JPWO2017150662A1 - 樹脂添加剤組成物、熱可塑性樹脂組成物、およびその成形体 - Google Patents
樹脂添加剤組成物、熱可塑性樹脂組成物、およびその成形体 Download PDFInfo
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- JPWO2017150662A1 JPWO2017150662A1 JP2018503394A JP2018503394A JPWO2017150662A1 JP WO2017150662 A1 JPWO2017150662 A1 JP WO2017150662A1 JP 2018503394 A JP2018503394 A JP 2018503394A JP 2018503394 A JP2018503394 A JP 2018503394A JP WO2017150662 A1 JPWO2017150662 A1 JP WO2017150662A1
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- ZHROMWXOTYBIMF-UHFFFAOYSA-M sodium;1,3,7,9-tetratert-butyl-11-oxido-5h-benzo[d][1,3,2]benzodioxaphosphocine 11-oxide Chemical compound [Na+].C1C2=CC(C(C)(C)C)=CC(C(C)(C)C)=C2OP([O-])(=O)OC2=C1C=C(C(C)(C)C)C=C2C(C)(C)C ZHROMWXOTYBIMF-UHFFFAOYSA-M 0.000 description 10
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- ARIBLUOFKZXDJW-UHFFFAOYSA-M potassium 1,1,1,3,3,3-hexafluoro-2-(trifluoromethyl)propane-2-sulfonate Chemical compound [K+].[O-]S(=O)(=O)C(C(F)(F)F)(C(F)(F)F)C(F)(F)F ARIBLUOFKZXDJW-UHFFFAOYSA-M 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- QMRNDFMLWNAFQR-UHFFFAOYSA-N prop-2-enenitrile;prop-2-enoic acid;styrene Chemical compound C=CC#N.OC(=O)C=C.C=CC1=CC=CC=C1 QMRNDFMLWNAFQR-UHFFFAOYSA-N 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical compound CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 description 1
- NCNISYUOWMIOPI-UHFFFAOYSA-N propane-1,1-dithiol Chemical compound CCC(S)S NCNISYUOWMIOPI-UHFFFAOYSA-N 0.000 description 1
- 229960000380 propiolactone Drugs 0.000 description 1
- 229940080818 propionamide Drugs 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 150000005599 propionic acid derivatives Chemical class 0.000 description 1
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000000979 retarding effect Effects 0.000 description 1
- SJOXEWUZWQYCGL-UHFFFAOYSA-N salicylic acid menthyl ester Natural products CC(C)C1CCC(C)CC1OC(=O)C1=CC=CC=C1O SJOXEWUZWQYCGL-UHFFFAOYSA-N 0.000 description 1
- 229910000275 saponite Inorganic materials 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- 229910021647 smectite Inorganic materials 0.000 description 1
- BTURAGWYSMTVOW-UHFFFAOYSA-M sodium dodecanoate Chemical compound [Na+].CCCCCCCCCCCC([O-])=O BTURAGWYSMTVOW-UHFFFAOYSA-M 0.000 description 1
- 229940082004 sodium laurate Drugs 0.000 description 1
- 229940045845 sodium myristate Drugs 0.000 description 1
- 229940045870 sodium palmitate Drugs 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- ZQOXGRIKWKXDIJ-UHFFFAOYSA-M sodium;1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-heptadecafluorooctane-1-sulfonate Chemical compound [Na+].[O-]S(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F ZQOXGRIKWKXDIJ-UHFFFAOYSA-M 0.000 description 1
- SNAQARSCIHDMGI-UHFFFAOYSA-M sodium;bis(4-tert-butylphenyl) phosphate Chemical compound [Na+].C1=CC(C(C)(C)C)=CC=C1OP([O-])(=O)OC1=CC=C(C(C)(C)C)C=C1 SNAQARSCIHDMGI-UHFFFAOYSA-M 0.000 description 1
- GGXKEBACDBNFAF-UHFFFAOYSA-M sodium;hexadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCC([O-])=O GGXKEBACDBNFAF-UHFFFAOYSA-M 0.000 description 1
- JUQGWKYSEXPRGL-UHFFFAOYSA-M sodium;tetradecanoate Chemical compound [Na+].CCCCCCCCCCCCCC([O-])=O JUQGWKYSEXPRGL-UHFFFAOYSA-M 0.000 description 1
- 239000001587 sorbitan monostearate Substances 0.000 description 1
- 235000011076 sorbitan monostearate Nutrition 0.000 description 1
- 229940035048 sorbitan monostearate Drugs 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- JIWBIWFOSCKQMA-UHFFFAOYSA-N stearidonic acid Natural products CCC=CCC=CCC=CCC=CCCCCC(O)=O JIWBIWFOSCKQMA-UHFFFAOYSA-N 0.000 description 1
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical compound C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 description 1
- 235000021286 stilbenes Nutrition 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- YPMOSINXXHVZIL-UHFFFAOYSA-N sulfanylideneantimony Chemical compound [Sb]=S YPMOSINXXHVZIL-UHFFFAOYSA-N 0.000 description 1
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
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- 229920001897 terpolymer Polymers 0.000 description 1
- LVEOKSIILWWVEO-UHFFFAOYSA-N tetradecyl 3-(3-oxo-3-tetradecoxypropyl)sulfanylpropanoate Chemical compound CCCCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCCCC LVEOKSIILWWVEO-UHFFFAOYSA-N 0.000 description 1
- WUPCFMITFBVJMS-UHFFFAOYSA-N tetrakis(1,2,2,6,6-pentamethylpiperidin-4-yl) butane-1,2,3,4-tetracarboxylate Chemical compound C1C(C)(C)N(C)C(C)(C)CC1OC(=O)CC(C(=O)OC1CC(C)(C)N(C)C(C)(C)C1)C(C(=O)OC1CC(C)(C)N(C)C(C)(C)C1)CC(=O)OC1CC(C)(C)N(C)C(C)(C)C1 WUPCFMITFBVJMS-UHFFFAOYSA-N 0.000 description 1
- QXUJUPKPFOELOL-UHFFFAOYSA-N tetramethyl butane-1,1,1,2-tetracarboxylate Chemical compound COC(=O)C(CC)C(C(=O)OC)(C(=O)OC)C(=O)OC QXUJUPKPFOELOL-UHFFFAOYSA-N 0.000 description 1
- QVASUALUCOYWST-UHFFFAOYSA-N tetramethyl butane-1,2,3,4-tetracarboxylate Chemical compound COC(=O)CC(C(=O)OC)C(C(=O)OC)CC(=O)OC QVASUALUCOYWST-UHFFFAOYSA-N 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
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- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 239000001017 thiazole dye Substances 0.000 description 1
- ANRHNWWPFJCPAZ-UHFFFAOYSA-M thionine Chemical compound [Cl-].C1=CC(N)=CC2=[S+]C3=CC(N)=CC=C3N=C21 ANRHNWWPFJCPAZ-UHFFFAOYSA-M 0.000 description 1
- XKZKQTCECFWKBN-UHFFFAOYSA-N trans-4-decenoic acid Natural products CCCCCC=CCCC(O)=O XKZKQTCECFWKBN-UHFFFAOYSA-N 0.000 description 1
- UWHZIFQPPBDJPM-BQYQJAHWSA-N trans-vaccenic acid Chemical compound CCCCCC\C=C\CCCCCCCCCC(O)=O UWHZIFQPPBDJPM-BQYQJAHWSA-N 0.000 description 1
- 239000001003 triarylmethane dye Substances 0.000 description 1
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 1
- XEZVDURJDFGERA-UHFFFAOYSA-N tricosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCCC(O)=O XEZVDURJDFGERA-UHFFFAOYSA-N 0.000 description 1
- MZHULIWXRDLGRR-UHFFFAOYSA-N tridecyl 3-(3-oxo-3-tridecoxypropyl)sulfanylpropanoate Chemical compound CCCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCCC MZHULIWXRDLGRR-UHFFFAOYSA-N 0.000 description 1
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 1
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 1
- CENHPXAQKISCGD-UHFFFAOYSA-N trioxathietane 4,4-dioxide Chemical compound O=S1(=O)OOO1 CENHPXAQKISCGD-UHFFFAOYSA-N 0.000 description 1
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 1
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 1
- LIPMRGQQBZJCTM-UHFFFAOYSA-N tris(2-propan-2-ylphenyl) phosphate Chemical compound CC(C)C1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C(C)C)OC1=CC=CC=C1C(C)C LIPMRGQQBZJCTM-UHFFFAOYSA-N 0.000 description 1
- SPUXJWDKFVXXBI-UHFFFAOYSA-N tris(2-tert-butylphenyl) phosphate Chemical compound CC(C)(C)C1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C(C)(C)C)OC1=CC=CC=C1C(C)(C)C SPUXJWDKFVXXBI-UHFFFAOYSA-N 0.000 description 1
- NSBGJRFJIJFMGW-UHFFFAOYSA-N trisodium;stiborate Chemical compound [Na+].[Na+].[Na+].[O-][Sb]([O-])([O-])=O NSBGJRFJIJFMGW-UHFFFAOYSA-N 0.000 description 1
- KPGXUAIFQMJJFB-UHFFFAOYSA-H tungsten hexachloride Chemical compound Cl[W](Cl)(Cl)(Cl)(Cl)Cl KPGXUAIFQMJJFB-UHFFFAOYSA-H 0.000 description 1
- 239000004762 twaron Substances 0.000 description 1
- 229920000785 ultra high molecular weight polyethylene Polymers 0.000 description 1
- 239000010455 vermiculite Substances 0.000 description 1
- 229910052902 vermiculite Inorganic materials 0.000 description 1
- 235000019354 vermiculite Nutrition 0.000 description 1
- KOZCZZVUFDCZGG-UHFFFAOYSA-N vinyl benzoate Chemical compound C=COC(=O)C1=CC=CC=C1 KOZCZZVUFDCZGG-UHFFFAOYSA-N 0.000 description 1
- UIYCHXAGWOYNNA-UHFFFAOYSA-N vinyl sulfide Chemical group C=CSC=C UIYCHXAGWOYNNA-UHFFFAOYSA-N 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
- 229910052882 wollastonite Inorganic materials 0.000 description 1
- 239000001018 xanthene dye Substances 0.000 description 1
- 125000002256 xylenyl group Chemical group C1(C(C=CC=C1)C)(C)* 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
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Abstract
Description
(式(1)中、R1〜R4は各々独立に、水素原子または炭素原子数1〜9の直鎖または分岐を有するアルキル基を表し、R5は、炭素原子数1〜4のアルキリデン基を表す。)で表されるリン酸エステル化合物、および、(B)下記一般式(2)、
(式(2)中、R6は、炭素原子数7〜30の脂肪族有機酸から導入される基を表す。)で表される脂肪酸ナトリウム塩が、質量比で、(B)/(A)=0.55〜2.0の範囲内であることを特徴とするものである。
(式(3)中、R7、R8は、各々独立して、炭素原子数1〜40のアルキル基、炭素原子数6〜40のアリール基を表す。)で表されるホスファイト化合物0.01〜10質量部を含有することが好ましい。
本発明の樹脂添加剤組成物は、(A)上記一般式(1)で表されるリン酸エステル化合物、および、(B)下記一般式(2)で表される脂肪酸ナトリウム塩からなる樹脂添加剤組成物であって、質量比で(B)/(A)が、0.55〜2.0である。かかる要件を満足することで、熱可塑性樹脂に対して優れた物性を付与することができる樹脂添加剤組成物となる。
本発明の一好適な実施の形態に係る熱可塑性樹脂組成物は、熱可塑性樹脂100質量部に対し、(A)一般式(1)で表されるリン酸エステル化合物が0.001〜10質量部となるように本発明の樹脂添加剤組成物を含有する。
また、本発明の他の好適な実施の形態に係る樹脂組成物は、熱可塑性樹脂100質量部に対し、(A)上記一般式(1)で表されるリン酸エステル化合物0.001〜10質量部、(B)上記一般式(2)で表される脂肪酸ナトリウム、(C)熱可塑性エラストマー1〜80質量部、および(D)充填剤1〜80質量部を含有する樹脂組成物である。本実施の形態に係る樹脂組成物においては、(A)成分に対し、(B)成分が、質量比で(B)/(A)=0.55〜2.0の範囲である。かかる要件を満足することで、耐衝撃性と剛性とを高度に両立させた成形体を得ることができる樹脂組成物となる。本実施の形態においては、本発明の樹脂添加剤組成物を用いてもよい。また、熱可塑性樹脂についても、上述のものを用いることができる。
本発明の他の好適な実施の形態に係る樹脂組成物に係る(C)熱可塑性エラストマーは、公知の熱可塑性エラストマーであれば制限はないが、エチレンと他の単量体の共重合であるものが、ポリオレフィン系樹脂との相溶性に優れるので好ましい。
本発明の他の好適な実施の形態に係る樹脂組成物において、(D)充填剤は、熱可塑性樹脂組成物に用いられる公知の充填剤を制限なく用いることができる。充填剤としては、例えば、タルク、炭酸カルシウム、硫酸マグネシウム繊維、シリカ、クレー、カオリン、アルミナ、カーボンブラック、ガラス繊維等が挙げられ、成形体の力学特性の点から、特にタルクが好ましい。また、タルクは、微粉化や微粒子化等の処理をされていてもよい。これらは1種を単独で用いてもよく、2種以上を併用して用いてもよい。
さらに、本発明のさらに他の好適な実施の形態に係る樹脂組成物は、熱可塑性樹脂100質量部に対し、(A)一般式(1)で表されるリン酸エステル化合物0.001〜10質量部、(B)一般式(2)で表される脂肪酸ナトリウム、および(E)下記一般式(3)で表されるホスファイト化合物0.01〜10質量部を含有する樹脂組成物であって、質量比で(B)/(A)が、0.55〜2.0の範囲であるの範囲である。かかる要件を満足することで、優れた結晶化作用を有し、かつ、熱履歴による変色防止効果に優れた成型体を提供することができる樹脂組成物となる。本実施の形態においても、本発明の樹脂添加剤組成物を用いてもよい。また、熱可塑性樹脂についても、上述のものを用いることができる。
本発明の樹脂組成物に係るホスファイト化合物は、下記式(3)、
で表され、式(3)中、R7、R8は、各々独立して、炭素原子数1〜40のアルキル基、炭素原子数6〜40のアリール基を表す。
本発明のさらに他の好適な実施の形態に係る樹脂組成物は、熱可塑性樹脂100質量部に対し、(A)一般式(1)で表されるリン酸エステル化合物0.001〜10質量部、(B)一般式(2)で表される脂肪酸ナトリウム、および(F)難燃剤1〜100質量部を含有する熱可塑性樹脂組成物であって、(A)成分に対し、(B)成分が、質量比で(B)/(A)=0.55〜2.0の範囲である。かかる要件を満足することで、高度の難燃性と優れた物性とを有する成形品を提供することができる熱可塑性樹脂組成物となる。本実施の形態においても、本発明の樹脂添加剤組成物を用いてもよい。また、熱可塑性樹脂についても、上述のものを用いることができる。
本発明のさらに他の好適な実施の形態に係る樹脂組成物においては、(F)難燃剤については特に制限はなく、公知の難燃剤を用いることができる。例えば、(F)難燃剤としてはリン酸エステル系化合物を挙げることができるが、本発明の樹脂組成物においては、一般式(6)で表されるリン酸エステル系難燃剤を用いることが好ましい。
本発明のさらに他の好適な実施の形態に係る樹脂組成物には、(G)難燃助剤を用いることができる。本発明のさらに他の好適な実施の形態に係る樹脂組成物においては、(G)難燃助剤としては特に制限はなく、公知のものを用いることができる。この中でも、(G)難燃助剤としての性能と入手の容易さの点から、アンチモン系化合物、ホウ素系化合物、金属酸化物、およびドリップ防止剤が好ましい。
本発明のさらに他の好適な実施の形態に係る樹脂組成物は、熱可塑性樹脂100質量部に対し、(A)上記一般式(1)で表されるリン酸エステル化合物が0.001〜10質量部、(B)上記一般式(2)で表される脂肪酸ナトリウム、および(H)光安定剤0.001〜10質量部を含有する熱可塑性樹脂組成物であって、(A)成分に対し、(B)成分が、質量比で(B)/(A)が、0.55〜2.0である。かかる要件を満足する樹脂組成物は、光安定剤を含有しつつも、優れた核剤効果を示す熱可塑性樹脂組成物およびその成形体することができる樹脂組成物となる。本実施の形態においても、本発明の樹脂添加剤組成物を用いてもよい。また、熱可塑性樹脂についても、上述のものを用いることができる。
次に、本発明のさらに他の実施の形態に係る樹脂組成物に用いる(H)光安定剤について説明する。本発明のさらに他の実施の形態に係る樹脂組成物において(H)光安定剤は、(I)ヒンダードアミン化合物および/または(J)紫外線吸収剤を含有するものが好ましい。
nが1の場合、R23は、水素原子、直鎖または分岐を有する炭素原子数1〜18のアルキル基、炭素原子数1〜18のヒドロキシアルキル基、炭素原子数1〜18のアルコキシ基、炭素原子数1〜18のヒドロキシアルコキシ基、炭素原子数7〜30のアルキルアリール基を表し、
nが2の場合、R23は、炭素原子数1〜20のアルカンジイル基を表し、R24、R25およびR26で表されるアルキル基、ヒドロキシアルキル基、アルコキシ基、ヒドロキシアルコキシ基、アルキルアリール基およびアルカンジイル基中のメチレン基が、エチレングリコール、プロピレングリコール、−O−、−CO−、−OCO−、−COO−で置換されていてもよい。
R28は水素原子、直鎖または分岐を有する炭素原子数1〜8のアルキル基または炭素原子数3〜8のアルケニル基を表し、
R29およびR30は水素原子、ヒドロキシ基、直鎖または分岐を有する炭素原子数1〜8のアルキル基を表し、
R31は水素原子、炭素原子数1〜8のアルキル基、炭素原子6〜20のアリール基または−O−R27を表し、
R27〜R31のアルキル基、アルケニル基、アルキルアリール基、アリールアルキル基中のメチレン基およびシクロアルキル基の環状構造を形成する炭素原子が、−O−、−S−、−CO−、−O−CO−、−CO−O−、―NR’−で置き換わっていてもよく、アルキル基、シクロアルキル基、アルケニル基、アリール基、アルキルアリール基およびアリールアルキル基の水素原子が、ヒドロキシ基、ハロゲン原子、炭素原子数1〜12のアルキル基、または炭素原子数1〜12のアルコキシ基で置換されていてもよく、R’は、水素原子または炭素原子数1〜18のアルキル基を表し、複数のR27、R28、R29、R30およびR31は、各々、同一であってもよく、異なるものであってもよい。
〔実施例1−1〜1−6および比較例1−1〜1−3〕
表1に示す割合で、(A)一般式(1)で表されるリン酸エステル化合物と(B)一般式(2)で表される脂肪酸ナトリウムの樹脂添加剤組成物を調製した。表中の配合量の単位は質量部である。得られた各組成物につき、下記の手順にしたがって、安息角の測定および付着性の評価を行なった。
円筒型容器(500mL)に、表1に記載の樹脂添加剤組成物を円筒容器の半分の容量となるように投入して蓋をしめ、筒井理化学器械株式会社製 安息角測定器(Revolv ing Cylinder Test)を用いて、2.0rpmの速度で等速回転させて試料の流動性を評価した。円筒型容器が回転すると、試料は回転する容器に沿って持ち上げられるが、高い位置から試料が崩れ落ちる。この崩れ落ちる試料で形成される斜面が一定の状態になったとき、試料の斜面と水平面がなす角度を安息角として測定した。得られた結果を表1に示す。なお、比較例1−1は、試料の崩落が断続的で斜面が平面状にならなかったため、安息角を測定しなかった。
表1に記載の配合の樹脂添加剤組成物2.5kgを、ヘンシェルミキサーを用いて、1000rpm×1minの条件でブレンドした後、ヘンシェルミキサーの撹拌層内の内壁に付着した樹脂添加剤組成物の状態を評価した。ヘンシェルミキサーの撹拌層内の内壁の5割以上で、樹脂添加剤組成物が付着していた場合は、「×」とし、壁面の5割未満で樹脂添加剤組成物が付着していた場合は、「△」とし、内壁に付着している樹脂添加剤組成物がわずかの場合は、「○」として評価した。得られた結果を表1に示す。
(樹脂組成物の評価)
ホモポリプロピレン(株式会社プライムポリマー社製品名「H700」,メルトフローレート=8.0g/10min(ISO規格1133準拠 2.16kg×230℃))100質量部に対し、フェノール系酸化防止剤(テトラキス[メチレン−3−(3’,5’−ジ−tert−ブチル−4’−ヒドロキシフェニル)プロピオネート]メタン)0.05質量部、リン系酸化防止剤(トリス(2,4−ジ−tert−ブチルフェニル)ホスファイト)0.1質量部、ステアリン酸カルシウム0.05質量部、および、表2、3に示す樹脂添加剤組成物を配合し、ヘンシェルミキサーで、1000rpm×1min混合後、二軸押出機を用いて、押出温度=230℃、スクリュー回転速度=150rpm、フィード速度=7.2kg/hの条件で混練し、ペレットを製造した。ただし、比較例2−5は、樹脂添加剤組成物を配合せずに混練してペレットを得た。表中の配合量の単位は質量部である。得られた樹脂組成物につき、下記の方法で評価した。得られた結果を表2、3に示す。
得られたペレットを少量切り取り、示差走査熱量測定器(ダイアモンド・パーキエルマー社製)を用いて結晶化温度を測定した。測定方法は、室温から50℃/minの速度で230℃まで昇温し、10分間保持後、10℃/minの速度で50℃まで冷却して得られたチャートにおいて、吸熱反応がピークトップとなる温度を結晶化温度とした。
得られたペレットを、射出成型機(EC100−2A;東芝機械株式会社製)にて、200℃の射出温度、50℃の金型温度の条件で射出成形し、寸法80mm×10mm×4mmの試験片を作成し、成形後直ちに23℃の恒温機にいれて48時間静置後、試験片を取り出してISO−178に準拠して試験片の曲げ弾性率(MPa)を測定した。
得られたペレットを、射出成型機(EC100−2A;東芝機械株式会社製)にて、200℃の射出温度、50℃の金型温度の条件で射出成形し、寸法60mm×60mm×1mmの試験片を作成し、成形後直ちに23℃の恒温機にいれて48時間静置後、試験片を取り出してISO−14782に準拠して試験片のHAZEを測定した。
(B)−1:ステアリン酸ナトリウム
(B)−2:ラウリン酸ナトリウム
(B)−3:ミリスチン酸ナトリウム
(B)−4:パルミチン酸ナトリウム
(B)’−1:ステアリン酸リチウム
(B)’−2:ステアリン酸マグネシウム
(B)’−3:ステアリン酸亜鉛
(B)’−4:ステアリン酸アルミニウム
ポリプロピレンのインパクトコポリマー(株式会社プライムポリマー社製品名「J705P」,メルトフローレート=11.5g/10min(ISO規格1133準拠 2.16kg×230℃))に過酸化物(2,5−ジメチル−2,5−ジ(tert−ブチルパーオキシ)ヘキサン)を加えて、メルトフローレートが40g/10minとなるように調製したポリオレフィン樹脂100質量部に対し、フェノール系酸化防止剤(テトラキス[メチレン−3−(3’,5’−ジ−tert−ブチル−4’−ヒドロキシフェニル)プロピオネート]メタン)0.05質量部、リン系酸化防止剤(トリス(2,4−ジ−tert−ブチルフェニル)ホスファイト)0.1質量部、ステアリン酸カルシウム0.05質量部、および、表4、5に示す樹脂添加剤組成物を配合し、ヘンシェルミキサーで、1000rpm×1min混合後、二軸押出機を用いて、押出温度=230℃、スクリュー回転速度=150rpm、フィード速度=7.2kg/hの条件で混練し、ペレットを製造した。ただし、比較例3−1は、樹脂添加剤組成物を配合せずに混練してペレットを得た。
比較核剤1:Milliken社製商品名「HPN−20E」(ジシクロヘキサン−1,2−ジカルボン酸カルシウム化合物)
(B)−1:ステアリン酸ナトリウム
ホモポリプロピレン(メルトフローレート=8.0g/10min(ISO規格1133準拠 2.16kg×230℃))100質量部に対し、フェノール系酸化防止剤(テトラキス[メチレン−3−(3’,5’−ジ−tert−ブチル−4’−ヒドロキシフェニル)プロピオネート]メタン)0.05質量部、リン系酸化防止剤(トリス(2,4−ジ−tert−ブチルフェニル)ホスファイト)0.1質量部、ステアリン酸カルシウム0.05質量部、および、表6、7記載の樹脂添加剤組成物を配合し、ヘンシェルミキサーで、1000rpm×1min混合後、二軸押出機を用いて、押出温度=230℃、スクリュー回転速度=150rpm、フィード速度=7.2kg/hの条件で混練し、ペレットを製造した。また、Y.I.(黄色度)を以下の手順で評価した。
得られたペレットを、射出成型機(EC100−2A;東芝機械株式会社製)を用いて、200℃の射出温度、50℃の金型温度の条件で、寸法60mm×60mm×2mmの試験片を成形した。成形後、直ちに室温23℃、湿度50%の標準状態下にて48時間放置後、分光測色計(SC−T;スガ試験機株式会社製)を用いて、試験片のY.I.を測定した。
比較核剤2:Milliken社製品名「Hyperform(R) HPN−20E」
比較核剤3:安息香酸ナトリウム
(B)−1:ステアリン酸ナトリウム
Blue Outremer 32:Holliday Pigments SAS製(カラーインデックス:pigment blue 29)
Violet Outremer 11:Holliday Pigments SAS製(カラーインデックス:pigment violet 15)
蛍光増白剤:2,5−thiophenediylbis(5−tert−butyl−1,3−benzoxazole)
ポリプロピレンのインパクトコポリマー{株式会社プライムポリマー社製品名「J708P」,メルトフローレート=45g/10min(ISO規格1133準拠 2.16kg×230℃)}100質量部に対し、フェノール系酸化防止剤;テトラキス[メチレン−3−(3’,5’−ジ第三ブチル−4’−ヒドロキシフェニル)プロピオネート]メタン0.083質量部、リン系酸化防止剤:トリス(2,4−ジ第三ブチルフェニル)ホスファイト0.167質量部、ステアリン酸カルシウム0.083質量部、および表8、9に示す(A)および(B)成分を配合し、ヘンシェルミキサー(FM200;三井鉱山(株)製)で1000rpm×1分間混合後、さらに、(C)、(D)成分を配合し、ロッキングミキサー(愛知電機株式会社製)で30分間混合後、二軸押出機(TEX−28V;日鋼TPK商事株式会社)を用いて、真空減圧にて230℃の押出温度で造粒し、ペレットを製造した。ペレットは、60℃で8時間乾燥してから、下記(7)〜(9)の評価を行った。なお、表8、9中の配合量の単位は質量部である。
得られたペレットを細かく破断して、5mg秤量してアルミパンに充填し、示差走査熱量測定機(装置:パーキンエルマー社製ダイアモンド)で結晶化温度および半結晶化時間を測定した。測定は、50℃/minの速度で230℃まで昇温し、5分間保持後、10℃/minで50℃まで冷却した際に、測定した発熱ピークの温度を結晶化温度として求めた。また半結晶化時間は、50℃/minの速度で230℃まで昇温し、5分間保持した後、100℃/minで135℃まで冷却保持した際に、測定した発熱ピーク総面積の50%時点より求めた。
得られたペレットを、射出成形機(装置:東芝機械株式会社製EC100−2A)を用いて、射出温度200℃、金型温度40℃の条件で射出成形し、80mm×10mm×4mmのノッチ付き試験片を成形した。ノッチ付き試験片は、成形後ただちに23℃湿度50%の恒温器に48時間静置後、試験片を取り出してISO−180に準拠して、アイゾット衝撃強度(J/m)を測定した。
得られたペレットを、射出成型機(EC100−2A;東芝機械株式会社製)を用いて、200℃の射出温度、50℃の金型温度の条件で、寸法60mm×60mm×2mmの試験片を成形した。成形後、直ちに室温23℃、湿度50%の標準状態下にて48時間放置後、分光測色計(SC−T;スガ試験機株式会社製)を用いて、試験片のY.I.を測定した。
(B)−1:ステアリン酸ナトリウム
(C)−1:Dow社製製品名ポリオレフィンエラストマー「Engage8200」
(D)−1:松村産業株式会社製品名「クラウンタルクPP」
比較核剤1:Milliken社製商品名「Hyperform HPN20E」
比較核剤2:安息香酸ナトリウム
インパクトコポリマー{株式会社プライムポリマー社製品名「J708P」,メルトフローレート=45g/10min(ISO規格1133準拠 2.16kg×230℃)}100質量部に対し、フェノール系酸化防止剤(テトラキス[メチレン−3−(3’,5’−ジ−tert−ブチル−4’−ヒドロキシフェニル)プロピオネート]メタン)0.05質量部、ステアリン酸カルシウム0.05質量部、および、表10〜12記載の樹脂添加剤組成物を配合し、ヘンシェルミキサーで、1000rpm×1min混合後、二軸押出機を用いて、230℃の押出温度で造粒した。造粒したペレットは、80℃で2時間乾燥させた後、同一の二軸押出機を用いて、230℃の押出温度で造粒を繰り返し、熱履歴による下記(10)〜(12)に対する影響を評価した。なお、表10〜12中の配合量の単位は質量部である。
熱履歴が異なるそれぞれのペレットについて、射出成型機(EC100−2A;東芝機械株式会社製)を用いて、200℃の射出温度、50℃の金型温度の条件で、寸法60mm×60mm×2mmの試験片を成形した。成形後、直ちに室温23℃、湿度50%の標準状態下にて48時間放置後、分光測色計(SC−T;スガ試験機株式会社製)を用いて、試験片のY.I.を測定した。
得られたペレットを少量切り取り、示差走査熱量測定器(ダイアモンド・パーキエルマー社製)を用いて結晶化温度を測定した。測定方法は、室温から50℃/minの速度で230℃まで昇温し、10分間保持後、−10℃/minの速度で50℃まで冷却して得られたチャートにおいて、吸熱反応がピークトップとなる温度を結晶化温度とした。
熱履歴が異なるそれぞれのペレットについて、射出成型機(EC100−2A;東芝機械株式会社製)にて、200℃の射出温度、50℃の金型温度の条件で射出成形し、寸法10mm×4mm×100mmのノッチ付き試験片を成形した。成形後、直ちに23℃の恒温機にいれて48時間静置後、試験片を取り出してISO−180に準拠してノッチ付き試験片のアイゾット衝撃強度率(J/m)を測定した。
(B)−1:ステアリン酸ナトリウム
(E)−1:PEP−24(3,9−ビス(2,4−ジ−tert−ブチルフェノキシ)−2,4,8,10−テトラオキサ−3,9−ジホスファスピロ[5.5]ウンデカン)
比較核剤:安息香酸ナトリウム
比較ホスファイト:トリス(2,4−ジ−tert−ブチルフェニル)ホスファイト
インパクトコポリマー{株式会社プライムポリマー社製品名「J708P」,メルトフローレート=45g/10min(ISO規格1133準拠 2.16kg×230℃)}100質量部に対し、フェノール系酸化防止剤(テトラキス[メチレン−3−(3’,5’−ジ−tert−ブチル−4’−ヒドロキシフェニル)プロピオネート]メタン)0.05質量部、ステアリン酸カルシウム0.05質量部、および、表13、14記載の樹脂添加剤組成物を配合し、ヘンシェルミキサーで、1000rpm×1min混合後、二軸押出機を用いて、230℃の押出温度で造粒した。造粒したペレットは、80℃で2時間乾燥させた後、同一の二軸押出機を用いて、230℃の押出温度で造粒を繰り返し、熱履歴によるメルトフローレート(MFR)への影響を評価した。なお、表中の配合量の単位は質量部である。
ISO1133規格に準じ、得られたペレットを230℃で溶融させ、2.16kgの荷重をかけて押し出された溶融樹脂の重量を計測し、10分換算での樹脂の吐出量をメルトフローレート(MFR:g/10min)とした。
比較核剤:安息香酸ナトリウム
(B)−1:ステアリン酸ナトリウム
(E)−2:PEP−36(3,9−ビス(2,6−ジ−tert−ブチル−4−メチルフェノキシ)−2,4,8,10−テトラオキサ−3,9−ジホスファスピロ[5.5]ウンデカン
フェノール系酸化防止剤(テトラキス[メチレン−3−(3’,5’−ジ−tert−ブチル−4’−ヒドロキシフェニル)プロピオネート]メタン)0.05質量部、リン系酸化防止剤(トリス(2,4−ジ−tert−ブチルフェニル)ホスファイト)0.1質量部、およびステアリン酸カルシウム0.05質量部および、下記の表15〜18に記載の樹脂組成物を配合し、ヘンシェルミキサーで、1000rpm×1min混合後、二軸押出機を用いて、押出温度=230℃、スクリュー回転速度=150rpm、フィード速度=7.2kg/hの条件で混練し、ペレットを製造した。ペレットを用いて、下記(14)〜(16)の評価を行った。なお、表15〜18中の配合量の単位は質量部である。
得られたペレットを少量切り取り、示差走査熱量測定器(ダイアモンド・パーキンエルマー社製)を用いて結晶化温度を測定した。測定方法は、室温から50℃/minの速度で230℃まで昇温し、10分間保持後、10℃/minの速度で50℃まで冷却して得られたチャートにおいて、吸熱反応がピークトップとなる温度を結晶化温度とした。
得られたペレットを、射出成型機(EC100−2A;東芝機械株式会社製)にて、200℃の射出温度、50℃の金型温度の条件で射出成形し、寸法80mm×10mm×4mmの試験片を作成し、成形後直ちに23℃の恒温機にいれて48時間静置後、試験片を取り出してISO−178に準拠して試験片の曲げ弾性率(MPa)を測定した。
得られた難燃性UL−94V試験用試験片(127mm×12.7mm×1.6mm)を垂直に保ち、下端にバーナーの火を10秒間接炎させた後で炎を取り除き、試験片に着火した火が消える時間を測定した。次に、火が消えると同時に2回目の接炎を10秒間行ない、1回目と同様にして着火した火が消える時間を測定した。また、落下する火種により試験片の下の綿が着火するか否かについても同時に評価した。1回目と2回目の燃焼時間、および綿着火の有無等から、UL−94V規格にしたがって燃焼ランクをつけた。燃焼ランクはV−0が最も難燃性に優れ、V−1、V−2となるにしたがって難燃性は低下し、V−0〜V−2のランクの何れにも該当しないものはNRとした。
(A)−1:ナトリウム−2,2’−メチレンビス(4,6−ジ−tert−ブチルフェニル)ホスフェート
比較核剤1:ジシクロヘキサン−1,2−ジカルボン酸カルシウム化合物
比較核剤2:安息香酸ナトリウム
(B)−1:ステアリン酸ナトリウム
(F)−1:イントメッセント系難燃剤;株式会社ADEKA製商品名(ADK STAB FP−2500S)
(F)−2:イントメッセント系難燃剤;株式会社ADEKA製商品名(ADK STAB FP−2100JC)
(F)−3:ポリリン酸アンモニウム
(F)−4:デカブロモジフェニルエタン
(G)−1:THEIC(トリス(2−ヒドロキシエチル)イソシアヌレート)
(G)−2:三酸化アンチモン
(G)−3:ポリテトラフルオロエチレン
インパクトコポリマー{株式会社プライムポリマー社製品名「J705P」,メルトフローレート=11.5g/10min(ISO規格1133準拠 2.16kg×230℃)}100質量部に対し、フェノール系酸化防止剤(テトラキス[メチレン−3−(3’,5’−ジ−tert−ブチル−4’−ヒドロキシフェニル)プロピオネート]メタン)0.05質量部、ステアリン酸カルシウム0.05質量部、および、表19〜23の樹脂添加剤組成物を配合し、ヘンシェルミキサーで、1000rpm×1min混合後、二軸押出機を用いて、230℃の押出温度で造粒し、ペレットを得た。なお、表19〜23中の配合量の単位は質量部である。
得られたペレットを細かく破断して、5mg秤量してアルミパンに充填し、示差走査熱量測定機(装置:パーキンエルマー社製ダイアモンド)で結晶化温度を測定した。測定は、50℃/minの速度で230℃まで昇温し、5分間保持後、10℃/minで50℃まで冷却した際に、測定した発熱ピークの温度を結晶化温度として求めた。
得られたペレットを、射出成型機(EC100−2A;東芝機械株式会社製)にて、200℃の射出温度、50℃の金型温度の条件で射出成形し、寸法80mm×10mm×4mmの試験片を作成し、成形後直ちに23℃の恒温機にいれて48時間静置後、試験片を取り出してISO−178に準拠して試験片の曲げ弾性率(MPa)を測定した。
(A)−1:株式会社ADEKA製商品名「アデカスタブNA−11」
比較核剤1:Milliken社製品名「Hyperform(R) HPN−20E」
比較核剤2:安息香酸ナトリウム
(B)−1:ステアリン酸ナトリウム
(I)−1:株式会社ADEKA製商品名「アデカスタブLA−77Y」
(I)−2:株式会社ADEKA製商品名「アデカスタブLA−72」
(I)−3:株式会社ADEKA製商品名「アデカスタブLA−52」
(I)−4:株式会社ADEKA製商品名「アデカスタブLA−502」
(I)−5:株式会社ADEKA製商品名「アデカスタブLA−63P」
(I)−6:株式会社ADEKA製商品名「アデカスタブT−1640L」
(I)−7:株式会社ADEKA製商品名「アデカスタブLA−81」
(I)−8:株式会社ADEKA製商品名「アデカスタブLA−704」
(I)−9:株式会社ADEKA製商品名「アデカスタブLA−40」
(I)−10:株式会社ADEKA製商品名「アデカスタブLA−402」
(I)−11:BASF社製商品名「Chimassorb944」
(I)−12:BASF社製商品名「Chimassorb2020」
(I)−13:Cytec社製商品名「CyasorbUV−3808PP5」
(I)−14:BASF社製商品名「Tinuvin XT−855FF」
(J)−1:株式会社ADEKA製商品名「アデカスタブLA−36」
(J)−2:株式会社ADEKA製商品名「アデカスタブLA−29」
(J)−3:Cytec社製商品名「Cyasorb UV−1164」
Claims (7)
- 熱可塑性樹脂100質量部に対し、前記(A)一般式(1)で表されるリン酸エステル化合物が0.001〜10質量部となるように請求項1記載の樹脂添加剤組成物を含有することを特徴とする熱可塑性樹脂組成物。
- 前記熱可塑性樹脂が、ポリオレフィン系樹脂である請求項2記載の熱可塑性樹脂組成物。
- さらに、(C)熱可塑性エラストマー1〜80質量部、および(D)充填剤1〜80質量部を含有する請求項2記載の熱可塑性樹脂組成物。
- 前記(C)熱可塑性エラストマーが、エチレンとα−オレフィンとの共重合体または、エチレンとビニルエステルとの共重合体である請求項4記載の熱可塑性樹脂組成物。
- 請求項2記載の熱可塑性樹脂組成物を用いてなることを特徴とする成形体。
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CN112300508B (zh) * | 2019-07-31 | 2023-02-17 | 乐天化学株式会社 | 热塑性树脂组合物和利用其的模制产品 |
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EP3424993A4 (en) | 2019-12-04 |
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AU2017226682B2 (en) | 2021-08-19 |
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AU2021269334A1 (en) | 2021-12-09 |
KR20210123416A (ko) | 2021-10-13 |
EP3424993A1 (en) | 2019-01-09 |
AU2017226682A1 (en) | 2018-10-18 |
RU2018134327A (ru) | 2020-04-02 |
KR102326800B1 (ko) | 2021-11-15 |
TWI787175B (zh) | 2022-12-21 |
EP3424993B1 (en) | 2024-05-01 |
CN108699291A (zh) | 2018-10-23 |
EP4372042A3 (en) | 2024-08-07 |
RU2771528C2 (ru) | 2022-05-05 |
JP6386208B2 (ja) | 2018-09-05 |
RU2018134327A3 (ja) | 2020-04-02 |
KR20180114222A (ko) | 2018-10-17 |
JP6861188B2 (ja) | 2021-04-21 |
BR112018067383A2 (pt) | 2019-01-15 |
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