.
<Requirement 2>
The average concentration of amino groups in the polyamide resin of component (A) is 40 mmol/kg or more.
Here, only those having an amino group concentration of 40 mmol/kg or more may be used, or by combining those having an amino group concentration of 40 mmol/kg or more with those having an amino group concentration of less than 40 mmol/kg, It may be one in which the average concentration of the group is 40 mmol/kg or more.
The average concentration of the amino group is preferably 40 to 100 mmol/kg, more preferably 40 to 80 mmol/kg.
In the present invention, it suffices that either one of requirement 1 or requirement 2 is satisfied, but both may be satisfied.
（Ａ）成分としては、ポリアミド６、ポリアミド６１２、ポリアミド１１およびポリアミド１２から選ばれるもののほかにも、ポリアミドエラストマーを使用することができる。
ポリアミドエラストマーは、特許第５４６６９２８号公報の段落００４６〜００５２に記載されているポリアミド１２からなるハードセグメントとポリエーテルからなるソフトセグメントを有するブロック共重合体が好ましい。
As the component (A), in addition to those selected from polyamide 6, polyamide 612, polyamide 11 and polyamide 12, a polyamide elastomer can be used.
The polyamide elastomer is preferably a block copolymer having a hard segment made of polyamide 12 and a soft segment made of polyether described in paragraphs 0046 to 0052 of Japanese Patent No. 5466928.
〔（Ｂ）成分〕
（Ｂ）成分のガラス繊維は、Ｅ−ガラス、Ｓ−ガラス、Ｃ−ガラス、ＡＲ−ガラス、Ｔ−ガラス、Ｄ−ガラス、Ｒ−ガラスなどの公知のガラス繊維が収束剤（表面処理剤も含む）で表面処理されたものである。
ガラス繊維は、外径が３〜４０μｍのものを使用することができる。
ガラス繊維は、多数のフィラメントを集めた束を、コイル状に巻きとったガラス繊維ロービングを使用することができる。
[(B) component]
As the glass fiber as the component (B), known glass fibers such as E-glass, S-glass, C-glass, AR-glass, T-glass, D-glass, and R-glass are used as a converging agent (also for a surface treatment agent). Including) is surface-treated.
Glass fibers having an outer diameter of 3 to 40 μm can be used.
As the glass fiber, a glass fiber roving obtained by winding a bundle of a large number of filaments into a coil can be used.
収束剤としては、無水マレイン酸系、ウレタン系、アクリル系、およびこれらの共重合体や混合物を含有するものを挙げることができる。
表面処理剤としては、アミノシラン系カップリング剤、エポキシ系シランカップリング剤、クロル系シランカップリング剤、およびカチオン系シランカップリング剤などを挙げることができる。
Examples of the sizing agent include maleic anhydride-based, urethane-based, acrylic-based, and copolymers and mixtures thereof.
Examples of the surface treatment agent include aminosilane-based coupling agents, epoxy-based silane coupling agents, chloro-based silane coupling agents, and cation-based silane coupling agents.
〔ポリアミド樹脂付着ガラス繊維束〕
本発明のポリアミド樹脂組成物は、（Ｂ）成分のガラス繊維が長さ方向に揃えて束ねられたものに、（Ａ）成分のポリアミド樹脂が付着一体化されたものが５〜２５ｍｍの長さに切断されたポリアミド樹脂付着ガラス繊維束を含むものである。
本発明のポリアミド樹脂組成物は、ポリアミド樹脂付着ガラス繊維束のみからなるものでもよいし、ポリアミド樹脂付着ガラス繊維束と、前記ポリアミド樹脂付着ガラス繊維束とは別に配合された他の成分からなるものでもよい。
（Ａ）成分のポリアミド樹脂は、全てがポリアミド樹脂付着ガラス繊維束に含まれているものでもよいし、ポリアミド樹脂付着ガラス繊維束に含まれているポリアミド樹脂と、ポリアミド樹脂付着ガラス繊維束に含まれていないポリアミド樹脂からなるものでもよい。
[Polyamide resin attached glass fiber bundle]
The polyamide resin composition of the present invention has a length of 5 to 25 mm when the glass fiber of the component (B) is aligned and bundled in the length direction and the polyamide resin of the component (A) is adhered and integrated. It includes a polyamide resin-attached glass fiber bundle cut into pieces.
The polyamide resin composition of the present invention may consist of a polyamide resin-adhered glass fiber bundle alone, or may comprise a polyamide resin-adhered glass fiber bundle and other components blended separately from the polyamide resin-adhered glass fiber bundle. But it's okay.
The polyamide resin as the component (A) may be wholly contained in the polyamide resin-attached glass fiber bundle, or may be contained in the polyamide resin-attached glass fiber bundle and the polyamide resin-attached glass fiber bundle. It may be made of a polyamide resin which is not included.
ポリアミド樹脂付着ガラス繊維束は、付着状態によって次の３つの形態に分けることができる。
（I）ガラス繊維束の中心部までポリアミド樹脂が浸透され（含浸され）、ガラス繊維束を構成する中心部のガラス繊維間にまでポリアミド樹脂が入り込んだ状態のもの（以下「ポリアミド樹脂含浸ガラス繊維束」という）。
（II）ガラス繊維束の表面のみがポリアミド樹脂で覆われた状態のもの（以下「ポリアミド樹脂表面被覆ガラス繊維束」という）。
（III）それらの中間のもの（ガラス繊維束の表面がポリアミド樹脂で覆われ、表面近傍のみにポリアミド樹脂が含浸され、中心部にまでポリアミド樹脂が入り込んでいないもの）（以下「ポリアミド樹脂一部含浸ガラス繊維束」という）。
（I）〜（III）の形態の樹脂付着繊維束の長さとガラス繊維の長さは同じである。本発明では、（III）のポリアミド樹脂含浸ガラス繊維束が好ましい。
（I）〜（III）の形態の樹脂付着繊維束は、特開２０１３−１０７９７９号公報に記載されている（但し、前記公報では、ポリアミド樹脂は使用されていない）。
The polyamide resin-adhered glass fiber bundle can be classified into the following three forms depending on the adhered state.
(I) A state in which the polyamide resin has penetrated (impregnated) to the center of the glass fiber bundle and the polyamide resin has entered between the glass fibers at the center of the glass fiber bundle (hereinafter referred to as “polyamide resin-impregnated glass fiber”). Bunch").
(II) A state in which only the surface of the glass fiber bundle is covered with the polyamide resin (hereinafter referred to as "polyamide resin surface-coated glass fiber bundle").
(III) Intermediate ones (the surface of the glass fiber bundle is covered with a polyamide resin, the polyamide resin is impregnated only in the vicinity of the surface, and the polyamide resin does not enter the central portion) (hereinafter, "part of the polyamide resin") Impregnated glass fiber bundle").
The lengths of the resin-attached fiber bundles of the forms (I) to (III) and the glass fibers are the same. In the present invention, the polyamide resin-impregnated glass fiber bundle (III) is preferable.
The resin-attached fiber bundles of the forms (I) to (III) are described in JP-A-2013-107979 (however, in the above-mentioned publication, a polyamide resin is not used).
本発明の組成物中の（Ａ）成分と（Ｂ）成分は、それらの合計量中のそれぞれの割合が、（Ａ）成分は４０〜９５質量％であり、４５〜９０質量％が好ましく、（Ｂ）成分は５〜６０質量％であり、１０〜５５質量％が好ましい。 The ratio of the component (A) and the component (B) in the composition of the present invention in the total amount thereof is such that the component (A) is 40 to 95% by mass, preferably 45 to 90% by mass, The component (B) is 5 to 60% by mass, preferably 10 to 55% by mass.
本発明の組成物は、本発明の課題を解決できる範囲内で、公知の他の成分、例えば、難燃剤、難燃助剤、熱安定剤、滑剤、光安定剤、酸化防止剤、着色剤、離型剤、帯電防止剤を含有することができる。
本発明の組成物は、前記他の成分をポリアミド樹脂付着ガラス繊維束に含有させてもよいし、ポリアミド樹脂付着ガラス繊維束とは別に含有していてもよい。
The composition of the present invention, within the scope capable of solving the problems of the present invention, other known components, for example, flame retardants, flame retardant aids, heat stabilizers, lubricants, light stabilizers, antioxidants, colorants. , A release agent, and an antistatic agent.
The composition of the present invention may contain the above-mentioned other components in the polyamide resin-attached glass fiber bundle, or may contain them separately from the polyamide resin-attached glass fiber bundle.
実施例および比較例で使用した成分は以下のとおりである。
（Ａ）成分
・ＰＡ−１：ＵＢＥ ＮＹＬＯＮ １０１１ＦＢ（宇部興産（株））（相対粘度２．２０、アミノ基濃度３６mmol／kg）
・ＰＡ−２：ユニチカナイロン６ Ａ１０２０ＢＲＬ（ユニチカ（株））（相対粘度２．１５アミノ基濃度８０mmol／kg ）
・ＰＡ−３：ＵＢＥ ＮＹＬＯＮ １０３０Ｂ（宇部興産（株））（相対粘度４．０４、アミノ基濃度３４mmol／kg）
The components used in the examples and comparative examples are as follows.
(A) component PA-1: UBE NYLON 1011FB (Ube Industries, Ltd.) (relative viscosity 2.20, amino group concentration 36 mmol/kg)
PA-2: Unitika Nylon 6 A1020BRL (Unitika Ltd.) (relative viscosity 2.15 amino group concentration 80 mmol/kg)
-PA-3: UBE NYLON 1030B (Ube Industries, Ltd.) (relative viscosity 4.04, amino group concentration 34 mmol/kg)
（Ｂ）成分
・ＧＦ−１：製品名「ＲＳ２４０ＱＲ−４８３」、日東紡績（株）製（収束剤で表面処理されたガラス繊維ロービング）
（その他）
安定剤：フェノール系酸化防止剤、イルガノックス1010FF，ＢＡＳＦジャパン
(B) Component/GF-1: Product name “RS240QR-483”, manufactured by Nitto Boseki Co., Ltd. (glass fiber roving surface-treated with a sizing agent)
(Other)
Stabilizer: Phenolic antioxidant, Irganox 1010FF, BASF Japan
＜相対粘度＞
温度２５℃、９６質量％硫酸中にポリアミド樹脂を1g／100mlの濃度で溶解させて測定した。
<Relative viscosity>
The polyamide resin was dissolved in 96% by mass sulfuric acid at a temperature of 25° C. at a concentration of 1 g/100 ml for measurement.
＜アミノ基濃度＞
サンプルとして用いるポリアミド樹脂組成物を約０．５ｇとり、これをフェノール／メタノール混合液（容量比９：１）４０ｍｌに溶解し、溶解を確認した後、さらにメタノールを１０ｍｌ加えた。これを試料とし、塩酸水溶液（０．０１Ｎ）で滴定により測定した。なお、装置としては、平沼産業株式会社製、平沼自動滴定装置ＣＯＭ−２００を用いた。
<Amino group concentration>
About 0.5 g of the polyamide resin composition used as a sample was taken, and this was dissolved in 40 ml of a phenol/methanol mixed solution (volume ratio 9:1). After confirming the dissolution, 10 ml of methanol was further added. This was used as a sample and measured by titration with an aqueous hydrochloric acid solution (0.01N). As an apparatus, Hiranuma Sangyo Co., Ltd. Hiranuma automatic titrator COM-200 was used.
＜残存繊維長＞
成形品から約３ｇの試料を切り出し、６５０℃で加熱して灰化させてガラス繊維を取り出した。取り出した繊維の一部（５００本）から重量平均繊維長を求めた。計算式は、特開２００６−２７４０６１号公報の段落００４４、００４５に記載のものを使用した。
<Residual fiber length>
A sample of about 3 g was cut out from the molded product, heated at 650° C. to be incinerated, and the glass fiber was taken out. The weight average fiber length was obtained from a part (500) of the taken out fibers. The calculation formulas used are those described in paragraphs 0044 and 0045 of JP-A-2006-274061.
＜シャルピー衝撃強度（ｋＪ／ｍ2）＞
ＩＳＯ１７９／１ｅＡに準拠して、ノッチ付きシャルピー衝撃強さを測定した。
<Charpy impact strength (kJ/m 2 )>
The Charpy impact strength with notch was measured according to ISO179/1eA.
実施例１、比較例１
ガラス繊維ロービングをクロスヘッドダイに通した。そのとき、クロスヘッドダイには、２軸押出機（シリンダー温度２８０℃）から溶融状態の表１に示す（Ａ）成分の内のＰＡ−１を表１に示す量供給し、その溶融物をガラス繊維ロービングに含浸させた。
その後、クロスヘッドダイ出口の賦形ノズルで賦形し、整形ロールで形を整えた後、ペレタイザーにより長さ９ｍｍに切断し、円柱状のポリアミド樹脂含浸繊維束を得た。
その後、ポリアミド樹脂含浸繊維束に表１に示すポリアミド樹脂を配合して、実施例１と比較例１の組成物を得た。
それぞれの組成物について、表１に示す残存繊維長、比重、シャルピー衝撃強度を測定した。
Example 1, Comparative Example 1
The glass fiber roving was passed through a crosshead die. At that time, PA-1 of the component (A) shown in Table 1 in a molten state was supplied to the crosshead die from the twin-screw extruder (cylinder temperature 280° C.) in the amount shown in Table 1, and the melt was obtained. The glass fiber roving was impregnated.
After that, it was shaped with a shaping nozzle at the exit of the crosshead die, the shape was adjusted with a shaping roll, and then cut into a length of 9 mm with a pelletizer to obtain a columnar polyamide resin-impregnated fiber bundle.
Then, the polyamide resin impregnated fiber bundle was mixed with the polyamide resin shown in Table 1 to obtain the compositions of Example 1 and Comparative Example 1.
For each composition, the residual fiber length, specific gravity and Charpy impact strength shown in Table 1 were measured.
表１に示すとおり、実施例１のポリアミド樹脂はアミノ基濃度の要件１、要件２を満たしており、さらにポリアミド樹脂とガラス繊維濃度の両方を所定範囲に調整することで、成形品のシャルピー衝撃強度を高めることができた。 As shown in Table 1, the polyamide resin of Example 1 satisfies the requirements 1 and 2 of the amino group concentration, and by further adjusting both the polyamide resin and the glass fiber concentration within a predetermined range, the Charpy impact of the molded product The strength could be increased.
本発明のポリアミド樹脂組成物は、電気・電子機器、通信機器、自動車部品、建築材料、日用品などで使用されている金属材料の代替品のほか、靴（好ましくはランニングシューズ、ウォーキングシューズなどのスポーツシューズ）、自転車のサドル（好ましくは自転車のサドルのベース部材）として使用することができる。 The polyamide resin composition of the present invention is a substitute for metallic materials used in electric/electronic devices, communication devices, automobile parts, building materials, daily necessities, etc., as well as shoes (preferably running shoes, walking shoes and other sports). Shoes), a bicycle saddle (preferably a bicycle saddle base member).
Claims (4)
前記（Ａ）成分のポリアミド樹脂が、相対粘度が１．４〜２．９であるポリアミド６、ポリアミド６１２、ポリアミド１１およびポリアミド１２から選ばれるものであり、
前記（Ａ）成分と前記（Ｂ）成分が、それらの合計量中の割合が、（Ａ）成分が４０〜９５質量％、（Ｂ）成分が５〜６０質量％であり、
前記（Ａ）成分のポリアミド樹脂が、アミノ基濃度が４０mmol／kg以上のものを２５質量％以上含有しており、
前記ポリアミド樹脂組成物が、前記（Ｂ）成分のガラス繊維が長さ方向に揃えて束ねられたものに、前記（Ａ）成分のポリアミド樹脂が付着一体化されたものが５〜２５ｍｍの長さに切断されたポリアミド樹脂付着ガラス繊維束を含むものである、ポリアミド樹脂組成物からなるランニングシューズ、ウォーキングシューズを含むスポーツシューズである成形品。 (A) A polyamide resin and (B) a glass fiber, the cross section having the following formula: flatness=reinforcement fiber cross-section major axis (d1)/reinforcement fiber cross-section minor axis (d2) with a flatness of 2.3 or more. A polyamide resin composition containing no reinforcing fiber,
The polyamide resin of the component (A) is selected from polyamide 6, polyamide 612, polyamide 11 and polyamide 12 having a relative viscosity of 1.4 to 2.9,
The ratio of the component (A) and the component (B) in the total amount thereof is 40 to 95% by mass for the component (A) and 5 to 60% by mass for the component (B),
The polyamide resin as the component (A) contains 25% by mass or more of one having an amino group concentration of 40 mmol/kg or more,
The polyamide resin composition has a glass fiber of the component (B) aligned in the length direction and bundled, and the polyamide resin of the component (A) adhered and integrated has a length of 5 to 25 mm. A molded article, which is a sports shoe including a running shoe and a walking shoe made of the polyamide resin composition , which contains the polyamide resin-attached glass fiber bundle cut into pieces.
前記（Ａ）成分のポリアミド樹脂が、相対粘度が１．４〜２．９であるポリアミド６、ポリアミド６１２、ポリアミド１１およびポリアミド１２から選ばれるものであり、The polyamide resin of the component (A) is selected from polyamide 6, polyamide 612, polyamide 11 and polyamide 12 having a relative viscosity of 1.4 to 2.9,
前記（Ａ）成分と前記（Ｂ）成分が、それらの合計量中の割合が、（Ａ）成分が４０〜９５質量％、（Ｂ）成分が５〜６０質量％であり、The ratio of the component (A) and the component (B) in the total amount thereof is 40 to 95% by mass for the component (A) and 5 to 60% by mass for the component (B),
前記（Ａ）成分のポリアミド樹脂が、アミノ基濃度が４０mmol／kg以上のものを２５質量％以上含有しており、The polyamide resin as the component (A) contains 25% by mass or more of one having an amino group concentration of 40 mmol/kg or more,
前記ポリアミド樹脂組成物が、前記（Ｂ）成分のガラス繊維が長さ方向に揃えて束ねられたものに、前記（Ａ）成分のポリアミド樹脂が付着一体化されたものが５〜２５ｍｍの長さに切断されたポリアミド樹脂付着ガラス繊維束を含むものである、ポリアミド樹脂組成物からなる自転車のサドルのベース部材である成形品。The polyamide resin composition has a glass fiber of the component (B) aligned in the length direction and bundled, and the polyamide resin of the component (A) adhered and integrated has a length of 5 to 25 mm. A molded product, which is a base member of a bicycle saddle made of a polyamide resin composition, containing a polyamide resin-attached glass fiber bundle cut into pieces.
前記（Ａ）成分のポリアミド樹脂が、相対粘度が１．４〜２．９であるポリアミド６、ポリアミド６１２、ポリアミド１１およびポリアミド１２から選ばれるものであり、
前記（Ａ）成分と前記（Ｂ）成分が、それらの合計量中の割合が、（Ａ）成分が４０〜９５質量％、（Ｂ）成分が５〜６０質量％であり、
前記（Ａ）成分のポリアミド樹脂中のアミノ基の平均濃度が４０mmol／kg以上であり、
前記ポリアミド樹脂組成物が、前記（Ｂ）成分のガラス繊維が長さ方向に揃えて束ねられたものに、前記（Ａ）成分のポリアミド樹脂が付着一体化されたものが５〜２５ｍｍの長さに切断されたポリアミド樹脂付着ガラス繊維束を含むものである、ポリアミド樹脂組成物からなるランニングシューズ、ウォーキングシューズを含むスポーツシューズである成形品。 (A) Polyamide resin and (B) Glass fiber, and the cross section has the following formula: flatness = flat shape with a flatness of 2.3 or more according to the major axis of the reinforcing fiber cross section (d1)/the minor axis of the reinforcing fiber cross section (d2). A polyamide resin composition containing no reinforcing fiber,
The polyamide resin of the component (A) is selected from polyamide 6, polyamide 612, polyamide 11 and polyamide 12 having a relative viscosity of 1.4 to 2.9,
The ratio of the component (A) and the component (B) in the total amount thereof is 40 to 95% by mass for the component (A) and 5 to 60% by mass for the component (B),
The average concentration of amino groups in the polyamide resin of component (A) is 40 mmol/kg or more,
The polyamide resin composition having a glass fiber of the component (B) aligned in the lengthwise direction and bundled with the polyamide resin of the component (A) has a length of 5 to 25 mm. A molded article which is a sports shoe including a running shoe and a walking shoe made of a polyamide resin composition , which contains a polyamide resin-attached glass fiber bundle cut into pieces.
前記（Ａ）成分のポリアミド樹脂が、相対粘度が１．４〜２．９であるポリアミド６、ポリアミド６１２、ポリアミド１１およびポリアミド１２から選ばれるものであり、The polyamide resin of the component (A) is selected from polyamide 6, polyamide 612, polyamide 11 and polyamide 12 having a relative viscosity of 1.4 to 2.9,
前記（Ａ）成分と前記（Ｂ）成分が、それらの合計量中の割合が、（Ａ）成分が４０〜９５質量％、（Ｂ）成分が５〜６０質量％であり、The ratio of the component (A) and the component (B) in the total amount thereof is 40 to 95% by mass for the component (A) and 5 to 60% by mass for the component (B),
前記（Ａ）成分のポリアミド樹脂中のアミノ基の平均濃度が４０mmol／kg以上であり、The average concentration of amino groups in the polyamide resin of component (A) is 40 mmol/kg or more,
前記ポリアミド樹脂組成物が、前記（Ｂ）成分のガラス繊維が長さ方向に揃えて束ねられたものに、前記（Ａ）成分のポリアミド樹脂が付着一体化されたものが５〜２５ｍｍの長さに切断されたポリアミド樹脂付着ガラス繊維束を含むものである、ポリアミド樹脂組成物からなる自転車のサドルのベース部材である成形品。The polyamide resin composition has a glass fiber of the component (B) aligned in the length direction and bundled, and the polyamide resin of the component (A) adhered and integrated has a length of 5 to 25 mm. A molded product, which is a base member of a bicycle saddle made of a polyamide resin composition, containing a polyamide resin-attached glass fiber bundle cut into pieces.
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