JP2004307615A - Resin composition for power tool sheath material - Google Patents
Resin composition for power tool sheath material Download PDFInfo
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- JP2004307615A JP2004307615A JP2003101753A JP2003101753A JP2004307615A JP 2004307615 A JP2004307615 A JP 2004307615A JP 2003101753 A JP2003101753 A JP 2003101753A JP 2003101753 A JP2003101753 A JP 2003101753A JP 2004307615 A JP2004307615 A JP 2004307615A
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- 239000000463 material Substances 0.000 title claims abstract description 21
- 239000011342 resin composition Substances 0.000 title claims abstract description 21
- 229920001400 block copolymer Polymers 0.000 claims abstract description 58
- -1 aromatic vinyl compound Chemical class 0.000 claims abstract description 30
- 229920006122 polyamide resin Polymers 0.000 claims abstract description 27
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 19
- 229920001577 copolymer Polymers 0.000 claims description 16
- 229920002292 Nylon 6 Polymers 0.000 claims description 14
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 13
- 229920002302 Nylon 6,6 Polymers 0.000 claims description 11
- 150000007934 α,β-unsaturated carboxylic acids Chemical class 0.000 claims description 8
- 229920001971 elastomer Polymers 0.000 claims description 7
- 239000000178 monomer Substances 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 238000004513 sizing Methods 0.000 claims description 5
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical class C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 claims description 4
- 238000002425 crystallisation Methods 0.000 claims description 4
- 230000008025 crystallization Effects 0.000 claims description 4
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 4
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 2
- 238000012986 modification Methods 0.000 claims description 2
- 230000004048 modification Effects 0.000 claims description 2
- 239000005060 rubber Substances 0.000 claims description 2
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims 1
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- 239000003365 glass fiber Substances 0.000 abstract description 26
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 16
- 239000000203 mixture Substances 0.000 description 14
- 239000011347 resin Substances 0.000 description 11
- 229920005989 resin Polymers 0.000 description 11
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 7
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- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 4
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 4
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- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 2
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 2
- SDJHPPZKZZWAKF-UHFFFAOYSA-N 2,3-dimethylbuta-1,3-diene Chemical compound CC(=C)C(C)=C SDJHPPZKZZWAKF-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
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- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 2
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- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
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- 239000008188 pellet Substances 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
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- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- RRKODOZNUZCUBN-CCAGOZQPSA-N (1z,3z)-cycloocta-1,3-diene Chemical compound C1CC\C=C/C=C\C1 RRKODOZNUZCUBN-CCAGOZQPSA-N 0.000 description 1
- WAEOXIOXMKNFLQ-UHFFFAOYSA-N 1-methyl-4-prop-2-enylbenzene Chemical group CC1=CC=C(CC=C)C=C1 WAEOXIOXMKNFLQ-UHFFFAOYSA-N 0.000 description 1
- IGGDKDTUCAWDAN-UHFFFAOYSA-N 1-vinylnaphthalene Chemical compound C1=CC=C2C(C=C)=CC=CC2=C1 IGGDKDTUCAWDAN-UHFFFAOYSA-N 0.000 description 1
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- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 0.000 description 1
- MUZDXNQOSGWMJJ-UHFFFAOYSA-N 2-methylprop-2-enoic acid;prop-2-enoic acid Chemical compound OC(=O)C=C.CC(=C)C(O)=O MUZDXNQOSGWMJJ-UHFFFAOYSA-N 0.000 description 1
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
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- LRQKBLKVPFOOQJ-YFKPBYRVSA-N L-norleucine Chemical compound CCCC[C@H]([NH3+])C([O-])=O LRQKBLKVPFOOQJ-YFKPBYRVSA-N 0.000 description 1
- 229920006065 Leona® Polymers 0.000 description 1
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- 239000001361 adipic acid Substances 0.000 description 1
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- 125000003118 aryl group Chemical group 0.000 description 1
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- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
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- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 125000002897 diene group Chemical group 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- LSHXECWFSXBAMI-UHFFFAOYSA-N disilanyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound C(C1CO1)OCCC[SiH2][SiH2][SiH3] LSHXECWFSXBAMI-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
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- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
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- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
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- ARYZCSRUUPFYMY-UHFFFAOYSA-N methoxysilane Chemical compound CO[SiH3] ARYZCSRUUPFYMY-UHFFFAOYSA-N 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
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- GEMHFKXPOCTAIP-UHFFFAOYSA-N n,n-dimethyl-n'-phenylcarbamimidoyl chloride Chemical compound CN(C)C(Cl)=NC1=CC=CC=C1 GEMHFKXPOCTAIP-UHFFFAOYSA-N 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
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- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【０００１】
【産業上の利用分野】
本発明は、ポリアミド樹脂、エラストマーおよびガラス繊維からなるポリアミド樹脂組成物に関するものである。さらに詳しくは、強度・剛性、耐衝撃性および外観に優れた電動工具外装材用の樹脂組成物に関するものである。
【０００２】
【従来の技術】
ポリアミド樹脂は優れた機械的強度、耐熱性、耐薬品性などの特徴を有するエンジニアリング樹脂として有用である。更にこのポリアミド樹脂に耐衝撃性を付与せしめて、より広い応用を開く技術も数多く、幅広い用途に使用されている。例として、近年の良外観の要求を強く要望するユーザーニーズから、良外観の樹脂を用いた電動工具の外装材等に、一部用いられるようになった。
電動工具の外装材用の要求性能は、大きな荷重、剛性、急激な衝撃に対しても割れないほどの充分な耐衝撃性および表面の高光沢性が必要とされている。
【０００３】
従来、良外観を有するにはポリアミド６をベースにし、強度・剛性を付与するためにガラス繊維を配合し、また耐衝撃性を付与するためにエラストマー成分を配合したポリアミド樹脂組成物が知られている。
しかし、ポリアミド６ベースの樹脂組成物を用いた場合、ポリアミド６の吸水による強度・剛性の低下により温度の高い雰囲気下で使用した際、変形・割れ等といった問題が生じ、そのため実際に使用される環境領域が制限されていた。
【０００４】
一般に、ポリアミド樹脂は吸水性のため吸水率の増加に伴い樹脂の強度・剛性は低下し、その吸水率は使用される樹脂の雰囲気温度湿度に左右される。したがって、吸水による強度・剛性の低下の少ない材料、すなわちポリアミド６よりも吸水性の低いポリアミド樹脂が電動工具用途に望まれている。ポリアミド６よりも吸水による強度・剛性の低下の小さい樹脂としてはポリアミド６６がある。しかし、ポリアミド６成分の変わりにポリアミド６６成分だけを用いた場合、強度・剛性の低下は抑えられるものの樹脂成形表面上にガラス繊維の浮き上がりが起こり、表面肌が荒れ、外観を損なってしまう。
【０００５】
また、芳香環を含有するポリアミド樹脂では、吸水に伴う強度・剛性の低下および樹脂成形品表面上のガラス繊維の浮き上がり（白化現象）は抑制されるが、結晶性が低いために成形時の固化時間が長くなる（特許文献１参照）。成形サイクルは樹脂の可塑化時間に支配されるよりもむしろ成形品金型内での冷却時間に左右される。したがって、結晶性の低い樹脂は、成形タイムサイクルが長くなるという問題があった。
また、大気平衡下の強度・剛性、耐衝撃性、外観を改良することを目的として、ポリアミド６６、ポリアミド６の組成からなるポリアミド樹脂と特定のエラストマー成分およびガラス繊維を配合したポリアミド樹脂組成物が提案されている。しかしながら、１種類の芳香族ビニル化合物含有量の変性ブロック共重合体であるため、ポリアミド樹脂とエラストマー成分の親和性が充分でなく、耐衝撃性を満足できるレベルに至らなかった（例えば、特許文献２参照）。
【０００６】
また、変性ブロック共重合体に加えて、ブロック共重合体を更にポリアミド樹脂に配合させて耐衝撃性を向上させ、かつ成形加工性の改良も試みられている（例えば、特許文献３参照）。しかしながら、本発明の如く２種類の異なる芳香族ビニル化合物含有量の変性ブロック共重合体を併用することについては開示されておらず、またこの実施例に開示された組成物では、成形加工性の点で十分満足できるレベルまでは至らなかった。
また、ポリアミド樹脂に水素添加ブロック共重合体、変性ブロック共重合体を配合させて耐衝撃性、成型加工性の改良が試みられている（例えば、特許文献４参照）。しかしながら、ガラス繊維を加えると外観を十分満足できるレベルまで到達しておらず、特に良外観を要求される電動工具の外装材に用いるには問題があった。
【０００７】
【特許文献１】
特開平４−１４９２３４号
【特許文献２】
特開平６−３２２２６４号
【特許文献３】
特開昭６２−１４９７５０号
【特許文献４】
特開平７−２９２２４３号
【０００８】
【発明が解決しようとする課題】
本発明の目的は、ポリアミド樹脂、エラストマーおよびガラス繊維を用いて、耐衝撃性、剛性に極めて優れ、かつ外観に優れた成形品が得られる電動工具外装材用の樹脂組成物を提供することにある。
【０００９】
【課題を解決するための手段】
本発明者等らは、鋭意研究を重ねた結果、特定のポリアミド樹脂に特定のブロック共重合体、ガラス繊維を特定の比率で配合した場合、その目的を達成し得ることを見出し、この知見に基づき本発明を完成するに至った。
即ち、本発明はポリアミド６６（ａ−１）成分１００重量部およびポリアミド６（ａ−２）成分５０〜２００重量部からなるポリアミド樹脂（Ａ）成分、芳香族ビニル化合物と共役ジエン化合物からなるブロック共重合体を水素添加した水素添加ブロック共重合体（Ｂ）成分、芳香族ビニル化合物１０〜３５重量％と共役ジエン化合物からなるブロック共重合体を水素添加した水素添加ブロック共重合体にα，β−不飽和カルボン酸またはその誘導体が結合した変性ブロック共重合体（ｃ−１）成分および芳香族ビニル化合物３８〜７０重量％と共役ジエン化合物からなるブロック共重合体に水素添加した水素添加ブロック共重合体にα，β−不飽和カルボン酸またはその誘導体が結合した変性ブロック共重合体（ｃ−２）からなる（Ｃ）成分、およびガラス繊維（Ｄ）成分からなることを特徴とする電動工具外装用樹脂組成物、およびそれからなる成形品である。
【００１０】
ただし、各成分（重量％）は式（１）〜（４）を満たす。
５０≦Ａ＋Ｂ＋Ｃ≦９５ 式（１）
５０≦Ｄ≦５ 式（２）
０．２≦（ｃ−１＋ｃ−２）／Ｂ≦４ 式（３）
０．１≦（ｃ−２／ｃ−１）≦１０ 式（４）
本発明において、（Ａ）成分であるポリアミド樹脂とは、ポリアミド６６（ａ−１）成分およびポリアミド６（ａ−２）成分をブレンドしたものである。必要に応じて、（ａ−１）および（ａ−２）成分の混和性を高めるためにポリアミド６６／６共重合体（ａ−３）成分を加えても差し支えない。本発明でいう（ａ−１）、（ａ−２）および（ａ−３）成分は、ヘキサメチレンジアミンとアジピン酸の塩、ε−カプロラクタム、α−アミノカプロン酸または、それらの混合原料を出発原料として、通常の溶融重合および固相重合して得られる樹脂である。分子量については特に制限はないが数平均分子量５，０００〜５０，０００のものが好適に用いられる。
【００１１】
本発明の（ａ−１）、（ａ−２）および（ａ−３）成分のブレンド比またはポリアミド６６／６の共重合体比は、組成物のＴｃが１７５〜２２０℃になるように選択することが必要である。ここでいうＴｃとは、ＪＩＳ Ｋ７１２１に準じてＤＳＣで樹脂組成物を窒素雰囲気下、２０℃／分で３００℃まで昇温し、５分間３００℃に保持し、２０℃／分で降温した時の結晶化ピークの温度のことをいい、好ましいＴｃは、１８０〜２１５℃である。
【００１２】
本発明において、（Ｂ）成分である芳香族ビニル化合物と共役ジエン化合物からなる水素添加ブロック共重合体とは、ビニル芳香族重合体ブロックと共役ジエン化合物重合体ブロックとよりなるブロック共重合体の共役ジエン部分を選択的に水素添加することによって得られるものである。
ここで用いられるビニル芳香族化合物として代表的な化合物には、スチレン，α−メチルスチレン，ビニルキシレン，エチルビニルキシレン，ビニルナフタリンおよびこれらの混合物が例示され、また共役ジエン系化合物には、ブタジエン，イソプレン，１，３−ペンタジエンまたは２，３−ジメチルブタジエン，およびこれらの混合物が挙げられる。好ましくは、ビニル芳香族化合物としてはスチレン、共役ジエン系化合物としてはブタジエンである。
【００１３】
これらのブロック共重合体の両末端ブロックは同じであっても異なっていてもよい。これらのブロック共重合体の数平均分子量は特に限定されないが、好ましくは１０，０００〜８００，０００、さらに好ましくは２０，０００〜５００，０００である。
また、ブロック共重合体中の芳香族ビニル化合物の含有量はとくに制限はないが１０〜７０重量％が好ましく、さらに好ましくは１０〜５５重量％である。本発明で使用する水素添加ブロック共重合体（Ｂ）成分は、前記ブロック共重合体の共役ジエン部分を選択的に水素添加することによって得られるものであり、例えばｎ−ヘキサンとシクロヘキサンの混合溶媒中でナフテン酸コバルトとトリエチルアルミニウムを触媒として水素を添加する方法で前記ブロック共重合体を水素添加することにより、ビニル芳香族化合物ブロックの芳香族二重結合の２０％をこえない部分および共役ジエン化合物重合体ブロックの脂肪族二重結合の少なくとも８０％が水素添加されている水素添加ブロック共重合体が合成することができる。
【００１４】
本発明で用いられる（ｃ−１）成分の変性ブロック共重合体は（Ｂ）成分である水素添加ブロック共重合体にα，β−不飽和カルボン酸またはその誘導体を付加させることにより得られるが、ここで用いる水素添加ブロック共重合体中の芳香族ビニル化合物の含有量は１０〜３５重量％、好ましくは１５〜３０重量％である。
また本発明で用いられる（ｃ−２）成分の変性ブロック共重合体も同様に水素添加ブロック共重合体（Ｂ）成分にα，β−不飽和カルボン酸またはその誘導体を付加させることにより得られるが、ここで用いる水素添加ブロック共重合体中の芳香族ビニル化合物の含有量は３８〜７０重量％、好ましくは４０〜６０重量％である。
成分（ｃ−１）および（ｃ−２）成分を調製する際に用いるα，β−不飽和カルボン酸またはその誘導体の例としては、マレイン酸，無水マレイン酸，フマル酸，イタコン酸，アクリル酸，メタクリル酸，コハク酸，無水コハク酸，クロトン酸，フタル酸，無水フタル酸等が挙げられるが、これらの中では無水マレイン酸が特に好ましい。
【００１５】
上記変性ブロック共重合体（ｃ−１）および（ｃ−２）成分は、例えば、水素添加ブロック共重合体にα，β−不飽和カルボン酸またはその誘導体を溶液状態または溶融状態において、ラジカル開始剤を使用あるいは使用せずに付加せしめることによって得られる。これら変性ブロック共重合体（ｃ−１）および（ｃ−２）成分の製造方法に関しては、本発明においては特に限定しないが、得られた変性ブロック共重合体（ｃ−１）および（ｃ−２）成分がゲル等の好ましくない成分を含んだり、その溶融粘度が著しく増大して加工性が悪化したりする製造方法は好ましくない。好ましい方法としては、押出機中において、ラジカル開始剤存在下で、水素添加ブロック共重合体とα，β−不飽和カルボン酸またはその誘導体と反応させる方法がある。
【００１６】
変性ブロック共重合体（ｃ−１）および（ｃ−２）成分の変性量は、それぞれ未変性の水素添加ブロック共重合体１００重量部あたり、いずれも耐衝撃性の観点から０．１以上であり、耐熱性、成形加工性の観点から３重量部以下であることが好ましく、さらに好ましくは０．１５〜１．８重量部である。
本発明の特徴は、特定のＴｃのポリアミド樹脂（Ａ）成分に、水素添加ブロック共重合体系（Ｂ）成分に１種類の変性ブロック共重合体ではなく、異なるビニル芳香族化合物含有量の変性ブロック共重合体（ｃ−１）（ｃ−２）併用し、ガラス繊維（Ｄ）成分を配合したところにあり、このことが耐衝撃性に極めて優れ、良外観の成形品が得られるとの本発明の特異的効果を発現させているのである。この理由については明確ではないが、ポリアミド樹脂（Ａ）成分と水素添加ブロック共重合体（Ｂ）成分との親和性が著しく高められたため、成形加工時における剪断応力下での分散粒子の変形が著しく抑制されたためと推定している。
【００１７】
本発明の組成物において、（Ａ）、（Ｂ）および（Ｃ）成分の量を（Ａ）＋（Ｂ）＋（Ｃ）＝１００重量部とし、４０≦Ａ≦９５、好ましくは５０≦Ａ≦９０、５≦Ｂ＋Ｃ≦６０、好ましくは１０≦Ｂ＋Ｃ≦５０、０．２≦（ｃ−１＋ｃ−２）／Ｂ≦４、好ましくは０．３≦（ｃ−１＋ｃ−２）／Ｂ≦３、０．１≦ｃ−２／ｃ−１≦１０、好ましくは０．５≦（ｃ−２／ｃ−１）≦７を満足することが必要である。ただし、それぞれの単位は重量部である。
本発明におけるガラス繊維（Ｄ）成分としては、ポリアミド樹脂の補強材として用いるものであれば良いが、ガラス繊維をポリアミド樹脂と溶融混合する際のハンドリング性の観点からガラス繊維長さ１〜１０ｍｍ、平均ガラス繊維直径８〜２５μｍのチョップドタイプの短繊維が好ましい。特に好ましいガラス繊維の形状は補強効果とガラス繊維分散性の点から、繊維長さ２〜７ｍｍ、平均繊維直径８〜１５μｍのガラス繊維である。
【００１８】
ガラス繊維表面には、無水マレイン酸と不飽和単量体との共重合体および通常公知のシラン系カップリング剤を付着させたものを用いることが更に好ましい。
集束材を構成する無水マレイン酸と不飽和単量体との共重合体としては具体的には、スチレン、α−メチルスチレン、ブタジエン、イソプレン、クロロプレン、２，３−ジクロロブタジエン、１，３−ペンタジエン、シクロオクタジエン等の不飽和単量体と無水マレイン酸との共重合体が挙げられ、その中でもブタジエン、スチレンと無水マレイン酸との共重合体が特に好ましい。さらにこれらの単量体は２種以上併用しても良いし、例えば、無水マレイン酸とブタジエンの共重合体に無水マレイン酸とスチレンの共重合体を混合して使用する等のブレンドによって使用しても構わない。上記無水マレイン酸と不飽和単量体との共重合体は平均分子量２，０００以上であることが好ましい。また、無水マレイン酸と不飽和単量体との割合は特に制限されない。さらに無水マレイン酸共重合体に加えてアクリル酸系共重合体やウレタン系ポリマーを併用しても何ら差し支えない。
【００１９】
ガラス繊維の集束材を構成するもう一つの成分であるシランカップリング剤としては、例えばγ−アミノプロピルトリメトキシシラン、γ−アミノプロピルトリエトキシシラン、ビニルトリエトキシシラン、γ−グリシドキシプロピルトリメトキシシランなどが利用できるが、アミノ系シランカップリング剤が好ましい。
本発明における（Ｄ）ガラス繊維の配合量は、（Ａ）＋（Ｂ）＋（Ｃ）＝１００重量部あたり１０〜７０重量部、好ましくは２０〜５５重量部である。
【００２０】
本発明の樹脂組成物は通常の高分子物質の混合に供される装置によって調製できる。これら混合装置としては、混練押出機、バンバリーミキサー、ニーダー等が挙げられる。
本発明の電動工具外装材用樹脂組成物を溶融混合する順番は、（Ａ）、（Ｂ）および（Ｃ）成分を同時に溶融混合し、（Ａ）、（Ｂ）および（Ｃ）成分が溶融している段階で（Ｄ）成分を添加することがガラス繊維長を長く保持し、強度・剛性を高くすることから好ましい。
【００２１】
本発明の樹脂組成物には、その成形性，物性を損なわない限りにおいて、他の成分、例えば顔料、染料、充填剤、熱安定剤、酸化劣化防止剤、耐候性改良剤、核剤、滑剤、可塑剤、帯電防止剤、離型剤、他の樹脂ポリマー等を添加することができる。
本発明の組成物は、射出成形、押出成形、ブロー成形など公知の成形方法によって各種成形品に成形される。
【００２２】
【実施例】
以下の実施例により本発明をさらに詳しく説明するが、本発明はこれに限定されるものではない。なお、実施例、比較例に用いた原材料および測定方法を以下に示す。
［１］原材料
（Ａ）ポリアミド樹脂
（ａ−１）ポリアミド６６；旭化成（株）製レオナ１４０２ Ｓ ０１１
（ａ−２）ポリアミド６；宇部興産（株）製ＳＦ１０１３Ａ
（Ｂ）水素添加ブロック共重合体
水素添加したスチレン−ブタジエン共重合体；旭化成（株）製タフテックＨ１０５２，スチレン成分約２０重量％
【００２３】
（Ｃ）変性ブロック共重合体
（ｃ−１）水素添加した無水マレイン酸変性スチレン−ブタジエン共重合体；旭化成（株）製タフテックＭ１９４３，スチレン成分約２０重量％，無水マレイン酸付加量約１．２重量部（ナトリウムメチラート滴定法で求めた）
（ｃ−２）水素添加した無水マレイン酸変性スチレン−ブタジエン共重合体；旭化成（株）製タフテックＭ１９５３，スチレン成分約４０重量％，無水マレイン酸付加量約１．２重量部（ナトリウムメチラート滴定法で求めた）
（Ｄ）ガラス繊維
ガラス繊維平均直径１０μｍ、ガラス繊維平均長さ３ｍｍ、集束剤主要成分［ブタジエン−無水マレイン酸共重合体、Ｎ−β（アミノエチル）γ−アミノプロピルトリエトキシシラン］、集束剤付着量０．４重量％
【００２４】
［２］試験片の作成
（１）アイゾット衝撃強度および曲げ試験片の作成；射出成形機（日精樹脂（株）製 ＰＳ４０Ｅ）を用い、シリンダー温度２９０℃、金型温度８０℃で、ＡＳＴＭ１号試験片を作成した。
【００２５】
（２）外観試験片の作成；ＪＩＳ Ｋ７１５０に従い、射出成形機（東芝（株）ＩＳ１５０Ｅ）を用い、シリンダー温度２９０℃、金型温度８０℃で、１３０ｍｍ×１３０ｍｍ×厚さ３ｍｍの試験片を作成した。
【００２６】
［３］試験方法
（１）アイゾット衝撃強度；ＡＳＴＭ−Ｄ２５６に従い、測定温度２３℃で評価した。
（２）剛性特性；曲げ弾性率を代用し、ＡＳＴＭ−Ｄ７９０に従い、測定温度２３℃で評価した。
（３）結晶化温度（Ｔｃ）；ＪＩＳ Ｋ７１２１に従い、ペレット１０ｍｇを精秤し、パーキンエルマー社製ＤＳＣ−７型示差走査熱量計を用いて、窒素ガス雰囲気下で２０℃／分で降温した時の結晶化ピークの温度をポリアミド樹脂のＴｃとした。
（４）成形品外観；成形品表面を測定した光沢度で行った。また、可塑化量６４ｍｍで、保圧切り換え位置１５ｍｍ、クッション量１０ｍｍである。全ての評価は充填時間を０．８秒に合わせて実施した。
【００２７】
［４］判定基準
成形品外観の評価は、以下の判定基準に基づいて実施した。
外観；光沢度（グロス％）
良好−○ ４０以上
普通−△ ４０〜２５
不良−× ２５以下
【００２８】
【実施例１】
（Ａ）ポリアミド６６（ａ−１）成分を１８．３重量％、ポリアミド６（ａ−２）成分を３４重量％、水素添加ブロック共重合体（Ｂ）成分を８．７重量％、（Ｃ）変性ブロック共重合体（Ｍ１９４３）（ｃ−１）成分を１．７重量％および変性ブロック共重合体（Ｍ１９５３）（ｃ−２）成分４．３重量％（表１参照）を計量し、タンブラー型ブレンダーを用いて予備混合した。これを二軸押出機（東芝機械（株）製 ＴＥＭ３５）を用いて、シリンダー設定温度２９０℃、スクリュー回転数３００ｒｐｍの条件下で溶融混練後、ストランド状に取り出したものを水冷し、カッターで造粒してペレット状の組成物を得た。なお、押出機の上流側に設けられたフィード口（トップフィード）より（Ａ）、（Ｂ）、（Ｃ）成分を、押出機の下流側に設けられたフィード口（サイドフィード）よりガラス繊維（Ｄ）成分３３重量％を投入した。得られたペレットを射出成形機で物性測定用の試験片に成形した。その結果を表１に示す。
【００２９】
【実施例２〜４、比較例１〜４】
表１に示す配合組成で、試料の作成、評価を実施例１と同様に実施した。その結果を表１に示す。
【００３０】
【表１】
【発明の効果】
本発明の組成物は、ゴム成分がポリアミド樹脂マトリックス相に均一に分散したモルフォロジーを有するために、耐衝撃性、外観に優れている成形用材料である。このような本発明の組成物は、衝撃性を要する電動工具用外装材として好適に用いることができる。[0001]
[Industrial applications]
The present invention relates to a polyamide resin composition comprising a polyamide resin, an elastomer, and glass fibers. More specifically, the present invention relates to a resin composition for a power tool exterior material excellent in strength / rigidity, impact resistance and appearance.
[0002]
[Prior art]
Polyamide resin is useful as an engineering resin having features such as excellent mechanical strength, heat resistance, and chemical resistance. Furthermore, there are many techniques for imparting impact resistance to this polyamide resin to open up a wider range of applications, and are used for a wide range of applications. For example, in recent years, due to user needs that strongly demand good appearance, some of them have been used as exterior materials of electric tools using resin of good appearance.
The performance required for an exterior material of a power tool requires a large load, rigidity, sufficient impact resistance so as not to be broken even by a sudden impact, and high glossiness of the surface.
[0003]
Conventionally, a polyamide resin composition based on polyamide 6 to have good appearance, glass fiber for imparting strength and rigidity, and an elastomer component for imparting impact resistance has been known. I have.
However, when a polyamide 6-based resin composition is used, problems such as deformation and cracking occur when the polyamide 6 is used in a high-temperature atmosphere due to a decrease in strength and rigidity due to water absorption of the polyamide 6, and the polyamide 6 is actually used. Environmental area was limited.
[0004]
In general, polyamide resin absorbs water, so that the strength and rigidity of the resin decrease with an increase in the water absorption, and the water absorption depends on the ambient temperature and humidity of the resin used. Therefore, a material with less decrease in strength and rigidity due to water absorption, that is, a polyamide resin having lower water absorption than polyamide 6 is desired for electric power tool applications. Polyamide 66 is a resin whose strength and rigidity are less reduced by water absorption than polyamide 6. However, when only the polyamide 66 component is used instead of the polyamide 6 component, the strength and rigidity are reduced, but the glass fibers are lifted on the resin molding surface, and the surface skin is roughened and the appearance is impaired.
[0005]
In addition, in the case of polyamide resin containing an aromatic ring, the strength and rigidity are reduced due to water absorption, and the lifting (whitening phenomenon) of glass fibers on the surface of the resin molded product is suppressed. The time becomes longer (see Patent Document 1). The molding cycle depends on the cooling time in the mold rather than on the plasticization time of the resin. Therefore, a resin having low crystallinity has a problem in that the molding time cycle becomes long.
Further, for the purpose of improving the strength / rigidity under atmospheric equilibrium, impact resistance, and appearance, a polyamide resin composition comprising a polyamide resin composed of polyamide 66 and polyamide 6, a specific elastomer component and glass fiber is used. Proposed. However, since it is a modified block copolymer containing one kind of aromatic vinyl compound, the affinity between the polyamide resin and the elastomer component is not sufficient, and the impact resistance has not reached a satisfactory level (for example, see Patent Document 1). 2).
[0006]
Further, in addition to a modified block copolymer, a block copolymer is further blended with a polyamide resin to improve impact resistance and to improve moldability (for example, see Patent Document 3). However, it does not disclose the use of two kinds of modified block copolymers having different aromatic vinyl compound contents as in the present invention, and the composition disclosed in this example does not show the molding processability. We did not reach a satisfactory level.
Also, attempts have been made to improve impact resistance and moldability by blending a hydrogenated block copolymer or a modified block copolymer with a polyamide resin (see, for example, Patent Document 4). However, when glass fiber is added, the appearance does not reach a sufficiently satisfactory level, and there is a problem in using it as an exterior material of a power tool that requires particularly good appearance.
[0007]
[Patent Document 1]
JP-A-4-149234 [Patent Document 2]
JP-A-6-322264 [Patent Document 3]
JP 62-149750 A [Patent Document 4]
JP-A-7-292243
[Problems to be solved by the invention]
An object of the present invention is to provide a resin composition for a power tool exterior material that can obtain a molded article having extremely excellent impact resistance, rigidity, and appearance by using a polyamide resin, an elastomer, and glass fiber. is there.
[0009]
[Means for Solving the Problems]
The present inventors have assiduously studied and, as a result, have found that when a specific polyamide resin is blended with a specific block copolymer and glass fiber in a specific ratio, the purpose can be achieved, and this finding is Based on this, the present invention has been completed.
That is, the present invention provides a polyamide resin (A) component comprising 100 parts by weight of a polyamide 66 (a-1) component and 50 to 200 parts by weight of a polyamide 6 (a-2) component, and a block comprising an aromatic vinyl compound and a conjugated diene compound. The hydrogenated block copolymer (B) component obtained by hydrogenating the copolymer, the hydrogenated block copolymer obtained by hydrogenating a block copolymer comprising 10 to 35% by weight of an aromatic vinyl compound and a conjugated diene compound, are added with α, hydrogenated block obtained by hydrogenating a modified block copolymer (c-1) component having β-unsaturated carboxylic acid or a derivative thereof bonded thereto and a block copolymer comprising 38 to 70% by weight of an aromatic vinyl compound and a conjugated diene compound Component (C) comprising a modified block copolymer (c-2) in which an α, β-unsaturated carboxylic acid or a derivative thereof is bonded to a copolymer. And power tools exterior resin composition characterized by comprising the glass fiber (D) component, and then becomes the molded article.
[0010]
However, each component (% by weight) satisfies the formulas (1) to (4).
50 ≦ A + B + C ≦ 95 Formula (1)
50 ≦ D ≦ 5 Equation (2)
0.2 ≦ (c−1 + c−2) / B ≦ 4 Equation (3)
0.1 ≦ (c−2 / c−1) ≦ 10 Equation (4)
In the present invention, the polyamide resin as the component (A) is a blend of the polyamide 66 (a-1) component and the polyamide 6 (a-2) component. If necessary, a component of the polyamide 66/6 copolymer (a-3) may be added to enhance the miscibility of the components (a-1) and (a-2). The components (a-1), (a-2) and (a-3) referred to in the present invention are a salt of hexamethylenediamine and adipic acid, ε-caprolactam, α-aminocaproic acid or a mixed material thereof as a starting material. Is a resin obtained by ordinary melt polymerization and solid phase polymerization. The molecular weight is not particularly limited, but those having a number average molecular weight of 5,000 to 50,000 are preferably used.
[0011]
The blend ratio of the components (a-1), (a-2) and (a-3) of the present invention or the copolymer ratio of the polyamide 66/6 is selected so that the Tc of the composition is 175 to 220 ° C. It is necessary to. The Tc referred to here is a value obtained by raising the temperature of the resin composition to 300 ° C. at a rate of 20 ° C./min in a nitrogen atmosphere by DSC according to JIS K7121, keeping the temperature at 300 ° C. for 5 minutes, and lowering the temperature at 20 ° C./min. Means the temperature of the crystallization peak, and the preferred Tc is 180 to 215 ° C.
[0012]
In the present invention, the hydrogenated block copolymer comprising an aromatic vinyl compound and a conjugated diene compound as the component (B) is a hydrogenated block copolymer comprising a vinyl aromatic polymer block and a conjugated diene compound polymer block. It is obtained by selectively hydrogenating a conjugated diene moiety.
Typical examples of the vinyl aromatic compound used herein include styrene, α-methylstyrene, vinyl xylene, ethyl vinyl xylene, vinyl naphthalene and a mixture thereof, and conjugated diene compounds include butadiene, Examples include isoprene, 1,3-pentadiene or 2,3-dimethylbutadiene, and mixtures thereof. Preferably, the vinyl aromatic compound is styrene, and the conjugated diene compound is butadiene.
[0013]
Both terminal blocks of these block copolymers may be the same or different. The number average molecular weight of these block copolymers is not particularly limited, but is preferably 10,000 to 800,000, and more preferably 20,000 to 500,000.
The content of the aromatic vinyl compound in the block copolymer is not particularly limited, but is preferably from 10 to 70% by weight, and more preferably from 10 to 55% by weight. The hydrogenated block copolymer (B) component used in the present invention is obtained by selectively hydrogenating the conjugated diene portion of the block copolymer. For example, a mixed solvent of n-hexane and cyclohexane Hydrogenation of the block copolymer by a method in which hydrogen is added using cobalt naphthenate and triethylaluminum as catalysts to form a portion not exceeding 20% of the aromatic double bond of the vinyl aromatic compound block and a conjugated diene; A hydrogenated block copolymer in which at least 80% of the aliphatic double bonds of the compound polymer block are hydrogenated can be synthesized.
[0014]
The modified block copolymer of the component (c-1) used in the present invention can be obtained by adding an α, β-unsaturated carboxylic acid or a derivative thereof to the hydrogenated block copolymer as the component (B). The content of the aromatic vinyl compound in the hydrogenated block copolymer used here is 10 to 35% by weight, preferably 15 to 30% by weight.
The modified block copolymer of the component (c-2) used in the present invention can also be obtained by adding an α, β-unsaturated carboxylic acid or a derivative thereof to the hydrogenated block copolymer (B). However, the content of the aromatic vinyl compound in the hydrogenated block copolymer used here is 38 to 70% by weight, preferably 40 to 60% by weight.
Examples of the α, β-unsaturated carboxylic acid or its derivative used for preparing the components (c-1) and (c-2) include maleic acid, maleic anhydride, fumaric acid, itaconic acid, acrylic acid Methacrylic acid, succinic acid, succinic anhydride, crotonic acid, phthalic acid, phthalic anhydride and the like. Of these, maleic anhydride is particularly preferred.
[0015]
The above-mentioned modified block copolymers (c-1) and (c-2) are, for example, radical-initiated by adding α, β-unsaturated carboxylic acid or its derivative to a hydrogenated block copolymer in a solution state or a molten state. It can be obtained by adding or not using an agent. The method for producing these modified block copolymers (c-1) and (c-2) is not particularly limited in the present invention, but the obtained modified block copolymers (c-1) and (c- 2) A production method in which the component contains an undesired component such as a gel or the melt viscosity is remarkably increased to deteriorate the processability is not preferred. A preferred method is to react the hydrogenated block copolymer with an α, β-unsaturated carboxylic acid or a derivative thereof in an extruder in the presence of a radical initiator.
[0016]
The amount of modification of each of the modified block copolymers (c-1) and (c-2) is 0.1 or more from the viewpoint of impact resistance, per 100 parts by weight of the unmodified hydrogenated block copolymer. The amount is preferably 3 parts by weight or less, more preferably 0.15 to 1.8 parts by weight from the viewpoint of heat resistance and moldability.
A feature of the present invention is that the polyamide resin (A) having a specific Tc is not a hydrogenated block copolymer system (B) component but a modified block copolymer having a different vinyl aromatic compound content instead of one modified block copolymer. The copolymer (c-1) and (c-2) are used in combination, and the glass fiber (D) component is blended. This is a book that is extremely excellent in impact resistance and that a molded article with good appearance can be obtained. The specific effects of the invention are exhibited. Although the reason for this is not clear, the affinity between the polyamide resin (A) component and the hydrogenated block copolymer (B) component has been remarkably increased, so that the deformation of the dispersed particles under shear stress during molding processing is reduced. It is estimated that it was significantly suppressed.
[0017]
In the composition of the present invention, the amounts of the components (A), (B) and (C) are (A) + (B) + (C) = 100 parts by weight, and 40 ≦ A ≦ 95, preferably 50 ≦ A. ≤90, 5≤B + C≤60, preferably 10≤B + C≤50, 0.2≤ (c-1 + c-2) / B≤4, preferably 0.3≤ (c-1 + c-2) / B≤3 , 0.1 ≦ c−2 / c−1 ≦ 10, preferably 0.5 ≦ (c−2 / c−1) ≦ 7. However, each unit is part by weight.
As the glass fiber (D) component in the present invention, any material may be used as long as it is used as a reinforcing material for the polyamide resin. From the viewpoint of handling properties when the glass fiber is melt-mixed with the polyamide resin, a glass fiber length of 1 to 10 mm, Chopped short fibers having an average glass fiber diameter of 8 to 25 μm are preferred. A particularly preferable shape of the glass fiber is a glass fiber having a fiber length of 2 to 7 mm and an average fiber diameter of 8 to 15 μm from the viewpoint of the reinforcing effect and the glass fiber dispersibility.
[0018]
More preferably, a glass fiber surface to which a copolymer of maleic anhydride and an unsaturated monomer and a generally known silane coupling agent are attached is used.
Specific examples of the copolymer of maleic anhydride and the unsaturated monomer constituting the sizing material include styrene, α-methylstyrene, butadiene, isoprene, chloroprene, 2,3-dichlorobutadiene, 1,3- Copolymers of unsaturated monomers such as pentadiene and cyclooctadiene with maleic anhydride are listed, and among them, copolymers of butadiene, styrene and maleic anhydride are particularly preferable. Further, these monomers may be used in combination of two or more kinds. For example, they may be used in a blend such as a mixture of maleic anhydride and butadiene mixed with a copolymer of maleic anhydride and styrene. It does not matter. The copolymer of maleic anhydride and unsaturated monomer preferably has an average molecular weight of 2,000 or more. Further, the ratio between maleic anhydride and the unsaturated monomer is not particularly limited. Further, an acrylic acid-based copolymer or a urethane-based polymer may be used in combination with the maleic anhydride copolymer at all.
[0019]
Examples of the silane coupling agent, which is another component constituting the glass fiber sizing material, include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, vinyltriethoxysilane, and γ-glycidoxypropyltrisilane. Although methoxysilane and the like can be used, an amino silane coupling agent is preferable.
The amount of the glass fiber (D) in the present invention is 10 to 70 parts by weight, preferably 20 to 55 parts by weight, per 100 parts by weight of (A) + (B) + (C).
[0020]
The resin composition of the present invention can be prepared by an apparatus used for mixing ordinary polymer substances. These mixing devices include a kneading extruder, a Banbury mixer, a kneader and the like.
The order of melt-mixing the resin composition for a power tool exterior material of the present invention is such that the components (A), (B) and (C) are simultaneously melt-mixed, and the components (A), (B) and (C) are melted. It is preferable to add the component (D) at this stage because the glass fiber length is maintained long and the strength and rigidity are increased.
[0021]
The resin composition of the present invention has other components such as a pigment, a dye, a filler, a heat stabilizer, an antioxidant, an antioxidant, a weather resistance improver, a nucleating agent, and a lubricant as long as the moldability and physical properties are not impaired. , A plasticizer, an antistatic agent, a release agent, and other resin polymers.
The composition of the present invention is formed into various molded products by a known molding method such as injection molding, extrusion molding, and blow molding.
[0022]
【Example】
The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto. In addition, the raw materials and measuring methods used in the examples and comparative examples are shown below.
[1] Raw material (A) polyamide resin (a-1) polyamide 66; Leona 1402 S 011 manufactured by Asahi Kasei Corporation
(A-2) Polyamide 6; SF1013A manufactured by Ube Industries, Ltd.
(B) Hydrogenated block copolymer Hydrogenated styrene-butadiene copolymer; Tuftec H1052 manufactured by Asahi Kasei Corporation, styrene component about 20% by weight
[0023]
(C) Modified block copolymer (c-1) Hydrogenated maleic anhydride-modified styrene-butadiene copolymer; Tuftec M1943 manufactured by Asahi Kasei Corporation, styrene component about 20% by weight, maleic anhydride addition amount about 1. 2 parts by weight (determined by sodium methylate titration)
(C-2) Hydrogenated maleic anhydride-modified styrene-butadiene copolymer; Tuftec M1953 manufactured by Asahi Kasei Corporation, about 40% by weight of styrene component, about 1.2 parts by weight of maleic anhydride added (sodium methylate titration) Determined by law)
(D) Glass fiber Glass fiber average diameter 10 μm, glass fiber average length 3 mm, sizing agent main components [butadiene-maleic anhydride copolymer, N-β (aminoethyl) γ-aminopropyltriethoxysilane], sizing agent 0.4% by weight
[0024]
[2] Preparation of test pieces (1) Preparation of Izod impact strength and bending test pieces; ASTM No. 1 test using an injection molding machine (PS40E manufactured by Nissei Plastics Co., Ltd.) at a cylinder temperature of 290 ° C. and a mold temperature of 80 ° C. A piece was made.
[0025]
(2) Preparation of appearance test piece: According to JIS K7150, using an injection molding machine (Toshiba Corporation IS150E), a test piece of 130 mm × 130 mm × thickness of 3 mm was prepared at a cylinder temperature of 290 ° C. and a mold temperature of 80 ° C. did.
[0026]
[3] Test method (1) Izod impact strength: Evaluated at a measurement temperature of 23 ° C. according to ASTM-D256.
(2) Rigidity: Evaluated at a measurement temperature of 23 ° C. according to ASTM-D790, substituting the flexural modulus.
(3) Crystallization temperature (Tc): In accordance with JIS K7121, 10 mg of pellets were precisely weighed, and the temperature was lowered at 20 ° C./min under a nitrogen gas atmosphere using a DSC-7 type differential scanning calorimeter manufactured by PerkinElmer. The temperature of the crystallization peak of was determined as Tc of the polyamide resin.
(4) Appearance of molded article: The gloss of the molded article surface was measured. In addition, the plasticization amount is 64 mm, the holding pressure switching position is 15 mm, and the cushion amount is 10 mm. All evaluations were performed with a fill time of 0.8 seconds.
[0027]
[4] Criteria for Evaluation The appearance of the molded product was evaluated based on the following criteria.
Appearance; gloss (gloss%)
Good- ○ 40 or more normal- △ 40-25
Defective-25 or less
Embodiment 1
(A) 18.3% by weight of polyamide 66 (a-1) component, 34% by weight of polyamide 6 (a-2) component, 8.7% by weight of hydrogenated block copolymer (B) component, (C) ) 1.7% by weight of the modified block copolymer (M1943) (c-1) component and 4.3% by weight of the modified block copolymer (M1953) (c-2) component (see Table 1), Premixing was performed using a tumbler type blender. This was melt-kneaded using a twin-screw extruder (TEM35, manufactured by Toshiba Machine Co., Ltd.) under the conditions of a cylinder set temperature of 290 ° C. and a screw rotation speed of 300 rpm. The pelletized composition was obtained. The components (A), (B), and (C) are supplied from a feed port (top feed) provided on the upstream side of the extruder, and glass fiber is supplied from a feed port (side feed) provided on the downstream side of the extruder. 33% by weight of the component (D) was added. The obtained pellets were formed into test pieces for measuring physical properties by an injection molding machine. Table 1 shows the results.
[0029]
Examples 2 to 4, Comparative Examples 1 to 4
Preparation and evaluation of samples were performed in the same manner as in Example 1 with the composition shown in Table 1. Table 1 shows the results.
[0030]
[Table 1]
【The invention's effect】
The composition of the present invention is a molding material excellent in impact resistance and appearance because it has a morphology in which a rubber component is uniformly dispersed in a polyamide resin matrix phase. Such a composition of the present invention can be suitably used as an exterior material for an electric tool requiring impact resistance.
Claims (7)
ただし、各成分（重量％）は式（１）〜（４）を満たす。
５０≦Ａ＋Ｂ＋Ｃ≦９５ 式（１）
５０≦Ｄ≦５ 式（２）
０．２≦（ｃ−１＋ｃ−２）／Ｂ≦４ 式（３）
０．１≦（ｃ−２／ｃ−１）≦１０ 式（４）A polyamide resin (A) component comprising 100 parts by weight of a polyamide 66 (a-1) component and 50 to 200 parts by weight of a polyamide 6 (a-2) component, and a block copolymer comprising an aromatic vinyl compound and a conjugated diene compound are hydrogenated. The α, β-unsaturated carboxylic acid is added to the hydrogenated block copolymer (B), which is a hydrogenated block copolymer obtained by hydrogenating a block copolymer comprising 10 to 35% by weight of an aromatic vinyl compound and a conjugated diene compound. Α is added to the hydrogenated block copolymer obtained by hydrogenating a modified block copolymer (c-1) component to which an acid or a derivative thereof is bonded and a block copolymer comprising 38 to 70% by weight of an aromatic vinyl compound and a conjugated diene compound. Component (C) comprising a modified block copolymer (c-2) to which .beta.-unsaturated carboxylic acid or a derivative thereof is bonded, and glass Wei (D) power tool exterior material for a resin composition characterized in that it consists of components.
However, each component (% by weight) satisfies the formulas (1) to (4).
50 ≦ A + B + C ≦ 95 Formula (1)
50 ≦ D ≦ 5 Equation (2)
0.2 ≦ (c−1 + c−2) / B ≦ 4 Equation (3)
0.1 ≦ (c−2 / c−1) ≦ 10 Equation (4)
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| JP2003101753A JP2004307615A (en) | 2003-04-04 | 2003-04-04 | Resin composition for power tool sheath material |
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| JP2003101753A JP2004307615A (en) | 2003-04-04 | 2003-04-04 | Resin composition for power tool sheath material |
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| JP2004307615A true JP2004307615A (en) | 2004-11-04 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011030778A1 (en) * | 2009-09-09 | 2011-03-17 | ダイセルポリマー株式会社 | Resin composition for use in coated molded article |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011030778A1 (en) * | 2009-09-09 | 2011-03-17 | ダイセルポリマー株式会社 | Resin composition for use in coated molded article |
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