JP5220333B2 - Master batch for adding nylon resin - Google Patents
Master batch for adding nylon resin Download PDFInfo
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- JP5220333B2 JP5220333B2 JP2007088168A JP2007088168A JP5220333B2 JP 5220333 B2 JP5220333 B2 JP 5220333B2 JP 2007088168 A JP2007088168 A JP 2007088168A JP 2007088168 A JP2007088168 A JP 2007088168A JP 5220333 B2 JP5220333 B2 JP 5220333B2
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- 229920005989 resin Polymers 0.000 title claims description 64
- 239000011347 resin Substances 0.000 title claims description 64
- 229920001778 nylon Polymers 0.000 title claims description 49
- 239000004677 Nylon Substances 0.000 title claims description 48
- 239000004594 Masterbatch (MB) Substances 0.000 title claims description 31
- 239000000178 monomer Substances 0.000 claims description 42
- 229920002292 Nylon 6 Polymers 0.000 claims description 36
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 claims description 22
- 229920005992 thermoplastic resin Polymers 0.000 claims description 21
- 229920000642 polymer Polymers 0.000 claims description 18
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 17
- 229920001577 copolymer Polymers 0.000 claims description 14
- 229920006111 poly(hexamethylene terephthalamide) Polymers 0.000 claims description 14
- 238000004898 kneading Methods 0.000 claims description 12
- 239000011342 resin composition Substances 0.000 claims description 11
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 229920002302 Nylon 6,6 Polymers 0.000 claims description 6
- 229920002554 vinyl polymer Polymers 0.000 claims description 6
- 150000001991 dicarboxylic acids Chemical class 0.000 claims description 5
- 229920000299 Nylon 12 Polymers 0.000 claims description 4
- 150000008064 anhydrides Chemical class 0.000 claims description 4
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 4
- SASYHUDIOGGZCN-ARJAWSKDSA-N (z)-2-ethylbut-2-enedioic acid Chemical compound CC\C(C(O)=O)=C\C(O)=O SASYHUDIOGGZCN-ARJAWSKDSA-N 0.000 claims description 3
- CQNPSIAJXGEDQS-VURMDHGXSA-N (z)-2-phenylbut-2-enedioic acid Chemical compound OC(=O)\C=C(/C(O)=O)C1=CC=CC=C1 CQNPSIAJXGEDQS-VURMDHGXSA-N 0.000 claims description 3
- HIDBROSJWZYGSZ-UHFFFAOYSA-N 1-phenylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC=C1 HIDBROSJWZYGSZ-UHFFFAOYSA-N 0.000 claims description 3
- DXIJHCSGLOHNES-UHFFFAOYSA-N 3,3-dimethylbut-1-enylbenzene Chemical compound CC(C)(C)C=CC1=CC=CC=C1 DXIJHCSGLOHNES-UHFFFAOYSA-N 0.000 claims description 3
- AYKYXWQEBUNJCN-UHFFFAOYSA-N 3-methylfuran-2,5-dione Chemical compound CC1=CC(=O)OC1=O AYKYXWQEBUNJCN-UHFFFAOYSA-N 0.000 claims description 3
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 claims description 3
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 claims description 3
- UCUUFSAXZMGPGH-UHFFFAOYSA-N penta-1,4-dien-3-one Chemical compound C=CC(=O)C=C UCUUFSAXZMGPGH-UHFFFAOYSA-N 0.000 claims description 3
- KPQOXMCRYWDRSB-UHFFFAOYSA-N 1-(2-chlorophenyl)pyrrole-2,5-dione Chemical compound ClC1=CC=CC=C1N1C(=O)C=CC1=O KPQOXMCRYWDRSB-UHFFFAOYSA-N 0.000 claims description 2
- LJDGDRYFCIHDPX-UHFFFAOYSA-N 1-(2-methoxyphenyl)pyrrole-2,5-dione Chemical compound COC1=CC=CC=C1N1C(=O)C=CC1=O LJDGDRYFCIHDPX-UHFFFAOYSA-N 0.000 claims description 2
- QYOJZFBQEAZNEW-UHFFFAOYSA-N 1-(2-methylphenyl)pyrrole-2,5-dione Chemical compound CC1=CC=CC=C1N1C(=O)C=CC1=O QYOJZFBQEAZNEW-UHFFFAOYSA-N 0.000 claims description 2
- BQTPKSBXMONSJI-UHFFFAOYSA-N 1-cyclohexylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1CCCCC1 BQTPKSBXMONSJI-UHFFFAOYSA-N 0.000 claims description 2
- NQDOCLXQTQYUDH-UHFFFAOYSA-N 1-propan-2-ylpyrrole-2,5-dione Chemical compound CC(C)N1C(=O)C=CC1=O NQDOCLXQTQYUDH-UHFFFAOYSA-N 0.000 claims description 2
- DABFKTHTXOELJF-UHFFFAOYSA-N 1-propylpyrrole-2,5-dione Chemical compound CCCN1C(=O)C=CC1=O DABFKTHTXOELJF-UHFFFAOYSA-N 0.000 claims description 2
- GHAZCVNUKKZTLG-UHFFFAOYSA-N N-ethyl-succinimide Natural products CCN1C(=O)CCC1=O GHAZCVNUKKZTLG-UHFFFAOYSA-N 0.000 claims description 2
- HDFGOPSGAURCEO-UHFFFAOYSA-N N-ethylmaleimide Chemical compound CCN1C(=O)C=CC1=O HDFGOPSGAURCEO-UHFFFAOYSA-N 0.000 claims description 2
- 229920003189 Nylon 4,6 Polymers 0.000 claims description 2
- 229920000007 Nylon MXD6 Polymers 0.000 claims description 2
- SEEYREPSKCQBBF-UHFFFAOYSA-N n-methylmaleimide Chemical compound CN1C(=O)C=CC1=O SEEYREPSKCQBBF-UHFFFAOYSA-N 0.000 claims description 2
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims 2
- UOZNXGJVAWDLQK-UHFFFAOYSA-N 1-(2,3-dimethylphenyl)pyrrole-2,5-dione Chemical compound CC1=CC=CC(N2C(C=CC2=O)=O)=C1C UOZNXGJVAWDLQK-UHFFFAOYSA-N 0.000 claims 1
- 125000005439 maleimidyl group Chemical group C1(C=CC(N1*)=O)=O 0.000 claims 1
- -1 Nt-butylmaleimide Chemical compound 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000000654 additive Substances 0.000 description 4
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 3
- 230000001965 increasing effect Effects 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- 101000837308 Homo sapiens Testis-expressed protein 30 Proteins 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- 229920000571 Nylon 11 Polymers 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 102100028631 Testis-expressed protein 30 Human genes 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229920005669 high impact polystyrene Polymers 0.000 description 2
- 239000004797 high-impact polystyrene Substances 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- 229920006123 polyhexamethylene isophthalamide Polymers 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 150000003440 styrenes Chemical class 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- BAWHYOHVWHQWFQ-UHFFFAOYSA-N 1-naphthalen-1-ylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC2=CC=CC=C12 BAWHYOHVWHQWFQ-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-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
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical compound NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 229920001890 Novodur Polymers 0.000 description 1
- 229920000572 Nylon 6/12 Polymers 0.000 description 1
- 229920000577 Nylon 6/66 Polymers 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 1
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 1
- 229920001893 acrylonitrile styrene Polymers 0.000 description 1
- 239000004596 additive masterbatch Substances 0.000 description 1
- TZYHIGCKINZLPD-UHFFFAOYSA-N azepan-2-one;hexane-1,6-diamine;hexanedioic acid Chemical compound NCCCCCCN.O=C1CCCCCN1.OC(=O)CCCCC(O)=O TZYHIGCKINZLPD-UHFFFAOYSA-N 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- YWJUZWOHLHBWQY-UHFFFAOYSA-N decanedioic acid;hexane-1,6-diamine Chemical compound NCCCCCCN.OC(=O)CCCCCCCCC(O)=O YWJUZWOHLHBWQY-UHFFFAOYSA-N 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- ZMUCVNSKULGPQG-UHFFFAOYSA-N dodecanedioic acid;hexane-1,6-diamine Chemical compound NCCCCCCN.OC(=O)CCCCCCCCCCC(O)=O ZMUCVNSKULGPQG-UHFFFAOYSA-N 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- ZETYUTMSJWMKNQ-UHFFFAOYSA-N n,n',n'-trimethylhexane-1,6-diamine Chemical compound CNCCCCCCN(C)C ZETYUTMSJWMKNQ-UHFFFAOYSA-N 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920006139 poly(hexamethylene adipamide-co-hexamethylene terephthalamide) Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- SCUZVMOVTVSBLE-UHFFFAOYSA-N prop-2-enenitrile;styrene Chemical compound C=CC#N.C=CC1=CC=CC=C1 SCUZVMOVTVSBLE-UHFFFAOYSA-N 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 239000011115 styrene butadiene Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
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- Processes Of Treating Macromolecular Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
本発明は、樹脂添加用のマスターバッチとその製造方法、前記マスターバッチを含有するナイロン樹脂組成物とそれから得られる成形体に関する。 The present invention relates to a master batch for resin addition, a method for producing the same, a nylon resin composition containing the master batch, and a molded product obtained therefrom.
ナイロン樹脂と他の熱可塑性樹脂を押出機等で混練する場合には均一に混練することが困難であり、相溶化剤を使用した場合でも、十分な改善はできなかった。例えば、ナイロン６６の混練時に相溶化剤としてマレイミド系モノマー単位を有する重合体を使用した場合は、ナイロン６６がゲル化してしまい、均一な混練ができなかった。
本発明は、ナイロン６を除く他のナイロン樹脂と熱可塑性樹脂（ナイロン樹脂を除く）の混練時における相溶性を高めることができる樹脂添加用のマスターバッチとその製造方法を提供することを課題とする。 It is an object of the present invention to provide a master batch for adding a resin capable of enhancing compatibility at the time of kneading a thermoplastic resin (excluding nylon resin) with other nylon resins except nylon 6 and a method for producing the same. To do.
また本発明は、前記マスターバッチを含有するナイロン樹脂組成物とそれから得られる成形体を提供することを他の課題とする。 Moreover, this invention makes it another subject to provide the nylon resin composition containing the said masterbatch, and the molded object obtained from it.
本発明は、ナイロン６とマレイミド系モノマー単位を有する重合体を含有しており、ナイロン６を除くナイロン樹脂を含む熱可塑性樹脂の混練時に使用する、樹脂添加用のマスターバッチを提供する。 The present invention provides a master batch for resin addition, which contains a polymer having nylon 6 and a maleimide monomer unit, and is used when kneading a thermoplastic resin including a nylon resin excluding nylon 6.
更に本発明は、請求項１〜５のいずれかに記載の樹脂添加用のマスターバッチの製造方法であり、ナイロン６とマレイミド系モノマー単位を有する重合体を溶融状態で混練する、樹脂添加用のマスターバッチの製造方法を提供する。 Furthermore, this invention is a manufacturing method of the masterbatch for resin addition in any one of Claims 1-5, and knead | mixes the polymer which has nylon 6 and a maleimide-type monomer unit in a molten state, For resin addition A method for producing a masterbatch is provided.
更に本発明は、ナイロン６を除くナイロン樹脂を含む熱可塑性樹脂９９〜５０質量％と、請求項６で製造された樹脂添加用のマスターバッチ１〜５０質量％を含有するナイロン樹脂組成物とそれから得られる成形体を提供する。 Furthermore, the present invention relates to a nylon resin composition containing 99 to 50% by mass of a thermoplastic resin containing a nylon resin excluding nylon 6, and 1 to 50% by mass of a masterbatch for resin addition produced in claim 6. The resulting molded body is provided.
本発明の樹脂添加剤用のマスターバッチを用いて、ナイロン６以外のナイロン樹脂を含む熱可塑性樹脂を混練することにより、ナイロン６以外のナイロン樹脂を含む熱可塑性樹脂及び相溶化剤を混練した場合と比べると、より均一に混練することができる。このため、混練後の樹脂組成物から得られる成形体に対して、バラツキの小さい、所望の物性を付与することができる。 When kneading a thermoplastic resin containing a nylon resin other than nylon 6 and a compatibilizer by kneading a thermoplastic resin containing a nylon resin other than nylon 6 using the master batch for the resin additive of the present invention. Compared to, kneading can be performed more uniformly. For this reason, it is possible to impart desired physical properties with small variations to the molded body obtained from the resin composition after kneading.
＜樹脂添加用のマスターバッチとその製造方法＞
ナイロン６と組み合わせるマレイミド系モノマー単位を有する重合体は、マレイミド系モノマー単位の重合体でもよいし、マレイミド系モノマー単位と他のモノマー単位との共重合体でもよい。
<Master batch for resin addition and its manufacturing method>
The polymer having maleimide monomer units combined with nylon 6 may be a polymer of maleimide monomer units or a copolymer of maleimide monomer units and other monomer units.
マレイミド系モノマー単位となるマレイミド系モノマーは、マレイミド、Ｎ−メチルマレイミド、Ｎ−エチルマレイミド、Ｎ−プロピルマレイミド、Ｎ−イソプロピルマレイミド、Ｎ−シクロヘキシルマレイミド、Ｎ−フェニルマレイミド、Ｎ−トルイルマレイミド、Ｎ−キシリールマレイミド、Ｎ−ナフチルマレイミド、Ｎ−ｔ−ブチルマレイミド、Ｎ−オルトクロルフェニルマレイミド、Ｎ−オルトメトキシフェニルマレイミドから選ばれる１又は２以上のものが好ましい。 Maleimide monomers that are maleimide monomer units are maleimide, N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, N-isopropylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide, N-toluylmaleimide, N- One or more selected from xylylmaleimide, N-naphthylmaleimide, Nt-butylmaleimide, N-orthochlorophenylmaleimide, and N-orthomethoxyphenylmaleimide are preferable.
他のモノマー単位となるモノマーとしては、スチレン、α-メチルスチレン、ビニルケトン、t−ブチルスチレン等の芳香族ビニル系化合物、無水マレイン酸、無水メチルマレイン酸、無水１,２−ジメチルマレイン酸、無水エチルマレイン酸、無水フェニルマレイン酸等の不飽和ジカルボン酸無水物等を挙げることができる。 Examples of other monomer units include aromatic vinyl compounds such as styrene, α-methyl styrene, vinyl ketone, and t-butyl styrene, maleic anhydride, methyl maleic anhydride, 1,2-dimethyl maleic anhydride, anhydrous ethyl maleic acid, and unsaturated dicarboxylic acid anhydride such as phenyl maleic acid.
マレイミド系モノマー単位を有する重合体は、マレイミド系モノマー、芳香族ビニルモノマー、不飽和ジカルボン酸無水物モノマーからなる共重合体が好ましい。この３種のモノマーを組み合わせる場合には、下記の割合であることが好ましい。 The polymer having a maleimide monomer unit is preferably a copolymer comprising a maleimide monomer, an aromatic vinyl monomer, and an unsaturated dicarboxylic anhydride monomer. When combining these three types of monomers, the following ratio is preferred.
マレイミド系モノマー単位の割合は、好ましくは１０〜８０質量％、より好ましくは３０〜６０質量％、更に好ましくは４０〜５５質量％であり；芳香族ビニル系モノマー単位の割合は、好ましくは１０〜８０質量％、より好ましくは３０〜６０質量％、更に好ましくは４０〜５５質量％であり；不飽和ジカルボン酸無水物モノマー単位の割合は、好ましくは０．１〜１０質量％、より好ましくは０．５〜５質量％、更に好ましくは０．５〜３質量％である。不飽和ジカルボン酸無水物モノマー単位の割合が１０質量％以下であると流動性が良くなり、０．１質量％以上であると耐衝撃強度が高くなる。 The proportion of the maleimide monomer unit is preferably 10 to 80% by mass, more preferably 30 to 60% by mass, still more preferably 40 to 55% by mass; the proportion of the aromatic vinyl monomer unit is preferably 10 to 10% by mass. 80 mass%, more preferably 30-60 mass%, still more preferably 40-55 mass%; the proportion of unsaturated dicarboxylic anhydride monomer units is preferably 0.1-10 mass%, more preferably 0 0.5 to 5% by mass, more preferably 0.5 to 3% by mass. When the ratio of the unsaturated dicarboxylic acid anhydride monomer unit is 10% by mass or less, the fluidity is improved, and when it is 0.1% by mass or more, the impact strength is increased.
ナイロン６とマレイミド系モノマー単位を有する重合体の割合は、
ナイロン６は９５〜１０質量％が好ましく、８０〜２０質量％がより好ましく、７０〜３０質量％が更に好ましく、
マレイミド系モノマー単位を有する重合体は９５〜５質量％が好ましく、８０〜２０質量％がより好ましく、７０〜３０質量％が更に好ましい。
The ratio of the polymer having nylon 6 and maleimide monomer units is
Nylon 6 is preferably 95 to 10% by mass, more preferably 80 to 20% by mass, still more preferably 70 to 30% by mass,
95-5 mass% is preferable, the polymer which has a maleimide-type monomer unit has more preferable 80-20 mass%, and 70-30 mass% is still more preferable.
本発明の樹脂添加用のマスターバッチは、公知の一軸又は二軸押出機を用いて、所定量のナイロン６とマレイミド系モノマー単位を有する重合体を溶融状態で混練して得ることができる。本発明のマスターバッチの形態は特に制限されないが、取り扱い性が良いため、ペレット状にすることが好ましい。 The master batch for resin addition of the present invention can be obtained by kneading a polymer having a predetermined amount of nylon 6 and a maleimide monomer unit in a molten state using a known single-screw or twin-screw extruder. Although the form of the masterbatch of the present invention is not particularly limited, it is preferable to make it into a pellet form because it is easy to handle.
本発明のマスターバッチは、ナイロン６以外のナイロン樹脂との相溶性が良く、ナイロン６以外のナイロン樹脂、又はナイロン６以外のナイロン樹脂と他の熱可塑性樹脂と共に混練した場合、それらに対する相溶化剤として作用するものである。 The masterbatch of the present invention has good compatibility with nylon resins other than nylon 6, and when kneaded together with nylon resins other than nylon 6, or nylon resins other than nylon 6 and other thermoplastic resins, a compatibilizing agent for them It acts as.
＜ナイロン樹脂組成物とそれから得られる成形体＞
本発明のナイロン樹脂組成物は、ナイロン６以外のナイロン樹脂又はナイロン６以外のナイロン樹脂と１種又は２種以上の熱可塑性樹脂（ナイロン樹脂を除いたもの）に対して、上記の樹脂添加用マスターバッチが配合されてなるものである。
<Nylon resin composition and molded product obtained therefrom>
The nylon resin composition of the present invention is for the above resin addition to nylon resins other than nylon 6 or nylon resins other than nylon 6 and one or more thermoplastic resins (excluding nylon resin). A master batch is blended.
ナイロン樹脂は、ナイロン６以外のものであり、ナイロン６６、ナイロン６・１０、ナイロン６・１２、ナイロン１２・１２、ナイロンＭＸＤ６、ナイロン４６及びこれらの混合物や共重合体；ナイロン６／６６、６Ｔ成分が５０モル％以下であるナイロン６６／６Ｔ（６Ｔ：ポリヘキサメチレンテレフタラミド）、６Ｉ成分が５０モル％以下であるナイロン６６／６Ｉ（６Ｉ：ポリヘキサメチレンイソフタラミド）、ナイロン６Ｔ／６Ｉ／６６、ナイロン６Ｔ／６Ｉ／６１０等の共重合体；ポリヘキサメチレンテレフタルアミド（ナイロン６Ｔ）、ポリヘキサメチレンイソフタルアミド（ナイロン６Ｉ）、ポリ（２−メチルペンタメチレン）テレフタルアミド（ナイロンＭ５Ｔ）、ポリ（２−メチルペンタメチレン）イソフタルアミド（ナイロンＭ５Ｉ）、ナイロン６Ｔ／６Ｉ、ナイロン６Ｔ／Ｍ５Ｔ等の共重合体を挙げることができ、そのほかアモルファスナイロンのような共重合ナイロンでもよく、アモルファスナイロンとしてはテレフタル酸とトリメチルヘキサメチレンジアミンの重縮合物等を挙げることができる。 Nylon resin other than nylon 6 is nylon 66, nylon 6/10, nylon 6/12, nylon 12/12, nylon MXD6, nylon 46, and mixtures and copolymers thereof; nylon 6/66, 6T Nylon 66 / 6T (6T: polyhexamethylene terephthalamide) whose component is 50 mol% or less, Nylon 66 / 6I (6I: polyhexamethylene isophthalamide) whose 6I component is 50 mol% or less, nylon 6T / Copolymers such as 6I / 66, nylon 6T / 6I / 610; polyhexamethylene terephthalamide (nylon 6T), polyhexamethylene isophthalamide (nylon 6I), poly (2-methylpentamethylene) terephthalamide (nylon M5T) , Poly (2-methylpentamethylene) isophthalamide (Na Ron M5I), Nylon 6T / 6I, Nylon 6T / M5T, etc., and other copolymer nylons such as amorphous nylon may be used. As amorphous nylon, polycondensation of terephthalic acid and trimethylhexamethylenediamine And the like.
更に、環状ラクタムの開環重合物、アミノカルボン酸の重縮合物及びこれらの成分からなる共重合体、具体的には、ポリ−ω−ウンデカナミド（ナイロン１１）、ポリ−ω−ドデカナミド（ナイロン１２）等の脂肪族ポリアミド樹脂及びこれらの共重合体、ジアミン、ジカルボン酸とからなるポリアミドとの共重合体、具体的にはナイロン６Ｔ／６、ナイロン６Ｔ／１１、ナイロン６Ｔ／１２、ナイロン６Ｔ／６Ｉ／１２
ナイロン樹脂以外の熱可塑性樹脂は特に制限されるものではないが、スチレン系樹脂が好ましい。
Further, a ring-opening polymer of cyclic lactam, a polycondensation product of aminocarboxylic acid, and a copolymer comprising these components, specifically, poly-ω-undecanamide (nylon 11), poly-ω-dodecanamide (nylon 12). ) And the like, and copolymers with these copolymers, diamines, polyamides comprising dicarboxylic acids, specifically nylon 6T / 6, nylon 6T / 11, nylon 6T / 12, nylon 6T / 6I / 12
The thermoplastic resin other than the nylon resin is not particularly limited, but a styrene resin is preferable.
スチレン系樹脂は、スチレン及びα置換、核置換スチレン等のスチレン誘導体の重合体を挙げることができる。また、これら単量体を主として、これらとアクリロニトリル、アクリル酸並びにメタクリル酸のようなビニル化合物及び／又はブタジエン、イソプレンのような共役ジエン化合物の単量体から構成される共重合体も含まれる。例えばポリスチレン、耐衝撃性ポリスチレン（ＨＩＰＳ）樹脂、アクリロニトリル−ブタジエン−スチレン共重合体（ＡＢＳ）樹脂、アクリロニトリル−スチレン共重合体（ＡＳ樹脂）、スチレン−メタクリレート共重合体（ＭＳ樹脂）、スチレン−ブタジエン共重合体（ＳＢＳ樹脂）等を挙げることができる。 Examples of the styrenic resin include polymers of styrene and styrene derivatives such as α-substituted and nucleus-substituted styrene. Also included are copolymers composed mainly of these monomers and monomers of vinyl compounds such as acrylonitrile, acrylic acid and methacrylic acid and / or conjugated diene compounds such as butadiene and isoprene. For example, polystyrene, high impact polystyrene (HIPS) resin, acrylonitrile-butadiene-styrene copolymer (ABS) resin, acrylonitrile-styrene copolymer (AS resin), styrene-methacrylate copolymer (MS resin), styrene-butadiene A copolymer (SBS resin) etc. can be mentioned.
ナイロン樹脂組成物が、ナイロン６以外のナイロン樹脂と樹脂添加剤用マスターバッチを含む場合の割合は、
ナイロン６以外のナイロン樹脂は９９〜５０質量％が好ましく、より好ましくは９５〜６０質量％、更に好ましくは９０〜７０質量％であり、
樹脂添加剤用マスターバッチは１〜５０質量％が好ましく、より好ましくは５〜４０質量％、更に好ましくは１０〜３０質量％である。
When the nylon resin composition includes a nylon resin other than nylon 6 and a master batch for resin additive,
Nylon resin other than nylon 6 is preferably 99 to 50% by mass, more preferably 95 to 60% by mass, still more preferably 90 to 70% by mass,
1-50 mass% is preferable, as for the masterbatch for resin additives, More preferably, it is 5-40 mass%, More preferably, it is 10-30 mass%.
ナイロン樹脂組成物が、ナイロン６以外のナイロン樹脂と他の熱可塑性樹脂（１種又は２種以上）と樹脂添加剤用マスターバッチを含む場合は、
ナイロン６以外のナイロン樹脂と他の熱可塑性樹脂の合計量は、９９〜５０質量％が好ましく、より好ましくは９５〜６０質量％、更に好ましくは９０〜７０質量％であり、
樹脂添加剤用マスターバッチは１〜５０質量％が好ましく、より好ましくは５〜４０質量％、更に好ましくは１０〜３０質量％である。
When the nylon resin composition contains a nylon resin other than nylon 6, other thermoplastic resins (one or more) and a resin additive masterbatch,
The total amount of the nylon resin other than nylon 6 and the other thermoplastic resin is preferably 99 to 50% by mass, more preferably 95 to 60% by mass, still more preferably 90 to 70% by mass,
1-50 mass% is preferable, as for the masterbatch for resin additives, More preferably, it is 5-40 mass%, More preferably, it is 10-30 mass%.
ここで、ナイロン６以外のナイロン樹脂と他の熱可塑性樹脂の合計量（１００質量％）中、ナイロン６以外のナイロン樹脂の割合は、９０〜１０質量％が好ましく、より好ましくは２０〜８０質量％であり、更に好ましくは３０〜６０質量％である。 Here, in the total amount (100% by mass) of the nylon resin other than nylon 6 and the other thermoplastic resin, the ratio of the nylon resin other than nylon 6 is preferably 90 to 10% by mass, and more preferably 20 to 80% by mass. %, And more preferably 30 to 60% by mass.
本発明の組成物は、求められる性質、用途等に応じて必要な他の成分を配合することができる。例えば、機械的強度を高める観点からは、各種無機充填材又は有機充填材を配合することができ、耐光性や耐熱性を高める観点からは、紫外線吸収剤、熱安定剤を配合することができる。 The composition of the present invention can be blended with other necessary components depending on the required properties and applications. For example, various inorganic fillers or organic fillers can be blended from the viewpoint of increasing mechanical strength, and ultraviolet absorbers and heat stabilizers can be blended from the viewpoint of increasing light resistance and heat resistance. .
本発明の組成物は、公知の一軸又は二軸押出機を用いて、所定量のナイロン樹脂又は所定量のナイロン樹脂とそれ以外の熱可塑性樹脂と、マスターバッチを溶融状態で混練して得ることができる。本発明の組成物は、ナイロン樹脂とそれ以外の熱可塑性樹脂に対して相溶化剤として作用するマスターバッチを含んでいるため、２種以上のナイロン樹脂とそれ以外の熱可塑性樹脂を混練した場合でも、均一に混練されている。 The composition of the present invention is obtained by kneading a master batch with a predetermined amount of nylon resin or a predetermined amount of nylon resin and other thermoplastic resins using a known single or twin screw extruder. Can do. The composition of the present invention contains a masterbatch that acts as a compatibilizer for nylon resins and other thermoplastic resins, so when two or more types of nylon resins and other thermoplastic resins are kneaded However, they are kneaded uniformly.
本発明の成形体は、本発明の組成物に対して公知の射出成形法等の樹脂成形法を適用することで、得ることができる。 The molded body of the present invention can be obtained by applying a known resin molding method such as an injection molding method to the composition of the present invention.
実施例及び比較例で使用した各成分と測定方法の詳細は、以下のとおりである。 The details of each component and measurement method used in Examples and Comparative Examples are as follows.
（熱可塑性樹脂）
（ＰＡ−１）：ポリアミド6，宇部興産株式会社製，UBEナイロン6 1013B，吸水率1.8％，230℃1kgでのメルトフローインデックス:17）
（ＰＡ−２）：ポリアミド６-６，宇部興産株式会社製，UBEナイロン6-6 2020B，吸水率1.3％）
（ＰＳ−１）：ＡＢＳ樹脂（スチレン量４５質量％、アクリロニトリル１５質量％、ゴム量４０質量％）
（マレイミド系モノマー単位を有する重合体）
スチレン−Nフェニルマレイミド−無水マレイン酸共重合体（スチレン４７質量％、Nフェニルマレイミド５１質量％、無水マレイン酸が２質量％，重量平均分子量が１４万５千，265℃10kgでのメルトフローインデックス:2）。
(Thermoplastic resin)
(PA-1): Polyamide 6, manufactured by Ube Industries, UBE nylon 6 1013B, water absorption 1.8%, melt flow index at 230 ° C. 1 kg: 17)
(PA-2): Polyamide 6-6, manufactured by Ube Industries, UBE nylon 6-6 2020B, water absorption rate 1.3%)
(PS-1): ABS resin (styrene content 45% by mass, acrylonitrile 15% by mass, rubber content 40% by mass)
(Polymer having maleimide monomer units)
Styrene-N-phenylmaleimide-maleic anhydride copolymer (47% by mass of styrene, 51% by mass of N-phenylmaleimide, 2% by mass of maleic anhydride, weight average molecular weight of 145,000, 265 ° C., 10 kg) : 2).
（測定方法）
シャルピー衝撃強度：ＩＳＯ１７９に準拠して測定。
(Measuring method)
Charpy impact strength: Measured according to ISO179.
実施例１、比較例１（樹脂添加用マスターバッチの製造）
表１記載の各成分をＶ型タンブラーで混合後、二軸押出機（日本製鋼製，ＴＥＸ３０，シリンダー温度２５０℃、回転数３５０rpm、吐出量３０kg/hr）にて溶融混練し、樹脂添加用のマスターバッチペレットを得た。しかし、比較例１は、ゲル化が起こり、マスターペッレットを得ることができなかった。
Example 1, Comparative Example 1 (Manufacture of master batch for resin addition)
After mixing each component shown in Table 1 with a V-shaped tumbler, it was melt-kneaded with a twin-screw extruder (manufactured by Nippon Steel, TEX30, cylinder temperature 250 ° C., rotation speed 350 rpm, discharge rate 30 kg / hr) for resin addition Master batch pellets were obtained. However, in Comparative Example 1, gelation occurred and a master pellet could not be obtained.
実施例２〜９、比較例２〜９
表２記載の各成分をＶ型タンブラーで混合後、二軸押出機（日本製鋼製，ＴＥＸ３０，シリンダー温度２５０℃、回転数３５０rpm、吐出量３０kg/hr）にて溶融混練し、ナイロン樹脂組成物を得た。次に、射出成形機（シリンダー温度２５０℃、金型温度６０℃）によりISOダンベル成形品を作成した。
Examples 2-9, Comparative Examples 2-9
After mixing each component shown in Table 2 with a V-type tumbler, it is melt kneaded with a twin-screw extruder (manufactured by Nippon Steel, TEX30, cylinder temperature 250 ° C., rotation speed 350 rpm, discharge rate 30 kg / hr), and a nylon resin composition Got. Next, an ISO dumbbell molded product was prepared by an injection molding machine (cylinder temperature 250 ° C., mold temperature 60 ° C.).
比較例２、３はゲル化して、押出できなかった。
Comparative Examples 2 and 3 gelled and could not be extruded.
Claims (7)
前記マレイミド系モノマー単位を有する重合体が、
マレイミド系モノマー、芳香族ビニル単量体、不飽和ジカルボン酸無水物単量体からなる共重合体であり、
芳香族ビニル単量体が、スチレン、α-メチルスチレン、ビニルケトン、t−ブチルスチレンから選ばれるものであり、
不飽和ジカルボン酸無水物単量体が、無水マレイン酸、無水メチルマレイン酸、無水１,２−ジメチルマレイン酸、無水エチルマレイン酸、無水フェニルマレイン酸から選ばれるものであり、
前記ナイロン６を除くナイロン樹脂を含む熱可塑性樹脂が、ナイロン６６、ナイロン６・１０、ナイロン６・１２、ナイロン１２・１２、ナイロンＭＸＤ６、ナイロン４６から選ばれるものと、スチレン系樹脂を含むものである、樹脂添加用のマスターバッチ。 A masterbatch for resin addition, which contains a polymer having nylon 6 and a maleimide monomer unit, and is used when kneading a thermoplastic resin including a nylon resin excluding nylon 6,
The polymer having the maleimide monomer unit,
A copolymer comprising a maleimide monomer, an aromatic vinyl monomer, and an unsaturated dicarboxylic anhydride monomer,
The aromatic vinyl monomer is selected from styrene, α-methyl styrene, vinyl ketone, t-butyl styrene,
Unsaturated dicarboxylic acid anhydride monomer, those selected maleic anhydride, methyl maleic anhydride, 1,2-dimethyl maleic anhydride, ethyl maleic acid, from absolute phenyl maleic acid,
The thermoplastic resin including the nylon resin excluding the nylon 6 is selected from nylon 66, nylon 6 · 10, nylon 6 · 12, nylon 12 · 12, nylon MXD6, nylon 46, and a styrene resin. Masterbatch for resin addition.
前記マレイミド系モノマー単位を有する重合体が、
マレイミド系モノマー、芳香族ビニル単量体、不飽和ジカルボン酸無水物単量体からなる共重合体であり、
芳香族ビニル単量体が、スチレン、α-メチルスチレン、ビニルケトン、t−ブチルスチレンから選ばれるものであり、
不飽和ジカルボン酸無水物単量体が、無水マレイン酸、無水メチルマレイン酸、無水１,２−ジメチルマレイン酸、無水エチルマレイン酸、無水フェニルマレイン酸から選ばれるものであり、
前記ナイロン６を除くナイロン樹脂を含む熱可塑性樹脂が、ナイロン６Ｔ、ナイロン６Ｉ、ナイロンＭ５Ｔ、ナイロンＭ５Ｉ、ナイロン６Ｔ／６Ｉ、ナイロン６Ｔ／Ｍ５Ｔから選ばれるものと、スチレン系樹脂を含むものである、樹脂添加用のマスターバッチ。 A masterbatch for resin addition, which contains a polymer having nylon 6 and a maleimide monomer unit, and is used when kneading a thermoplastic resin including a nylon resin excluding nylon 6,
The polymer having the maleimide monomer unit,
A copolymer comprising a maleimide monomer, an aromatic vinyl monomer, and an unsaturated dicarboxylic anhydride monomer,
The aromatic vinyl monomer is selected from styrene, α-methyl styrene, vinyl ketone, t-butyl styrene,
Unsaturated dicarboxylic acid anhydride monomer, those selected maleic anhydride, methyl maleic anhydride, 1,2-dimethyl maleic anhydride, ethyl maleic acid, from absolute phenyl maleic acid,
The thermoplastic resin containing a nylon resin excluding the nylon 6 is selected from nylon 6T, nylon 6I, nylon M5T, nylon M5I, nylon 6T / 6I, nylon 6T / M5T, and a resin containing a styrene resin. Masterbatch for.
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