JP2007153952A - Method for producing modified polyethylene naphthalate resin composition - Google Patents
Method for producing modified polyethylene naphthalate resin composition Download PDFInfo
- Publication number
- JP2007153952A JP2007153952A JP2005347789A JP2005347789A JP2007153952A JP 2007153952 A JP2007153952 A JP 2007153952A JP 2005347789 A JP2005347789 A JP 2005347789A JP 2005347789 A JP2005347789 A JP 2005347789A JP 2007153952 A JP2007153952 A JP 2007153952A
- Authority
- JP
- Japan
- Prior art keywords
- resin
- polyethylene naphthalate
- thermoplastic
- resin composition
- naphthalate resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- -1 polyethylene naphthalate Polymers 0.000 title claims abstract description 101
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 title claims abstract description 96
- 239000011112 polyethylene naphthalate Substances 0.000 title claims abstract description 96
- 239000011342 resin composition Substances 0.000 title claims abstract description 56
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 22
- 229920005989 resin Polymers 0.000 claims abstract description 82
- 239000011347 resin Substances 0.000 claims abstract description 82
- 229920001169 thermoplastic Polymers 0.000 claims abstract description 59
- 239000004416 thermosoftening plastic Substances 0.000 claims abstract description 59
- 229920005992 thermoplastic resin Polymers 0.000 claims abstract description 52
- 229920006127 amorphous resin Polymers 0.000 claims abstract description 48
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 41
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 41
- 238000004898 kneading Methods 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 13
- 125000003700 epoxy group Chemical group 0.000 claims description 11
- 238000007142 ring opening reaction Methods 0.000 claims description 11
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 9
- 239000000155 melt Substances 0.000 claims description 9
- 125000003504 2-oxazolinyl group Chemical group O1C(=NCC1)* 0.000 claims description 8
- 239000004793 Polystyrene Substances 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- 229920002223 polystyrene Polymers 0.000 claims description 7
- UHPJWJRERDJHOJ-UHFFFAOYSA-N ethene;naphthalene-1-carboxylic acid Chemical compound C=C.C1=CC=C2C(C(=O)O)=CC=CC2=C1 UHPJWJRERDJHOJ-UHFFFAOYSA-N 0.000 claims description 6
- 229920005672 polyolefin resin Polymers 0.000 claims description 3
- BQBSIHIZDSHADD-UHFFFAOYSA-N 2-ethenyl-4,5-dihydro-1,3-oxazole Chemical compound C=CC1=NCCO1 BQBSIHIZDSHADD-UHFFFAOYSA-N 0.000 claims 1
- 238000002407 reforming Methods 0.000 claims 1
- 238000002156 mixing Methods 0.000 abstract description 7
- 230000000694 effects Effects 0.000 description 8
- 229920001577 copolymer Polymers 0.000 description 7
- 239000000523 sample Substances 0.000 description 7
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- 230000006866 deterioration Effects 0.000 description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 description 3
- 238000005809 transesterification reaction Methods 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 229920002125 Sokalan® Polymers 0.000 description 2
- 229920010524 Syndiotactic polystyrene Polymers 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
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 235000019445 benzyl alcohol Nutrition 0.000 description 2
- 239000003990 capacitor Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 238000006266 etherification reaction Methods 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 239000012760 heat stabilizer Substances 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 239000004611 light stabiliser Substances 0.000 description 2
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 238000005191 phase separation Methods 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 239000004584 polyacrylic acid Substances 0.000 description 2
- 239000004926 polymethyl methacrylate Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- BYEAHWXPCBROCE-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropan-2-ol Chemical compound FC(F)(F)C(O)C(F)(F)F BYEAHWXPCBROCE-UHFFFAOYSA-N 0.000 description 1
- IMSODMZESSGVBE-UHFFFAOYSA-N 2-Oxazoline Chemical group C1CN=CO1 IMSODMZESSGVBE-UHFFFAOYSA-N 0.000 description 1
- LLLVZDVNHNWSDS-UHFFFAOYSA-N 4-methylidene-3,5-dioxabicyclo[5.2.2]undeca-1(9),7,10-triene-2,6-dione Chemical compound C1(C2=CC=C(C(=O)OC(=C)O1)C=C2)=O LLLVZDVNHNWSDS-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- BELBBZDIHDAJOR-UHFFFAOYSA-N Phenolsulfonephthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2S(=O)(=O)O1 BELBBZDIHDAJOR-UHFFFAOYSA-N 0.000 description 1
- QLZHNIAADXEJJP-UHFFFAOYSA-N Phenylphosphonic acid Chemical compound OP(O)(=O)C1=CC=CC=C1 QLZHNIAADXEJJP-UHFFFAOYSA-N 0.000 description 1
- 229920002845 Poly(methacrylic acid) Polymers 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000000071 blow moulding Methods 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 238000010538 cationic polymerization reaction Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000006757 chemical reactions by type Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229920006038 crystalline resin Polymers 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- CSNCOKSAYUDNIE-UHFFFAOYSA-N diethyl naphthalene-2,6-dicarboxylate Chemical compound C1=C(C(=O)OCC)C=CC2=CC(C(=O)OCC)=CC=C21 CSNCOKSAYUDNIE-UHFFFAOYSA-N 0.000 description 1
- OCSXMIBZIHMVCP-UHFFFAOYSA-N dimethyl naphthalene-1,4-dicarboxylate Chemical compound C1=CC=C2C(C(=O)OC)=CC=C(C(=O)OC)C2=C1 OCSXMIBZIHMVCP-UHFFFAOYSA-N 0.000 description 1
- CUDOKCQJXWWKTD-UHFFFAOYSA-N dimethyl naphthalene-1,5-dicarboxylate Chemical compound C1=CC=C2C(C(=O)OC)=CC=CC2=C1C(=O)OC CUDOKCQJXWWKTD-UHFFFAOYSA-N 0.000 description 1
- GYUVMLBYMPKZAZ-UHFFFAOYSA-N dimethyl naphthalene-2,6-dicarboxylate Chemical compound C1=C(C(=O)OC)C=CC2=CC(C(=O)OC)=CC=C21 GYUVMLBYMPKZAZ-UHFFFAOYSA-N 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 125000005487 naphthalate group Chemical group 0.000 description 1
- CHDRADPXNRULGA-UHFFFAOYSA-N naphthalene-1,3-dicarboxylic acid Chemical compound C1=CC=CC2=CC(C(=O)O)=CC(C(O)=O)=C21 CHDRADPXNRULGA-UHFFFAOYSA-N 0.000 description 1
- ABMFBCRYHDZLRD-UHFFFAOYSA-N naphthalene-1,4-dicarboxylic acid Chemical compound C1=CC=C2C(C(=O)O)=CC=C(C(O)=O)C2=C1 ABMFBCRYHDZLRD-UHFFFAOYSA-N 0.000 description 1
- DFFZOPXDTCDZDP-UHFFFAOYSA-N naphthalene-1,5-dicarboxylic acid Chemical compound C1=CC=C2C(C(=O)O)=CC=CC2=C1C(O)=O DFFZOPXDTCDZDP-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 229960003531 phenolsulfonphthalein Drugs 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 229920006112 polar polymer Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920005553 polystyrene-acrylate Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 230000002040 relaxant effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000012488 sample solution Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
【課題】優れた湿度変化に対する寸法安定性や優れた電気特性を効率的に具備させることができる改質ポリエチレンナフタレート樹脂組成物の製造方法の提供。
【解決手段】ポリエチレンナフタレート樹脂（Ａ）に、特定の溶解性パラメーターの熱可塑性非晶樹脂（Ｃ）を、１〜１０重量％配合して熱可塑性樹脂組成物（ＡＣ）を製造し、該樹脂組成物（ＡＣ）と該樹脂（Ａ）に対して非相溶なビニル系熱可塑性樹脂（Ｂ）とを、該樹脂（Ｂ）の割合が１〜３０重量％および樹脂（Ｃ）の割合が０．１〜５重量％となるように溶融混錬する改質ポリエチレンナフタレート樹脂組成物の製造方法。
【選択図】なしThe present invention provides a method for producing a modified polyethylene naphthalate resin composition capable of efficiently providing excellent dimensional stability against humidity changes and excellent electrical properties.
A thermoplastic resin composition (AC) is produced by blending 1 to 10% by weight of a thermoplastic amorphous resin (C) having a specific solubility parameter with a polyethylene naphthalate resin (A). A resin composition (AC) and a vinyl-based thermoplastic resin (B) that is incompatible with the resin (A), a proportion of the resin (B) of 1 to 30% by weight and a proportion of the resin (C) The manufacturing method of the modified polyethylene naphthalate resin composition melt-kneaded so that it may become 0.1 to 5 weight%.
[Selection figure] None
Description
本発明は、ポリエチレンナフタレート樹脂に非相溶なビニル系熱可塑性樹脂を安定的にかつ均一に分散せしめる改質ポリエチレンナフタレート樹脂組成物の製造方法に関する。 The present invention relates to a method for producing a modified polyethylene naphthalate resin composition in which a vinyl thermoplastic resin incompatible with a polyethylene naphthalate resin is stably and uniformly dispersed.
ポリエチレンナフタレート樹脂は、優れた熱特性および機械特性を有することから、例えばフィルムにして磁気記録媒体、コンデンサー、フレキシブル基板、光学部材、食品包装、装飾用などの様々な用途で用いられている。 Since polyethylene naphthalate resin has excellent thermal and mechanical properties, it is used as a film in various applications such as magnetic recording media, capacitors, flexible substrates, optical members, food packaging, and decoration.
このように優れた特性を有するポリエチレンナフタレート樹脂ではあるが、極性ポリマーであるがゆえに、磁気記録媒体などのベースフィルムに用いるには湿度変化による寸法変化の改良が求められ、またコンデンサーのベースフィルムに用いるにはさらなる電気特性の改良が求められている。 Although it is a polyethylene naphthalate resin with such excellent properties, it is a polar polymer, so it needs to be improved in dimensional changes due to changes in humidity in order to be used as a base film for magnetic recording media. Further improvements in electrical properties are required for use in the field.
そこで、国際公開第２００５／７３３１８号パンフレットでは、ポリエチレンナフタレート樹脂に、ポリエチレンナフタレート樹脂に非相溶なビニル系熱可塑性を分散させることが提案され、そのとき特定の溶解性パラメーターを有する熱可塑性非晶樹脂を併用することでその分散性を高められることが提案されている。
上記特許文献１の教示に基づき、ポリエチレンナフタレート樹脂に非相溶なビニル系熱可塑性と、特定の溶解性パラメーターを有する熱可塑性非晶樹脂とを用いれば、ビニル系熱可塑性を均一に分散できポリエチレンナフタレート樹脂の極性を抑えられる。 Based on the teaching of the above-mentioned Patent Document 1, vinyl-based thermoplasticity can be uniformly dispersed by using a vinyl-based thermoplastic that is incompatible with polyethylene naphthalate resin and a thermoplastic amorphous resin having a specific solubility parameter. The polarity of polyethylene naphthalate resin can be suppressed.
しかしながら、本発明者らのその後の研究により、熱可塑性非晶樹脂の割合を少なくしたときに、得られる分散性が低下しやすく、熱可塑性非晶樹脂が必ずしも存在する量に応じて効率的に機能していないことが判明した。 However, as a result of subsequent studies by the present inventors, when the proportion of the thermoplastic amorphous resin is reduced, the resulting dispersibility tends to be lowered, and the amount of the thermoplastic amorphous resin is not necessarily increased. Turned out not to work.
したがって、本発明の課題は、ポリエチレンナフタレート樹脂に非相溶なビニル系熱可塑性を特定の溶解性パラメーターを有する熱可塑性非晶樹脂によって、均一にかつ効率よく分散できるポリエチレンナフタレート樹脂組成物の製造方法を提供することにある。 Accordingly, an object of the present invention is to provide a polyethylene naphthalate resin composition that can uniformly and efficiently disperse vinyl-based thermoplastics that are incompatible with polyethylene naphthalate resins with thermoplastic amorphous resins having specific solubility parameters. It is to provide a manufacturing method.
本発明者らは上述の目的を達成するために鋭意研究した結果、ポリエチレンナフタレート樹脂にビニル系熱可塑性樹脂を溶融混錬させる際に、特定の溶解性パラメーターを有する熱可塑性非晶樹脂をまずポリエチレンナフタレート樹脂に配合してポリエチレンナフタレート樹脂と熱可塑性非晶樹脂との組成物、いわゆるマスターチップを製造することによって、熱可塑性非晶樹脂によるビニル系熱可塑性樹脂の分散性をより効率的に向上できることを見出し、本発明に到達した。 As a result of diligent research to achieve the above-mentioned object, the present inventors have first made a thermoplastic amorphous resin having a specific solubility parameter when melt-kneading a vinyl-based thermoplastic resin into a polyethylene naphthalate resin. By blending with polyethylene naphthalate resin to produce a composition of polyethylene naphthalate resin and thermoplastic amorphous resin, so-called master chip, the dispersibility of vinyl thermoplastic resin by thermoplastic amorphous resin is made more efficient The present invention has been found.
かくして本発明によれば、本発明の目的は、エチレンナフタレートを主たる繰り返し単位とするポリエチレンナフタレート樹脂（Ａ）に、溶解性パラメーターが２１．０〜２６．０（MJ／m３）０．５の範囲にある熱可塑性非晶樹脂（Ｃ）を、ポリエチレンナフタレート樹脂（Ａ）と熱可塑性非晶樹脂（Ｃ）の合計重量を基準として、１〜１０重量％配合して熱可塑性樹脂組成物（ＡＣ）を製造する第１工程と、
該熱可塑性樹脂組成物（ＡＣ）とポリエチレンナフタレート樹脂（Ａ）に対して非相溶なビニル系熱可塑性樹脂（Ｂ）とを、得られる改質ポリエチレンナフタレート樹脂組成物の重量を基準としたときの、熱可塑性ビニル系熱可塑性樹脂（Ｂ）の割合が１〜３０重量％および熱可塑性非晶樹脂（Ｃ）の割合が０．１〜５重量％となるように溶融混錬する第２工程とからなる改質ポリエチレンナフタレート樹脂組成物の製造方法によって達成される。
Thus, according to the present invention, the object of the present invention is to have a solubility parameter of 21.0 to 26.0 (MJ / m 3 ) in polyethylene naphthalate resin (A) having ethylene naphthalate as the main repeating unit . A thermoplastic amorphous resin (C) in the range of 5 is blended in an amount of 1 to 10 wt% based on the total weight of the polyethylene naphthalate resin (A) and the thermoplastic amorphous resin (C). A first step of manufacturing an article (AC);
Based on the weight of the resulting modified polyethylene naphthalate resin composition, the thermoplastic resin composition (AC) and the vinyl thermoplastic resin (B) incompatible with the polyethylene naphthalate resin (A). The melt-kneading is performed so that the ratio of the thermoplastic vinyl-based thermoplastic resin (B) is 1 to 30% by weight and the ratio of the thermoplastic amorphous resin (C) is 0.1 to 5% by weight. This is achieved by a method for producing a modified polyethylene naphthalate resin composition comprising two steps.
また、本発明の好ましい態様として、第２工程が、該熱可塑性樹脂組成物（ＡＣ）とビニル系熱可塑性樹脂（Ｂ）のほかに、ポリエチレンナフタレート樹脂（Ａ）を溶融混錬すること、第１工程が溶融混錬で、かつ二軸溶融混錬押出機を用いて、樹脂に付与する比エネルギーが０．２８〜０．３５ｋＷｈ／ｋｇの範囲で行われること、第２工程が二軸溶融混錬押出機を用いて、樹脂に付与する比エネルギーが０．２８〜０．３５ｋＷｈ／ｋｇの範囲で行われること、ビニル系熱可塑性樹脂（Ｂ）が、ポリスチレンであること、熱可塑性非晶樹脂（Ｃ）が、ビニルオキサゾリン共重合ポリオレフィン系樹脂で、第１工程において、ポリエチレンナフタレート樹脂（Ａ）と開環結合しているオキサゾリン基の割合を、熱可塑性非晶樹脂（Ｃ）中のオキサゾリン基のモル数を基準として、１〜１０モル％の範囲とすること、熱可塑性非晶樹脂（Ｃ）がエポキシ基を有し、第１工程において、ポリエチレンナフタレート樹脂（Ａ）と開環結合しているエポキシ基の割合を、熱可塑性非晶樹脂（Ｃ）中のエポキシ基のモル数を基準として、１〜１０モル％の範囲とすること、および第１工程において、熱可塑性樹脂組成物（ＡＣ）中のカルボキシル基末端数を、第１工程に供するポリエチレンナフタレート樹脂（Ａ）のカルボキシル基末端数に対して、３０〜９７モル％の範囲にすることの少なくともいずれかを具備する改質ポリエチレンナフタレート樹脂組成物の製造方法も提供される。 Moreover, as a preferred embodiment of the present invention, the second step includes melt kneading the polyethylene naphthalate resin (A) in addition to the thermoplastic resin composition (AC) and the vinyl thermoplastic resin (B), The first step is melt kneading, and the specific energy applied to the resin is performed in the range of 0.28 to 0.35 kWh / kg using a biaxial melt kneading extruder, and the second step is biaxial. Using a melt-kneading extruder, the specific energy applied to the resin is 0.28 to 0.35 kWh / kg, the vinyl-based thermoplastic resin (B) is polystyrene, The crystalline resin (C) is a vinyl oxazoline copolymer polyolefin resin, and in the first step, the ratio of the oxazoline group that is ring-opened to the polyethylene naphthalate resin (A) is determined in the thermoplastic amorphous resin (C). of Based on the number of moles of the xazoline group, the range is from 1 to 10 mol%, the thermoplastic amorphous resin (C) has an epoxy group, and in the first step, the ring opening with the polyethylene naphthalate resin (A) The ratio of the bonded epoxy groups is in the range of 1 to 10 mol% based on the number of moles of epoxy groups in the thermoplastic amorphous resin (C), and in the first step, the thermoplastic resin composition It comprises at least one of setting the number of carboxyl groups in the product (AC) in the range of 30 to 97 mol% with respect to the number of carboxyl groups in the polyethylene naphthalate resin (A) used in the first step. A method for producing a modified polyethylene naphthalate resin composition is also provided.
本発明の改質ポリエチレンナフタレート樹脂組成物の製造方法を用いれば、熱可塑性非晶樹脂（Ｃ）をポリエチレンナフタレート樹脂（Ａ）と事前に配合し、いわゆるマスターチップを製造することから、ビニル系熱可塑性樹脂中に取り込まれて分散性に寄与しない熱可塑性非晶樹脂（Ｃ）の割合を抑制でき、しかもポリエチレンナフタレート樹脂（Ａ）と熱可塑性非晶樹脂（Ｃ）とが事前に部分的に反応していることで、最終的に得られる改質ポリエチレンナフタレート樹脂組成物中のビニル系熱可塑性樹脂（Ｂ）の分散性を効率的に向上することできる。 If the manufacturing method of the modified polyethylene naphthalate resin composition of the present invention is used, the thermoplastic amorphous resin (C) is pre-blended with the polyethylene naphthalate resin (A) to produce a so-called master chip. The ratio of the thermoplastic amorphous resin (C) that is taken into the thermoplastic resin and does not contribute to dispersibility can be suppressed, and the polyethylene naphthalate resin (A) and the thermoplastic amorphous resin (C) are partially divided in advance. Thus, the dispersibility of the vinyl thermoplastic resin (B) in the finally obtained modified polyethylene naphthalate resin composition can be efficiently improved.
まず、本発明における、ポリエチレンナフタレート樹脂（Ａ）、ポリエチレンナフタレート樹脂（Ａ）に対して非相溶な熱可塑性ビニル系熱可塑性樹脂（Ｂ）および熱可塑性非晶樹脂（Ｃ）について、それぞれ説明する。 First, in the present invention, polyethylene naphthalate resin (A), thermoplastic vinyl thermoplastic resin (B) and thermoplastic amorphous resin (C) that are incompatible with polyethylene naphthalate resin (A), respectively. explain.
本発明におけるエチレンナフタレートを主たる繰り返し単位とするポリエチレンナフタレート樹脂（Ａ）とは、その繰り返し単位の８０モル％以上、好ましくは９０モル％以上、さらに好ましくは９５モル％以上が、エチレンナフタレートであるポリエチレンナフタレート樹脂である。エチレンナフタレート成分の割合が下限未満であると、得られる樹脂組成物の強度などの機械的特性が乏しくなる。このようなポリエチレンナフタレート樹脂（Ａ）を重合する際の原料となる酸成分としては、ナフタレンジカルボン酸および／またはナフタレンジカルボン酸エステルが挙げられる。具体的なナフタレンジカルボン酸としては、２，６−ナフタレンジカルボン酸、１，４−ナフタレンジカルボン酸、１，５−ナフタレンジカルボン酸、１，３−ナフタレンジカルボン酸などが挙げられる。また、具体的なナフタレンジカルボン酸のエステルとしては、２，６−ナフタレンジカルボン酸ジメチル、２，６−ナフタレンジカルボン酸ジエチル、１，４−ナフタレンジカルボン酸ジメチル、１，５−ナフタレンジカルボン酸ジメチルなどが挙げられる。これらの中でも、強度を高めやすいことから、ナフタレン成分が２，６−ナフタレンジカルボン酸成分であるポリエチレンナフタレート樹脂（Ａ）が好ましい。なお、エチレンナフタレート成分以外の共重合成分としては、一般にポリエチレンナフタレートに共重合して用いられものであれば同様に使用でき、また、ポリエチレンナフタレート樹脂（Ａ）自体の製造方法についても、それ自体公知の方法が採用できる。例えばエステル交換法、直接エステル化法等の溶融重合法または溶液重合法を挙げることが出来る。もちろん、エステル交換触媒、エステル化触媒、エーテル化防止剤、また重合に用いる重合触媒、熱安定剤、光安定剤等の各種安定剤、重合調整剤なども、制限されず、一般にポリエチレンナフタレートに使用されるものを好適に使用できる。具体的には、エステル交換触媒としては、マンガン、コバルト、亜鉛、チタン、カルシウムなどの化合物が例示でき、エーテル化防止剤としてアミン化合物などが例示でき、重縮合触媒としてはゲルマニウム、アンチモン、スズ、チタンなどの化合物が例示でき、熱安定剤としてはリン酸、亜リン酸、フェニルホスホン酸などの各種リン化合物が例示できる。また、本発明の効果を損なわない範囲で、例えば光安定剤、耐電防止剤、滑剤、酸化防止剤、離型剤などを加えても良い。 The polyethylene naphthalate resin (A) having ethylene naphthalate as the main repeating unit in the present invention is 80 mol% or more, preferably 90 mol% or more, more preferably 95 mol% or more of the repeating unit. It is a polyethylene naphthalate resin. If the proportion of the ethylene naphthalate component is less than the lower limit, the mechanical properties such as strength of the resulting resin composition will be poor. As an acid component used as a raw material at the time of superposing | polymerizing such a polyethylene naphthalate resin (A), naphthalene dicarboxylic acid and / or naphthalene dicarboxylic acid ester are mentioned. Specific naphthalenedicarboxylic acids include 2,6-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 1,3-naphthalenedicarboxylic acid, and the like. Specific esters of naphthalenedicarboxylic acid include dimethyl 2,6-naphthalenedicarboxylate, diethyl 2,6-naphthalenedicarboxylate, dimethyl 1,4-naphthalenedicarboxylate, dimethyl 1,5-naphthalenedicarboxylate, and the like. Can be mentioned. Among these, polyethylene naphthalate resin (A) in which the naphthalene component is a 2,6-naphthalenedicarboxylic acid component is preferable because the strength is easily increased. In addition, as a copolymer component other than the ethylene naphthalate component, it can be used in the same manner as long as it is generally copolymerized with polyethylene naphthalate, and also for the production method of the polyethylene naphthalate resin (A) itself, A method known per se can be employed. Examples thereof include a melt polymerization method such as a transesterification method and a direct esterification method, or a solution polymerization method. Of course, transesterification catalysts, esterification catalysts, etherification inhibitors, polymerization catalysts used in polymerization, various stabilizers such as heat stabilizers and light stabilizers, polymerization regulators, etc. are not limited and are generally used in polyethylene naphthalate. What is used can be used conveniently. Specifically, examples of the transesterification catalyst include compounds such as manganese, cobalt, zinc, titanium, and calcium, examples of the etherification inhibitor include amine compounds, and examples of the polycondensation catalyst include germanium, antimony, tin, Compounds such as titanium can be exemplified, and examples of the heat stabilizer include various phosphorus compounds such as phosphoric acid, phosphorous acid, and phenylphosphonic acid. Moreover, you may add a light stabilizer, an antistatic agent, a lubricant, antioxidant, a mold release agent etc. in the range which does not impair the effect of this invention.
本発明におけるポリエチレンナフタレートに非相溶なビニル系熱可塑性樹脂（Ｂ）としては、ポリエチレン、ポリプロピレン、ポリスチレン、ポリメチルメタクリレート、ポリ塩化ビニルなどが好ましく挙げられる。もちろん、ビニル系熱可塑性樹脂（Ｂ）はホモポリマーでも共重合ポリマーでもよい。特に高強度、高寸法安定性、耐湿熱性、高絶縁破壊電圧を得られることから、ポリスチレン、ポリメチルメタクリレートが好ましい。また、これらの置換ビニル系樹脂には、さらに立体規則性が存在し、例えばイソタクト型、シンジオタクト型、アタクト型が知られているが、シンジオタクト型が、高強度、高寸法安定性の点から好ましく、特にシンジオタクト型ポリスチレンが好ましい。また、ポリエチレンナフタレート樹脂（Ａ）中へのビニル系熱可塑性樹脂（Ｂ）の分散度を高めるため、ビニル系熱可塑性樹脂（Ｂ）とポリエチレンナフタレート樹脂（Ａ）との溶融粘度は近い方が好ましい。この点から、ポリエチレンナフタレート樹脂（Ａ）と熱可塑性ビニル系熱可塑性樹脂（Ｂ）の溶融粘度の比は、１：４〜１：１の範囲にあることが好ましい。このような粘度比とするため、熱可塑性ビニル系熱可塑性樹脂（Ｂ）の分子量は、５万〜４０万、さらに１０万〜３０万の範囲にあることが好ましい。 Preferred examples of the vinyl thermoplastic resin (B) incompatible with polyethylene naphthalate in the present invention include polyethylene, polypropylene, polystyrene, polymethyl methacrylate, and polyvinyl chloride. Of course, the vinyl-based thermoplastic resin (B) may be a homopolymer or a copolymer. In particular, polystyrene and polymethyl methacrylate are preferable because high strength, high dimensional stability, heat and humidity resistance, and high breakdown voltage can be obtained. Further, these substituted vinyl resins have further stereoregularity, for example, isotactic type, syndiotact type, and attack type are known. Syndiotact type has high strength and high dimensional stability. From the above point, syndiotact polystyrene is particularly preferable. Also, in order to increase the degree of dispersion of the vinyl thermoplastic resin (B) in the polyethylene naphthalate resin (A), the melt viscosity of the vinyl thermoplastic resin (B) and the polyethylene naphthalate resin (A) is closer. Is preferred. From this point, the ratio of the melt viscosity of the polyethylene naphthalate resin (A) and the thermoplastic vinyl-based thermoplastic resin (B) is preferably in the range of 1: 4 to 1: 1. In order to obtain such a viscosity ratio, the molecular weight of the thermoplastic vinyl-based thermoplastic resin (B) is preferably in the range of 50,000 to 400,000, more preferably 100,000 to 300,000.
本発明において、ポリエチレンナフタレート樹脂（Ａ）に混練させるビニル系熱可塑性樹脂（Ｂ）の割合は、得られる樹脂組成物の重量を基準として、１〜３０重量％の範囲である。熱可塑性ビニル系熱可塑性樹脂（Ｂ）の割合が下限未満であると、ポリエチレンナフタレート樹脂（Ａ）の極性を緩和する効果が不十分で、成形品にしたときに寸法安定性や耐電圧などの向上効果が十分に発現されず、他方、上限を超えると押出機中でサージングが発生し、成形性が損なわれる。好ましい熱可塑性ビニル系熱可塑性樹脂（Ｂ）の割合は、２〜２５重量％であり、さらに５〜２０重量％である。 In the present invention, the proportion of the vinyl thermoplastic resin (B) to be kneaded with the polyethylene naphthalate resin (A) is in the range of 1 to 30% by weight based on the weight of the resulting resin composition. If the ratio of the thermoplastic vinyl-based thermoplastic resin (B) is less than the lower limit, the effect of relaxing the polarity of the polyethylene naphthalate resin (A) is insufficient, and dimensional stability, withstand voltage, etc. when formed into a molded product On the other hand, when the upper limit is exceeded, surging occurs in the extruder and the moldability is impaired. The ratio of a preferable thermoplastic vinyl-type thermoplastic resin (B) is 2-25 weight%, Furthermore, it is 5-20 weight%.
本発明における熱可塑性非晶樹脂（Ｃ）は、２１．０〜２６．０（MJ／m３）０．５の範囲にある溶解性パラメーターを有する。ここでいう溶解性パラメーターとは、分子の凝集エネルギーを数値化する概念で、Ｆｅｄｏｒらにより算出方法が提案されている数（Ｆｅｄｏｒ Ｐｏｌｙｍ． Ｅｎｇ． Ｓｃｉ． １４（１９７４）， １４７ ４７２）である。熱可塑性非晶樹脂（Ｃ）の溶解性パラメーターが上記範囲内にあることで、ポリエチレンナフタレート樹脂（Ａ）とビニル系熱可塑性樹脂（Ｂ）との相分離を抑制し、両者を均一に分散させることができ、得られる成形品が斑や筋などのない品位の高い成形品とすることができる。好ましい溶解性パラメーターは２３．０〜２５．５（ＭＪ／ｍ３）０．５の範囲である。このような熱可塑性非晶樹脂（Ｃ）としては、ポリスチレン−ポリアクリル酸共重合体、ポリスチレン−ポリメタクリル酸共重合体、ポリスチレン−ポリビニルオキザゾリンなどが挙げられる。また、熱可塑性非晶樹脂（Ｃ）の割合は、ポリエチレンナフタレート樹脂組成物の重量を基準として、０．１〜５重量％の範囲であり、好ましくは０．５〜４．０％の範囲である。熱可塑性非晶樹脂（Ｃ）の割合が上記範囲内にあることで、ポリエチレンナフタレート樹脂（Ａ）と熱可塑性ビニル系熱可塑性樹脂（Ｂ）との相分離を抑制し、両者を均一に分散させることができ、得られる成形品が斑や筋などのない品位の高い成形品とすることができる。 The thermoplastic amorphous resin (C) in the present invention has a solubility parameter in the range of 21.0 to 26.0 (MJ / m 3 ) 0.5 . Here, the solubility parameter is a concept for quantifying the cohesive energy of molecules, and is a number proposed by Fedor et al. (Fedor Polym. Eng. Sci. 14 (1974), 147 472). When the solubility parameter of the thermoplastic amorphous resin (C) is within the above range, phase separation between the polyethylene naphthalate resin (A) and the vinyl thermoplastic resin (B) is suppressed, and both are uniformly dispersed. The molded product obtained can be a high-quality molded product free from spots and streaks. A preferred solubility parameter is in the range of 23.0 to 25.5 (MJ / m 3 ) 0.5 . Examples of such thermoplastic amorphous resin (C) include polystyrene-polyacrylic acid copolymer, polystyrene-polymethacrylic acid copolymer, and polystyrene-polyvinyloxazoline. The proportion of the thermoplastic amorphous resin (C) is in the range of 0.1 to 5% by weight, preferably in the range of 0.5 to 4.0%, based on the weight of the polyethylene naphthalate resin composition. It is. When the ratio of the thermoplastic amorphous resin (C) is within the above range, the phase separation between the polyethylene naphthalate resin (A) and the thermoplastic vinyl thermoplastic resin (B) is suppressed, and both are uniformly dispersed. The molded product obtained can be a high-quality molded product free from spots and streaks.
なお、本発明で使用する熱可塑性ビニル系熱可塑性樹脂（Ｂ）および熱可塑性非晶樹脂（Ｃ）のそれ自体の製造方法については、ポリエチレンナフタレート樹脂（Ａ）と同じく、特に制限されず、例えばオレフィン系ポリマーであれば、反応の分類ではラジカル重合、カチオン重合、アニオン重合のいずれでもよく、重合方法の分類では、塊状重合、溶液重合、懸濁重合、乳化重合のいずれを採用してもよい。 Incidentally, the method for producing the thermoplastic vinyl-based thermoplastic resin (B) and the thermoplastic amorphous resin (C) used in the present invention is not particularly limited as in the case of the polyethylene naphthalate resin (A), For example, for an olefin polymer, any of radical polymerization, cationic polymerization, and anionic polymerization may be used for the reaction classification, and any of bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization may be used for the classification of the polymerization method. Good.
本発明の改質ポリエチレンナフタレート樹脂組成物の製造方法は、第１工程として、ポリエチレンナフタレート樹脂（Ａ）とビニル系熱可塑性樹脂（Ｂ）と熱可塑性非晶樹脂（Ｃ）とを溶融混錬するまえに、まずポリエチレンナフタレート樹脂（Ａ）と熱可塑性非晶樹脂（Ｃ）とを配合しておくことが必要である。あらかじめポリエチレンナフタレート樹脂（Ａ）と熱可塑性非晶樹脂（Ｃ）とからなる熱可塑性樹脂組成物（ＡＣ）を得ておくことで、ビニル系熱可塑性樹脂（Ｂ）中に取り込まれて分散性に寄与できなくなる熱可塑性非晶樹脂（Ｃ）の割合を抑制でき、効率的に分散性を向上させることができる。 In the production method of the modified polyethylene naphthalate resin composition of the present invention, as a first step, a polyethylene naphthalate resin (A), a vinyl-based thermoplastic resin (B), and a thermoplastic amorphous resin (C) are melt-mixed. Before smelting, it is necessary to blend the polyethylene naphthalate resin (A) and the thermoplastic amorphous resin (C) first. By obtaining a thermoplastic resin composition (AC) comprising a polyethylene naphthalate resin (A) and a thermoplastic amorphous resin (C) in advance, it is incorporated into the vinyl-based thermoplastic resin (B) and is dispersible. The ratio of the thermoplastic amorphous resin (C) that can no longer contribute to the temperature can be suppressed, and the dispersibility can be improved efficiently.
配合比は、熱可塑性非晶性樹脂（Ｃ）を、熱可塑性樹脂組成物（ＡＣ）の全重量を基準として１〜１０重量％の範囲である。この範囲にすることで、分散性効果と耐熱安定性とを高度に発現させることができる。好ましい配合比は、１．５〜９重量である。 The blending ratio is in the range of 1 to 10% by weight of the thermoplastic amorphous resin (C) based on the total weight of the thermoplastic resin composition (AC). By setting it within this range, the dispersibility effect and the heat stability can be highly developed. A preferable blending ratio is 1.5 to 9 weights.
また、本発明の改質ポリエチレンナフタレート樹脂組成物の製造方法は、第２工程として、上述の該熱可塑性樹脂組成物（ＡＣ）とビニル系熱可塑性樹脂（Ｂ）とを、得られる改質ポリエチレンナフタレート樹脂組成物の重量を基準としたときの、ビニル系熱可塑性樹脂（Ｂ）の割合が１〜３０重量％および熱可塑性非晶樹脂（Ｃ）の割合が０．１〜５重量％となるように溶融混錬することが必要であり、熱可塑性非晶樹脂（Ｃ）をビニル系熱可塑性樹脂（Ｂ）と同時に用いるのではなく、熱可塑性樹脂組成物（ＡＣ）として用いることで、熱可塑性非晶樹脂（Ｃ）をポリエチレンナフタレート樹脂（Ａ）とビニル系熱可塑性樹脂（Ｂ）との界面に優先的に存在させることができ、結果として効率的に分散性を向上させることができる。 Moreover, the manufacturing method of the modified polyethylene naphthalate resin composition of the present invention is a modification in which the thermoplastic resin composition (AC) and the vinyl thermoplastic resin (B) are obtained as the second step. Based on the weight of the polyethylene naphthalate resin composition, the proportion of the vinyl thermoplastic resin (B) is 1 to 30% by weight and the proportion of the thermoplastic amorphous resin (C) is 0.1 to 5% by weight. It is necessary to melt and knead such that the thermoplastic amorphous resin (C) is not used simultaneously with the vinyl-based thermoplastic resin (B), but is used as the thermoplastic resin composition (AC). The thermoplastic amorphous resin (C) can be preferentially present at the interface between the polyethylene naphthalate resin (A) and the vinyl-based thermoplastic resin (B), and as a result, the dispersibility can be improved efficiently. Can do.
さらに本発明の好ましい態様について説明する。
まず、第１工程の配合の方法は従来公知のいずれの方法を採用してもよく、熱可塑性非晶樹脂（Ｃ）をポリエチレンナフタレート樹脂（Ａ）の溶融重合の末期に添加してもよく、バッチ式高速混練機を用いて配合してもよい。また、溶融混錬は１軸または２軸押出機を用いて配合してもよい。これらの中でも、ポリエチレンナフタレート樹脂（Ａ）と熱可塑性非晶樹脂（Ｃ）を二軸混練押出機を用いて、かつポリエチレンナフタレート樹脂組成物に付与する比エネルギーを０．２８〜０．３５ｋＷｈ／ｋｇとなるように溶融混錬するのが好ましい。なお、ここでいう二軸押出機とは、並行する２本のスクリューを有し、スクリューと外壁とのクリアランスおよびスクリュー間のクリアランスに樹脂を導通し、せん断応力による混練分散を行う装置である。また、本発明における比エネルギーとは、スクリューの回転によって樹脂単位重量当たりに与えられたエネルギー量であり、混練スクリューの駆動モーター動力から算出できる。この比エネルギーは、樹脂の流量、滞留時間、樹脂温度、混練スクリューの回転数、装置形状により制御することができる。好ましい比エネルギーの範囲は０．２９〜０．３４ｋＷ・ｈ／ｋｇである。第１工程における配合が、二軸混練押出機で、かつ上記比エネルギーの範囲にある溶融混錬であることにより、分散性を向上しつつ、樹脂の劣化による粘度の低下などを抑制でき、本発明の効果をさらに発現しやすくなる。また、溶融重合時に添加した場合に比べ、熱可塑性非晶樹脂（Ｃ）自体の劣化やゲル化も抑制できる。
Furthermore, the preferable aspect of this invention is demonstrated.
First, any conventionally known method may be adopted as the blending method in the first step, and the thermoplastic amorphous resin (C) may be added at the end of the melt polymerization of the polyethylene naphthalate resin (A). You may mix | blend using a batch type high-speed kneading machine. The melt kneading may be blended using a single screw or twin screw extruder. Among these, the specific energy which gives a polyethylene naphthalate resin (A) and a thermoplastic amorphous resin (C) to a polyethylene naphthalate resin composition using a biaxial kneading extruder is 0.28 to 0.35 kWh. It is preferable to melt and knead so as to be / kg. The twin-screw extruder referred to here is an apparatus that has two screws in parallel, conducts resin to the clearance between the screw and the outer wall, and the clearance between the screws, and performs kneading and dispersion by shear stress. The specific energy in the present invention is the amount of energy given per unit weight of the resin by the rotation of the screw and can be calculated from the drive motor power of the kneading screw. This specific energy can be controlled by the flow rate of resin, the residence time, the resin temperature, the rotational speed of the kneading screw, and the apparatus shape. A preferable specific energy range is 0.29 to 0.34 kW · h / kg. The blending in the first step is a twin-screw kneading extruder and melt kneading in the above specific energy range, so that it is possible to suppress a decrease in viscosity due to deterioration of the resin while improving dispersibility. The effect of the invention is further easily expressed. Moreover, compared with the case where it adds at the time of melt polymerization, deterioration and gelatinization of thermoplastic amorphous resin (C) itself can also be suppressed.
ところで、熱可塑性非晶樹脂（Ｃ）が、ビニルオキサゾリン共重合ポリオレフィン系樹脂である場合、熱可塑性非晶樹脂（Ｃ）中のオキサゾリン基のモル数を基準そして、ポリエチレンナフタレート樹脂（Ａ）と開環結合しているオキサゾリン基の割合が１〜１０モル％であることが好ましい。開環結合しているオキサゾリン基の割合が上記範囲にあることで、分散性向上効果が発現しやすく、かつ樹脂組成物（ＡＣ）の架橋による物性の低下も抑制できる。好ましい開環結合しているオキサゾリン基の割合は、１．５〜９モル％である。一方、熱可塑性非晶樹脂（Ｃ）が、エポキシ基を有する場合、熱可塑性非晶樹脂（Ｃ）中のエポキシ基のモル数を基準そして、ポリエチレンナフタレート樹脂（Ａ）と開環結合しているエポキシ基の割合が１〜１０モル％であることが好ましい。開環結合しているエポキシ基の割合が上記範囲にあることで、分散性向上効果が発現しやすく、かつ樹脂組成物（ＡＣ）の架橋による物性の低下も抑制できる。好ましい開環結合しているエポキシ基の割合は、１．５〜９モル％である。 By the way, when the thermoplastic amorphous resin (C) is a vinyl oxazoline copolymer polyolefin resin, the number of moles of the oxazoline group in the thermoplastic amorphous resin (C) is used as a reference, and the polyethylene naphthalate resin (A) The ratio of the oxazoline group having a ring-opening bond is preferably 1 to 10 mol%. When the ratio of the oxazoline group having a ring-opening bond is in the above range, the effect of improving dispersibility is easily exhibited, and the deterioration of physical properties due to crosslinking of the resin composition (AC) can be suppressed. A preferable ratio of the oxazoline group having a ring-opening bond is 1.5 to 9 mol%. On the other hand, when the thermoplastic amorphous resin (C) has an epoxy group, it is based on the number of moles of the epoxy group in the thermoplastic amorphous resin (C) and is ring-opened with the polyethylene naphthalate resin (A). It is preferable that the ratio of the epoxy group which is 1 to 10 mol%. When the ratio of the epoxy group having a ring-opening bond is in the above range, the effect of improving dispersibility is easily exhibited, and the deterioration of physical properties due to crosslinking of the resin composition (AC) can also be suppressed. The ratio of the epoxy group which has a preferable ring-opening bond is 1.5-9 mol%.
また、熱可塑性樹脂組成物（ＡＣ）中のカルボキシル基末端数を、第１工程に供するポリエチレンナフタレート樹脂（Ａ）のカルボキシル基末端数に対して、３０〜９７モル％の範囲とすることが、耐湿熱加水分解性の点から好ましい。また、下限を下回ると組成物（ＡＣ）がゲル化し最終組成物の成型性が悪化することがあり、上限を越えるとオリゴマーなどの点で好ましくない。好ましい末端数の割合は、５０〜９５モル％の範囲である。 In addition, the number of carboxyl group terminals in the thermoplastic resin composition (AC) may be in the range of 30 to 97 mol% with respect to the number of carboxyl group terminals of the polyethylene naphthalate resin (A) used in the first step. From the viewpoint of resistance to moist heat hydrolysis. On the other hand, if the lower limit is not reached, the composition (AC) may be gelled and the moldability of the final composition may be deteriorated. A preferable ratio of the number of terminals is in the range of 50 to 95 mol%.
つぎに、第２工程の溶融混錬は、１軸または２軸押出機を用いて配合してもよいが、樹脂（ＡＣ）とビニル系熱可塑性樹脂（Ｂ）を二軸混練押出機を用いて、かつポリエチレンナフタレート樹脂組成物に付与する比エネルギーを０．２８〜０．３５ｋＷｈ／ｋｇとなるように溶融混錬するのが好ましい。なお、ここでいう二軸押出機および比エネルギーは、前述の第１工程で説明したのと同様である。好ましい比エネルギーの範囲は０．２９〜０．３４ｋＷ・ｈ／ｋｇである。第２工程における配合が、二軸混練押出機で、かつ上記比エネルギーの範囲にある溶融混錬であることにより、ポリエチレンナフタレート樹脂（Ａ）とビニル系熱可塑性樹脂（Ｂ）との反応が進行し、分散性を向上しつつ、樹脂の劣化による粘度の低下などを抑制でき、本発明の効果をさらに発現しやすくなる。また、樹脂組成物（ＡＣ）とビニル系熱可塑性樹脂（Ｂ）に加え、さらにポリエチレンナフタレート樹脂（Ａ）を溶融混錬することは、複数の樹脂組成物（ＡＣ）のマスターポリマーを用意しなくても、種種の組成のポリマーを製造できることから好ましく、しかも樹脂組成物（ＡＣ）を用いているので、本発明の効果も十分に発現される。 Next, melt kneading in the second step may be performed using a single-screw or twin-screw extruder, but a resin (AC) and a vinyl-based thermoplastic resin (B) are mixed using a twin-screw kneading extruder. In addition, it is preferable to melt and knead such that the specific energy applied to the polyethylene naphthalate resin composition is 0.28 to 0.35 kWh / kg. The twin-screw extruder and the specific energy here are the same as those described in the first step. A preferable specific energy range is 0.29 to 0.34 kW · h / kg. When the blending in the second step is a twin-screw kneading extruder and melt kneading in the above specific energy range, the reaction between the polyethylene naphthalate resin (A) and the vinyl thermoplastic resin (B) As it progresses and the dispersibility is improved, a decrease in viscosity due to the deterioration of the resin can be suppressed, and the effects of the present invention are more easily exhibited. Moreover, in addition to the resin composition (AC) and the vinyl-based thermoplastic resin (B), further melt kneading the polyethylene naphthalate resin (A) prepares a master polymer of a plurality of resin compositions (AC). Even if it is not preferable, it is preferable because polymers having various compositions can be produced, and since the resin composition (AC) is used, the effects of the present invention are sufficiently exhibited.
ところで、本発明では、さらに得られる改質ポリエチレンナフタレート樹脂組成物が含有するエチレンナフタレートの１〜５量体オリゴマー量の和を、その全重量を基準として、０．４〜１．０重量％の範囲にすることが好ましい。オリゴマーの和が下限未満であると、成形時の流動性が低下して、一方上限を超えると成形時に、オリゴマーによる金型汚れなどが起こりやすくなるなど成形工程が不安定化しやすい。オリゴマー含有量の好ましい範囲は、０．５〜０．９重量％である。このようなオリゴマー量は、ポリエチレンナフタレート樹脂Ａ自体のオリゴマー量や前述の溶融混練の条件などによって調整できる。 By the way, in the present invention, the sum of the amounts of 1 to 5 oligomers of ethylene naphthalate contained in the modified polyethylene naphthalate resin composition further obtained is 0.4 to 1.0 weight based on the total weight. % Is preferable. If the sum of the oligomers is less than the lower limit, the fluidity at the time of molding is lowered. On the other hand, if the upper limit is exceeded, mold fouling due to the oligomer tends to occur at the time of molding and the molding process tends to become unstable. A preferable range of the oligomer content is 0.5 to 0.9% by weight. Such oligomer amount can be adjusted by the oligomer amount of the polyethylene naphthalate resin A itself, the above-mentioned melt-kneading conditions, and the like.
また、本発明では、さらに得られる改質ポリエチレンナフタレート樹脂の３００℃、１０００（１／ｓｅｃ）における全樹脂組成物の溶融粘度を、２００〜４００Ｐａ・ｓの範囲にすることが好ましい。該溶融粘度を上記範囲にすることで、耐熱性を維持しつつ、製膜などにおける吐出斑やミクロボイドなどの発生を抑制しやすくなる。好ましい溶融粘度の範囲は、２２０Ｐａ・ｓ〜３００Ｐａ・ｓである。このような溶融粘度は、前述の溶融混錬の比エネルギーなどの条件によって調整できる。 Moreover, in this invention, it is preferable to make the melt viscosity of all the resin compositions in 300 degreeC and 1000 (1 / sec) of the modified polyethylene naphthalate resin obtained further into the range of 200-400 Pa.s. By setting the melt viscosity within the above range, it becomes easy to suppress the occurrence of ejection spots and microvoids in film formation and the like while maintaining heat resistance. The range of preferable melt viscosity is 220 Pa · s to 300 Pa · s. Such a melt viscosity can be adjusted by conditions such as the specific energy of the aforementioned melt kneading.
本発明によれば、射出成形品、Ｔダイ法、共押出法などで、得られる無延伸あるいは低倍率の単層シート及び多層シート、それらを延伸したフィルム及び低延伸倍率の深絞り容器、並びに成形後も無延伸の状態であるダイレクトブロー成形及び延伸ブロー成形体として用いても、ビニル系熱可塑性樹脂（Ｂ）が均一に分散された、すなわちビニル系熱可塑性樹脂（Ｂ）による前述の寸法安定性や電気特性が向上される耐電圧が向上される得られる改質ポリエチレンナフタレート樹脂組成物が安定的にかつ効率的に製造できる。 According to the present invention, an injection-molded article, a T-die method, a co-extrusion method, and the like obtained are non-stretched or low-magnification single-layer sheets and multilayer sheets, films obtained by stretching them, and a deep-drawn container with a low-stretch ratio, and Even if it is used as a direct blow molding and a stretch blow molded article which are in an unstretched state after molding, the above-mentioned dimensions are obtained by uniformly dispersing the vinyl-based thermoplastic resin (B), that is, by the vinyl-based thermoplastic resin (B). The resulting modified polyethylene naphthalate resin composition with improved withstand voltage and improved stability and electrical properties can be produced stably and efficiently.
以下、実施例により、本発明を更に具体的に説明する。但し、本発明はこれらの実施例により限定されるものではない。
本発明のポリエチレンナフタレート樹脂についての各種性状の測定方法は、以下の通りである。
Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples.
Various properties of the polyethylene naphthalate resin of the present invention are measured as follows.
（１）溶融粘度
測定装置は、島津製作所製フローテスターＣＦ−５００を用い、測定温度３００℃、予熱時間：１分、ノズル径：１ｍｍ、ノズル長：１０ｍｍ、で測定し、回帰式より剪断速度１０００（１／秒）における剪断速度を求める。
(1) Melt Viscosity The measuring apparatus uses a flow tester CF-500 manufactured by Shimadzu Corporation, measured at a measurement temperature of 300 ° C., a preheating time of 1 minute, a nozzle diameter of 1 mm, and a nozzle length of 10 mm. The shear rate at 1000 (1 / second) is determined.
（２）オリゴマー
樹脂１０ｍｇをクロロホルム／ヘキサフルオロイソプロパノール（容量比３／２）混液２ｍｌに溶解し、その後クロロホルムを加えて１０ｍｌとしてサンプル液とし、キャリアーにクロロホルムを用いたＧＰＣ（カラムは東ソー製ＴＳＫｇｅｌ−Ｇ２０００Ｈ８７．５ｍｍＩＤ×６０ｃｍを使用）により、検量線法にて１〜５量体それぞれを定量した。
(2) Oligomer 10 mg of resin is dissolved in 2 ml of a chloroform / hexafluoroisopropanol (volume ratio 3/2) mixed solution, and then chloroform is added to obtain a 10 ml sample solution. G2000H87.5 mm ID × 60 cm was used), and each of the 1 to 5 mers was quantified by the calibration curve method.
（３）分散性
得られたポリエチレンナフタレート樹脂組成物を、ミクロトームにより、厚さ０．１μｍに裁断し、トプコン製透過型電子顕微鏡ＬＥＭ−２０００によって、倍率１００００倍で観察し、ビニル系熱可塑性樹脂（Ｂ）のそれぞれの面積を５０個求め、それらの平均の面積円相当径を、直径として分散径を算出した。分散径が小さいほど、分散性に優れることを意味する。
(3) Dispersibility The obtained polyethylene naphthalate resin composition was cut into a thickness of 0.1 μm with a microtome, and observed with a transmission electron microscope LEM-2000 manufactured by Topcon at a magnification of 10,000 times. 50 areas of each of the resins (B) were obtained, and the dispersion diameter was calculated using the average area circle equivalent diameter as the diameter. It means that the smaller the dispersion diameter, the better the dispersibility.
（４）シートの作成
各実施例で得られたポリエチレンナフタレート樹脂組成物からなるペレットを、１７０℃で５時間乾燥した後、１軸の溶融混練押出機に供給し、２９０℃まで加熱して溶融状態でダイから回転冷却ドラムの上に、シート状に押出し、急冷固化して、１２５℃にて製膜方向および幅方向にそれぞれ３．５倍延伸し、厚み７５μｍの二軸配向フィルムを得た。
(4) Preparation of sheet The pellets made of the polyethylene naphthalate resin composition obtained in each example were dried at 170 ° C for 5 hours, then supplied to a uniaxial melt-kneading extruder and heated to 290 ° C. Extruded into a sheet from a die on a rotary cooling drum in a molten state, rapidly cooled and solidified, and stretched 3.5 times in the film forming direction and in the width direction at 125 ° C. to obtain a biaxially oriented film having a thickness of 75 μm It was.
（５）絶縁破壊電圧
上記（４）のシートサンプルを用い、ＪＩＳ Ｃ２１５１記載の平板電極法に準拠して、東京精電株式会社製 ＩＴＳ−６００３を用いて、直流電流で昇圧速度１６０Ｖ／ｓによって絶縁破壊電圧を測定した。
(5) Dielectric breakdown voltage Using the sheet sample of (4) above, in accordance with the plate electrode method described in JIS C2151, using an ITS-6003 made by Tokyo Seiden Co., Ltd., with a boosting speed of 160 V / s at a direct current. The breakdown voltage was measured.
（６）湿度膨張係数（αｈ）
上記（４）で作成したシートサンプルを幅方向が測定方向となるように長さ１５ｍｍ、幅５ｍｍに切り出し、真空理工製ＴＭＡ３０００にセットし、３０℃の雰囲気下で、窒素雰囲気下から、湿度３０％ＲＨ、および湿度７０％ＲＨの一定に保ち、その時のサンプルの長さを測定し、次式にて湿度膨張係数を算出する。なお、測定方向が試料の長手方向であり、１０個の試料について行い、その平均値をαｈとした。
αＨ（ｐｐｍ／ＲＨ％）＝｛（Ｌ７０−Ｌ３０）／（Ｌ３０×△Ｈ）｝×１０６
ここで、Ｌ３０：３０％ＲＨのときのサンプル長（ｍｍ）
Ｌ７０：７０％ＲＨのときのサンプル長（ｍｍ）
△Ｈ：４０（＝７０−３０）％ＲＨである。
(6) Humidity expansion coefficient (αh)
The sheet sample prepared in the above (4) is cut into a length of 15 mm and a width of 5 mm so that the width direction becomes the measurement direction, and is set in TMA3000 manufactured by Vacuum Riko Co., Ltd. % RH and humidity 70% RH are kept constant, the length of the sample at that time is measured, and the humidity expansion coefficient is calculated by the following equation. Note that the measurement direction was the longitudinal direction of the sample, 10 samples were measured, and the average value was αh.
αH (ppm / RH%) = {(L70−L30) / (L30 × ΔH)} × 10 6
Here, sample length (mm) when L30: 30% RH
L70: Sample length at 70% RH (mm)
ΔH: 40 (= 70-30)% RH.
（７）開環率
サーモニコレー製フーリエ変換型赤外分光光度計ＦＴ−ＩＲ６７００を用いて、オキサゾリン基に由来する吸収（１６６０ｃｍ−１）、および開環構造より得られるアミドエステル基（１６８０ｃｍ−１）のピーク高の和を１００％とし、アミドエステル基の割合を開環率とした。
(7) Ring-opening rate Absorption derived from an oxazoline group (1660 cm-1) and an amide ester group (1680 cm-1) obtained from a ring-opening structure using a Fourier transform infrared spectrophotometer FT-IR6700 manufactured by Thermo Nicolet ) Was 100%, and the ratio of amide ester groups was the ring opening rate.
（８）末端カルボキシル基量
試料０．１ｇを試験管に精秤し、ベンジルアルコールを１０ｍｌ添加し、２００℃で４分間拡販溶解したのち、０．１ｍｏｌ／ｌのＮａＯＨベンジルアルコールにより、フェノールレッドを指示薬として滴定して定量した。
(8) Amount of terminal carboxyl group 0.1 g of a sample is precisely weighed in a test tube, 10 ml of benzyl alcohol is added, and after sales expansion at 200 ° C. for 4 minutes, phenol red is dissolved with 0.1 mol / l NaOH benzyl alcohol. Titration as indicator and quantification.
［実施例１］
２台の定量供給フィーダーを備えた東芝機械製二軸押出機ＳＳ−６０に、表１に示すようにポリエチレンナフタレート樹脂（Ａ）として、ホモポリエチレンナフタレートペレット（固有粘度０．６２、カルボシキル末端基３５ｅｑ／トン、オリゴマー量１．１ｗｔ％）、および熱可塑性非晶樹脂（Ｃ）としてポリスチレン／アクリル酸／エポキシ共重合体（東亞合成製アルフォンＵＧ−４０７０、溶解性パラメーター２１．５（ＭＪ／ｍ３）０．５）をそれぞれ、２２５ｋｇ／ｈ、５ｋｇ／ｈで供給し、樹脂（ＡＣ）を得た。得られた樹脂（ＡＣ）のオキサゾリンの開環率およびカルボシキル末端基数は、表１に示すようにそれぞれ５％、と３３ｅｑ／ｔｏｎであった。
[Example 1]
As shown in Table 1, homopolyethylene naphthalate pellets (intrinsic viscosity 0.62, carboxyl end) were used as a polyethylene naphthalate resin (A) as shown in Table 1 in a Toshiba Machine twin screw extruder SS-60 equipped with two quantitative supply feeders. 35 eq / ton, oligomer amount 1.1 wt%), and polystyrene / acrylic acid / epoxy copolymer (Alfon UG-4070 manufactured by Toagosei Co., Ltd., solubility parameter 21.5 (MJ / M) m 3 ) 0.5 ) was supplied at 225 kg / h and 5 kg / h, respectively, to obtain a resin (AC). As shown in Table 1, the oxazoline ring-opening rate and the number of carboxyl end groups of the obtained resin (AC) were 5% and 33 eq / ton, respectively.
ついで樹脂（ＡＣ）を、表２に示すようにベントを２箇所配した神戸製鋼製二軸押出機ＫＴＸ−４６にポリエチレンナフタレート樹脂（Ａ）としてポリエチレンナフタレートを３５ｋｇ／ｈ、ビニル系熱可塑性樹脂（Ｂ）として、シンジオタクティックポリスチレン（重量平均分子量３０万）を７．５ｋｇ／ｈ、樹脂（ＡＣ）を７．５ｋｇ／ｈを同一の供給機より供給し、これらのポリマー溶融混練して、ポリエチレンナフタレート樹脂組成物を製造した。なお、二軸押出機の条件は、２６０℃、２５０ｒｐｍで、モーター動力は１６ｋＷであった。このようにして混練されたポリマーを、直径６ｍｍの孔を２つ備えたダイプレートを通して水冷バスに吐出し、小型ペレタイザー（いすず化工機製、ＨＳＣＦ２００）にてペレット化した。得られた樹脂組成物およびシートの特性を表３に示す。 Next, as shown in Table 2, Kobe Steel twin-screw extruder KTX-46 with two vents as shown in Table 2, polyethylene naphthalate resin (A) as polyethylene naphthalate 35 kg / h, vinyl thermoplastic As resin (B), syndiotactic polystyrene (weight average molecular weight 300,000) 7.5 kg / h and resin (AC) 7.5 kg / h are supplied from the same feeder, and these polymers are melt-kneaded. A polyethylene naphthalate resin composition was produced. The conditions of the twin screw extruder were 260 ° C., 250 rpm, and the motor power was 16 kW. The polymer kneaded in this manner was discharged to a water-cooled bath through a die plate having two holes with a diameter of 6 mm, and pelletized with a small pelletizer (manufactured by Isuzu Chemical Industries, Ltd., HSCF200). The properties of the obtained resin composition and sheet are shown in Table 3.
［実施例２〜７および比較例１〜５］
表１〜３に示すとおり、樹脂の種類、比率および比エネルギーなどの条件を変更した以外は、実施例１と同様な操作を繰り返した。得られた樹脂組成物およびシートの特性を表３に示す。なお、比較例１は第１工程を省略し、第２工程で実施例１と同じ非晶樹脂（Ｃ）を混練した。
[Examples 2-7 and Comparative Examples 1-5]
As shown in Tables 1 to 3, the same operation as in Example 1 was repeated except that conditions such as the type, ratio, and specific energy of the resin were changed. The properties of the obtained resin composition and sheet are shown in Table 3. In Comparative Example 1, the first step was omitted, and the same amorphous resin (C) as in Example 1 was kneaded in the second step.
表１〜３中の、Ａ−１はホモポリエチレン−２，６−ナフタレート、Ａ−２はテレフタル酸を全酸成分に対して１０モル％共重合したポリエチレン−２，６−ナフタレート、Ａ−３はイソフタル酸を全酸成分に対して３０モル％共重合したポリエチレンテレフタレート、Ｃ−１はポリスチレン／アクリル酸／エポキシ共重合体（東亞合成製アルフォンＵＧ−４０７０）、Ｃ−２は日本触媒製エポクロスＲＰＳ−１００５、Ｂ−１はシンジオタクチックポリスチレン、Ｃ−３はポリアクリル酸（分子量：５万）、Ｃ−４はポリスチレン／α−メチルスチレン（９０／１０（ｍｏｌ／ｍｏｌ））共重合体（分子量：１万）、および比較例２のオリゴマーはエチレンテレフタレートの１〜５量体を意味する。 In Tables 1 to 3, A-1 is homopolyethylene-2,6-naphthalate, A-2 is polyethylene-2,6-naphthalate copolymerized with 10 mol% of terephthalic acid based on the total acid component, and A-3. Is a polyethylene terephthalate copolymerized with 30 mol% of isophthalic acid based on the total acid component, C-1 is a polystyrene / acrylic acid / epoxy copolymer (Alfon UG-4070 manufactured by Toagosei Co., Ltd.), and C-2 is Epochros manufactured by Nippon Shokubai Co., Ltd. RPS-1005, B-1 is syndiotactic polystyrene, C-3 is polyacrylic acid (molecular weight: 50,000), C-4 is polystyrene / α-methylstyrene (90/10 (mol / mol)) copolymer (Molecular weight: 10,000) and the oligomer of Comparative Example 2 mean 1- to 5-mer of ethylene terephthalate.
本発明の改質ポリエチレンナフタレート樹脂組成物の製造方法によって得られた改質ポリエチレンナフタレート樹脂組成物は、フィルムやボトルなどの原料として好適に用いることができる。特に湿度に対する寸法安定性や耐電圧を高度にかつ効率的に得られる成形品に具備させることができることから、自動車用部品、電子部品、磁気記録媒体、コンデンサー、電気絶縁シートなどに供するフィルムに好適に用いることができ、その工業的意義は大きい。 The modified polyethylene naphthalate resin composition obtained by the method for producing a modified polyethylene naphthalate resin composition of the present invention can be suitably used as a raw material for films, bottles and the like. Particularly suitable for films used for automotive parts, electronic parts, magnetic recording media, capacitors, electrical insulation sheets, etc., because it can be provided in molded products that are highly and efficiently obtained with dimensional stability and withstand voltage against humidity. The industrial significance is great.
Claims (8)
該熱可塑性樹脂組成物（ＡＣ）とポリエチレンナフタレート樹脂（Ａ）に対して非相溶なビニル系熱可塑性樹脂（Ｂ）とを、得られる改質ポリエチレンナフタレート樹脂組成物の重量を基準としたときの、熱可塑性ビニル系熱可塑性樹脂（Ｂ）の割合が１〜３０重量％および熱可塑性非晶樹脂（Ｃ）の割合が０．１〜５重量％となるように溶融混錬する第２工程とからなることを特徴とする改質ポリエチレンナフタレート樹脂組成物の製造方法。 Thermoplastic amorphous resin (C) having a solubility parameter in the range of 21.0 to 26.0 (MJ / m 3 ) 0.5 in polyethylene naphthalate resin (A) having ethylene naphthalate as the main repeating unit 1 to 10% by weight based on the total weight of the polyethylene naphthalate resin (A) and the thermoplastic amorphous resin (C) to produce a thermoplastic resin composition (AC),
Based on the weight of the resulting modified polyethylene naphthalate resin composition, the thermoplastic resin composition (AC) and the vinyl thermoplastic resin (B) incompatible with the polyethylene naphthalate resin (A). The melt-kneading is performed so that the ratio of the thermoplastic vinyl-based thermoplastic resin (B) is 1 to 30% by weight and the ratio of the thermoplastic amorphous resin (C) is 0.1 to 5% by weight. A method for producing a modified polyethylene naphthalate resin composition, comprising two steps.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2005347789A JP5027406B2 (en) | 2005-12-01 | 2005-12-01 | Method for producing modified polyethylene naphthalate resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2005347789A JP5027406B2 (en) | 2005-12-01 | 2005-12-01 | Method for producing modified polyethylene naphthalate resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2007153952A true JP2007153952A (en) | 2007-06-21 |
| JP5027406B2 JP5027406B2 (en) | 2012-09-19 |
Family
ID=38238728
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2005347789A Expired - Fee Related JP5027406B2 (en) | 2005-12-01 | 2005-12-01 | Method for producing modified polyethylene naphthalate resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP5027406B2 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009263566A (en) * | 2008-04-28 | 2009-11-12 | Sumitomo Chemical Co Ltd | Method for producing methacrylic resin composition |
| US8338887B2 (en) | 2005-07-06 | 2012-12-25 | Infineon Technologies Ag | Buried gate transistor |
| WO2013001847A1 (en) * | 2011-06-27 | 2013-01-03 | 帝人化成株式会社 | Resin for scintillator |
| JP2014106149A (en) * | 2012-11-28 | 2014-06-09 | Teijin Ltd | Scintillator for radiation detector |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01297466A (en) * | 1988-05-24 | 1989-11-30 | Toyobo Co Ltd | Thermoplastic resin composition |
| JPH08259772A (en) * | 1995-03-28 | 1996-10-08 | Kanegafuchi Chem Ind Co Ltd | Resin composition for molding |
| JP2000506994A (en) * | 1996-02-29 | 2000-06-06 | ミネソタ マイニング アンド マニュファクチャリング カンパニー | Optical film with increased gain at non-normal incidence angles |
| JP2003206396A (en) * | 2002-01-16 | 2003-07-22 | Idemitsu Petrochem Co Ltd | Resin composition and molding |
| WO2005073318A1 (en) * | 2004-01-29 | 2005-08-11 | Teijin Dupont Films Japan Limited | Biaxially oriented film |
-
2005
- 2005-12-01 JP JP2005347789A patent/JP5027406B2/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01297466A (en) * | 1988-05-24 | 1989-11-30 | Toyobo Co Ltd | Thermoplastic resin composition |
| JPH08259772A (en) * | 1995-03-28 | 1996-10-08 | Kanegafuchi Chem Ind Co Ltd | Resin composition for molding |
| JP2000506994A (en) * | 1996-02-29 | 2000-06-06 | ミネソタ マイニング アンド マニュファクチャリング カンパニー | Optical film with increased gain at non-normal incidence angles |
| JP2003206396A (en) * | 2002-01-16 | 2003-07-22 | Idemitsu Petrochem Co Ltd | Resin composition and molding |
| WO2005073318A1 (en) * | 2004-01-29 | 2005-08-11 | Teijin Dupont Films Japan Limited | Biaxially oriented film |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8338887B2 (en) | 2005-07-06 | 2012-12-25 | Infineon Technologies Ag | Buried gate transistor |
| JP2009263566A (en) * | 2008-04-28 | 2009-11-12 | Sumitomo Chemical Co Ltd | Method for producing methacrylic resin composition |
| WO2013001847A1 (en) * | 2011-06-27 | 2013-01-03 | 帝人化成株式会社 | Resin for scintillator |
| JP2013032479A (en) * | 2011-06-27 | 2013-02-14 | Teijin Chem Ltd | Scintillator |
| CN103228760A (en) * | 2011-06-27 | 2013-07-31 | 帝人化成株式会社 | Resin for scintillator |
| JP2014106149A (en) * | 2012-11-28 | 2014-06-09 | Teijin Ltd | Scintillator for radiation detector |
Also Published As
| Publication number | Publication date |
|---|---|
| JP5027406B2 (en) | 2012-09-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP2000302952A (en) | Polyester resin composition | |
| CN102459461A (en) | High Melt Strength Polyesters for Foaming Applications | |
| KR101386672B1 (en) | White film and A method of manufacturing Opaque White film | |
| JP5396692B2 (en) | Method for producing polyester resin composition | |
| JP5594005B2 (en) | Biaxially oriented polyarylene sulfide film | |
| JP5027406B2 (en) | Method for producing modified polyethylene naphthalate resin composition | |
| JP6263428B2 (en) | Thermoplastic polyester resin pellet blend, method for producing pellet blend and molded product | |
| JP5423464B2 (en) | Biaxially oriented laminated film | |
| JP4552633B2 (en) | Low dielectric resin film | |
| TWI383020B (en) | A thermoplastic resin composition and a molded article | |
| JP6712040B1 (en) | Polyester resin composition | |
| JP2005169971A (en) | Biaxially oriented laminated film | |
| JP5098373B2 (en) | Method for producing polyester resin composition | |
| JP2021031671A (en) | Polyester resin composition | |
| JP2006335930A (en) | Modified polyethylene naphthalate resin composition and method for producing the same | |
| JP5533170B2 (en) | Method for producing polyester molded body | |
| JP4787547B2 (en) | Polyester composition and biaxially oriented film comprising the same | |
| JP2005169972A (en) | Biaxially oriented laminated film and its manufacturing method | |
| JP2016145267A (en) | Biaxially oriented polyester film | |
| EP4491654A1 (en) | Modified polyester-based elastomer and method for producing same | |
| CN118749005A (en) | Modified polyester elastomer and method for producing the same | |
| JP2005342978A (en) | Biaxially oriented laminated film | |
| TW201627347A (en) | Biaxially oriented polyester film | |
| JP5098374B2 (en) | Polyester resin composition | |
| JP2007002115A (en) | Polymer composition and biaxially oriented film |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20080813 |
|
| A711 | Notification of change in applicant |
Free format text: JAPANESE INTERMEDIATE CODE: A711 Effective date: 20091030 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A821 Effective date: 20091030 |
|
| RD02 | Notification of acceptance of power of attorney |
Free format text: JAPANESE INTERMEDIATE CODE: A7422 Effective date: 20110711 |
|
| RD04 | Notification of resignation of power of attorney |
Free format text: JAPANESE INTERMEDIATE CODE: A7424 Effective date: 20110711 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20111020 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20111025 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20120529 |
|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20120622 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20150629 Year of fee payment: 3 |
|
| R150 | Certificate of patent or registration of utility model |
Free format text: JAPANESE INTERMEDIATE CODE: R150 Ref document number: 5027406 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| LAPS | Cancellation because of no payment of annual fees |