JP2014012796A - Polyester and producing method thereof - Google Patents
Polyester and producing method thereof Download PDFInfo
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- JP2014012796A JP2014012796A JP2012151466A JP2012151466A JP2014012796A JP 2014012796 A JP2014012796 A JP 2014012796A JP 2012151466 A JP2012151466 A JP 2012151466A JP 2012151466 A JP2012151466 A JP 2012151466A JP 2014012796 A JP2014012796 A JP 2014012796A
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- oxalic acid
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- 229920000728 polyester Polymers 0.000 title claims abstract description 111
- 238000000034 method Methods 0.000 title description 17
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 77
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Natural products OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 72
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 67
- -1 oxalic acid glycol ester Chemical class 0.000 claims abstract description 43
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims abstract description 36
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 31
- 235000006408 oxalic acid Nutrition 0.000 claims abstract description 29
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 24
- 239000002253 acid Substances 0.000 claims abstract description 23
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 19
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims abstract description 11
- 125000003118 aryl group Chemical group 0.000 claims abstract description 11
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 8
- 238000005809 transesterification reaction Methods 0.000 claims description 28
- 238000004519 manufacturing process Methods 0.000 claims description 21
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 6
- 239000000155 melt Substances 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 230000007062 hydrolysis Effects 0.000 abstract description 13
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 13
- 125000004429 atom Chemical group 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 26
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 238000001308 synthesis method Methods 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 238000011156 evaluation Methods 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000002844 melting Methods 0.000 description 6
- 230000008018 melting Effects 0.000 description 6
- 229910052698 phosphorus Inorganic materials 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 230000007547 defect Effects 0.000 description 5
- 238000004821 distillation Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000005886 esterification reaction Methods 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 229940082328 manganese acetate tetrahydrate Drugs 0.000 description 5
- CESXSDZNZGSWSP-UHFFFAOYSA-L manganese(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Mn+2].CC([O-])=O.CC([O-])=O CESXSDZNZGSWSP-UHFFFAOYSA-L 0.000 description 5
- 239000012299 nitrogen atmosphere Substances 0.000 description 5
- 239000011574 phosphorus Substances 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 229920000139 polyethylene terephthalate Polymers 0.000 description 4
- 239000005020 polyethylene terephthalate Substances 0.000 description 4
- 239000007790 solid phase Substances 0.000 description 4
- 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 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- QLZHNIAADXEJJP-UHFFFAOYSA-N Phenylphosphonic acid Chemical compound OP(O)(=O)C1=CC=CC=C1 QLZHNIAADXEJJP-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000006837 decompression Effects 0.000 description 3
- WYACBZDAHNBPPB-UHFFFAOYSA-N diethyl oxalate Chemical compound CCOC(=O)C(=O)OCC WYACBZDAHNBPPB-UHFFFAOYSA-N 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000006068 polycondensation reaction Methods 0.000 description 3
- 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 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 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
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000005187 foaming Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000001771 impaired effect Effects 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
- 150000002681 magnesium compounds Chemical class 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical class O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 2
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 1
- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-N 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- LOMVENUNSWAXEN-UHFFFAOYSA-N Methyl oxalate Chemical compound COC(=O)C(=O)OC LOMVENUNSWAXEN-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001339 alkali metal compounds Chemical class 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- FNGGVJIEWDRLFV-UHFFFAOYSA-N anthracene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=CC3=C(C(O)=O)C(C(=O)O)=CC=C3C=C21 FNGGVJIEWDRLFV-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229940043430 calcium compound Drugs 0.000 description 1
- 150000001674 calcium compounds Chemical class 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical group 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000003925 fat Substances 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 238000004895 liquid chromatography mass spectrometry Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 description 1
- 239000011654 magnesium acetate Substances 0.000 description 1
- 229940069446 magnesium acetate Drugs 0.000 description 1
- 235000011285 magnesium acetate Nutrition 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 150000002697 manganese compounds Chemical class 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 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 1
- WPUMVKJOWWJPRK-UHFFFAOYSA-N naphthalene-2,7-dicarboxylic acid Chemical compound C1=CC(C(O)=O)=CC2=CC(C(=O)O)=CC=C21 WPUMVKJOWWJPRK-UHFFFAOYSA-N 0.000 description 1
- 238000002663 nebulization Methods 0.000 description 1
- MPQXHAGKBWFSNV-UHFFFAOYSA-N oxidophosphanium Chemical class [PH3]=O MPQXHAGKBWFSNV-UHFFFAOYSA-N 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- 150000003009 phosphonic acids Chemical class 0.000 description 1
- XRBCRPZXSCBRTK-UHFFFAOYSA-N phosphonous acid Chemical class OPO XRBCRPZXSCBRTK-UHFFFAOYSA-N 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 230000036314 physical performance Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Landscapes
- Polyesters Or Polycarbonates (AREA)
Abstract
Description
本発明は、耐加水分解性に優れたポリエステルおよびその製造方法に関するものである。さらに詳しくは、耐湿熱特性に優れたフィルム等の成形品を得るに適したポリエステルおよびその製造方法に関するものである。 The present invention relates to a polyester excellent in hydrolysis resistance and a method for producing the same. More specifically, the present invention relates to a polyester suitable for obtaining a molded article such as a film excellent in moisture and heat resistance and a method for producing the same.
ポリエステル、特にポリエチレンテレフタレートは優れた生産性、機械的性質、熱的性質、電気的性質、化学特性および寸法安定性を有するため広く使用されてきた。しかし、大部分のポリエステルは、高温・多湿の環境で使用すると、加水分解して物理的性能が低下しやすく、使用期間や使用条件が制限される問題があった。 Polyesters, especially polyethylene terephthalate, have been widely used because of their excellent productivity, mechanical properties, thermal properties, electrical properties, chemical properties and dimensional stability. However, when most polyesters are used in a high-temperature and high-humidity environment, there is a problem that the physical performance tends to deteriorate due to hydrolysis and the use period and use conditions are limited.
近年、過酷な自然環境下で使用される太陽電池用途において、その長期信頼性を向上することが要望されており、太陽電池保護膜としてポリエステルフィルムを用いる場合には、優れた耐加水分解性を付与することが必要である。 In recent years, in solar cell applications used in harsh natural environments, it has been demanded to improve long-term reliability. When a polyester film is used as a solar cell protective film, it has excellent hydrolysis resistance. It is necessary to grant.
ポリエステルの耐加水分解性の向上には、従来から種々の提案がなされている。そのような中で、特許文献１〜３では、シュウ酸成分を共重合することで、耐加水分解性に大きく影響するポリエステルの末端カルボキシル基量を低減できることが開示されている。具体的には、特許文献１ではシュウ酸のグリコールエステルおよび／またはその低重合度オリゴマーを添加する方法が提案されている。また特許文献２ではポリブチレンナフタレートに、シュウ酸のグリコールエステルおよび／またはその低重合度オリゴマーを添加する方法が提案されている。さらにまた、特許文献３では、シュウ酸をそのまま重縮合工程で添加することが提案されている。 Various proposals have conventionally been made to improve the hydrolysis resistance of polyester. Under such circumstances, Patent Documents 1 to 3 disclose that by copolymerizing an oxalic acid component, it is possible to reduce the amount of terminal carboxyl groups of a polyester that greatly affects hydrolysis resistance. Specifically, Patent Document 1 proposes a method of adding an oxalic acid glycol ester and / or an oligomer having a low polymerization degree thereof. Patent Document 2 proposes a method of adding oxalic acid glycol ester and / or its low polymerization degree oligomer to polybutylene naphthalate. Furthermore, Patent Document 3 proposes adding oxalic acid as it is in the polycondensation step.
しかしながら、これらの方法で製造されたポリエステルは末端カルボキシル基量が低減されて耐加水分解性は向上するものの、例えばフィルム製膜工程等の熱履歴を受けた場合の末端カルボキシル基量の増加が大きくなるという新たな問題が潜在していることを本発明者らは見出した。 However, although the polyester produced by these methods has a reduced amount of terminal carboxyl groups and improved hydrolysis resistance, for example, the increase in the amount of terminal carboxyl groups when subjected to a thermal history such as a film-forming process is large. The inventors have found that there is a new problem of becoming.
本発明は、上記の背景技術に鑑みなされたもので、その目的は、耐加水分解性に優れ、しかもフィルム等に溶融成形した際の末端カルボキシ基量の増加も抑制されたポリエステルおよびその製造方法を提供することにある。 The present invention has been made in view of the above-mentioned background art, and its object is to provide a polyester excellent in hydrolysis resistance and also suppressed in the increase in the amount of terminal carboxy groups when melt-molded into a film or the like, and a method for producing the same Is to provide.
本発明者らは、上記目的を達成するために鋭意検討した結果、アルキルエステル末端基を特定割合で含有するシュウ酸のグリコールエステルおよび／またはその低重合度オリゴマーを添加すれば、末端カルボキシル基量が低減されると同時に、得られたポリエステルのフィルム製膜工程等の溶融成形工程での末端カルボキシル基量の増加も低減できることを見出し、本発明に到達した。 As a result of intensive studies to achieve the above object, the present inventors have found that the amount of terminal carboxyl group can be increased by adding a glycol ester of oxalic acid and / or a low-polymerization degree oligomer thereof containing an alkyl ester end group in a specific ratio. At the same time, the inventors have found that the increase in the amount of terminal carboxyl groups in the melt-molding process such as a film forming process of the obtained polyester can be reduced, and the present invention has been achieved.
かくして本発明によれば、芳香族ジカルボン酸を主たる酸成分とし、炭素数２〜４のアルキレングリコールをグリコール成分とするポリエステルを溶融重合するに際し、該ポリエステルの固有粘度が０．２ｄｌ／ｇ以上になった段階で、下記式（１）で示され、平均重合度が１〜８で、かつアルキル基を少なくとも一方の末端に有するものの割合が２％以上であるシュウ酸グリコールエステルおよび／またはその低重合度オリゴマー（以下、総称してＰＡＯと略記することがある）を、ポリエステルの全酸成分に対してシュウ酸成分が０．１〜５．０ｍｏｌ％となる割合で添加し、さらに重合反応を行うことを特徴とするポリエステルの製造方法が提供される。
Ｘ１Ｏ−［Ｃ（Ｏ）Ｃ（Ｏ）ＯＲＯ］ｎ−Ｃ（Ｏ）Ｃ（Ｏ）ＯＸ２ （１）
（式中、Ｒは炭素数２〜４のアルキレン基、Ｘ１，Ｘ２は夫々炭素数４以下のアルキル基または−ＲＯＨ基、ｎは０以上の整数（但し、Ｘ１，Ｘ２が共にアルキル基の場合にはｎは１以上）を表わす。）
Thus, according to the present invention, when a polyester having an aromatic dicarboxylic acid as a main acid component and an alkylene glycol having 2 to 4 carbon atoms as a glycol component is melt-polymerized, the intrinsic viscosity of the polyester becomes 0.2 dl / g or more. At this stage, the oxalic acid glycol ester represented by the following formula (1) and having an average degree of polymerization of 1 to 8 and having an alkyl group at least at one terminal is 2% or more and / or its low A polymerization degree oligomer (hereinafter sometimes abbreviated as PAO) is added at a ratio of 0.1 to 5.0 mol% of the oxalic acid component to the total acid component of the polyester, and the polymerization reaction is further performed. A method for producing a polyester is provided.
X 1 O- [C (O) C (O) ORO] n -C (O) C (O) OX 2 (1)
(Wherein R is an alkylene group having 2 to 4 carbon atoms, X 1 and X 2 are each an alkyl group or —ROH group having 4 or less carbon atoms, and n is an integer of 0 or more (provided that both X 1 and X 2 are In the case of an alkyl group, n represents 1 or more).
さらに好ましい態様として、ＰＡＯのアルキル基がメチル基またはエチル基であること、ＰＡＯがシュウ酸アルキルエステルとアルキレングリコールとをエステル交換反応率７０〜９２％の範囲でエステル交換反応させ、さらに重合反応させて得られるものであること、ＰＡＯを複数回に分けて添加することの少なくともいずれかを具備するポリエステルの製造方法も提供される。 In a more preferred embodiment, the alkyl group of PAO is a methyl group or an ethyl group, and PAO undergoes a transesterification reaction within a range of 70 to 92% transesterification rate of an oxalic acid alkyl ester and an alkylene glycol, and further causes a polymerization reaction. There is also provided a method for producing a polyester comprising at least one of being obtained by adding PAO in a plurality of times.
また、本発明によれば、芳香族ジカルボン酸を主たる酸成分とし炭素数２〜４のアルキレングリコールをグリコール成分とする溶融重合によって製造されたポリエステルであって、下記式（１）で示され、平均重合度が１〜８で、かつアルキル基を少なくとも一方の末端に有するものの割合が２％以上であるシュウ酸グリコールエステルおよび／またはその低重合度オリゴマーが、ポリエステルの全酸成分に対してシュウ酸成分が０．１〜５．０ｍｏｌ％となる割合で添加・溶融重合されたもので、末端カルボキシル基量が１０ｅｑ／ｔｏｎ以下、固有粘度が０．６０〜０．８５ｄｌ／ｇであるポリエステルも提供される。
Ｘ１Ｏ−［Ｃ（Ｏ）Ｃ（Ｏ）ＯＲＯ］ｎ−Ｃ（Ｏ）Ｃ（Ｏ）ＯＸ２ （１）
（式中、Ｒは炭素数２〜４のアルキレン基、Ｘ１，Ｘ２は夫々炭素数４以下のアルキル基または−ＲＯＨ基、ｎは０以上の整数（但し、Ｘ１，Ｘ２が共にアルキル基の場合にはｎは１以上）を表わす。）
さらに好ましい態様として、フィルムに用いられること、特に太陽電池バックシート用フィルムに用いられることを具備するポリエステルも提供される。
Moreover, according to the present invention, a polyester produced by melt polymerization using an aromatic dicarboxylic acid as a main acid component and an alkylene glycol having 2 to 4 carbon atoms as a glycol component, represented by the following formula (1), An oxalic acid glycol ester having an average degree of polymerization of 1 to 8 and an alkyl group having at least one terminal is 2% or more and / or an oligomer having a low degree of polymerization of A polyester having an acid component added and melt-polymerized at a ratio of 0.1 to 5.0 mol%, having a terminal carboxyl group amount of 10 eq / ton or less and an intrinsic viscosity of 0.60 to 0.85 dl / g Provided.
X 1 O- [C (O) C (O) ORO] n -C (O) C (O) OX 2 (1)
(Wherein R is an alkylene group having 2 to 4 carbon atoms, X 1 and X 2 are each an alkyl group or —ROH group having 4 or less carbon atoms, and n is an integer of 0 or more (provided that both X 1 and X 2 are In the case of an alkyl group, n represents 1 or more).
As a more preferred embodiment, a polyester that is used in a film, particularly used in a film for a solar battery back sheet, is also provided.
本発明によれば、シュウ酸グリコールエステルおよび／またはその低重合度オリゴマーとして、平均重合度が１〜８で、かつ末端にアルキル基を有するもの割合が２％以上であるものを用いているので、末端カルボキシ基量が少なく、しかもフィルム等に溶融成形する際の末端カルボキシ基量の増加も小さく、耐加水分解性に優れた太陽電池バックシートなどのフィルム用原料として好適なポリエステルを容易に製造することができる。 According to the present invention, as the oxalic acid glycol ester and / or its low polymerization degree oligomer, those having an average polymerization degree of 1 to 8 and having an alkyl group at the terminal of 2% or more are used. Easily produce polyester suitable as a raw material for films such as solar cell backsheets with low terminal carboxy group content and small increase in terminal carboxy group content when melt-molded into films, etc. can do.
＜ポリエステル＞
本発明におけるポリエステルとは、芳香族ジカルボン酸を主たる酸成分とし、炭素数２〜４のアルキレングリコールを主たるグリコール成分とするポリエステルである。かかるポリエステルは実質的に線状であり、そしてフィルム形成性、特に溶融成形によるフィルム形成性を有することが好ましい。具体的な芳香族ジカルボン酸としては、例えばテレフタル酸、２，６−ナフタレンジカルボン酸、２，７−ナフタレンジカルボン酸、イソフタル酸，ジフェニルケトンジカルボン酸，アンスラセンジカルボン酸などを挙げることができる。また、具体的なアルキレングリコールとしては、エチレングリコール、トリメチレングリコール、テトラメチレングリコールを挙げることができる。これらの中でも、アルキレンテレフタレートやアルキレン−２，６−ナフタレンジカルボキシレートを主たる繰り返し単位とするものが好ましく、特にエチレンテレフタレート，エチレン−２，６−ナフタレンジカルボキシレートを主たる繰り返し単位とするポリエステルが好ましい。なお、本発明におけるポリエステルが、エチレンテレフタレートやエチレン−２，６−ナフタレンジカルボキシレートを主たる繰り返し単位とするポリエステルである場合、本発明の効果を損なわない範囲で、例えば全酸成分のモル数を基準として、２０モル％以下、さらに１０モル％以下の範囲で、共重合したものであってもよい。具体的な共重合成分としては、先に例示した他の芳香族ジカルボン酸成分やアルキレングリコール成分、またアジピン酸，セバチン酸等の如き脂肪族ジカルボン酸，シクロヘキサン−１，４−ジカルボン酸の如き脂環族ジカルボン酸などを挙げることができる。また、例えばヒドロキシ安息香酸の如き芳香族オキシ酸，ω−ヒドロキシカプロン酸の如き脂肪族オキシ酸等のオキシカルボン酸成分も挙げることができる。さらに本発明におけるポリエステルは、実質的に線状である範囲の量であり、かつ、本発明の効果を損なわないかぎり、例えば全酸成分に対し２ｍｏｌ％以下の量で、３官能以上のポリカルボン酸またはポリヒドロキシ化合物、例えばトリメリット酸，ペンタエルスリトール等を共重合してもよい。
<Polyester>
The polyester in the present invention is a polyester having an aromatic dicarboxylic acid as a main acid component and an alkylene glycol having 2 to 4 carbon atoms as a main glycol component. Such polyesters are substantially linear and preferably have film-forming properties, particularly film-forming properties by melt molding. Specific examples of the aromatic dicarboxylic acid include terephthalic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, isophthalic acid, diphenyl ketone dicarboxylic acid, and anthracene dicarboxylic acid. Specific examples of the alkylene glycol include ethylene glycol, trimethylene glycol, and tetramethylene glycol. Among these, those having alkylene terephthalate or alkylene-2,6-naphthalenedicarboxylate as the main repeating unit are preferable, and polyesters having ethylene terephthalate or ethylene-2,6-naphthalenedicarboxylate as the main repeating unit are particularly preferable. . In addition, when the polyester in the present invention is a polyester having ethylene terephthalate or ethylene-2,6-naphthalenedicarboxylate as a main repeating unit, the number of moles of all acid components is within a range that does not impair the effects of the present invention. As a reference, it may be copolymerized within a range of 20 mol% or less, and further 10 mol% or less. Specific examples of the copolymer component include other aromatic dicarboxylic acid components and alkylene glycol components exemplified above, aliphatic dicarboxylic acids such as adipic acid and sebacic acid, and fats such as cyclohexane-1,4-dicarboxylic acid. Examples thereof include cyclic dicarboxylic acids. Moreover, for example, oxycarboxylic acid components such as aromatic oxyacids such as hydroxybenzoic acid and aliphatic oxyacids such as ω-hydroxycaproic acid can also be mentioned. Furthermore, the polyester in the present invention is in an amount in a substantially linear range, and unless the effects of the present invention are impaired, for example, an amount of 2 mol% or less relative to the total acid component is a trifunctional or higher polycarboxylic acid. An acid or a polyhydroxy compound such as trimellitic acid or pentaerythritol may be copolymerized.
＜シュウ酸グリコールエステルおよび／またはその低重合度オリゴマー（ＰＡＯ）＞
本発明におけるシュウ酸グリコールエステルおよび／またはその低重合度オリゴマー（ＰＡＯ）は、下記式（１）で表わされ、平均重合度が１〜８、好ましくは１．１〜３．６、さらに好ましくは１．２〜２．０で、かつアルキル基、好ましくはメチル基またはエチル基を少なくとも一方の末端に有するものの割合が２％以上、好ましくは２〜５０％の範囲である必要がある。
Ｘ１Ｏ−［Ｃ（Ｏ）Ｃ（Ｏ）ＯＲＯ］ｎ−Ｃ（Ｏ）Ｃ（Ｏ）ＯＸ２ （１）
<Oxalic acid glycol ester and / or its low polymerization degree oligomer (PAO)>
The oxalic acid glycol ester and / or its low polymerization degree oligomer (PAO) in the present invention is represented by the following formula (1), and the average degree of polymerization is 1 to 8, preferably 1.1 to 3.6, more preferably. Is 1.2 to 2.0, and the ratio of those having an alkyl group, preferably a methyl group or an ethyl group at at least one end, is 2% or more, preferably 2 to 50%.
X 1 O- [C (O) C (O) ORO] n -C (O) C (O) OX 2 (1)
式中、Ｒは炭素数２〜４のアルキレン基、Ｘ１，Ｘ２は夫々炭素数４以下のアルキル基または−ＲＯＨ基、ｎは０以上の整数（但し、Ｘ１，Ｘ２が共にアルキル基の場合にはｎは１以上）を表わす。また、平均重合度は、分子中に含まれる［−Ｃ（Ｏ）Ｃ（Ｏ）ＯＲＯ−］で表される結合単位数の数平均を表わす。 In the formula, R is an alkylene group having 2 to 4 carbon atoms, X 1 and X 2 are each an alkyl group or —ROH group having 4 or less carbon atoms, and n is an integer of 0 or more (provided that both X 1 and X 2 are alkyls) In the case of a group, n represents 1 or more). The average degree of polymerization represents the number average of the number of bond units represented by [—C (O) C (O) ORO—] contained in the molecule.
かかるＰＡＯは、一般的によく知られている重合反応（好ましくは溶融重合）により、シュウ酸ジアルキルエステルとアルキレングリコールから製造される。例えば、シュウ酸ジアルキルエステルと炭素数２〜４のアルキレングリコール（モル比１：２）を触媒と共に反応器に充填してエステル交換反応および重合反応することにより製造できる。この際、エステル交換反応率は、７０〜９５％の範囲とすることが好ましく、この反応率が７０％未満では、得られるＰＡＯ中の未反応シュウ酸ジアルキルエステルの割合が多くなり、ポリエステルに添加した後の重合反応が不良となりやすく、逆に９５％超では、アルキル基を少なくとも一方の末端に有するシュウ酸グリコールエステルおよび／またはその低重合度オリゴマーの割合が２％以上のものを得ることが難しくなりやすい。触媒としては、Ｐ、Ｔｉ、Ｇｅ、Ｚｎ、Ｆｅ、Ｓｎ、Ｍｎ、Ｃｏ、Ｚｒ、Ｖ、Ｉｒ、Ｌａ、Ｃｅ、Ｌｉ、Ｃａ、Ｈｆなどの化合物が好ましい。なお、重合反応においては、熱劣化防止のため、必要であれば耐熱剤を添加しておいてもよい。また、反応終了後にリン酸エステル化合物（リン酸エステル等）のような触媒失活剤を添加することもできる。 Such PAO is produced from oxalic acid dialkyl ester and alkylene glycol by a generally well-known polymerization reaction (preferably melt polymerization). For example, it can be produced by transesterifying and polymerizing a dialkyl oxalate ester and an alkylene glycol having 2 to 4 carbon atoms (molar ratio 1: 2) together with a catalyst. At this time, the transesterification reaction rate is preferably in the range of 70 to 95%. If the reaction rate is less than 70%, the proportion of the unreacted dialkyl oxalate in the PAO is increased and added to the polyester. The polymerization reaction after the reaction tends to be poor, and conversely, if it exceeds 95%, an oxalic acid glycol ester having an alkyl group at at least one end and / or a low polymerization degree oligomer ratio thereof can be 2% or more. It tends to be difficult. As the catalyst, compounds such as P, Ti, Ge, Zn, Fe, Sn, Mn, Co, Zr, V, Ir, La, Ce, Li, Ca, and Hf are preferable. In the polymerization reaction, a heat-resistant agent may be added if necessary to prevent thermal degradation. Moreover, a catalyst deactivator such as a phosphoric acid ester compound (such as a phosphoric acid ester) can be added after completion of the reaction.
本発明のＰＡＯにおいて、少なくとも一方の末端にアルキル基を有するものの割合が２％未満の場合には、その詳細な理由は不明であるが、得られたポリエステルを溶融成形する際のカルボキシル基量の増加が大きくなるので好ましくない。なお、少なくとも一方の末端にアルキル基を有するものの割合は、シュウ酸グリコールエステルおよび／またはその低重合度オリゴマーをジメチルスルホキシドに溶解後、液体クロマトグラフィー質量分析法にてＵＶ２１０ｎｍにおけるピーク面積割合から求めた。 In the PAO of the present invention, when the proportion of those having an alkyl group at least at one end is less than 2%, the detailed reason is unknown, but the amount of carboxyl groups when the obtained polyester is melt-molded is unknown. This is not preferable because the increase is large. The ratio of those having an alkyl group at at least one terminal was determined from the peak area ratio at UV 210 nm by liquid chromatography mass spectrometry after dissolving oxalic acid glycol ester and / or its low polymerization degree oligomer in dimethyl sulfoxide. .
本発明において、ＰＡＯによる末端カルボキシル基の低濃度化の機構は、ポリエステルの末端カルボキシル基とアルキレンオクサレートとの反応によるものであり、上記式中のＲで表されるアルキレン基はポリエステル主鎖中に取り込まれる。そのため、ポリエステルを構成する主たるグリコール成分と同じアルキレン基であることが、融点の低下や結晶性の低下を抑制する上で好ましい。
また、本発明で用いるＰＡＯは、平均重合度が１〜８の単量体もしくは低重合体である必要があり。平均重合度が上限を超えると、ＰＡＯ自体の融点が高くなって取り扱いが難しくなる。
In the present invention, the mechanism for reducing the concentration of terminal carboxyl groups by PAO is due to the reaction between the terminal carboxyl group of the polyester and alkylene oxalate, and the alkylene group represented by R in the above formula is in the polyester main chain. Is taken in. For this reason, the same alkylene group as the main glycol component constituting the polyester is preferable in terms of suppressing a decrease in melting point and a decrease in crystallinity.
Further, the PAO used in the present invention needs to be a monomer or a low polymer having an average degree of polymerization of 1 to 8. When the average degree of polymerization exceeds the upper limit, the melting point of PAO itself becomes high and handling becomes difficult.
＜ポリエステルの製造方法＞
本発明のポリエステルの製造方法は、前述の芳香族ジカルボン酸を主たる酸成分とし、炭素数２〜４のアルキレングリコールを主たるグリコール成分とし、それらを反応させてポリエステル前躯体とし、さらに重合反応によって所望の固有粘度を有するポリエステルとするものである。そして、この重合反応は、以下の２工程、好ましくは後述する第２の工程が溶融重合工程と固相重合工程とを含むものである。以下、順に説明する。
<Production method of polyester>
The polyester production method of the present invention comprises the above aromatic dicarboxylic acid as a main acid component, an alkylene glycol having 2 to 4 carbon atoms as a main glycol component, these are reacted to form a polyester precursor, and further desired by a polymerization reaction. A polyester having an intrinsic viscosity of In this polymerization reaction, the following two steps, preferably the second step described later, includes a melt polymerization step and a solid phase polymerization step. Hereinafter, it demonstrates in order.
まず、本発明の重合反応における第１工程は、重合反応時に前述のＰＡＯを添加する工程である。
本発明ではＰＡＯを１００℃以上に加熱溶融し液体状態として添加することが好ましく、液体状態とすることで添加作業が容易になると共に、理由は定かでは無いがポリエステルに添加した際の拡散性がよくなるためか、得られるポリエステル中の気泡を少なくできる。なお、ＰＡＯの液体状態の粘度は０．１〜１０ポイズの範囲、さらに１〜１０ポイズの範囲が好ましい。
First, the first step in the polymerization reaction of the present invention is a step of adding the aforementioned PAO during the polymerization reaction.
In the present invention, PAO is preferably heated and melted to 100 ° C. or more and added in a liquid state. The addition operation is facilitated by making the liquid state, and the diffusibility when added to polyester is not clear, although the reason is not clear. Perhaps because it becomes better, the bubbles in the resulting polyester can be reduced. The liquid state viscosity of PAO is preferably in the range of 0.1 to 10 poise, and more preferably in the range of 1 to 10 poise.
ＰＡＯの添加に際しては添加する直前の重合反応の系内を０．１５ｋＰａ以下の減圧に保つことが好ましい。従来の手法ではＰＡＯやＰＡＯ類似物を添加する場合、一度、窒素で重縮合反応の系内を常圧に戻して添加後、再び減圧作業を実施していた。この手法では時間を要し無駄なポリエステルの分解を発生させるばかりか、系内の脱気が遅くなりポリエステル中の気泡が残りやすくなっていた。 When adding PAO, it is preferable to keep the pressure of the polymerization reaction immediately before the addition at a reduced pressure of 0.15 kPa or less. In the conventional method, when PAO or a PAO analog is added, the pressure reduction operation is once again performed after adding the system by returning the inside of the polycondensation reaction to normal pressure with nitrogen. This method not only took time and caused unnecessary polyester decomposition, but also slowed the degassing in the system and left bubbles in the polyester easily remaining.
本発明では、前述の如くＰＡＯを液体状態とすることが好ましく、それにより減圧下の状態での添加を容易にしている。例えば加熱および真空保持の可能な容器（例えば真空ホッパー）を用いて溶融保持したＰＡＯを系内に添加する。この際、ＰＡＯの添加直後より、炭酸ガス発生のため真空度は低下するが、その際の系内の真空度を８０ｋＰａ以下とすることが好ましい。さらに好ましくは５０ｋＰａ以下である。この真空度が８０ｋＰａを超えるとポリエステル中に気泡が残りやすくなる。 In the present invention, it is preferable to make PAO in a liquid state as described above, thereby facilitating addition in a state under reduced pressure. For example, PAO melted and held using a container that can be heated and held in vacuum (for example, a vacuum hopper) is added to the system. At this time, the degree of vacuum decreases due to the generation of carbon dioxide immediately after the addition of PAO, but the degree of vacuum in the system at that time is preferably 80 kPa or less. More preferably, it is 50 kPa or less. When this degree of vacuum exceeds 80 kPa, bubbles tend to remain in the polyester.
また、ＰＡＯの添加時期は、前記ポリエステルの固有粘度が０．２ｄｌ／ｇ以上に到達した以降である。固有粘度が０．２ｄｌ／ｇ未満の段階ではポリエステル中のカルボキシル基自体が少ないため、カルボキシル基を低下させる効果が少ない。さらにＰＡＯ添加は２回以上に分けて分割添加することも有効である。例えば固有粘度が０．２〜０．３ｄｌ／ｇの段階でＰＡＯ全投入量の５０〜９０質量％添加し、さらに固有粘度が０．４ｄｌ／ｇ以上の段階で残りの１０〜５０質量％添加することが好ましい。ＰＡＯ添加によりポリエステル中のカルボキシル基末端は低下するが、添加後の重合反応経時で多少なりともカルボキシル基末端はまた増加をはじめる。分割投入することで再発生するカルボキシル基末端を抑制することが可能である。 The PAO is added after the intrinsic viscosity of the polyester reaches 0.2 dl / g or more. At the stage where the intrinsic viscosity is less than 0.2 dl / g, since the carboxyl group itself in the polyester is small, the effect of reducing the carboxyl group is small. It is also effective to add PAO in two or more divided portions. For example, when the intrinsic viscosity is 0.2 to 0.3 dl / g, 50 to 90% by mass of the total amount of PAO added is added, and when the intrinsic viscosity is 0.4 dl / g or more, the remaining 10 to 50% by mass is added. It is preferable to do. The addition of PAO reduces the carboxyl group terminal in the polyester, but the carboxyl group terminal also begins to increase more or less over the course of the polymerization reaction after the addition. It is possible to suppress the carboxyl group terminal to be regenerated by dividing the charging.
ＰＡＯの添加量は、ポリエステルを形成する全酸成分に対して、シュウ酸成分が０．１〜５．０モル％となる割合、好ましくは０．５〜３．０モル％となる割合にする必要がある。添加量がこの下限より少ないと充分低い末端カルボキシル基量のポリエステルが得られず、逆に添加量が多すぎると添加後の固有粘度の低下が大きい上、著しい発泡を生じ、反応工程上のトラブルや、フィルムとした際に気泡による表面欠点が発生しやすくなる。 The amount of PAO added is such that the oxalic acid component is 0.1 to 5.0 mol%, preferably 0.5 to 3.0 mol%, based on the total acid component forming the polyester. There is a need. If the amount added is less than this lower limit, a polyester having a sufficiently low amount of terminal carboxyl groups cannot be obtained. On the other hand, if the amount added is too large, the inherent viscosity after addition is greatly reduced, and significant foaming occurs, resulting in trouble in the reaction process In addition, when the film is used, surface defects due to bubbles tend to occur.
次に、本発明の製造方法における第２の工程は、第１工程終了後、重合反応を継続して所望の固有粘度、好ましくは０．６０〜０．８５ｄｌ／ｇの固有粘度に到達せしめる工程である。
本発明のポリエステルの製造方法では、所望の固有粘度、好ましくは０．６０〜０．８５ｄｌ／ｇの範囲となるように行う。固有粘度が０．６０ｄｌ／ｇ未満である場合には、得られるポリエステルの分子量が低すぎて十分な機械物性が得難い。一方、固有粘度が０．８５ｄｌ／ｇを超える場合、重合時間が過度に長くなる問題があるばかりか、製膜工程においてポリエステルを再溶融し押出する際、溶融粘度が高いことにより溶融押出し設備等への負荷が大きくなる問題がある。
Next, the second step in the production method of the present invention is a step of continuing the polymerization reaction after the first step to reach a desired intrinsic viscosity, preferably 0.60 to 0.85 dl / g. It is.
In the method for producing the polyester of the present invention, it is carried out so as to have a desired intrinsic viscosity, preferably in the range of 0.60 to 0.85 dl / g. When the intrinsic viscosity is less than 0.60 dl / g, it is difficult to obtain sufficient mechanical properties because the molecular weight of the obtained polyester is too low. On the other hand, when the intrinsic viscosity exceeds 0.85 dl / g, there is not only a problem that the polymerization time is excessively long, but also when the polyester is remelted and extruded in the film forming process, the melt viscosity is high due to the high melt viscosity. There is a problem that the load on
本発明をさらに効果的なものとするための重合反応温度は、得られるポリエステルの融点以上〜融点＋２０℃の範囲、さらには融点以上〜融点＋１０℃の範囲で行うことが好ましい。例えばポリエチレンテレフタレートでは通常２８０〜３００℃で重合反応が行われるが、ＰＡＯ添加ポリエチレンテレフタレートは重合反応促進効果を有することから、低い温度でも重合反応速度を維持しつつ、末端カルボキシル基量を低減させることができる。ポリエチレンテレフタレートでは２６８〜２７５℃が好ましく、さらには２７０〜２７３℃が好ましい。 The polymerization reaction temperature for making the present invention more effective is preferably in the range of from the melting point of the obtained polyester to the melting point + 20 ° C., more preferably in the range of the melting point to the melting point + 10 ° C. For example, polyethylene terephthalate usually undergoes a polymerization reaction at 280 to 300 ° C., but PAO-added polyethylene terephthalate has a polymerization reaction promoting effect, so that the amount of terminal carboxyl groups can be reduced while maintaining the polymerization reaction rate even at low temperatures. Can do. In polyethylene terephthalate, 268-275 degreeC is preferable, and 270-273 degreeC is more preferable.
なお、第２工程は上記の溶融重合反応だけで行ってもよいが、オリゴマーも併せて抑制する場合、溶融重合によりまず固有粘度を０．４５〜０．６０ｄｌ／ｇの範囲とし、次いで従来公知の方法により固相重合して、固有粘度を０．０５ｄｌ／ｇ以上、特に０．０７ｄｌ／ｇ以上高くするのが好ましい。このようにして得られるポリエステルは、ポリマー中のオリゴマー量が０．５質量％以下であることが好ましく、さらに０．３質量％以下であることが好ましい。オリゴマーが０．５質量％以下であると、フィルム製膜工程でオリゴマー起因の白粉が生じ難くなり、オリゴマーに起因する表面欠点の発生が少ないフィルムを得ることができる。 The second step may be performed only by the above melt polymerization reaction. However, when the oligomer is also suppressed, the intrinsic viscosity is first set in the range of 0.45 to 0.60 dl / g by melt polymerization, and then conventionally known. It is preferable that the intrinsic viscosity be increased by 0.05 dl / g or more, particularly 0.07 dl / g or more by solid-phase polymerization by the above method. In the polyester thus obtained, the amount of oligomer in the polymer is preferably 0.5% by mass or less, and more preferably 0.3% by mass or less. When the oligomer is 0.5% by mass or less, white powder derived from the oligomer is hardly generated in the film-forming process, and a film with less surface defects due to the oligomer can be obtained.
本発明のポリエステルの製造方法について、さらに詳述する。本発明のポリエステルの製造方法では、上記重合反応を行う前に、エステル化反応もしくはエステル交換反応を行い、芳香族ジカルボン酸成分とアルキレングリコール成分とを反応させる。エステル交換反応を経由する場合に用いるエステル交換反応触媒としては、カルシウム化合物、マグネシウム化合物、マンガン化合物、チタン化合物などが好適に挙げられる。また、本発明の製造方法ではエステル化反応もしくはエステル交換反応開始前から反応初期の間に、得られるポリエステルの末端カルボキシル基量をさらに低減するために、微量の水酸化カリウムなどのアルカリ金属化合物を添加しても良い。また、静電印加特性の向上を図るために、エステル化反応もしくはエステル交換反応終了から重合反応初期までの間に、微量の酢酸マグネシウムなどのマグネシウム化合物を添加しても良い。
このようにしてエステル化反応もしくはエステル交換反応を経由して得られた前駆体を、溶融状態で重合反応させればよい。
The method for producing the polyester of the present invention will be further described in detail. In the method for producing a polyester of the present invention, an esterification reaction or a transesterification reaction is performed before the polymerization reaction to react an aromatic dicarboxylic acid component with an alkylene glycol component. Suitable examples of the transesterification reaction catalyst used in the case of passing through the transesterification reaction include calcium compounds, magnesium compounds, manganese compounds, and titanium compounds. Further, in the production method of the present invention, in order to further reduce the amount of terminal carboxyl groups of the obtained polyester before the esterification reaction or the transesterification reaction and before the initial reaction, a trace amount of an alkali metal compound such as potassium hydroxide is added. It may be added. In order to improve electrostatic application characteristics, a trace amount of a magnesium compound such as magnesium acetate may be added between the end of the esterification reaction or transesterification reaction and the beginning of the polymerization reaction.
The precursor thus obtained via the esterification reaction or transesterification reaction may be polymerized in a molten state.
ところで、本発明のポリエステルの製造方法では、重合反応の初期段階までに、好ましくはエステル化反応もしくはエステル交換反応終了後から固有粘度０．３ｄｌ／ｇになるまでの重合反応中にリン化合物を添加することが好ましい。リン化合物としては特に限定はされないが、フェニルホスホン酸、ホスホン酸系化合物、ホスフィン酸系化合物、ホスフィンオキサイド系化合物、亜ホスホン酸系化合物、亜ホスフィン酸系化合物、ホスフィン系化合物からなる群より選ばれる一種または二種以上の化合物を用いると触媒活性の向上効果が大きく好ましい。これらのうちでフェニルホスホン酸が特に好ましい。含有させるリン化合物量は、得られるポリエステルの全酸成分のモル数を基準として、リン元素量で１〜１００ｍｍｏｌ％、さらに５〜５０ｍｍｏｌ％の範囲が好ましい。 By the way, in the polyester production method of the present invention, a phosphorus compound is added during the polymerization reaction until the initial stage of the polymerization reaction, preferably after completion of the esterification reaction or transesterification reaction until the intrinsic viscosity becomes 0.3 dl / g. It is preferable to do. The phosphorus compound is not particularly limited, but is selected from the group consisting of phenylphosphonic acid, phosphonic acid compounds, phosphinic acid compounds, phosphine oxide compounds, phosphonous acid compounds, phosphinic acid compounds, and phosphine compounds. The use of one or two or more compounds is preferable because the effect of improving the catalytic activity is great. Of these, phenylphosphonic acid is particularly preferred. The amount of the phosphorus compound to be contained is preferably in the range of 1 to 100 mmol%, more preferably 5 to 50 mmol% in terms of the amount of phosphorus element, based on the number of moles of all acid components of the resulting polyester.
＜ポリエステル＞
本発明のポリエステルは、上述のポリエステルの製造方法によって製造できる。以下、本発明のポリエステルを詳述する。
本発明のポリエステルは、前記式で示されるＰＡＯを、ポリエステルの全酸成分のモル数に対して、シュウ酸成分の割合として０．１〜５モル％の範囲で添加したものである。
ＰＡＯの添加量が、下限より少ないと充分低い末端カルボキシル基量のポリエステルが得られず、逆にＰＡＯの添加量が多すぎると固有粘度の低下が大きくなったり、著しい発泡を生じ、反応工程上のトラブルをまねいたり、フィルムとした際に気泡による表面欠点が発生しやすくなる。好ましいＰＡＯの添加量は、０．５〜３．０モル％の範囲である。
<Polyester>
The polyester of the present invention can be produced by the above-described polyester production method. Hereinafter, the polyester of the present invention will be described in detail.
The polyester of the present invention is obtained by adding PAO represented by the above formula in the range of 0.1 to 5 mol% as the ratio of the oxalic acid component to the total number of moles of the acid component of the polyester.
If the amount of PAO added is less than the lower limit, a polyester having a sufficiently low amount of terminal carboxyl groups cannot be obtained. Conversely, if the amount of PAO added is too large, the decrease in intrinsic viscosity increases or significant foaming occurs. When a film is produced, surface defects due to air bubbles are likely to occur. A preferable PAO addition amount is in the range of 0.5 to 3.0 mol%.
また、本発明のポリエステルは、その末端カルボキシル基量は、耐加水分解性の点から、１０ｅｑ／ｔ以下であることが必要であり、さらに８ｅｑ／ｔ以下であることが好ましい。下限は特に制限されないが生産性などの点から３ｅｑ／ｔ以上である。また、上述の固相重合を行った場合には、８ｅｑ／ｔ以下、さらに６ｅｑ／ｔ以下であることが好ましい。 In addition, the terminal carboxyl group amount of the polyester of the present invention is required to be 10 eq / t or less and more preferably 8 eq / t or less from the viewpoint of hydrolysis resistance. Although a minimum in particular is not restrict | limited, From points, such as productivity, it is 3 eq / t or more. Moreover, when the above-mentioned solid phase polymerization is performed, it is preferably 8 eq / t or less, more preferably 6 eq / t or less.
本発明のポリエステルの固有粘度は、０．６０〜０．８５ｄｌ／ｇの範囲であることが必要である。固有粘度が下限未満である場合、フィルムなどにしたときに十分な機械物性が得られない。他方、固有粘度が上限を超える場合、製膜工程においてポリエステルを再溶融し押出する際、溶融粘度が高いことにより溶融押出し設備等への負荷が大きくなる問題がある。
さらに、本発明のポリエステルは、固相重合を行ってオリゴマー量を低減する場合、好ましい態様として、固有粘度が０．７０〜０．８５ｄｌ／ｇの範囲で、かつオリゴマー含有量が０．５重量％以下であることが耐加水分解性とオリゴマーに基づく問題を抑制できることから好ましい。
The intrinsic viscosity of the polyester of the present invention needs to be in the range of 0.60 to 0.85 dl / g. When the intrinsic viscosity is less than the lower limit, sufficient mechanical properties cannot be obtained when the film is formed. On the other hand, when the intrinsic viscosity exceeds the upper limit, there is a problem that, when the polyester is remelted and extruded in the film forming process, the load on the melt extrusion equipment is increased due to the high melt viscosity.
Further, when the polyester of the present invention is subjected to solid phase polymerization to reduce the amount of oligomer, as a preferred embodiment, the intrinsic viscosity is in the range of 0.70 to 0.85 dl / g and the oligomer content is 0.5 wt. % Or less is preferable because hydrolysis resistance and problems due to oligomers can be suppressed.
このような本発明のポリエステルは、末端カルボキシ基量が少なく、しかも溶融成形する際の末端カルボキシ基量の増加も小さいので、フィルム用として好適に用いることができる。特に耐加水分解性に優れながらも表面欠点が少ないフィルムが容易に得られることから、太陽電池バックシート用フィルムとして好適に利用できる。
なお、本発明のポリエステルは、本発明の効果を損なわない範囲であれば、例えば滑剤，顔料，染料，酸化防止剤，光安定剤，遮光剤（例えばカーボンブラック，酸化チタン等）の如きそれ自体公知の添加剤を、必要に応じて含有させることもできる。
Such a polyester of the present invention has a small amount of terminal carboxy groups and also has a small increase in the amount of terminal carboxy groups when melt-molded, and therefore can be suitably used for films. In particular, since a film having excellent surface resistance and few surface defects can be easily obtained, it can be suitably used as a film for a solar battery back sheet.
The polyester of the present invention itself is, for example, a lubricant, a pigment, a dye, an antioxidant, a light stabilizer, a light-shielding agent (for example, carbon black, titanium oxide, etc.) as long as the effects of the present invention are not impaired. Known additives may be included as necessary.
１）ＰＡＯ合成時のエステル交換反応率
エステル交換反応で発生する留出液を計量し、理論発生量との比率で求めた。
1) Transesterification reaction rate during PAO synthesis The distillate generated in the transesterification reaction was weighed and obtained as a ratio to the theoretical amount.
２）ＰＡＯの少なくとも一方の末端がアルキル基であるＰＡＯの割合、平均重合度
得られたＰＡＯのサンプル約１ｍｇを１ｍｌのアセトニトリルに溶解し、ＬＣ（ＬＣ２０Ａ、島津製作所製）で次の条件で質量分析し（カラム：Ｄｅｖｅｌｏｓｉｌ Ｃ３０−ＵＧ−３、流量：０．２ｍｌ／ｍｉｎ、検出波長：２１０ｎｍ、カラム温度：４０℃）、次にＭＳ（ＬＣＭＳ−ＩＴ−ＴＯＦ、島津製作所製）でイオン源：ＥＳＩ（正イオン、負イオン同時測定）、プローブ電圧：正イオン：＋４．５ｋＶ、負イオン：−３．５ｋＶネブライズ（窒素）ガス流量：１．５Ｌ／ｍｉｎ、ＣＤＬ温度：２００℃、乾燥（窒素）ガス流量：１００ｋＰａ、検出器電圧：１．６８ｋＶ、質量範囲：ｍ／ｚ ８０〜２０００で分析を行なって各成分を特定し、ＵＶ２１０ｎｍ検出におけるピーク面積割合から夫々算出した。
2) Ratio of PAO in which at least one terminal of PAO is an alkyl group, average degree of polymerization About 1 mg of the obtained PAO sample was dissolved in 1 ml of acetonitrile and massed under the following conditions by LC (LC20A, manufactured by Shimadzu Corporation) Analyze (column: Develosil C30-UG-3, flow rate: 0.2 ml / min, detection wavelength: 210 nm, column temperature: 40 ° C.), then MS (LCMS-IT-TOF, manufactured by Shimadzu Corporation) ion source: ESI (simultaneous measurement of positive ion and negative ion), probe voltage: positive ion: +4.5 kV, negative ion: -3.5 kV nebulization (nitrogen) gas flow rate: 1.5 L / min, CDL temperature: 200 ° C., dry (nitrogen) ) Gas flow rate: 100 kPa, detector voltage: 1.68 kV, mass range: m / z 80-2000 to identify each component, UV They were respectively calculated from the peak area ratio in the 10nm detection.
３）固有粘度
反応途中に反応系から採取したポリエステルおよび重合完了後のポリエステルを、それぞれ重量比が６：４のフェノール：トリクロロエタン混合溶媒に溶解して、３５℃の温度にて、オストワルド粘度計を用いて測定した。単位は［ｄｌ／ｇ］で示す。
3) Intrinsic viscosity The polyester collected from the reaction system during the reaction and the polyester after polymerization were dissolved in a phenol: trichloroethane mixed solvent having a weight ratio of 6: 4, respectively, and an Ostwald viscometer was used at a temperature of 35 ° C. And measured. The unit is indicated by [dl / g].
４）末端カルボキシル基量
得られたポリエステルを、窒素雰囲気下、２００℃でベンジルアルコールに溶解させた後、滴定法により、ポリエステル重量１ｔ当りの当量数として、末端カルボキシル基量（ｅｑ／ｔ）を測定した。
4) Amount of terminal carboxyl groups After the obtained polyester was dissolved in benzyl alcohol at 200 ° C. in a nitrogen atmosphere, the amount of terminal carboxyl groups (eq / t) was determined as the number of equivalents per 1 t of polyester weight by titration. It was measured.
５）耐加水分解性
得られたポリエステルを電気乾燥機内で１６０℃、６Ｈｒ乾燥処理後、日立製作所製押出し機（Ｐ４０−２２ＡＢ型）にて２９８℃にて溶融押出し、日本製鋼所製２形フィルム製造装置（横形移動式）で厚さ３５０μｍのポリエステルシートを作製した。次いで、これをロング延伸機で延伸を行って厚み４０μｍのフィルムを得た。このフィルムを平山製作所（株）製、ＰＣ−３０１１型プレッシャークッカーを用い温度１２０℃、湿度１００％ＲＨの条件下で９６時間処理した後、このサンプルにつき末端カルボキシル基量を測定し、プレッシャークッカー処理前後の末端カルボキシル基量増加値で評価した。カルボン酸末端基数の増加が低いほど耐加水分解性は良好である。
5) Hydrolysis resistance After the obtained polyester was dried at 160 ° C. for 6 hours in an electric dryer, it was melt-extruded at 298 ° C. with an extruder (P40-22AB type) manufactured by Hitachi, Ltd. A polyester sheet having a thickness of 350 μm was produced using a production apparatus (horizontal moving type). Subsequently, this was stretched with a long stretching machine to obtain a film having a thickness of 40 μm. This film was treated with a PC-3011 type pressure cooker manufactured by Hirayama Seisakusho for 96 hours under the conditions of a temperature of 120 ° C. and a humidity of 100% RH. It evaluated by the amount increase amount of the terminal carboxyl group before and behind. The lower the increase in the number of carboxylic acid end groups, the better the hydrolysis resistance.
６）フィルムの表面欠点数
得られたポリエステルを電気乾燥機内で１６０℃、６時間乾燥処理後、日立製作所製押出し機（Ｐ４０−２２ＡＢ型）にて２９５℃にて溶融押出し、日本製鋼所製２形フィルム製造装置（横形移動式）で厚さ１２５μｍのポリエステルシートを作製した。次に、これをロング延伸機でポリエステルのガラス転移温度より１０℃高い温度で、製膜方向に３．５倍、幅方向に３．５倍延伸を行い、厚み１２μｍのフィルムを得た。このフィルムを顕微鏡にて偏光下で観察し、気泡起因による表面突起数を下記の基準で評価した。なお、測定は、フィルム面積２５ｃｍ２のフィルムを５枚用意し、それぞれのフィルムについて、長径２５μｍ以上の表面突起を抽出し、フィルム面積２５ｃｍ２における抽出された突起数を、以下の基準で評価した。
◎（極めて良好） ：０個≦表面突起数≦５個
○（良好） ：５個＜表面突起数≦１０個
×（やや不良） ：１０個＜表面突起数≦１５個
××（多目のため使用不可）：１５個＜表面突起数
6) Number of surface defects of the film The obtained polyester was dried in an electric dryer at 160 ° C. for 6 hours and then melt extruded at 295 ° C. with an extruder manufactured by Hitachi, Ltd. (P40-22AB type). A polyester sheet having a thickness of 125 μm was produced using a shape film production apparatus (horizontal movement type). Next, this was stretched 3.5 times in the film forming direction and 3.5 times in the width direction at a temperature 10 ° C. higher than the glass transition temperature of the polyester with a long stretching machine to obtain a film having a thickness of 12 μm. This film was observed under polarized light with a microscope, and the number of surface protrusions due to bubbles was evaluated according to the following criteria. The measurement, the films of the film area 25 cm 2 five pieces, each of the film, to extract more surface protrusions diameter 25 [mu] m, the number of projections which are extracted in the film area 25 cm 2, were evaluated by the following criteria .
◎ (very good): 0 ≤ number of surface protrusions ≤ 5 ◯ (good): 5 <number of surface protrusions ≤ 10 x (slightly bad): 10 <number of surface protrusions ≤ 15 x Not usable): 15 <number of surface protrusions
［合成例１］
エチレングリコール１８６２部に酢酸マンガン４水塩１．８３９部を溶かし、シュウ酸ジエチル２１９２部を加え、１６０℃まで加熱してエステル交換反応を進め、エチルアルコールを１２００部留出させた（エステル交換反応時の理論留出量の比からエステル交換反応率は８６．８％）。次に亜燐酸０．６１５部を加え、その後、窒素雰囲気のもとで徐々に減圧にし、２．７ｋｐａのもとでエチレングリコール留出させ約１３０分間加熱反応させた。得られたＰＡＯ中、末端の一部がエチル基であるＰＡＯ含有割合は３７．９％、平均重合度は１．２であった。このようにして得られたＰＡＯを合成法１とした。
[Synthesis Example 1]
Dissolve 1.839 parts of manganese acetate tetrahydrate in 1862 parts of ethylene glycol, add 2192 parts of diethyl oxalate and heat to 160 ° C. to proceed the transesterification reaction to distill 1200 parts of ethyl alcohol (transesterification reaction). The transesterification rate is 86.8% based on the ratio of theoretical distillation amount at the time). Next, 0.615 part of phosphorous acid was added, and then the pressure was gradually reduced under a nitrogen atmosphere, and ethylene glycol was distilled off under 2.7 kpa, followed by heating for about 130 minutes. In the obtained PAO, the PAO content ratio in which part of the terminals was an ethyl group was 37.9%, and the average degree of polymerization was 1.2. The PAO thus obtained was defined as Synthesis Method 1.
［合成例２］
エチレングリコール１２４１部に酢酸マンガン４水塩１．２２６部を溶かし、シュウ酸ジメチル１１８１部を加え、１６０℃まで加熱してエステル交換反応を進め、メチルアルコールを５０５部留出させた（エステル交換反応時の理論留出量の比からエステル交換反応率は７８．８％）。次に亜燐酸０．４１０部を加え、その後、窒素雰囲気のもとで徐々に減圧にし、２．７ｋｐａのもとでエチレングリコール留出させ約１３０分間加熱反応させた。得られたＰＡＯ中、末端の一部がメチル基であるＰＡＯ含有割合は４８．１％、平均重合度は１．４であった。このようにして得られたＰＡＯを合成法２とした。
[Synthesis Example 2]
Dissolve 1.226 parts of manganese acetate tetrahydrate in 1241 parts of ethylene glycol, add 1181 parts of dimethyl oxalate and heat to 160 ° C. to proceed the transesterification reaction to distill 505 parts of methyl alcohol (transesterification reaction). The transesterification rate is 78.8% from the ratio of the theoretical distillation amount at the time). Next, 0.410 part of phosphorous acid was added, and then the pressure was gradually reduced under a nitrogen atmosphere, and ethylene glycol was distilled off at 2.7 kpa, followed by heating for about 130 minutes. In the obtained PAO, the PAO content ratio in which a part of the terminals is a methyl group was 48.1%, and the average degree of polymerization was 1.4. The PAO thus obtained was designated as synthesis method 2.
［合成例３］
エチレングリコール１８６２部に酢酸マンガン４水塩１．８３９部を溶かし、シュウ酸ジエチル２１９２部を加え、１６０℃まで加熱してエステル交換反応を進め、エチルアルコールを１２９９部留出させた（エステル交換反応時の理論留出量の比からエステル交換反応率は９４．０％）。次に亜燐酸０．６１５部を加え、その後、窒素雰囲気のもとで徐々に減圧にし、２．７ｋｐａのもとでエチレングリコール留出させ約１３０分間加熱反応させた。得られたＰＡＯ中、末端の一部がエチル基であるＰＡＯ含有割合率は３．３％、平均重合度は１．３であった。このようにして得られたＰＡＯを合成法３とした。
[Synthesis Example 3]
Dissolve 1.839 parts of manganese acetate tetrahydrate in 1862 parts of ethylene glycol, add 2192 parts of diethyl oxalate, and heat to 160 ° C. to proceed the transesterification reaction to distill 1299 parts of ethyl alcohol (transesterification reaction). The transesterification rate is 94.0% from the ratio of theoretical distillation amount at the time). Next, 0.615 part of phosphorous acid was added, and then the pressure was gradually reduced under a nitrogen atmosphere, and ethylene glycol was distilled off under 2.7 kpa, followed by heating for about 130 minutes. In the obtained PAO, the PAO content ratio in which a part of the terminals was an ethyl group was 3.3%, and the average degree of polymerization was 1.3. The PAO thus obtained was designated as synthesis method 3.
［合成例４（比較例）］
エチレングリコール１８６２部に酢酸マンガン４水塩１．８３９部を溶かし、シュウ酸ジエチル２１９２部を加え、１６０℃まで加熱してエステル交換反応を進め、エチルアルコールを１３１９部留出させた（エステル交換反応時の理論留出量の比からエステル交換反応率は９５．５％）。次に亜燐酸０．６１５部を加え、その後、窒素雰囲気のもとで徐々に減圧にし、２．７ｋｐａのもとでエチレングリコール留出させ約１３０分間加熱反応させた。得られたＰＡＯ中、末端の一部がエチル基であるＰＡＯ含有割合率は１．８％、平均重合度は１．５であった。このようにして得られたＰＡＯを合成法４とした。
[Synthesis Example 4 (Comparative Example)]
Dissolve 1.839 parts of manganese acetate tetrahydrate in 1862 parts of ethylene glycol, add 2192 parts of diethyl oxalate, and heat to 160 ° C. to proceed the transesterification reaction to distill 1319 parts of ethyl alcohol (transesterification reaction). The transesterification rate is 95.5% from the ratio of theoretical distillation amount at the time). Next, 0.615 part of phosphorous acid was added, and then the pressure was gradually reduced under a nitrogen atmosphere, and ethylene glycol was distilled off under 2.7 kpa, followed by heating for about 130 minutes. In the obtained PAO, the PAO content ratio in which part of the terminals was an ethyl group was 1.8%, and the average degree of polymerization was 1.5. The PAO thus obtained was designated as synthesis method 4.
［実施例１］
エステル交換反応容器にテレフタル酸ジメチルを１００重量部、エチレングリコールを６０重量部、酢酸マンガン四水塩０．０１９重量部を仕込み、１５０℃に加熱して溶融し撹拌した。反応容器内温度をゆっくりと２３５℃まで昇温しながら反応を進め、生成するメタノールを反応容器外へ留出させた。メタノールの留出が終了したらリン化合物としてフェニルホスホン酸０．０１４重量部（テレフタル酸ジメチルのモル数を基準として１７ｍｍｏｌ％）を添加し、エステル交換反応（以下、ＥＩ反応と略す）を終了させた。続いて５分後に重合触媒として、三酸化アンチモン０．０３８重量部およびテトラブトキシチタネート０．００５重量部を添加し、２４０℃まで加熱して一部のエチレングリコールを留出させた後、反応物を内部に撹拌翼を有する重縮合装置に移行した。
ＥＩ反応終了後、反応物を重合反応（ＰＮ反応と略す）のため、徐々に真空ポンプで真空度を高めながら３５分間を要して、反応温度を２７０℃に到達せしめた。この温度を保持して真空度を０．１５ｋＰａ以下に保ちＰＮ反応を１５分間行った。ここで真空ポンプとＰＮ反応釜をむすぶ真空バルブを閉とし、攪拌翼は回転させたままの状態で、直ちに真空ホッパー内で加熱し液状とした合成法１のＰＡＯ０．８重量部（ポリエステルを構成する全酸成分に対しシュウ酸成分０．９ｍｏｌ％）を添加した後、直ちに真空バルブを開けて減圧処理を再開した。ＰＡＯ添加時のポリエステル固有粘度は０．２２ｄｌ／ｇであった。その後、所望の固有粘度に到達するまでＰＮ反応を続けた。次にポリマー吐出作業を行うため攪拌翼を停止させた後、ＰＮ反応釜系内を窒素ガスで０．１７Ｍｐａに加圧し、ダイホールよりポリエステルをストランド状に押出した。その後、冷却バスでポリエステルを冷却した後、ペレタイザーでカッテングを行い、長径約４ｍｍ、短径約２ｍｍ、長さ約４ｍｍのポリエステルチップを得た。得られたポリエステルチップの評価結果を表１に記す。
[Example 1]
A transesterification vessel was charged with 100 parts by weight of dimethyl terephthalate, 60 parts by weight of ethylene glycol, and 0.019 parts by weight of manganese acetate tetrahydrate, heated to 150 ° C., melted and stirred. The reaction was advanced while the temperature inside the reaction vessel was slowly raised to 235 ° C., and the methanol produced was distilled out of the reaction vessel. When the distillation of methanol was completed, 0.014 part by weight of phenylphosphonic acid (17 mmol% based on the number of moles of dimethyl terephthalate) was added as a phosphorus compound to complete the transesterification reaction (hereinafter abbreviated as EI reaction). . Then, after 5 minutes, 0.038 parts by weight of antimony trioxide and 0.005 parts by weight of tetrabutoxy titanate were added as polymerization catalysts and heated to 240 ° C. to distill some ethylene glycol, Was transferred to a polycondensation apparatus having a stirring blade inside.
After completion of the EI reaction, the reaction product was polymerized (abbreviated as PN reaction), and the reaction temperature was allowed to reach 270 ° C. over 35 minutes while gradually increasing the degree of vacuum with a vacuum pump. While maintaining this temperature, the degree of vacuum was kept at 0.15 kPa or less, and PN reaction was carried out for 15 minutes. Here, the vacuum valve connecting the vacuum pump and the PN reaction kettle was closed, and the stirring blade was kept rotating, and immediately heated in a vacuum hopper to make it liquid, 0.8 parts by weight of PAO of Synthesis Method 1 The oxalic acid component (0.9 mol%) was added to the total acid component, and the vacuum valve was immediately opened to resume the decompression process. The intrinsic viscosity of the polyester when PAO was added was 0.22 dl / g. Thereafter, the PN reaction was continued until the desired intrinsic viscosity was reached. Next, after the stirring blade was stopped to perform the polymer discharging operation, the inside of the PN reaction kettle system was pressurized to 0.17 MPa with nitrogen gas, and the polyester was extruded from the die hole into a strand shape. Thereafter, the polyester was cooled with a cooling bath, and then cut with a pelletizer to obtain a polyester chip having a major axis of about 4 mm, a minor axis of about 2 mm, and a length of about 4 mm. The evaluation results of the obtained polyester chip are shown in Table 1.
［実施例２〜４］
ＰＡＯ添加量を表１に示すとおり変更した以外は、実施例１と同様な操作を繰り返した。得られたポリエステルチップの評価結果を表１に示す。
[Examples 2 to 4]
The same operation as in Example 1 was repeated except that the PAO addition amount was changed as shown in Table 1. The evaluation results of the obtained polyester chip are shown in Table 1.
［実施例５］
ＰＡＯ添加を次の内容で２回に分割して行う以外は実施例１と同様に行った。ＥＩ反応終了後、反応物をＰＮ反応のため、徐々に真空ポンプで真空度を高めながら３５分間を要して、反応温度を２７０℃に到達せしめた。この温度を保持して真空度を０．１５ｋＰａ以下に保ちＰＮ反応を１５分間行った。ここで真空ポンプとＰＮ反応釜をむすぶ真空バルブを閉とし、攪拌翼は回転させたままの状態で直ちに真空ホッパー内で加熱し液状とした合成例１のＰＡＯ重合体０．６２重量部（ポリエステルを構成する全酸成分に対しシュウ酸成分０．７ｍｏｌ％）を添加した後、直ちに真空バルブを開けて減圧処理を再開した。ＰＡＯ添加時のポリエステル固有粘度は０．２５ｄｌ／ｇであった。
次に２回目のＰＡＯ添加として真空度を０．１５ｋＰａ以下に保ちポリエステル固有粘度が０．４５ｄｌ／ｇになった時点で真空バルブを閉とし、攪拌翼は回転させたままの状態で直ちに真空ホッパー内で加熱し液状とした合成法１のＰＡＯ０．１８重量部（ポリエステルを構成する全酸成分に対しシュウ酸成分０．２ｍｏｌ％）を添加した後、直ちに真空バルブを開けて減圧処理を再開した。その後、所望の固有粘度に到達するまでＰＮ反応を続けた。次にポリマー吐出作業を行うため攪拌翼を停止させた後、ＰＮ反応釜系内を窒素ガスで０．１７Ｍｐａに加圧し、ダイホールよりポリエステルをストランド状に押出した。その後、冷却バスでポリエステルを冷却した後、ペレタイザーでカッテングを行い、長径約４ｍｍ、短径約２ｍｍ、長さ約４ｍｍのポリエステルチップを得た。得られたポリエステルチップの評価結果を表１に示す。
[Example 5]
The same procedure as in Example 1 was performed except that the PAO addition was performed in two portions with the following contents. After completion of the EI reaction, the reaction product was subjected to PN reaction, and the reaction temperature was allowed to reach 270 ° C. over 35 minutes while gradually increasing the degree of vacuum with a vacuum pump. While maintaining this temperature, the degree of vacuum was kept at 0.15 kPa or less, and PN reaction was carried out for 15 minutes. Here, the vacuum valve connecting the vacuum pump and the PN reaction kettle was closed, and the stirring blade was kept rotating, and immediately heated in a vacuum hopper to be liquid, 0.62 parts by weight of the PAO polymer of Synthesis Example 1 (polyester) Then, the oxalic acid component 0.7 mol%) was added to the total acid component, and the vacuum valve was immediately opened to resume the decompression process. The intrinsic viscosity of the polyester when PAO was added was 0.25 dl / g.
Next, as the second PAO addition, when the degree of vacuum is kept at 0.15 kPa or less and the intrinsic viscosity of the polyester reaches 0.45 dl / g, the vacuum valve is closed and the stirring wing is kept rotating and the vacuum hopper is immediately turned on. After adding 0.18 parts by weight of PAO of Synthesis Method 1 heated to a liquid (0.2 mol% of oxalic acid component with respect to all acid components constituting the polyester), the vacuum valve was immediately opened to resume the decompression process. . Thereafter, the PN reaction was continued until the desired intrinsic viscosity was reached. Next, after the stirring blade was stopped to perform the polymer discharging operation, the inside of the PN reaction kettle system was pressurized to 0.17 MPa with nitrogen gas, and the polyester was extruded from the die hole into a strand shape. Thereafter, the polyester was cooled with a cooling bath, and then cut with a pelletizer to obtain a polyester chip having a major axis of about 4 mm, a minor axis of about 2 mm, and a length of about 4 mm. The evaluation results of the obtained polyester chip are shown in Table 1.
［比較例１］
ＰＡＯを添加しない以外は実施例１と同様な操作を繰り返した。得られたポリエステルチップの評価結果を表１に示す。
[Comparative Example 1]
The same operation as in Example 1 was repeated except that PAO was not added. The evaluation results of the obtained polyester chip are shown in Table 1.
［比較例２］
合成法３のＰＡＯを用いる以外は実施例１と同様な操作を繰り返した。得られたポリエステルチップの評価結果を表１に示す。
[Comparative Example 2]
The same operation as in Example 1 was repeated except that PAO of Synthesis Method 3 was used. The evaluation results of the obtained polyester chip are shown in Table 1.
［比較例３〜４］
ＰＡＯの添加量を表１の値に変更する以外は実施例１と同様な操作を繰り返した。得られたポリエステルチップの評価結果を表１に示す。
[Comparative Examples 3 to 4]
The same operation as in Example 1 was repeated except that the amount of PAO added was changed to the value shown in Table 1. The evaluation results of the obtained polyester chip are shown in Table 1.
［実施例６〜７］
添加するＰＡＯを表１で示す通り、合成法２または合成法３で合成したものを用いる以外は、実施例１と同様な操作を繰り返した。得られたポリエステルチップの評価結果を表１に示す。
[Examples 6 to 7]
As shown in Table 1, the same procedure as in Example 1 was repeated except that the PAO to be added was synthesized by the synthesis method 2 or the synthesis method 3. The evaluation results of the obtained polyester chip are shown in Table 1.
本発明の製造方法により得られるポリエステルは、末端カルボキシル基量が少なく耐加水分解性に優れるだけでなく、フィルム等に溶融成形した際の末端カルボキシ基量の増加も少ないことから、特に耐加水分解性が求められる太陽電池バックシート用フィルムに極めて好適に使用できる。 The polyester obtained by the production method of the present invention not only has a small amount of terminal carboxyl groups and is excellent in hydrolysis resistance, but also has a small increase in the amount of terminal carboxyl groups when melt-molded into a film or the like. It can be used very suitably for a film for a solar battery backsheet that is required to have high performance.
Claims (7)
Ｘ１Ｏ−［Ｃ（Ｏ）Ｃ（Ｏ）ＯＲＯ］ｎ−Ｃ（Ｏ）Ｃ（Ｏ）ＯＸ２ （１）
（式中、Ｒは炭素数２〜４のアルキレン基、Ｘ１，Ｘ２は夫々炭素数４以下のアルキル基または−ＲＯＨ基、ｎは０以上の整数（但し、Ｘ１，Ｘ２が共にアルキル基の場合にはｎは１以上）を表わす。） In the melt polymerization of a polyester having an aromatic dicarboxylic acid as a main acid component and an alkylene glycol having 2 to 4 carbon atoms as a glycol component, when the intrinsic viscosity of the polyester becomes 0.2 dl / g or more, the following formula An oxalic acid glycol ester represented by (1) having an average degree of polymerization of 1 to 8 and having an alkyl group at least at one terminal is 2% or more, and / or its low degree of polymerization oligomer, A method for producing a polyester, wherein the oxalic acid component is added at a ratio of 0.1 to 5.0 mol% with respect to the total acid component, and further a polymerization reaction is performed.
X 1 O- [C (O) C (O) ORO] n -C (O) C (O) OX 2 (1)
(Wherein R is an alkylene group having 2 to 4 carbon atoms, X 1 and X 2 are each an alkyl group or —ROH group having 4 or less carbon atoms, and n is an integer of 0 or more (provided that both X 1 and X 2 are In the case of an alkyl group, n represents 1 or more).
Ｘ１Ｏ−［Ｃ（Ｏ）Ｃ（Ｏ）ＯＲＯ］ｎ−Ｃ（Ｏ）Ｃ（Ｏ）ＯＸ２ （１）
（式中、Ｒは炭素数２〜４のアルキレン基、Ｘ１，Ｘ２は夫々炭素数４以下のアルキル基または−ＲＯＨ基、ｎは０以上の整数（但し、Ｘ１，Ｘ２が共にアルキル基の場合にはｎは１以上）を表わす。） A polyester produced by melt polymerization using an aromatic dicarboxylic acid as a main acid component and an alkylene glycol having 2 to 4 carbon atoms as a glycol component, represented by the following formula (1), and having an average degree of polymerization of 1 to 8 And an oxalic acid glycol ester and / or a low polymerization degree oligomer thereof having an alkyl group at least at one end of 2% or more has an oxalic acid component of 0.1 to 5 with respect to the total acid component of the polyester. A polyester having a terminal carboxyl group content of 10 eq / ton or less and an intrinsic viscosity of 0.60 to 0.85 dl / g.
X 1 O- [C (O) C (O) ORO] n -C (O) C (O) OX 2 (1)
(Wherein R is an alkylene group having 2 to 4 carbon atoms, X 1 and X 2 are each an alkyl group or —ROH group having 4 or less carbon atoms, and n is an integer of 0 or more (provided that both X 1 and X 2 are In the case of an alkyl group, n represents 1 or more).
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| CN106700043A (en) * | 2016-09-27 | 2017-05-24 | 无锡卡卡生物科技有限公司 | Direct polymerization preparation method of fiber-grade polyethylene glycol naphthalene-2,3-dicarboxylate material |
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