JP5194565B2 - Method for producing polyester resin composition - Google Patents
Method for producing polyester resin composition Download PDFInfo
- Publication number
- JP5194565B2 JP5194565B2 JP2007141734A JP2007141734A JP5194565B2 JP 5194565 B2 JP5194565 B2 JP 5194565B2 JP 2007141734 A JP2007141734 A JP 2007141734A JP 2007141734 A JP2007141734 A JP 2007141734A JP 5194565 B2 JP5194565 B2 JP 5194565B2
- Authority
- JP
- Japan
- Prior art keywords
- polyester resin
- resin composition
- component
- producing
- polyester
- 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.)
- Expired - Fee Related
Links
- 229920001225 polyester resin Polymers 0.000 title claims description 72
- 239000004645 polyester resin Substances 0.000 title claims description 72
- 239000000203 mixture Substances 0.000 title claims description 59
- 238000004519 manufacturing process Methods 0.000 title claims description 26
- -1 alicyclic diol Chemical class 0.000 claims description 48
- 229910052698 phosphorus Inorganic materials 0.000 claims description 40
- 239000011574 phosphorus Substances 0.000 claims description 40
- 238000006068 polycondensation reaction Methods 0.000 claims description 39
- 239000003054 catalyst Substances 0.000 claims description 35
- 229920000728 polyester Polymers 0.000 claims description 32
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 27
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 24
- 125000002723 alicyclic group Chemical group 0.000 claims description 19
- 150000003609 titanium compounds Chemical class 0.000 claims description 17
- 125000003118 aryl group Chemical group 0.000 claims description 14
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 13
- DYLIWHYUXAJDOJ-OWOJBTEDSA-N (e)-4-(6-aminopurin-9-yl)but-2-en-1-ol Chemical compound NC1=NC=NC2=C1N=CN2C\C=C\CO DYLIWHYUXAJDOJ-OWOJBTEDSA-N 0.000 claims description 11
- QYQADNCHXSEGJT-UHFFFAOYSA-N cyclohexane-1,1-dicarboxylate;hydron Chemical group OC(=O)C1(C(O)=O)CCCCC1 QYQADNCHXSEGJT-UHFFFAOYSA-N 0.000 claims description 10
- 238000004898 kneading Methods 0.000 claims description 10
- 239000003963 antioxidant agent Substances 0.000 claims description 7
- 239000011734 sodium Substances 0.000 claims description 7
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 6
- 230000003078 antioxidant effect Effects 0.000 claims description 6
- 125000000524 functional group Chemical group 0.000 claims description 6
- 230000009477 glass transition Effects 0.000 claims description 6
- 229910052708 sodium Inorganic materials 0.000 claims description 6
- 125000003545 alkoxy group Chemical group 0.000 claims description 5
- 150000002009 diols Chemical class 0.000 claims description 4
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 claims description 4
- ODIGIKRIUKFKHP-UHFFFAOYSA-N (n-propan-2-yloxycarbonylanilino) acetate Chemical group CC(C)OC(=O)N(OC(C)=O)C1=CC=CC=C1 ODIGIKRIUKFKHP-UHFFFAOYSA-N 0.000 claims description 3
- 125000003277 amino group Chemical group 0.000 claims description 3
- 238000000113 differential scanning calorimetry Methods 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 125000001424 substituent group Chemical group 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical group OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 53
- 238000006116 polymerization reaction Methods 0.000 description 28
- 229920000139 polyethylene terephthalate Polymers 0.000 description 27
- 239000005020 polyethylene terephthalate Substances 0.000 description 27
- 238000001879 gelation Methods 0.000 description 23
- 239000010936 titanium Substances 0.000 description 21
- 229920000642 polymer Polymers 0.000 description 19
- 238000000034 method Methods 0.000 description 18
- 229920005989 resin Polymers 0.000 description 17
- 239000011347 resin Substances 0.000 description 17
- 238000005809 transesterification reaction Methods 0.000 description 16
- 229910052719 titanium Inorganic materials 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 239000000047 product Substances 0.000 description 11
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- 239000010410 layer Substances 0.000 description 9
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 8
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical group OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 6
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 6
- 238000002844 melting Methods 0.000 description 6
- 230000008018 melting Effects 0.000 description 6
- 229920006267 polyester film Polymers 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 239000011572 manganese Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 238000001579 optical reflectometry Methods 0.000 description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- KLDXJTOLSGUMSJ-JGWLITMVSA-N Isosorbide Chemical compound O[C@@H]1CO[C@@H]2[C@@H](O)CO[C@@H]21 KLDXJTOLSGUMSJ-JGWLITMVSA-N 0.000 description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000013522 chelant Substances 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 229960002479 isosorbide Drugs 0.000 description 4
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical group CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 4
- 229910052748 manganese Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 4
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical group C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical group OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 238000003776 cleavage reaction Methods 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000005886 esterification reaction Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000010030 laminating Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000004973 liquid crystal related substance Substances 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 239000002685 polymerization catalyst Substances 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 230000007017 scission Effects 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- WBWXVCMXGYSMQA-UHFFFAOYSA-N 3,9-bis[2,4-bis(2-phenylpropan-2-yl)phenoxy]-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane Chemical compound C=1C=C(OP2OCC3(CO2)COP(OC=2C(=CC(=CC=2)C(C)(C)C=2C=CC=CC=2)C(C)(C)C=2C=CC=CC=2)OC3)C(C(C)(C)C=2C=CC=CC=2)=CC=1C(C)(C)C1=CC=CC=C1 WBWXVCMXGYSMQA-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- FRCLQKLLFQYUJJ-UHFFFAOYSA-N P(O)(O)O.P(O)(O)O.C(C)(C)(C)C1=C(C(=CC(=C1)C)C(C)(C)C)C(O)(C(CO)(CO)CO)C1=C(C=C(C=C1C(C)(C)C)C)C(C)(C)C Chemical compound P(O)(O)O.P(O)(O)O.C(C)(C)(C)C1=C(C(=CC(=C1)C)C(C)(C)C)C(O)(C(CO)(CO)CO)C1=C(C=C(C=C1C(C)(C)C)C)C(C)(C)C FRCLQKLLFQYUJJ-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical group CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- 239000001361 adipic acid Substances 0.000 description 2
- 235000011037 adipic acid Nutrition 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 229910052787 antimony Inorganic materials 0.000 description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 2
- UJMDYLWCYJJYMO-UHFFFAOYSA-N benzene-1,2,3-tricarboxylic acid Chemical group OC(=O)C1=CC=CC(C(O)=O)=C1C(O)=O UJMDYLWCYJJYMO-UHFFFAOYSA-N 0.000 description 2
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical group OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical group 0.000 description 2
- 229960004106 citric acid Drugs 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 2
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 239000004310 lactic acid Chemical group 0.000 description 2
- 235000014655 lactic acid Nutrition 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical group OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 230000037048 polymerization activity Effects 0.000 description 2
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical group OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000002310 reflectometry Methods 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical group OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 2
- 125000003003 spiro group Chemical group 0.000 description 2
- 230000001629 suppression Effects 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- GGUBFICZYGKNTD-UHFFFAOYSA-N triethyl phosphonoacetate Chemical compound CCOC(=O)CP(=O)(OCC)OCC GGUBFICZYGKNTD-UHFFFAOYSA-N 0.000 description 2
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical group OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- FEODVXCWZVOEIR-UHFFFAOYSA-N (2,4-ditert-butylphenyl) octyl hydrogen phosphite Chemical compound CCCCCCCCOP(O)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C FEODVXCWZVOEIR-UHFFFAOYSA-N 0.000 description 1
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical group OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- RGASRBUYZODJTG-UHFFFAOYSA-N 1,1-bis(2,4-ditert-butylphenyl)-2,2-bis(hydroxymethyl)propane-1,3-diol dihydroxyphosphanyl dihydrogen phosphite Chemical compound OP(O)OP(O)O.C(C)(C)(C)C1=C(C=CC(=C1)C(C)(C)C)C(O)(C(CO)(CO)CO)C1=C(C=C(C=C1)C(C)(C)C)C(C)(C)C RGASRBUYZODJTG-UHFFFAOYSA-N 0.000 description 1
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- BPZIYBJCZRUDEG-UHFFFAOYSA-N 2-[3-(1-hydroxy-2-methylpropan-2-yl)-2,4,8,10-tetraoxaspiro[5.5]undecan-9-yl]-2-methylpropan-1-ol Chemical compound C1OC(C(C)(CO)C)OCC21COC(C(C)(C)CO)OC2 BPZIYBJCZRUDEG-UHFFFAOYSA-N 0.000 description 1
- ZUZKLIUNFZHSJB-UHFFFAOYSA-N 2-[carboxy(carboxymethyl)amino]acetic acid Chemical compound OC(=O)CN(C(O)=O)CC(O)=O ZUZKLIUNFZHSJB-UHFFFAOYSA-N 0.000 description 1
- GGJBWKXZCQRJAV-UHFFFAOYSA-N 2-[carboxymethyl(2-methoxyethyl)amino]acetic acid Chemical compound COCCN(CC(O)=O)CC(O)=O GGJBWKXZCQRJAV-UHFFFAOYSA-N 0.000 description 1
- MSYNCHLYGJCFFY-UHFFFAOYSA-B 2-hydroxypropane-1,2,3-tricarboxylate;titanium(4+) Chemical compound [Ti+4].[Ti+4].[Ti+4].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O MSYNCHLYGJCFFY-UHFFFAOYSA-B 0.000 description 1
- TXPKUUXHNFRBPS-UHFFFAOYSA-N 3-(2-carboxyethylamino)propanoic acid Chemical compound OC(=O)CCNCCC(O)=O TXPKUUXHNFRBPS-UHFFFAOYSA-N 0.000 description 1
- OINWUNFJHGRRPU-UHFFFAOYSA-N 3-[2-carboxyethyl(2-hydroxyethyl)amino]propanoic acid Chemical compound OC(=O)CCN(CCO)CCC(O)=O OINWUNFJHGRRPU-UHFFFAOYSA-N 0.000 description 1
- OZPCFHQGYPXBGG-UHFFFAOYSA-N 3-[2-carboxyethyl(carboxymethyl)amino]propanoic acid Chemical compound OC(=O)CCN(CC(O)=O)CCC(O)=O OZPCFHQGYPXBGG-UHFFFAOYSA-N 0.000 description 1
- IWTIBPIVCKUAHK-UHFFFAOYSA-N 3-[bis(2-carboxyethyl)amino]propanoic acid Chemical compound OC(=O)CCN(CCC(O)=O)CCC(O)=O IWTIBPIVCKUAHK-UHFFFAOYSA-N 0.000 description 1
- HTUUWXZWNIEGLB-UHFFFAOYSA-N 3-acetyl-1,3-di(propan-2-yloxy)pentane-2,4-dione Chemical compound CC(C)OCC(=O)C(C(C)=O)(C(C)=O)OC(C)C HTUUWXZWNIEGLB-UHFFFAOYSA-N 0.000 description 1
- JSVDMQKVGLGYCM-UHFFFAOYSA-N 5,5-dimethyl-2-phenoxy-1,3,2-dioxaphosphinane Chemical compound O1CC(C)(C)COP1OC1=CC=CC=C1 JSVDMQKVGLGYCM-UHFFFAOYSA-N 0.000 description 1
- 239000004251 Ammonium lactate Substances 0.000 description 1
- 208000023514 Barrett esophagus Diseases 0.000 description 1
- 229920002799 BoPET Polymers 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- YASYEJJMZJALEJ-UHFFFAOYSA-N Citric acid monohydrate Chemical compound O.OC(=O)CC(O)(C(O)=O)CC(O)=O YASYEJJMZJALEJ-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical group OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- WRQNANDWMGAFTP-UHFFFAOYSA-N Methylacetoacetic acid Chemical group COC(=O)CC(C)=O WRQNANDWMGAFTP-UHFFFAOYSA-N 0.000 description 1
- JYXGIOKAKDAARW-UHFFFAOYSA-N N-(2-hydroxyethyl)iminodiacetic acid Chemical compound OCCN(CC(O)=O)CC(O)=O JYXGIOKAKDAARW-UHFFFAOYSA-N 0.000 description 1
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Chemical group OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Chemical group [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- ORLQHILJRHBSAY-UHFFFAOYSA-N [1-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1(CO)CCCCC1 ORLQHILJRHBSAY-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001334 alicyclic compounds Chemical class 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229940059265 ammonium lactate Drugs 0.000 description 1
- 235000019286 ammonium lactate Nutrition 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- FAWGZAFXDJGWBB-UHFFFAOYSA-N antimony(3+) Chemical compound [Sb+3] FAWGZAFXDJGWBB-UHFFFAOYSA-N 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- RZOBLYBZQXQGFY-HSHFZTNMSA-N azanium;(2r)-2-hydroxypropanoate Chemical compound [NH4+].C[C@@H](O)C([O-])=O RZOBLYBZQXQGFY-HSHFZTNMSA-N 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical group O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 229960002303 citric acid monohydrate Drugs 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000005094 computer simulation Methods 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 229940051043 cresylate Drugs 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- GLOQRSIADGSLRX-UHFFFAOYSA-N decyl diphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OCCCCCCCCCC)OC1=CC=CC=C1 GLOQRSIADGSLRX-UHFFFAOYSA-N 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- GGCUUOGRTPMFQK-UHFFFAOYSA-N dimethyl cyclohexane-1,1-dicarboxylate Chemical compound COC(=O)C1(C(=O)OC)CCCCC1 GGCUUOGRTPMFQK-UHFFFAOYSA-N 0.000 description 1
- LNGAGQAGYITKCW-UHFFFAOYSA-N dimethyl cyclohexane-1,4-dicarboxylate Chemical compound COC(=O)C1CCC(C(=O)OC)CC1 LNGAGQAGYITKCW-UHFFFAOYSA-N 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- GWZCCUDJHOGOSO-UHFFFAOYSA-N diphenic acid Chemical compound OC(=O)C1=CC=CC=C1C1=CC=CC=C1C(O)=O GWZCCUDJHOGOSO-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- ZUNGGJHBMLMRFJ-UHFFFAOYSA-O ethoxy-hydroxy-oxophosphanium Chemical compound CCO[P+](O)=O ZUNGGJHBMLMRFJ-UHFFFAOYSA-O 0.000 description 1
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical group CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical compound OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 229940001447 lactate Drugs 0.000 description 1
- 150000003893 lactate salts Chemical group 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 229940099690 malic acid Drugs 0.000 description 1
- 229940071125 manganese acetate Drugs 0.000 description 1
- 229940082328 manganese acetate tetrahydrate Drugs 0.000 description 1
- 150000002697 manganese compounds Chemical class 0.000 description 1
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 1
- 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 1
- 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 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
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical group CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- AXRSHKZFNKUGQB-UHFFFAOYSA-N octyl diphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OCCCCCCCC)OC1=CC=CC=C1 AXRSHKZFNKUGQB-UHFFFAOYSA-N 0.000 description 1
- 238000006384 oligomerization reaction Methods 0.000 description 1
- 239000011146 organic particle Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Chemical group OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 1
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- OGHBATFHNDZKSO-UHFFFAOYSA-N propan-2-olate Chemical compound CC(C)[O-] OGHBATFHNDZKSO-UHFFFAOYSA-N 0.000 description 1
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical compound CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000011975 tartaric acid Chemical group 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 229960001367 tartaric acid Drugs 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
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 1
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 description 1
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 1
- MGMXGCZJYUCMGY-UHFFFAOYSA-N tris(4-nonylphenyl) phosphite Chemical compound C1=CC(CCCCCCCCC)=CC=C1OP(OC=1C=CC(CCCCCCCCC)=CC=1)OC1=CC=C(CCCCCCCCC)C=C1 MGMXGCZJYUCMGY-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- PXXNTAGJWPJAGM-UHFFFAOYSA-N vertaline Natural products C1C2C=3C=C(OC)C(OC)=CC=3OC(C=C3)=CC=C3CCC(=O)OC1CC1N2CCCC1 PXXNTAGJWPJAGM-UHFFFAOYSA-N 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Polyesters Or Polycarbonates (AREA)
Description
本発明は、脂環族ジカルボン酸成分および脂環族ジオール成分を含有する耐熱性の劣るポリエステル樹脂組成物の製造方法の改良技術に関するものである。 The present invention relates to a technique for improving a method for producing a polyester resin composition having poor heat resistance, which contains an alicyclic dicarboxylic acid component and an alicyclic diol component.
脂環族成分を含有するポリエステルは、ポリエチレンテレフタレート（以下ＰＥＴ）などの芳香族ポリエステルとは異なった光学特性、結晶化特性、機械特性を有しており、該ポリエステル単独で、または芳香族ポリエステルと組み合わせて使用される。 Polyester containing an alicyclic component has optical properties, crystallization properties, and mechanical properties different from those of aromatic polyesters such as polyethylene terephthalate (hereinafter referred to as PET). Used in combination.
例えば、特許文献１では、環状アセタール骨格を有したポリエステル樹脂組成物に対して、リン系酸化防止剤等を配合させたポリエステル樹脂が、特許文献２では、チタン化合物の存在下でエステル交換反応を進め、黄色度が小さいポリエステル樹脂を得る製造方法が示されている。 For example, in Patent Document 1, a polyester resin in which a phosphorus-based antioxidant or the like is blended with a polyester resin composition having a cyclic acetal skeleton, a transesterification reaction is performed in Patent Document 2 in the presence of a titanium compound. A manufacturing method for obtaining a polyester resin with a low yellowness is shown.
しかしながら、特許文献１では、アンチモン触媒にてポリエステル樹脂を製造し、その後にリン系酸化防止剤をブレンド・混練するものであり、ポリエステル樹脂製造中におけるアンチモン触媒による脂環族成分の開裂等によるゲル化（高架橋化）の問題には対応できない。また、特許文献２ではチタン化合物をエステル交換などのオリゴマー化工程に存在させて脂環族成分をポリエステル樹脂に共重合させることで黄色度が小さく、昇華物の少ないポリマーが得られることについて記載されているが、チタン化合物を使用することによりゲル化はある程度抑制されるものの、重縮合反応中に３価のリン化合物を添加していないため重縮合反応中にゲル化が発生したり、リン化合物を重縮合反応前に添加しているため、重縮合触媒が失活しない程度の量しかリン化合物を添加することができず、ポリエステル樹脂を製造後、長期的にフィルムを製造する等の後工程において、熱劣化により脂環族成分の開裂等が起こるためゲル化抑制としては不十分である。
本発明の目的は、上記した従来の課題を解決し、熱安定性に優れた脂環族成分含有ポリエステル樹脂組成物の製造方法を提供することにある。 An object of the present invention is to solve the above-described conventional problems and to provide a method for producing an alicyclic component-containing polyester resin composition excellent in thermal stability.
前記した本発明の目的は、少なくとも脂環族ジカルボン酸成分および脂環族ジオール成分を含む下記式（１）〜（４）を満足するポリエステル樹脂組成物を製造するに際して、重縮合触媒としてチタン化合物、酸化防止剤として３価のリン化合物を含有せしめて重縮合反応を行い、重縮合反応終了後、更に３価のリン化合物を混練することを特徴とするポリエステル樹脂組成物の製造方法によって達成される。 An object of the present invention described above is to produce a titanium compound as a polycondensation catalyst when producing a polyester resin composition satisfying the following formulas (1) to (4) containing at least an alicyclic dicarboxylic acid component and an alicyclic diol component. And a polycondensation reaction by adding a trivalent phosphorus compound as an antioxidant, and after completion of the polycondensation reaction, the trivalent phosphorus compound is further kneaded. The
６５℃≦示差走査熱量測定によるガラス転移点温度≦８６℃・・・（１）
１．５００≦ナトリウムＤ線での屈折率≦１．５７０・・・（２）
０．５≦チタン元素≦５０ｐｐｍ・・・（３）
２０７≦リン元素≦１０００ｐｐｍ・・・（４）
65 ° C. ≦ Glass transition temperature by differential scanning calorimetry ≦ 86 ° C. (1)
1.500 ≦ refractive index at sodium D line ≦ 1.570 (2)
0.5 ≦ Titanium element ≦ 50 ppm (3)
207 ≦ Phosphorus Element ≦ 1000 ppm (4)
本発明によれば、重合触媒としてチタン化合物、酸化防止剤として３価のリン化合物を用いることで、重縮合反応中での脂環族成分の解裂によるゲル等の発生が少なく、また、重縮合反応後においても３価のリン化合物を多量に混練しているため、長期間にわたってフィルム等を製造する場合に熱安定性に優れたゲルの少ない脂環族成分含有ポリエステル樹脂成型体を製造することができる。 According to the present invention, by using a titanium compound as a polymerization catalyst and a trivalent phosphorus compound as an antioxidant, there is little occurrence of gel or the like due to the cleavage of the alicyclic component during the polycondensation reaction, Since the trivalent phosphorus compound is kneaded in a large amount even after the condensation reaction, an alicyclic component-containing polyester resin molded article with less gel and excellent thermal stability is produced when a film or the like is produced over a long period of time. be able to.
本発明によるポリエステル樹脂組成物の製造方法は、液晶ディスプレイに好適な低光弾性係数を有したポリエステル樹脂組成物を得ることができ、また光反射性に優れた積層ポリエステルフィルムを得ることができる。 The method for producing a polyester resin composition according to the present invention can obtain a polyester resin composition having a low photoelastic coefficient suitable for a liquid crystal display, and can obtain a laminated polyester film excellent in light reflectivity.
本発明のポリエステル樹脂組成物の製造方法は、少なくとも脂環族ジカルボン酸成分および脂環族ジオール成分を含む下記式（１）〜（４）を満足するポリエステル樹脂組成物を製造するに際して、重縮合触媒としてチタン化合物、酸化防止剤として３価のリン化合物を含有せしめて重縮合反応を行い、重縮合反応終了後、更に３価のリン化合物を混練することを特徴とするポリエステル樹脂組成物の製造方法である。 The method for producing a polyester resin composition of the present invention comprises polycondensation in producing a polyester resin composition satisfying the following formulas (1) to (4) containing at least an alicyclic dicarboxylic acid component and an alicyclic diol component. Production of a polyester resin composition characterized by containing a titanium compound as a catalyst and a trivalent phosphorus compound as an antioxidant and conducting a polycondensation reaction, and further kneading the trivalent phosphorus compound after completion of the polycondensation reaction. Is the method.
６５℃≦示差走査熱量測定によるガラス転移点温度≦８６℃・・・（１）
１．５００≦ナトリウムＤ線での屈折率≦１．５７０・・・（２）
０．５≦チタン元素≦５０ｐｐｍ・・・（３）
２０７≦リン元素≦１０００ｐｐｍ・・・（４）
本発明の製造方法によるポリエステル樹脂組成物は、ガラス転移点温度（以下Ｔｇ）が６５℃から８６℃の範囲にあることが必要である。
65 ° C. ≦ Glass transition temperature by differential scanning calorimetry ≦ 86 ° C. (1)
1.500 ≦ refractive index at sodium D line ≦ 1.570 (2)
0.5 ≦ Titanium element ≦ 50 ppm (3)
207 ≦ Phosphorus Element ≦ 1000 ppm (4)
The polyester resin composition according to the production method of the present invention needs to have a glass transition temperature (hereinafter referred to as Tg) in the range of 65 ° C to 86 ° C.
Ｔｇが６５℃未満の場合、耐熱性が不足するため、本製造方法によって得られたポリエステル樹脂組成物またはその成形体の光学特性が経時変化しやすく、またポリエチレンテレフタレート等と積層製膜する際には積層樹脂間のＴｇ差が大きくなるために積層ムラ等発生し、製膜安定性が損なわれる。積層フィルムとする場合、本発明の製造方法によって得られるポリエステル樹脂のＴｇを積層ポリマーのＴｇと合致させることが好ましく、積層ポリマーのＴｇ（Ｔｇ１）と本発明におけるポリエステル樹脂のＴｇ（Ｔｇ２）の差（｜Ｔｇ１−Ｔｇ２｜）が１０℃以内、さらには５℃以内であることが好ましい。 When the Tg is less than 65 ° C., the heat resistance is insufficient, so that the optical properties of the polyester resin composition obtained by the present production method or the molded product thereof are likely to change with time, and when the laminated film is formed with polyethylene terephthalate or the like. However, since the Tg difference between the laminated resins becomes large, unevenness of the lamination occurs, and the film forming stability is impaired. In the case of a laminated film, it is preferable to match the Tg of the polyester resin obtained by the production method of the present invention with the Tg of the laminated polymer, and the difference between the Tg (Tg1) of the laminated polymer and the Tg (Tg2) of the polyester resin in the present invention. (| Tg1-Tg2 |) is preferably within 10 ° C., more preferably within 5 ° C.
Ｔｇが８６℃を超える場合には、ＰＥＴ等を積層する際にＴｇ差が大きくなりすぎるために、上記同様、積層ムラ等が発生し、製膜安定性が損なわれ、またポリエステル樹脂の屈折率を低くすることが困難になってくる。よって本発明におけるポリエステル樹脂のＴｇは、７０以上の範囲が好ましく、さらには７５〜８５℃の範囲が好ましい。 When the Tg exceeds 86 ° C., the Tg difference becomes too large when laminating PET and the like, and as described above, laminating unevenness and the like occur, film formation stability is impaired, and the refractive index of the polyester resin. It will be difficult to lower. Therefore, the Tg of the polyester resin in the present invention is preferably in the range of 70 or more , and more preferably in the range of 75 to 85 ° C.
本発明の製造方法によって得られるポリエステル樹脂の屈折率については、１．５００〜１．５７０の範囲にあることが必要である。屈折率を１．５００未満とすることはポリエステル樹脂では困難であり、１．５７０を超える場合には、積層ポリマーとの屈折率差が小さくなるため、得られた積層フィルムの光反射性が小さくなる。さらに本発明の製造方法によって得られるポリエステル樹脂の屈折率は、１．５１０〜１．５６０の範囲であることが好ましい。なお、本発明における屈折率は、２３℃の条件にてナトリウムＤ線を用いて測定した屈折率を指す。 About the refractive index of the polyester resin obtained by the manufacturing method of this invention, it needs to exist in the range of 1.500-1.570. It is difficult for a polyester resin to have a refractive index of less than 1.500. When the refractive index exceeds 1.570, the difference in refractive index from the laminated polymer is small, so that the resulting film has low light reflectivity. Become. Furthermore, the refractive index of the polyester resin obtained by the production method of the present invention is preferably in the range of 1.510 to 1.560. In addition, the refractive index in this invention points out the refractive index measured using the sodium D line | wire on 23 degreeC conditions.
本発明の製造方法では、前記した特性を与えるために、ポリエステル樹脂は少なくとも脂環族ジカルボン酸成分および脂環族ジオール成分を含むことが必要である。ポリエステル樹脂に含まれる芳香環はＴｇを高める効果があるが、同時に屈折率を高め、光弾性係数を高める効果がある。光弾性係数が大きい場合、フィルムに応力が作用した際に位相差が大きく変化するため、液晶ディスプレイ用途のフィルムには不適当である。 In the production method of the present invention, the polyester resin needs to contain at least an alicyclic dicarboxylic acid component and an alicyclic diol component in order to give the above-described properties. The aromatic ring contained in the polyester resin has the effect of increasing Tg, but at the same time has the effect of increasing the refractive index and increasing the photoelastic coefficient. When the photoelastic coefficient is large, the phase difference changes greatly when a stress is applied to the film, so that it is not suitable for a film for use in a liquid crystal display.
そこで、本発明では、この芳香環成分を脂環族ジカルボン酸成分や脂環族ジオールで置換することにより、屈折率や光弾性係数を低減させている。本発明における脂環族ジカルボン酸成分としては、シクロヘキサンジカルボン酸成分やデカリンジカルボン酸成分等を挙げることができる。特に入手の容易性や重合反応性の観点からはシクロヘキサンジカルボン酸成分が好ましい。シクロヘキサンジカルボン酸成分は、シクロヘキサンジカルボン酸やそのエステルを原料として用いることができる。 Therefore, in the present invention, the refractive index and the photoelastic coefficient are reduced by substituting this aromatic ring component with an alicyclic dicarboxylic acid component or an alicyclic diol. Examples of the alicyclic dicarboxylic acid component in the present invention include a cyclohexane dicarboxylic acid component and a decalin dicarboxylic acid component. In particular, a cyclohexanedicarboxylic acid component is preferable from the viewpoint of availability and polymerization reactivity. As the cyclohexanedicarboxylic acid component, cyclohexanedicarboxylic acid or an ester thereof can be used as a raw material.
なお、シクロヘキサンジカルボン酸成分など脂環族成分には立体異性体として、シス体、トランス体が存在するが、本発明ではトランス体比率が４０％以下であることが好ましい。トランス体比率が高いと光弾性係数が大きくなるため劣る傾向にある。また、トランス体は、シス体に比べ、融点が高いため、トランス体比率が高くなると、室温程度で保管、または、輸送中等に、容易に凝固し、沈降してしまい、不均一となり反応性が悪くなるだけでなく、取り扱い上においても作業性が悪くなる。よって、トランス体比率は、好ましくは、３５％以下、より好ましくは、３０％以下である。 The alicyclic component such as the cyclohexanedicarboxylic acid component includes a cis isomer and a trans isomer as stereoisomers. In the present invention, the trans isomer ratio is preferably 40% or less. If the ratio of the transformer body is high, the photoelastic coefficient tends to be large, so that it tends to be poor. In addition, since the trans isomer has a higher melting point than the cis isomer, if the trans isomer ratio is high, it easily coagulates and settles during storage at room temperature or during transportation, resulting in heterogeneity and reactivity. Not only is it worse, but workability is also worse in handling. Therefore, the trans isomer ratio is preferably 35% or less, and more preferably 30% or less.
本発明における脂環族ジオールとしては、スピログリコール成分やイソソルビド成分が好ましく、特に得られるポリエステルの色調の観点からスピログリコール成分が好ましい。ここでスピログリコールとは３，９−ビス（２−ヒドロキシ−１，１−ジメチルエチル）−２，４，８，１０−テトラオキサスピロ［５，５］ウンデカンを指す。 As an alicyclic diol in this invention, a spiroglycol component and an isosorbide component are preferable, and a spiroglycol component is preferable from a viewpoint of the color tone of the polyester obtained especially. Here, spiroglycol refers to 3,9-bis (2-hydroxy-1,1-dimethylethyl) -2,4,8,10-tetraoxaspiro [5,5] undecane.
本発明において、例えばＰＥＴの場合、テレフタル酸成分（芳香環成分）をシクロヘキサンジカルボン酸等で置換するとＴｇが低下する。そこでスピログリコール成分やイソソルビド成分など脂環族ジオール成分をエチレングリコール成分に置換することでＴｇが上昇し、結果として本発明のポリエステル組成物と積層するＰＥＴと同程度のＴｇに調整することができる。Ｔｇを上昇させる効果はスピログリコール成分やイソソルビド成分において顕著である。 In the present invention, for example, in the case of PET, Tg decreases when the terephthalic acid component (aromatic ring component) is substituted with cyclohexanedicarboxylic acid or the like. Then, Tg rises by substituting alicyclic diol components, such as a spiroglycol component and an isosorbide component, with an ethylene glycol component, and as a result, it can be adjusted to Tg comparable to PET laminated | stacked with the polyester composition of this invention. . The effect of increasing Tg is significant in spiroglycol components and isosorbide components.
本発明のポリエステル樹脂組成物は、ゲル化率が５０％以下であるポリエステル樹脂組成物を得ることができる。ゲル化率とは、ポリエステル樹脂組成物を大気下、３００℃×２．５ｈｒの条件で加熱処理後、オルト―クロロフェノール不溶物重量の全体に対する割合である。スピログリコールを共重合したポリエステル樹脂組成物は、スピロ環を有することから、酸性、水分含有下、熱により分解してゲル化する特徴がある。よって、このゲル化率が５０％以上の場合、ポリエステル樹脂組成物が著しくゲル化しやすいポリマーであることを意味し、例えば、重縮合後、ストランド状に吐出する際に、形状がフシ糸状となって、カッターでカッティングできなくなることや製膜する際のフィルター濾過工程で多量のゲルにより濾圧が異常に上昇したり、積層フィルムの表面欠点が増加したり、多層積層フィルムの積層厚みが変動する等の問題を生じることがある。 The polyester resin composition of the present invention can provide a polyester resin composition having a gelation rate of 50% or less. The gelation rate is a ratio of the weight of the ortho-chlorophenol insoluble matter after heat treatment of the polyester resin composition under the conditions of 300 ° C. × 2.5 hr in the air. Since the polyester resin composition copolymerized with spiroglycol has a spiro ring, it has the characteristic of being decomposed by heat and gelation under the presence of acidity and moisture. Therefore, when the gelation rate is 50% or more, it means that the polyester resin composition is a polymer that is remarkably easily gelled. For example, when the polyester resin composition is discharged into a strand after polycondensation, the shape becomes fussy. In addition, it becomes impossible to cut with a cutter, the filtration pressure increases abnormally due to a large amount of gel in the filter filtration process when forming a film, the surface defect of the laminated film increases, and the laminated thickness of the multilayer laminated film varies May cause problems.
本発明の製造方法では、ゲル化の抑制の観点から、反応活性が高く少量で重縮合反応できるチタン化合物を用いることが好ましく、チタン元素として０．５〜５０ｐｐｍ含有することが必要である。５０ｐｐｍを越える場合は、含有する金属量が増えることからゲル化が促進されたり、色調ｂ値が著しく高くなる。また、０．５ｐｐｍ未満の場合は、重合活性が十分でないため、目標のＩＶまで到達しないことや結果的に高温下での滞留時間が長くなることでゲル化が促進されるため好ましくない。よって、チタン原子の含有量は、好ましくは３〜４０ｐｐｍ、より好ましくは５〜３０ｐｐｍである。 In the production method of the present invention, from the viewpoint of suppression of gelation, it is preferable to use a titanium compound having a high reaction activity and capable of polycondensation reaction in a small amount, and it is necessary to contain 0.5 to 50 ppm as a titanium element. If it exceeds 50 ppm, the amount of metal contained increases, so that gelation is promoted and the color tone b value is remarkably increased. On the other hand, if it is less than 0.5 ppm, the polymerization activity is not sufficient, so that the target IV is not reached, and as a result, the residence time at a high temperature is prolonged, which is not preferable because gelation is promoted. Therefore, the content of titanium atoms is preferably 3 to 40 ppm, more preferably 5 to 30 ppm.
本発明のポリエステル樹脂組成物において、重縮合用触媒としてのチタン化合物の置換基がアルコキシ基、フェノキシ基、アシレート基、アミノ基、水酸基の少なくとも１種であるチタン化合物が好ましく用いられる。 In the polyester resin composition of the present invention, a titanium compound in which the substituent of the titanium compound as the polycondensation catalyst is at least one of an alkoxy group, a phenoxy group, an acylate group, an amino group, and a hydroxyl group is preferably used.
具体的なアルコキシ基には、テトラエトキシド、テトラプロポキシド、テトライソプロポキシド、テトラブトキシド、テトラ−２−エチルヘキソキシド等のチタンテトラアルコキシド、アセチルアセトン等のβ−ジケトン系官能基、乳酸、リンゴ酸、酒石酸、サリチル酸、クエン酸等のヒドロキシ多価カルボン酸系官能基、アセト酢酸メチル、アセト酢酸エチル等のケトエステル系官能基が挙げられ、特に脂肪族アルコキシ基が好ましい。また、フェノキシ基には、フェノキシ、クレシレイト等が挙げられる。また、アシレート基には、ラクテート、ステアレート等のテトラアシレート基、フタル酸、トリメリット酸、トリメシン酸、ヘミメリット酸、ピロメリット酸、シュウ酸、マロン酸、コハク酸、グルタル酸、アジピン酸、セバシン酸、マレイン酸、フマル酸、シクロヘキサンジカルボン酸またはそれらの無水物等の多価カルボン酸系官能基、エチレンジアミン四酢酸、ニトリロ三プロピオン酸、カルボキシイミノ二酢酸、カルボキシメチルイミノ二プロピオン酸、ジエチレントリアミノ五酢酸、トリエチレンテトラミノ六酢酸、イミノ二酢酸、イミノ二プロピオン酸、ヒドロキシエチルイミノ二酢酸、ヒドロキシエチルイミノ二プロピオン酸、メトキシエチルイミノ二酢酸等の含窒素多価カルボン酸系官能基が挙げられ、特に脂肪族アシレート基が好ましい。また、アミノ基には、アニリン、フェニルアミン、ジフェニルアミン等が挙げられる。また、これらの置換基を２種含んでなるジイソプロポキシビスアセチルアセトンやトリエタノールアミネートイソプロポキシド等が挙げられる。 Specific alkoxy groups include tetraethoxide, tetrapropoxide, tetraisopropoxide, tetrabutoxide, titanium tetraalkoxide such as tetra-2-ethylhexoxide, β-diketone functional groups such as acetylacetone, lactic acid, Examples include hydroxy polyvalent carboxylic acid functional groups such as malic acid, tartaric acid, salicylic acid, citric acid, and ketoester functional groups such as methyl acetoacetate and ethyl acetoacetate, with aliphatic alkoxy groups being particularly preferred. Examples of the phenoxy group include phenoxy and cresylate. The acylate groups include tetraacylate groups such as lactate and stearate, phthalic acid, trimellitic acid, trimesic acid, hemimellitic acid, pyromellitic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid , Functional groups of polycarboxylic acids such as sebacic acid, maleic acid, fumaric acid, cyclohexanedicarboxylic acid or their anhydrides, ethylenediaminetetraacetic acid, nitrilotripropionic acid, carboxyiminodiacetic acid, carboxymethyliminodipropionic acid, diethylenetria Nitrogenous polyvalent carboxylic acid functional groups such as minopentaacetic acid, triethylenetetraminohexaacetic acid, iminodiacetic acid, iminodipropionic acid, hydroxyethyliminodiacetic acid, hydroxyethyliminodipropionic acid, methoxyethyliminodiacetic acid Especially aliphatic asylum Group is preferred. Examples of the amino group include aniline, phenylamine, diphenylamine and the like. Further, diisopropoxybisacetylacetone and triethanolaminate isopropoxide containing two kinds of these substituents can be mentioned.
本発明の製造方法において、前記チタン触媒は、重合反応器内の減圧を始める前に反応系へ添加させることが好ましい。しかしながら、ジカルボン酸成分とグリコール成分からエステル交換反応やエステル化反応によって低重合体を製造する段階においては、チタン触媒は存在させない方が好ましい。低重合体を得る反応前または反応中にチタン触媒を添加した場合、チタン触媒に起因した微細粒子が発生し、得られたポリエステル樹脂に濁りが発生するため好ましくない。チタン触媒の添加時期は、低重合体を得るエステル交換反応やエステル化反応が実質的に終了した後から反応容器内を減圧する前の間を選択することが最も好ましい。 In the production method of the present invention, the titanium catalyst is preferably added to the reaction system before depressurization in the polymerization reactor is started. However, it is preferable that no titanium catalyst be present in the step of producing a low polymer from the dicarboxylic acid component and the glycol component by transesterification or esterification reaction. When a titanium catalyst is added before or during the reaction for obtaining a low polymer, fine particles resulting from the titanium catalyst are generated, and turbidity is generated in the obtained polyester resin. Most preferably, the timing of addition of the titanium catalyst is selected after the transesterification reaction or esterification reaction for obtaining the low polymer is substantially completed and before the pressure in the reaction vessel is reduced.
本発明において、得られるポリエステル樹脂組成物は、リン化合物をリン元素換算で２０７〜１０００ｐｐｍ含有することが必要である。リン化合物の含有量がリン元素換算で２０７ｐｐｍ未満である場合、ポリエステル樹脂組成物の熱安定性は不足しており、重縮合反応中に熱劣化異物を発生させたり、長期間におよんで製膜する際に熱劣化物がフィルム欠点として発生する。一方、リン化合物の含有量がリン元素換算で１０００ｐｐｍを超える場合、反応触媒等と反応して内部粒子を生成し、フィルムの欠点となったり、ヘイズが高くなってしまう。 In the present invention, the obtained polyester resin composition needs to contain 207 to 1000 ppm of a phosphorus compound in terms of phosphorus element. When the content of the phosphorus compound is less than 207 ppm in terms of phosphorus element, the polyester resin composition has insufficient thermal stability, and heat-deteriorated foreign matter is generated during the polycondensation reaction, or the product is produced over a long period of time. When the film is formed, a thermally deteriorated product is generated as a film defect. On the other hand, when the content of the phosphorus compound exceeds 1000 ppm in terms of phosphorus element, it reacts with a reaction catalyst or the like to generate internal particles, resulting in a film defect or increased haze.
本発明において、使用されるリン化合物は、３価のリン元素であることが必要である。３価のリン化合物は、ポリエステル樹脂組成物の重縮合反応中における熱劣化を抑制する効果や色調を改善させる効果が大きい。 In the present invention, the phosphorus compound to be used needs to be a trivalent phosphorus element. The trivalent phosphorus compound has a great effect of suppressing thermal deterioration and improving the color tone during the polycondensation reaction of the polyester resin composition.
このような３価のリン化合物として、例えば亜リン酸エステル、ジアリール亜ホスフィン酸アルキル、ジアリール亜ホスフィン酸アリール、アリール亜ホスホン酸ジアルキル、アリール亜ホスホン酸ジアリールを挙げることができ、具体的にはトリフェニルホスファイト、トリス（４−モノノニルフェニル）ホスファイト、トリ（モノノニル／ジノニル・フェニル）ホスファイト、トリス（２，４−ジ−ｔｅｒｔ−ブチルフェニル）ホスファイト、モノオクチルジフェニルホスファイト、モノデシルジフェニルホスファイト、ビス［２，４−（ビス１，１−ジメチルエチル）−６−メチルフェニル］エチルホスファイト、テトラキス（２，４−ジ−ｔｅｒｔ−ブチルフェニル）４，４’−ビフェニレンジホスファイト、トリス（２，４−ジ−ｔｅｒｔ−ブチルフェニル）ホスファイト、ビス（２，６−ジ−ｔｅｒｔ−ブチル−４−メチルフェニル）ペンタエリスリトール−ジ−ホスファイト、ビス（２，４−ジ−ｔｅｒｔ−ブチルフェニル）ペンタエリスリトール−ジ−ホスファイト、３，９―ビス（２，４−ジクミルフェノキシ）−２，４，８，１０−テトラオキサ−３，９−ジホスファスピロ［５．５］ウンデカン、フェニル−ネオペンチレングリコール−ホスファイト、２，２−メチレンビス（４，６−ジ−ｔｅｒｔ−ブチルフェニル）オクチルホスファイト、ビス（２，４―ジクミルフェニル）ペンタエリスリトールジフォスファイト、テトラ（Ｃ１２〜Ｃ１５アルキル）−４，４’−イソプロピリデンジフェニルジホスファイト等を挙げることができるがこれに限定されるものではない。 Examples of such trivalent phosphorus compounds include phosphites, alkyl diarylphosphites, aryl diarylphosphites, dialkylarylphosphonites, and arylarylphosphonites. Phenyl phosphite, tris (4-monononylphenyl) phosphite, tri (monononyl / dinonyl phenyl) phosphite, tris (2,4-di-tert-butylphenyl) phosphite, monooctyl diphenyl phosphite, monodecyl Diphenyl phosphite, bis [2,4- (bis1,1-dimethylethyl) -6-methylphenyl] ethyl phosphite, tetrakis (2,4-di-tert-butylphenyl) 4,4′-biphenylenediphos Fight, Tris (2,4-di- ert-butylphenyl) phosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol-di-phosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol-di Phosphite, 3,9-bis (2,4-dicumylphenoxy) -2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane, phenyl-neopentylene glycol phosphite 2,2-methylenebis (4,6-di-tert-butylphenyl) octyl phosphite, bis (2,4-dicumylphenyl) pentaerythritol diphosphite, tetra (C12-C15 alkyl) -4,4 ′ -Isopropylidene diphenyl diphosphite, etc. Not.
また、５価のリン化合物については、特に限定されないが、例えばリン酸系、亜リン酸系、ホスホン酸系、ホスフィン酸系化合物等を挙げることができ、中でもこれらのエステル化合物が、３価のリン化合物と併用して好ましく使用される。 The pentavalent phosphorus compound is not particularly limited, and examples thereof include phosphoric acid-based compounds, phosphorous acid-based compounds, phosphonic acid-based compounds, phosphinic acid-based compounds, and the like. It is preferably used in combination with a phosphorus compound.
３価のリン化合物の添加方法としては、通常一般的に実施されているエステル化もしくはエステル交換反応後、重縮合反応前に添加することに加えて、重縮合反応が終了したポリマーに別途混練機で練り込む必要がある。脂環族化合物を含む該ポリエステル樹脂組成物は、耐熱性が悪いため、ゲル化抑制の観点から重縮合触媒として、チタン化合物を使用している。しかし、このチタン化合物は、リン化合物の存在下、失活することが知られており、そのため、重縮合反応前の３価のリン化合物の添加量はおのずと制限され、チタン化合物の添加量で失活しない最大量の３価のリン化合物を、重縮合反応中のゲル化や熱劣化を抑制するために添加する必要がある。そして、重縮合反応前に添加できなかった３価のリン化合物については、製膜してフィルムにする際にフィルムの表面欠点等を発生させない程度の十分な量の３価のリン化合物量を、重縮反応後のポリマーに別途混練機を用いて練り込む必要がある。また、このような３価のリン化合物を多量に添加する際には、３価のリン化合物のポリマー中への分散性においても、重合反応装置内で添加するよりも、混練機で練り込む方が均一に分散され好ましい。 As a method for adding the trivalent phosphorus compound, in addition to the addition of the polycondensation reaction after the usual esterification or transesterification reaction and before the polycondensation reaction, a separate kneader is added to the polymer after the completion of the polycondensation reaction. It is necessary to knead with. Since the polyester resin composition containing an alicyclic compound has poor heat resistance, a titanium compound is used as a polycondensation catalyst from the viewpoint of suppressing gelation. However, this titanium compound is known to be deactivated in the presence of a phosphorus compound. Therefore, the amount of trivalent phosphorus compound added before the polycondensation reaction is naturally limited, and the amount of titanium compound added is lost. It is necessary to add the maximum amount of the trivalent phosphorus compound that is not activated in order to suppress gelation and thermal degradation during the polycondensation reaction. And about the trivalent phosphorus compound which could not be added before the polycondensation reaction, a sufficient amount of the trivalent phosphorus compound not to cause the surface defects of the film when the film is formed into a film, It is necessary to knead the polymer after the polycondensation reaction separately using a kneader. Further, when such a trivalent phosphorus compound is added in a large amount, the dispersibility of the trivalent phosphorus compound in the polymer is kneaded with a kneader rather than being added in the polymerization reactor. Is preferably dispersed uniformly.
ポリエステル樹脂組成物に、３価のリン化合物を混合、混練する方法は、種々公知の方法、例えばヘンシェルミキサー、Ｖ−ブレンダー、リボンブレンダー、タンブラーブレンダー等で混合した後、スクリューを有する押出機にて溶融混練することが好ましい。また、押出機については、このような非晶性のポリエステル化合物においては、乾燥・結晶化工程を必要としないベント式の混練押出機を使用することが好ましい。 The polyester resin composition is mixed and kneaded with a trivalent phosphorus compound by various known methods such as a Henschel mixer, a V-blender, a ribbon blender, a tumbler blender, etc., and then an extruder having a screw. It is preferable to melt and knead. As for the extruder, for such an amorphous polyester compound, it is preferable to use a vent type kneading extruder which does not require a drying / crystallization step.
本発明において、重合中のポリエステル樹脂の熱劣化、着色抑制の観点から重合温度は２６０〜２９０℃の出来るだけ低温で実施することが好ましい。重縮合温度とは、通常、２３０〜２４０℃から徐々に温度を上げていき、ある目標の温度に到達した後は一定の温度で重縮合するため、その最終の一定温度のことである。２９０℃より高い場合は、重合は促進されるものの、熱劣化物が発生しやすく、また、２６０℃より低い場合は、重合活性が落ち、重合時間が遅延することで熱劣化物が発生しやすいために好ましくない。 In the present invention, the polymerization temperature is preferably as low as possible, from 260 to 290 ° C., from the viewpoint of thermal degradation of the polyester resin during polymerization and suppression of coloring. The polycondensation temperature is usually the final constant temperature because the temperature is gradually raised from 230 to 240 ° C., and after reaching a certain target temperature, polycondensation is performed at a constant temperature. When it is higher than 290 ° C., polymerization is promoted, but heat-degraded products are likely to be generated. When it is lower than 260 ° C., polymerization activity is reduced, and heat-degraded products are likely to be generated by delaying the polymerization time. Therefore, it is not preferable.
本発明において、ポリエステル樹脂組成物は、屈折率や光弾性係数を低下させるために、ポリエステル樹脂組成物１ｋｇ中に含有される芳香環モル数を４．８モル以下とすることが好ましい。４．８モルを超える場合には屈折率や光弾性係数が増大する傾向にあるため好ましくない。なお、本発明における芳香環モル数とはベンゼン環モル数を基本単位としている。本発明における定義をＰＥＴとＰＥＮを例にして説明する。 In the present invention, the polyester resin composition preferably has a molar number of aromatic rings contained in 1 kg of the polyester resin composition of 4.8 mol or less in order to reduce the refractive index and the photoelastic coefficient. When it exceeds 4.8 mol, the refractive index and the photoelastic coefficient tend to increase, which is not preferable. The number of moles of aromatic rings in the present invention is based on the number of moles of benzene rings. The definition in the present invention will be described using PET and PEN as examples.
ＰＥＴの場合、基本繰り返し単位の分子量は１９２であるため、ポリマー１ｋｇ当たりの基本繰り返し単位数は５．２となる。基本繰り返し単位中にテレフタル酸成分（ベンゼン環１個相当）は１モル含まれるため、ＰＥＴの芳香環モル数は５．２と計算される。一方、ＰＥＮの場合、基本繰り返し単位の分子量は２４２であり、ポリマー１ｋｇ当たりの基本繰り返し単位数は４．１である。基本繰り返し単位中にナフタレンジカルボン酸成分は１モル含まれるが、ナフタレン環はベンゼン環２個に相当するため、ＰＥＮの芳香環モル数は８．２モルと計算する。 In the case of PET, since the molecular weight of the basic repeating unit is 192, the number of basic repeating units per kg of the polymer is 5.2. Since 1 mol of the terephthalic acid component (corresponding to one benzene ring) is contained in the basic repeating unit, the number of moles of aromatic ring of PET is calculated to be 5.2. On the other hand, in the case of PEN, the molecular weight of the basic repeating unit is 242 and the number of basic repeating units per kg of the polymer is 4.1. Although 1 mole of naphthalene dicarboxylic acid component is contained in the basic repeating unit, since the naphthalene ring corresponds to 2 benzene rings, the number of moles of aromatic ring of PEN is calculated as 8.2 moles.
本発明において、ポリエステル樹脂組成物は、少なくとも脂環族ジカルボン酸成分および脂環族ジオール成分を含むが、その他ジカルボン酸成分としては、２，６−ナフタレンジカルボン酸成分、テレフタル酸成分、イソフタル酸成分から選択される少なくとも一種のジカルボン酸成分を全ジカルボン酸成分に対して２０〜９５モル％含有することが好ましい。またグリコール成分については、エチレングリコール成分をグリコール成分として２０〜９５モル％含有することが好ましい。前記した芳香族ジカルボン酸成分が２０モル％未満の場合、Ｔｇを６５℃以上にすることが難しくなったり、例えばＰＥＴやＰＥＮと積層する際にはこれらの樹脂との層間接着性が悪化してくる。同様にエチレングリコール成分が２０モル％未満の場合、ＰＥＴやＰＥＮと積層した際、これらの樹脂との層間接着性が悪化してくる。一方、芳香族ジカルボン酸成分が９５モル％を超える場合、屈折率や光弾性係数を低減することが難しくなり、エチレングリコール成分が９５モル％を超える場合にはＴｇを６５℃以上にすることが難しくなる。 In the present invention, the polyester resin composition contains at least an alicyclic dicarboxylic acid component and an alicyclic diol component, and other dicarboxylic acid components include 2,6-naphthalenedicarboxylic acid component, terephthalic acid component, and isophthalic acid component. It is preferable to contain 20 to 95 mol% of at least one dicarboxylic acid component selected from among the total dicarboxylic acid components. Moreover, about a glycol component, it is preferable to contain 20-95 mol% of ethylene glycol components as a glycol component. When the above-mentioned aromatic dicarboxylic acid component is less than 20 mol%, it becomes difficult to make Tg 65 ° C. or higher, for example, when laminating with PET or PEN, the interlaminar adhesion with these resins deteriorates. come. Similarly, when the ethylene glycol component is less than 20 mol%, interlayer adhesion with these resins deteriorates when laminated with PET or PEN. On the other hand, when the aromatic dicarboxylic acid component exceeds 95 mol%, it is difficult to reduce the refractive index and the photoelastic coefficient. When the ethylene glycol component exceeds 95 mol%, the Tg may be 65 ° C. or higher. It becomes difficult.
本発明のポリエステル樹脂組成物において、脂環族ジカルボン酸成分、脂環族ジオールの含有量は、前記記載よりそれぞれ５〜８０モル％の範囲が好ましく、さらに８〜５０モル％が好ましい。 In the polyester resin composition of the present invention, the content of the alicyclic dicarboxylic acid component and the alicyclic diol is preferably in the range of 5 to 80 mol%, more preferably 8 to 50 mol% from the above description.
本発明において、ポリエステル樹脂組成物は、非晶性であることが好ましく、また前記した共重合範囲では実質的に非晶性である。本発明における非晶性とは、ＤＳＣ測定において融解熱量が４Ｊ／ｇ以下であることをいう。このような非晶性のポリエステル樹脂組成物はフィルム製造においてその光学特性が変化しにくく、好ましい。 In the present invention, the polyester resin composition is preferably amorphous, and is substantially amorphous within the above-described copolymerization range. The term “amorphous” in the present invention means that the heat of fusion is 4 J / g or less in DSC measurement. Such an amorphous polyester resin composition is preferable because its optical properties hardly change during film production.
本発明におけるポリエステル樹脂組成物に含有される芳香族ジカルボン酸成分は、前記した種類から少なくとも選択されるが、屈折率や光弾性係数の観点からテレフタル酸成分やイソフタル酸成分が好ましく、これらは同時に使用してもかわまない。特にテレフタル酸成分はその他ポリエステル樹脂組成物との接着性等の観点から主に使用することが好ましい。その他ジカルボン酸成分としては、特性の許す限り従来公知のものを共重合しても構わない、グリコール成分についても同様である。このような成分としては、例えばアジピン酸、セバシン酸等の脂肪族ジカルボン酸やそのエステル、４，４’−ビスフェニレンジカルボン酸、５−ソジウムスルホイソフタル酸、ジフェン酸等の芳香族ジカルボン酸やそのエステル、ジエチレングリコール、ブタンジオール、プロパンジオール、ポリエチレングリコール、ポリテトラメチレングリコール等のグリコール成分を挙げることができる。さらに無機粒子、有機粒子、染料、顔料、帯電防止剤、酸化防止剤、ワックス等を含有させても構わない。 The aromatic dicarboxylic acid component contained in the polyester resin composition in the present invention is at least selected from the above-mentioned types, but a terephthalic acid component and an isophthalic acid component are preferable from the viewpoint of a refractive index and a photoelastic coefficient, and these are simultaneously You can use it. In particular, the terephthalic acid component is preferably used mainly from the viewpoint of adhesion to other polyester resin compositions. As other dicarboxylic acid components, conventionally known ones may be copolymerized as long as the characteristics allow, and the same applies to glycol components. Examples of such components include aliphatic dicarboxylic acids such as adipic acid and sebacic acid and esters thereof, aromatic dicarboxylic acids such as 4,4′-bisphenylenedicarboxylic acid, 5-sodiumsulfoisophthalic acid, diphenic acid, and the like. Examples thereof include glycol components such as esters, diethylene glycol, butanediol, propanediol, polyethylene glycol, and polytetramethylene glycol. Further, inorganic particles, organic particles, dyes, pigments, antistatic agents, antioxidants, waxes and the like may be contained.
本発明において、ポリエステル樹脂組成物は、金属成分としてアルカリ金属、アルカリ土類金属、Ｚｎ、Ｃｏ、Ｍｎから選択される元素を含有することが好ましい。これらの金属元素を含有することでポリエステル樹脂組成物をフィルム成形する際の静電印加性が向上する。なおアルカリ金属の場合、Ｎａはポリエステル樹脂組成物を黄色く着色しやすいので、Ｋがより好ましい。アルカリ土類金属ではＣａは異物を形成し易いので、Ｍｇがより好ましい。Ｚｎ、Ｃｏ、ＭｎではＭｎが異物や色調の点から好ましい。このなかでもＭｇとＭｎが樹脂の透明性の観点から好ましく、特にＭｎが好ましい。 In the present invention, the polyester resin composition preferably contains an element selected from an alkali metal, an alkaline earth metal, Zn, Co, and Mn as a metal component. By containing these metal elements, electrostatic applicability at the time of film-forming the polyester resin composition is improved. In the case of an alkali metal, Na is more preferable because K easily colors the polyester resin composition yellow. In the alkaline earth metal, Mg is more preferable because Ca easily forms foreign matters. Of Zn, Co, and Mn, Mn is preferable from the viewpoint of foreign matter and color tone. Among these, Mg and Mn are preferable from the viewpoint of the transparency of the resin, and Mn is particularly preferable.
前記した金属化合物は、エステル交換反応触媒を兼ねても構わない。特にマンガン化合物はエステル交換反応での活性が強く、好ましい。金属化合物はポリエステルに可溶なものが好ましく、水酸化物や塩化物、酢酸塩が好ましく、特に酢酸塩が好ましい。 The aforementioned metal compound may also serve as a transesterification catalyst. In particular, a manganese compound is preferable because of its strong activity in transesterification. The metal compound is preferably soluble in polyester, and is preferably a hydroxide, chloride or acetate, and particularly preferably acetate.
次に本発明のポリエステル樹脂組成物およびフィルムの各製造方法について詳しく説明する。 Next, each manufacturing method of the polyester resin composition and film of this invention is demonstrated in detail.
本発明のポリエステル樹脂組成物の製造方法は、ジカルボン酸とジオールとをエステル化させて低重合体を合成し、次いでこれを重縮合する方法とジカルボン酸エステルとジオールとをエステル交換反応させて低重合体を合成し、次いでこれを重縮合する方法を採用することができる。スピログリコールは酸成分によって分解しやすいため、分解を避けるためにエステル交換反応によって重合することが好ましい。 The method for producing the polyester resin composition of the present invention comprises a method in which a dicarboxylic acid and a diol are esterified to synthesize a low polymer, and then a polycondensation of the dicarboxylic acid and a diol, and a dicarboxylic acid ester and a diol are subjected to a transesterification reaction. A method in which a polymer is synthesized and then polycondensed can be employed. Since spiroglycol is easily decomposed by an acid component, it is preferably polymerized by transesterification to avoid decomposition.
エステル交換法の場合、原料として例えばテレフタル酸ジメチル、シクロヘキサンジカルボン酸ジメチル、エチレングリコール、スピログリコールを所定のポリマー組成となるように反応缶へ仕込む。この際には、エチレングリコールを全ジカルボン酸成分に対して１．７〜２．３モル倍添加すれば反応性が良好となる。これらを１５０℃程度で溶融したのち酢酸マンガンなどをエステル交換反応触媒として添加する。１５０℃では、これらのモノマー成分は均一な溶融液体となる。次いで反応容器内を２３５℃まで昇温しながらメタノールを留出させ、エステル交換反応を実施する。このようにしてエステル交換反応が終了した後トリメチルリン酸等のエステル交換反応触媒失活剤を添加する。 In the case of the transesterification method, for example, dimethyl terephthalate, dimethyl cyclohexanedicarboxylate, ethylene glycol, and spiro glycol as raw materials are charged into a reaction can so as to have a predetermined polymer composition. In this case, if ethylene glycol is added by 1.7 to 2.3 mole times the total dicarboxylic acid component, the reactivity is improved. After melting these at about 150 ° C., manganese acetate or the like is added as a transesterification catalyst. At 150 ° C., these monomer components become a homogeneous molten liquid. Next, methanol is distilled while raising the temperature in the reaction vessel to 235 ° C., and the ester exchange reaction is carried out. After the transesterification is thus completed, a transesterification catalyst deactivator such as trimethyl phosphoric acid is added.
次いでクエン酸チタンキレートやテトラブチルチタネート等のチタン系重合触媒を添加する。重合触媒の添加が終了したら反応物を重合装置へ仕込み、装置内温度をゆっくり２８５℃まで昇温しながら装置内圧力を常圧から１３３Ｐａ以下まで減圧する。重合反応の進行に従って反応物の粘度が上昇する。所定の撹拌トルクとなった時点で反応を終了し、重合装置からポリエステルを水槽へ吐出する。吐出されたポリエステルは水槽で急冷して、カッターでチップとする。 Next, a titanium-based polymerization catalyst such as titanium citrate chelate or tetrabutyl titanate is added. When the addition of the polymerization catalyst is completed, the reaction product is charged into the polymerization apparatus, and the internal pressure of the apparatus is reduced from normal pressure to 133 Pa or lower while the internal temperature is slowly raised to 285 ° C. As the polymerization reaction proceeds, the viscosity of the reaction product increases. When the predetermined stirring torque is reached, the reaction is terminated, and the polyester is discharged from the polymerization apparatus into a water tank. The discharged polyester is quenched in a water tank and made into chips with a cutter.
このようにしてポリエステル樹脂組成物を得ることができるが、上記は一例であって、モノマーや触媒および重合条件はこれに限定されるわけではない。 Although a polyester resin composition can be obtained in this way, the above is an example, and the monomer, catalyst, and polymerization conditions are not limited thereto.
このようにして得られたポリエステル樹脂組成物は、光弾性係数が低く、液晶ディスプレイ用フィルムとして好適である。またＰＥＴ等を交互に積層したフィルムは光反射性に優れ、反射材用途に好適である。 The polyester resin composition thus obtained has a low photoelastic coefficient and is suitable as a film for a liquid crystal display. Moreover, the film which laminated | stacked PET etc. alternately is excellent in light reflectivity, and is suitable for a reflector use.
以下に実施例を挙げて、本発明をさらに具体的に説明する。 The present invention will be described more specifically with reference to the following examples.
なお、物性の測定方法、効果の評価方法は次の方法に従って行った。
（１）ポリエステルの熱特性（ガラス転移点、結晶融解熱量）
測定するサンプルを約１０ｍｇ秤量し、アルミニウム製パン、パンカバーを用いて封入し、示差走査熱量計（パーキンエルマー社製 ＤＳＣ７型）によって測定した。測定においては窒素雰囲気中で２０℃から２８５℃まで１６℃／分の速度で昇温した後液体窒素を用いて急冷し、再び窒素雰囲気中で２０℃から２８５℃まで１６℃／分の速度で昇温する。この２度目の昇温過程でガラス転移点を測定した。
In addition, the measuring method of a physical property and the evaluation method of an effect were performed in accordance with the following method.
(1) Thermal properties of polyester (glass transition point, heat of crystal melting)
About 10 mg of the sample to be measured was weighed, sealed with an aluminum pan and pan cover, and measured with a differential scanning calorimeter (DSC7 model, manufactured by Perkin Elmer). In the measurement, the temperature was raised from 20 ° C. to 285 ° C. at a rate of 16 ° C./min in a nitrogen atmosphere, then rapidly cooled with liquid nitrogen, and again from 20 ° C. to 285 ° C. at a rate of 16 ° C./min. Raise the temperature. The glass transition point was measured in the second temperature raising process.
また、結晶融解熱量は、２度目の昇温過程で現れる結晶融解ピークの面積から算出した。
（２）ポリエステルの屈折率
ポリエステル樹脂組成物を溶融押し出しすることで厚さ１００μｍの未延伸シートを得る。ついで光源としてナトリウムＤ線を用い２３℃の温度条件にて株式会社アタゴ製 「アッベ式屈折率計 ＮＡＲ−４Ｔ」で屈折率を測定した。
（３）固有粘度
固有粘度はオルトクロロフェノールを溶媒とし、２５℃で測定した。
（４）ゲル化率
ポリエステル樹脂組成物１ｇを凍結粉砕して直径３００μｍ以下の粉体状とし真空乾燥する。この試料を、オーブン中で、大気下、３００℃で２．５時間熱処理する。これを、５０ｍｌのオルトクロロフェノール（ＯＣＰ）中、８０〜１５０℃の温度で０．５時間溶解させる。続いて、ブフナー型ガラス濾過器（最大細孔の大きさ２０〜３０μｍ）で濾過し、洗浄・真空乾燥する。濾過前後の濾過器の重量の増分より、フィルターに残留したＯＣＰ不溶物の重量を算出し、ＯＣＰ不溶物のポリエステル樹脂組成物重量（１ｇ）に対する重量分率を求め、ゲル化率（％）とした。
（５）シクロヘキサンジカルボン酸のシス、トランス体比率
試料をメタノールで５〜６倍に希釈し、その希釈溶液を０．４μｌを液体クロマトグラフィーで下記条件にて測定した。
装置：島津製ＬＣ−１０ＡＤｖｐ
カラム：キャピラリーカラム Ａｇｉｌｅｎｔ Ｔｅｃｈｎｏｌｏｇｉｅｓ社製ＤＢ−１７（長さ３０ｍ、内径０．３２ｍｍ、膜厚０．２５μｍ）
昇温条件：初期温度１１０℃、初期時間２５分、昇温速度６℃／ｍｉｎ、最終温度２００℃
（６）ポリエステルの色調
ポリエステルチップを色差計（スガ試験機社製、ＳＭカラーコンピュータ型式ＳＭ−Ｔ４５）を用いて、ハンター値（Ｌ，ｂ値）として測定した。
（７）ポリマーのヘイズ値
ポリエステルチップ２ｇをｏ−クロロフェノール２０ｍｌに溶解し、光路長２０ｍｍの石英セルおよびヘイズメーター（スガ試験機社製 ＨＧＭ−２ＤＰ型）を用い、積分球式光電光度法によって溶液のヘイズ値を測定した。
（８）ポリエステル樹脂組成物中のチタン元素、リン元素、アンチモン元素の含有量
堀場製作所製蛍光Ｘ線装置（型番ＭＥＳＡ−５００Ｗ）を用い、ポリマの蛍光Ｘ線の強度を測定した。この値を含有量既知のサンプルで予め作成した検量線を用い、金属含有量に換算した。
（９）光弾性係数（×１０−１２Ｐａ−１）
短辺１ｃｍ長辺７ｃｍのサンプルを切り出した。このサンプルの厚みをｄ（μｍ）とする。このサンプルを（株）島津製作所社製ＴＲＡＮＳＤＵＣＥＲ Ｕ３Ｃ１−５Ｋを用いて、上下１ｃｍずつをチェックに挟み長辺方向に１ｋｇ／ｍｍ２（９．８１×１０６Ｐａ）の張力（Ｆ）をかけた。この状態で、ニコン（株）社製偏光顕微鏡５８９２を用いて位相差Ｒ（ｎｍ）を測定した。光源としてはナトリウムＤ線（５８９ｎｍ）を用いた。これらの数値を光弾性係数＝Ｒ／（ｄ×Ｆ）にあてはめて光弾性係数を計算した。
The amount of heat of crystal melting was calculated from the area of the crystal melting peak appearing in the second temperature raising process.
(2) Refractive index of polyester An unstretched sheet having a thickness of 100 μm is obtained by melt-extruding the polyester resin composition. Subsequently, the refractive index was measured with an “Abbe refractometer NAR-4T” manufactured by Atago Co., Ltd. under a temperature condition of 23 ° C. using sodium D line as a light source.
(3) Intrinsic viscosity Intrinsic viscosity was measured at 25 ° C using orthochlorophenol as a solvent.
(4) Gelation rate 1 g of the polyester resin composition is freeze-pulverized to form a powder having a diameter of 300 μm or less and vacuum-dried. The sample is heat treated in an oven at 300 ° C. for 2.5 hours in the atmosphere. This is dissolved in 50 ml of orthochlorophenol (OCP) at a temperature of 80-150 ° C. for 0.5 hour. Subsequently, it is filtered through a Buchner type glass filter (maximum pore size 20-30 μm), washed and vacuum dried. The weight of the OCP insoluble matter remaining on the filter is calculated from the increase in the weight of the filter before and after the filtration, and the weight fraction of the OCP insoluble matter with respect to the polyester resin composition weight (1 g) is obtained. did.
(5) Cysic and trans isomer ratio of cyclohexanedicarboxylic acid A sample was diluted 5 to 6 times with methanol, and 0.4 μl of the diluted solution was measured by liquid chromatography under the following conditions.
Device: Shimadzu LC-10ADvp
Column: Capillary column DB-17 manufactured by Agilent Technologies (length 30 m, inner diameter 0.32 mm, film thickness 0.25 μm)
Temperature rising conditions: initial temperature 110 ° C., initial time 25 minutes, temperature rising rate 6 ° C./min, final temperature 200 ° C.
(6) Color tone of polyester The polyester chip was measured as a Hunter value (L, b value) using a color difference meter (SM color computer model SM-T45, manufactured by Suga Test Instruments Co., Ltd.).
(7) Haze value of polymer 2 g of polyester chip was dissolved in 20 ml of o-chlorophenol, and a quartz cell having a light path length of 20 mm and a haze meter (HGM-2DP type, manufactured by Suga Test Instruments Co., Ltd.) were used. The haze value of the solution was measured.
(8) Content of Titanium Element, Phosphorus Element, and Antimony Element in Polyester Resin Composition Using a fluorescent X-ray apparatus (model number MESA-500W) manufactured by Horiba, the intensity of the fluorescent X-ray of the polymer was measured. This value was converted to metal content using a calibration curve prepared in advance with a sample with known content.
(9) Photoelastic coefficient (× 10 −12 Pa −1 )
A sample having a short side of 1 cm and a long side of 7 cm was cut out. The thickness of this sample is d (μm). Using this sample, TRANSDUCER U3C1-5K manufactured by Shimadzu Corp., a tension of 1 kg / mm 2 (9.81 × 10 6 Pa) was applied in the long side direction with 1 cm between the top and bottom. . In this state, the phase difference R (nm) was measured using a polarizing microscope 5892 manufactured by Nikon Corporation. Sodium D line (589 nm) was used as a light source. These numerical values were applied to photoelastic coefficient = R / (d × F) to calculate the photoelastic coefficient.
光弾性係数が１００未満の場合を合格とした。
（１０）反射率
日立製作所製 分光光度計（Ｕ−３４１０ Ｓｐｅｃｔｒｏｐｈｏｔｏｍｅｔｅｒ）にφ６０積分球１３０−０６３２（（株）日立製作所）および１０°傾斜スペーサーを取り付け反射率のピーク値を測定した。なお、バンドパラメーターは２／ｓｅｒｖｏとし、ゲインは３と設定し、１８７ｎｍ〜２６００ｎｍの範囲を１２０ｎｍ／ｍｉｎ．の検出速度で測定した。また、反射率を基準化するため、標準反射板として付属のＢａＳＯ４板を用いた。なお、本評価法では相対反射率となるため、反射率は１００％以上となる場合もある。
（１１）剥離性
ＪＩＳ Ｋ５６００（２００２年）に従って試験を行った。なお、フィルムを硬い素地とみなし、２ｍｍ間隔で２５個の格子状パターンを切り込んだ。また、約７５ｍｍの長さに切ったテープを格子の部分に接着し、テープを６０°に近い角度で０．５〜１．０秒の時間で引き剥がした。ここで、テープにはセキスイ製セロテープ（登録商標）Ｎｏ．２５２（幅１８ｍｍ）を用いた。評価結果は、格子１つ分が完全に剥離した格子の数で表した。また、試験フィルムの厚みが１００μｍより薄い場合には、厚さ１００μｍの二軸延伸ＰＥＴフィルム（東レ製“ルミラー”Ｔ６０）に試験フィルムを接着剤で強固に貼りあわせしたサンプルを剥離試験に用いた。この際には、試験サンプルを貫通しないように試験サンプルの面に格子を切り込んでテストを実施した。剥離個数が４個以下を合格とした。
The case where the photoelastic coefficient was less than 100 was regarded as acceptable.
(10) Reflectivity A spectrophotometer (U-3410 Spectrophotometer) manufactured by Hitachi, Ltd. was fitted with a φ60 integrating sphere 130-0632 (Hitachi Ltd.) and a 10 ° inclined spacer, and the peak value of reflectivity was measured. The band parameter was set to 2 / servo, the gain was set to 3, and the range from 187 nm to 2600 nm was set to 120 nm / min. Measured at a detection speed of. In order to standardize the reflectance, an attached BaSO 4 plate was used as a standard reflecting plate. In this evaluation method, since the relative reflectance is obtained, the reflectance may be 100% or more.
(11) Peelability The test was conducted according to JIS K5600 (2002). The film was regarded as a hard substrate, and 25 lattice patterns were cut at intervals of 2 mm. Further, a tape cut to a length of about 75 mm was adhered to the lattice portion, and the tape was peeled off at an angle close to 60 ° in a time of 0.5 to 1.0 seconds. Here, Sekisui's cello tape (registered trademark) no. 252 (width 18 mm) was used. The evaluation result was expressed by the number of lattices in which one lattice was completely separated. When the thickness of the test film was less than 100 μm, a sample in which the test film was firmly bonded to the biaxially stretched PET film (Toray “Lumirror” T60) having a thickness of 100 μm with an adhesive was used for the peel test. . At this time, a test was performed by cutting a grid in the surface of the test sample so as not to penetrate the test sample. The number of peeling was 4 or less.
なお、以下に触媒の合成方法を記す。 The method for synthesizing the catalyst is described below.
参考例１（触媒Ａ．クエン酸キレートチタン化合物の合成方法）
撹拌機、凝縮器及び温度計を備えた３Ｌのフラスコ中に温水（３７１ｇ）にクエン酸・一水和物（５３２ｇ、２．５２モル）を溶解させた。この撹拌されている溶液に滴下漏斗からチタンテトライソプロポキシド（２８８ｇ、１．００モル）をゆっくり加えた。この混合物を１時間加熱、還流させて曇った溶液を生成させ、これよりイソプロパノール／水混合物を真空下で蒸留した。その生成物を７０℃より低い温度まで冷却し、そしてその撹拌されている溶液にＮａＯＨ（３８０ｇ、３．０４モル）の３２重量／重量％水溶液を滴下漏斗によりゆっくり加えた。得られた生成物をろ過し、次いでエチレングリコール（５０４ｇ、８０モル）と混合し、そして真空下で加熱してイソプロパノール／水を除去し、わずかに曇った淡黄色の生成物（Ｔｉ含有量３．８５重量％）を得た。
Reference Example 1 (Catalyst A. Method for Synthesizing Citric Acid Chelate Titanium Compound)
Citric acid monohydrate (532 g, 2.52 mol) was dissolved in warm water (371 g) in a 3 L flask equipped with a stirrer, condenser and thermometer. To this stirred solution was slowly added titanium tetraisopropoxide (288 g, 1.00 mol) from the addition funnel. The mixture was heated to reflux for 1 hour to produce a cloudy solution from which the isopropanol / water mixture was distilled under vacuum. The product was cooled to a temperature below 70 ° C., and a 32 wt / wt% aqueous solution of NaOH (380 g, 3.04 mol) was slowly added via a dropping funnel to the stirred solution. The resulting product was filtered and then mixed with ethylene glycol (504 g, 80 mol) and heated under vacuum to remove isopropanol / water and a slightly cloudy light yellow product (Ti content 3 .85% by weight).
参考例２（触媒Ｂ．乳酸キレートチタン化合物の合成方法）
撹拌機、凝縮器及び温度計を備えた２Ｌのフラスコ中に撹拌されているチタンテトライソプロポキシド（２８５ｇ、１．００モル）に滴下漏斗からエチレングリコール（２１８ｇ、３．５１モル）を加えた。添加速度は、反応熱がフラスコ内容物を約５０℃に加温するように調節された。その反応混合物を１５分間撹拌し、そしてその反応フラスコに乳酸アンモニウム（２５２ｇ、２．００モル）の８５重量／重量％水溶液を加えると、透明な淡黄色の生成物（Ｔｉ含有量６．５４重量％）を得た。
Reference Example 2 (Catalyst B. Method for Synthesizing Lactic Acid Chelate Titanium Compound)
Ethylene glycol (218 g, 3.51 mol) was added from a dropping funnel to titanium tetraisopropoxide (285 g, 1.00 mol) stirred in a 2 L flask equipped with a stirrer, condenser and thermometer. . The rate of addition was adjusted so that the heat of reaction warmed the flask contents to about 50 ° C. The reaction mixture was stirred for 15 minutes and an 85 wt / wt% aqueous solution of ammonium lactate (252 g, 2.00 mol) was added to the reaction flask to give a clear pale yellow product (Ti content 6.54 wt. %).
参考例３（触媒Ｃ．チタンアルコキシド化合物の合成方法）
撹拌機、凝縮器及び温度計を備えた２Ｌのフラスコ中に撹拌されているチタンテトライソプロポキシド（２８５ｇ、１．００モル）に滴下漏斗からエチレングリコール（４９６ｇ、８．００モル）を加えた。添加速度は、反応熱がフラスコ内容物を約５０℃に加温するように調節された。その反応フラスコに、ＮａＯＨ（１２５ｇ、１．００モル）の３２重量／重量％水溶液を滴下漏斗によりゆっくり加えて透明な黄色の液体を得た（Ｔｉ含有量４．４４重量％）。
Reference Example 3 (Catalyst C. Synthesis Method of Titanium Alkoxide Compound)
Ethylene glycol (496 g, 8.00 mol) was added from a dropping funnel to titanium tetraisopropoxide (285 g, 1.00 mol) stirred in a 2 L flask equipped with a stirrer, condenser and thermometer. . The rate of addition was adjusted so that the heat of reaction warmed the flask contents to about 50 ° C. To the reaction flask, a 32 wt / wt% aqueous solution of NaOH (125 g, 1.00 mol) was slowly added via a dropping funnel to give a clear yellow liquid (Ti content 4.44 wt%).
実施例１
（ポリエステルの合成）
テレフタル酸ジメチルを６７．６重量部、シス／トランス体比率が７５／２５である１，４−シクロヘキサンジカルボン酸ジメチル（以下、ＣＨＤＡ）を１７．４重量部、エチレングリコールを５４重量部、スピログリコール（以下、ＳＰＧ）を２０重量部、酢酸マンガン四水塩を０．０４重量部をそれぞれ計量し、エステル交換反応装置に仕込んだ。内容物を１５０℃で溶解させて撹拌した。
Example 1
(Synthesis of polyester)
67.6 parts by weight of dimethyl terephthalate, 17.4 parts by weight of dimethyl 1,4-cyclohexanedicarboxylate (hereinafter referred to as CHDA) having a cis / trans ratio of 75/25, 54 parts by weight of ethylene glycol, and spiroglycol 20 parts by weight (hereinafter referred to as SPG) and 0.04 parts by weight of manganese acetate tetrahydrate were weighed and charged into a transesterification reactor. The contents were dissolved at 150 ° C. and stirred.
撹拌しながら反応内容物の温度を２３５℃までゆっくり昇温しながらメタノールを留出させた。所定量のメタノールが留出したのち、トリエチルホスホノアセテート（以下、ＴＥＰＡ）を０．０２重量部（Ｐ元素として２８ｐｐｍ）含んだエチレングリコール溶液および旭電化工業（株）製ビス（２，６−ジ−ｔｅｒｔ−ブチル−４−メチルフェニル）ペンタエリスリトール−ジ−ホスファイト）０．１５重量部（Ｐ元素として１４７ｐｐｍ、以下、ＰＥＰ３６）を添加しエステル交換反応を終了した。トリエチルホスホノアセテートを添加した後１０分間撹拌してチタン触媒Ａをチタン原子として２０ｐｐｍとなるように添加した。その後エステル交換反応物を重合装置に移行した。 While stirring, methanol was distilled while slowly raising the temperature of the reaction contents to 235 ° C. After distillation of a predetermined amount of methanol, an ethylene glycol solution containing 0.02 part by weight of triethylphosphonoacetate (hereinafter TEPA) (28 ppm as P element) and bis (2,6- Di-tert-butyl-4-methylphenyl) pentaerythritol di-phosphite) 0.15 parts by weight (147 ppm as P element, hereinafter referred to as PEP36) was added to complete the transesterification reaction. After adding triethylphosphonoacetate, the mixture was stirred for 10 minutes, and the titanium catalyst A was added to 20 ppm as titanium atoms. Thereafter, the transesterification reaction product was transferred to a polymerization apparatus.
次いで重合装置内容物を撹拌しながら減圧および昇温し、エチレングリコールを留出させながら重合をおこなった。なお、減圧は９０分かけて常圧から１３３Ｐａ以下に減圧し、昇温は９０分かけて２３５℃から２８５℃まで昇温した。 Next, the content of the polymerization apparatus was stirred and the pressure was reduced and the temperature was raised, and polymerization was carried out while distilling ethylene glycol. The reduced pressure was reduced from normal pressure to 133 Pa or less over 90 minutes, and the temperature was raised from 235 ° C. to 285 ° C. over 90 minutes.
重合装置の撹拌トルクが所定の値に達したら重合装置内を窒素ガスにて常圧へ戻し、重合装置下部のバルブを開けてガット状のポリマーを水槽へ吐出した。水槽で冷却されたポリエステルガットはカッターにてカッティングし、固有粘度０．７２のチップを得た。 When the stirring torque of the polymerization apparatus reached a predetermined value, the inside of the polymerization apparatus was returned to normal pressure with nitrogen gas, the valve at the bottom of the polymerization apparatus was opened, and a gut-shaped polymer was discharged into the water tank. The polyester gut cooled in the water tank was cut with a cutter to obtain a chip with an intrinsic viscosity of 0.72.
上記チップにＰＥＰ３６を重量比で０．１５ｗｔ％となるようにブレンドした後、６５ｍｍ、Ｌ／Ｄが３１．５のベント式二軸押出機で、２５０℃で溶融押し出しし、固有粘度０．６５、ゲル化率１．０％、色調ｂ値１０、ヘイズ１．０と耐熱性に優れたポリエステル樹脂組成物を得た。 After the PEP36 was blended to the above chip to a weight ratio of 0.15 wt%, it was melt extruded at 250 ° C. with a bent twin screw extruder of 65 mm and L / D of 31.5, and an intrinsic viscosity of 0.65. A polyester resin composition excellent in heat resistance with a gelation rate of 1.0%, a color tone b value of 10, and a haze of 1.0 was obtained.
同様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６４重量部用いる以外は前記と同様にしてＰＥＴ樹脂を重合した。得られたＰＥＴ樹脂の固有粘度は０．６５でありＴｇは８０℃であり、結晶融解熱ピークは観察されなかった。 Similarly, a PET resin was polymerized in the same manner as described above except that 100 parts by weight of dimethyl terephthalate and 64 parts by weight of ethylene glycol were used. The obtained PET resin had an intrinsic viscosity of 0.65, a Tg of 80 ° C., and no crystal melting heat peak was observed.
（単層２軸延伸フィルムの製膜）
ポリエステルチップを上記ベント式二軸押出機に供給し、溶融後、金属不織布フィルターによって濾過されたのち、Ｔダイから溶融シートとして押し出した。溶融シートは静電印加法（電極は直径０．１５ミリのタングステンワイヤーを使用）によって表面温度が２５℃に制御された鏡面ドラム上で冷却固化され、未延伸シートとなった。該未延伸シートを用いて光弾性係数を測定した。
(Formation of single-layer biaxially stretched film)
The polyester chip was supplied to the vent type twin screw extruder, melted, filtered through a metal nonwoven fabric filter, and then extruded from a T die as a molten sheet. The molten sheet was cooled and solidified on a specular drum whose surface temperature was controlled at 25 ° C. by an electrostatic application method (electrodes used a tungsten wire having a diameter of 0.15 mm) to form an unstretched sheet. The photoelastic coefficient was measured using the unstretched sheet.
光弾性係数は８５×１０−１２Ｐａ−１であった。 The photoelastic coefficient was 85 × 10 −12 Pa −1 .
（積層ポリエステルフィルムの製膜）
前記ポリエステルＡおよびＰＥＴ樹脂をそれぞれ２台のベント式二軸押出機にそれぞれ供給した。
(Formation of laminated polyester film)
The polyester A and the PET resin were respectively supplied to two vent type twin screw extruders.
ポリエステルＡおよびＰＥＴ樹脂は、それぞれ、押出機にて溶融状態とし、ギヤポンプおよびフィルタを介した後、１０１層のフィードブロックにて合流させた。このとき、積層フィルムの両表層がＰＥＴ樹脂層となるようにし、積層厚みはポリエステルＡ層／ＰＥＴ樹脂層が１／２となるように交互に積層した。すなわちポリエステルＡ層は５０層、ＰＥＴ層は５１層となるように交互に積層した。 Polyester A and PET resin were each melted by an extruder, passed through a gear pump and a filter, and then joined by a 101-layer feed block. At this time, both surface layers of the laminated film were made to be PET resin layers, and the laminated thickness was alternately laminated so that the polyester A layer / PET resin layer was ½. That is, the polyester A layer was laminated alternately so that 50 layers and the PET layer were 51 layers.
このようにして得られた１０１層からなる積層体を、ダイに供給し、シート状に押し出し、静電印加（直流電圧８ｋＶ）にて表面温度２５℃に保たれたキャスティングドラム上で急冷固化した。 The 101-layer laminate thus obtained was supplied to a die, extruded into a sheet, and rapidly cooled and solidified on a casting drum maintained at a surface temperature of 25 ° C. by electrostatic application (DC voltage 8 kV). .
得られたキャストフィルムは、ロール式縦延伸機に導き、９０℃に加熱されたロール群によって加熱し、周速の異なるロール間で長手方向に３倍に延伸した。縦方向に延伸が終了したフィルムは、次いでテンター式横延伸機に導いた。フィルムはテンター内で１００℃の熱風で予熱し、横方向に３．３倍に延伸した。延伸されたフィルムはそのままテンター内で２００℃の熱風にて熱処理した。このようにして厚さ５０μｍのフィルムを得ることができた。 The obtained cast film was led to a roll type longitudinal stretching machine, heated by a group of rolls heated to 90 ° C., and stretched 3 times in the longitudinal direction between rolls having different peripheral speeds. The film that had been stretched in the machine direction was then led to a tenter-type transverse stretcher. The film was preheated with hot air at 100 ° C. in a tenter and stretched 3.3 times in the transverse direction. The stretched film was directly heat treated with hot air at 200 ° C. in a tenter. In this way, a film having a thickness of 50 μm could be obtained.
得られたポリエステル樹脂組成物とフィルムの特性を表１、２に示す。本発明のポリエステル樹脂組成物は光弾性係数が８５×１０−１２Ｐａ−１であり、屈折率１．５５０も低いために積層フィルムとした際には優れた光反射性を有していた。 The characteristics of the obtained polyester resin composition and film are shown in Tables 1 and 2. The polyester resin composition of the present invention had a photoelastic coefficient of 85 × 10 −12 Pa −1 and a low refractive index of 1.550, and therefore had excellent light reflectivity when used as a laminated film.
実施例２
チタン触媒の種類を変更する以外は実施例１と同様にしてポリエステルを重合した。さらに実施例１で重合したＰＥＴ樹脂を用い、同様の条件で積層フィルムを得た。結果を表１、２に示す。チタン触媒の種類による物性の変化をほとんどなく満足すべき特性を示した。
Example 2
A polyester was polymerized in the same manner as in Example 1 except that the type of titanium catalyst was changed. Furthermore, using the PET resin polymerized in Example 1, a laminated film was obtained under the same conditions. The results are shown in Tables 1 and 2. The properties were satisfactory with almost no change in physical properties depending on the type of titanium catalyst.
実施例３
チタン触媒の種類をキレートからアルコキシドに変更する以外は実施例１と同様にしてポリエステルを重合した。さらに実施例１で重合したＰＥＴ樹脂を用い、同様の条件で積層フィルムを得た。結果を表１、２に示す。実施例１に比べ、ゲル化率、色調ｂ値、ヘイズが若干悪化したものの、品質として満足すべき特性を示した。
Example 3
Polyester was polymerized in the same manner as in Example 1 except that the type of titanium catalyst was changed from chelate to alkoxide. Furthermore, using the PET resin polymerized in Example 1, a laminated film was obtained under the same conditions. The results are shown in Tables 1 and 2. Although the gelation rate, the color tone b value, and the haze were slightly deteriorated as compared with Example 1, the characteristics satisfactory as the quality were exhibited.
実施例４〜５
ＣＨＤＡ、ＳＰＧの量比を変更する以外は実施例１と同様にしてポリエステルを重合した。さらに実施例１で重合したＰＥＴ樹脂を用い、同様の条件で積層フィルムを得た。
Examples 4-5
A polyester was polymerized in the same manner as in Example 1 except that the amount ratio of CHDA and SPG was changed. Furthermore, using the PET resin polymerized in Example 1, a laminated film was obtained under the same conditions.
結果を表１、２に示す。実施例４も満足すべき特性を示したが、芳香環モル数が大きいために光弾性率が若干増加した。また実施例５は屈折率が十分低いために優れた光反射性を示したが、共重合成分量が増加したためにＰＥＴとの相溶性が低下し、層間剥離性が弱く、ＳＰＧの共重合量が多いためゲル化率が若干高くなった。 The results are shown in Tables 1 and 2. Example 4 also showed satisfactory properties, but the photoelastic modulus slightly increased due to the large number of moles of aromatic rings. Further, Example 5 showed excellent light reflectivity because the refractive index was sufficiently low, but since the amount of copolymerization component was increased, the compatibility with PET was lowered, the delamination property was weak, and the copolymerization amount of SPG. As a result, the gelation rate increased slightly.
実施例６〜７
Ｔｉ触媒量を変更する以外は実施例１と同様とした。結果を表１、２に示すが、実施例６はＴｉ触媒量が多いため若干ゲル化率が高く、ｂ値が上昇した。一方、実施例７は、Ｔｉ触媒量を少なくしたため、反対に、ゲル化率、ｂ値共に低い良好な結果を得た。
Examples 6-7
The procedure was the same as Example 1 except that the amount of Ti catalyst was changed. The results are shown in Tables 1 and 2. As Example 6 had a large amount of Ti catalyst, the gelation rate was slightly high, and the b value increased. On the other hand, in Example 7, since the Ti catalyst amount was decreased, on the contrary, good results were obtained in which both the gelation rate and the b value were low.
参考例８、実施例９〜１１
混練に用いるＰＥＰ３６を０．０５、０．５０、１．００、１．３０ｗｔ％とした以外は実施例１と同様にしてポリエステルフィルムを得た。結果を表１、２に示す。参考例８は、混練後のポリエステルのリン量が７５ｐｐｍと少ないため、ゲル化率が若干上がる結果となった。
また、実施例９は、混練後のポリエステルのリン量が４２０ｐｐｍであるためゲル化率は低くなったが若干へイズが上昇した。実施例１０、１１も実施例９と同様の傾向を示した。
Reference Example 8, Examples 9 to 11
A polyester film was obtained in the same manner as in Example 1 except that PEP36 used for kneading was changed to 0.05, 0.50, 1.00, and 1.30 wt%. The results are shown in Tables 1 and 2. In Reference Example 8, since the amount of phosphorus in the polyester after kneading was as small as 75 ppm, the gelation rate slightly increased.
In Example 9, since the amount of phosphorus in the polyester after kneading was 420 ppm, the gelation rate was low, but the haze was slightly increased. Examples 10 and 11 also showed the same tendency as Example 9.
実施例１２
ＣＨＤＡのシス、トランス体の比が、トランス体４０％のものを使用した以外は実施例１と同様にしてポリエステルフィルムを得た。結果を表１、２に示す。重合時にトランス体の析出により仕込み配管等が若干詰まり気味になり、得られたフィルムもトランス体が多いことから若干光弾性係数が高くなった。
Example 12
A polyester film was obtained in the same manner as in Example 1 except that a cis / trans isomer ratio of CHDA was 40%. The results are shown in Tables 1 and 2. Due to precipitation of the trans isomer during the polymerization, the charged piping and the like were slightly clogged, and the resulting film also had a slightly higher photoelastic coefficient due to the large amount of the trans isomer.
実施例１３
ＣＨＤＡの代わりにデカリン酸ジメチル２５ｍｏｌに変更する以外は実施例１と同様にしてポリエステルフィルムを得た。結果を表１、２に示す。品質は満足したものの若干剥離性が悪いものであった。
Example 13
A polyester film was obtained in the same manner as in Example 1 except that dimethyl decalate was changed to 25 mol instead of CHDA. The results are shown in Tables 1 and 2. Although the quality was satisfactory, the peelability was slightly poor.
実施例１４
ＳＰＧの代わりにイソソルビド１０ｍｏｌに変更する以外は実施例１と同様にしてポリエステルフィルムを得た。結果を表１、２に示す。品質は満足したものの若干色調ｂ値が高いものであった。
Example 14
A polyester film was obtained in the same manner as in Example 1 except that 10 mol of isosorbide was used instead of SPG. The results are shown in Tables 1 and 2. Although the quality was satisfactory, the color tone b value was slightly high.
比較例１
実施例１のＰＥＴ樹脂の重合において、ＣＨＤＡの代わりにイソフタル酸を１５ｍｏｌ共重合し、スピログリコールは共重合せず、重縮合触媒として通常の三酸化アンチモン０．０２ｗｔ％を使用する以外は実施例１と同様にしてポリエステルを重合し、積層フィルムを得た。結果を表１、２に示すが、脂環族ジカルボン酸成分、脂環族ジオール成分のいずれも含有しないために屈折率、光弾性係数が大きく、積層フィルムの反射率も小さいものであった。
Comparative Example 1
In polymerization of PET resin of Example 1, 15 mol of isophthalic acid was copolymerized instead of CHDA, spiroglycol was not copolymerized, and 0.02 wt% of ordinary antimony trioxide was used as a polycondensation catalyst. Polyester was polymerized in the same manner as in Example 1 to obtain a laminated film. Although a result is shown in Table 1, 2, since neither an alicyclic dicarboxylic acid component nor an alicyclic diol component is contained, the refractive index and the photoelastic coefficient were large, and the reflectance of the laminated film was also small.
比較例２
実施例１のＰＥＴ樹脂の重合において、ＣＨＤＡは共重合せず、ＳＰＧの代わりにシクロヘキサンジメタノール成分を３０ｍｏｌ共重合して、重縮合触媒として通常の三酸化アンチモン０．０２ｗｔ％を使用する以外は同様にしてポリエステルを重合し、積層フィルムを得た。結果を表１、２に示すが、屈折率は低下したものの、若干光弾性係数が大きく、積層フィルムの反射率も若干劣るものであった。
Comparative Example 2
In the polymerization of the PET resin of Example 1, CHDA is not copolymerized, 30 mol of cyclohexanedimethanol component is copolymerized instead of SPG, and 0.02 wt% of ordinary antimony trioxide is used as a polycondensation catalyst. Similarly, polyester was polymerized to obtain a laminated film. The results are shown in Tables 1 and 2. Although the refractive index was lowered, the photoelastic coefficient was slightly large, and the reflectance of the laminated film was slightly inferior.
比較例３
実施例１のＰＥＴ樹脂の重合において、ＣＨＤＡは共重合せず、ＳＰＧを４５ｍｏｌ共重合して、重縮合触媒として通常の三酸化アンチモン０．０２ｗｔ％を使用する以外は同様にしてポリエステルを重合し、積層フィルムを得た。結果を表１、２に示すが、Ｔｇ、ゲル化率が非常に高く、積層フィルムの剥離性も劣るものであった。また、重縮合反応中に低分子量物の飛沫が多く、真空回路を少し閉塞し、真空度不良が発生した。
Comparative Example 3
In polymerization of the PET resin of Example 1, CHDA was not copolymerized, 45 mol of SPG was copolymerized, and polyester was polymerized in the same manner except that 0.02 wt% of ordinary antimony trioxide was used as a polycondensation catalyst. A laminated film was obtained. The results are shown in Tables 1 and 2. The Tg and gelation rate were very high, and the peelability of the laminated film was inferior. In addition, there were many low molecular weight droplets during the polycondensation reaction, and the vacuum circuit was slightly blocked, resulting in poor vacuum.
比較例４
実施例１のＰＥＴ樹脂の重合において、ＣＨＤＡを２５ｍｏｌ共重合し、ＳＰＧは共重合せず、重縮合触媒として通常の三酸化アンチモン０．０２ｗｔ％を使用する以外は同様にしてポリエステルを重合し、積層フィルムを得た。結果を表１、２に示すが、屈折率は目標範囲内であるが、Ｔｇが下がり、積層フィルムの剥離性に劣り、反射率も小さいものであった。
Comparative Example 4
In the polymerization of the PET resin of Example 1, 25 mol of CHDA was copolymerized, SPG was not copolymerized, and a polyester was polymerized in the same manner except that 0.02 wt% of ordinary antimony trioxide was used as a polycondensation catalyst. A laminated film was obtained. The results are shown in Tables 1 and 2. Although the refractive index is within the target range, the Tg was lowered, the peelability of the laminated film was inferior, and the reflectance was small.
比較例５
チタン触媒をチタン元素として６０ｐｐｍ添加する以外は、実施例１と同様の方法で積層フィルムを得た。結果を表１、２に示すが、チタン原子が多量であったため非常にゲル化が促進され、ｂ値が高いものであった。
Comparative Example 5
A laminated film was obtained in the same manner as in Example 1 except that 60 ppm of titanium catalyst was added as a titanium element. The results are shown in Tables 1 and 2. As the amount of titanium atoms was large, gelation was promoted very much and the b value was high.
比較例６
チタン触媒をチタン元素として０．４ｐｐｍ添加する以外は、実施例１と同様の方法で重合したが、結果を表１、２に示すように、チタン原子が微量であったため、重合時間は延長し、結局、目標の重合度のものは得ることができなかった。
Comparative Example 6
Polymerization was carried out in the same manner as in Example 1 except that the titanium catalyst was added in an amount of 0.4 ppm as a titanium element. However, as shown in Tables 1 and 2, since the amount of titanium atoms was very small, the polymerization time was extended. Eventually, the target polymerization degree could not be obtained.
比較例７
混練に使用するリン化合物を１．５０ｗｔ％に変更する以外は実施１と同様の方法で積層フィルムを得た。結果を表１、２に示すが、混練後のポリエステル中のリン量は、１１００ｐｐｍと非常に多くなり、ゲル化率は非常に低くなったものの、ヘイズが５．５％と高いものしか得られなかった。
Comparative Example 7
A laminated film was obtained in the same manner as in Example 1 except that the phosphorus compound used for kneading was changed to 1.50 wt%. The results are shown in Tables 1 and 2, and the amount of phosphorus in the polyester after kneading is as large as 1100 ppm, and the gelation rate is very low, but only a high haze of 5.5% is obtained. There wasn't.
比較例８
重縮合反応前にＰＥＰ３６を１．５０ｗｔ％添加する以外は、実施例１と同様の方法で重合したが、表１、２に示すように、Ｔｉ触媒が失活してしまい、目標の重合度のポリエステルを得ることはできなかった。
Comparative Example 8
Polymerization was carried out in the same manner as in Example 1 except that 1.50 wt% of PEP36 was added before the polycondensation reaction. However, as shown in Tables 1 and 2, the Ti catalyst was deactivated, and the target polymerization degree was reached. Of polyester could not be obtained.
比較例９
重縮合反応前にＰＥＰ３６を添加しないこと以外は、実施例１と同様の方法で実施したが、表１、２に示すように、混練工程において、恐らく重縮合時に生成したゲルや分解した低分子量物が、ベントラインに詰まり、途中で混練工程を停止せざる得なかった。
Comparative Example 9
Except that PEP36 was not added before the polycondensation reaction, it was carried out in the same manner as in Example 1. However, as shown in Tables 1 and 2, in the kneading step, the gel probably formed during polycondensation and decomposed low molecular weight The product was clogged in the vent line, and the kneading process had to be stopped halfway.
比較例１０
重縮合反応の後半でＰＥＰ３６を０．４０ｗｔ％（添加後のＦＬＸリン量合計は、３１０ｐｐｍ）添加する以外は、実施例１と同様の方法で重合したが、添加直後に重合時の攪拌トルクが急激に上昇し、ストランド状に吐出するときにも太細ストランドが多数発生し、目的のものを得ることができなかった。該方法は、ＰＥＰ３６多量添加には不向きな処方であった。
Comparative Example 10
Polymerization was carried out in the same manner as in Example 1 except that 0.40 wt% of PEP36 was added in the latter half of the polycondensation reaction (the total amount of FLX phosphorus after addition was 310 ppm). When it rose rapidly and was discharged in the form of a strand, many thick strands were generated, and the desired product could not be obtained. This method was unsuitable for adding a large amount of PEP36.
Claims (7)
６５℃≦示差走査熱量測定によるガラス転移点温度≦８６℃・・・（１）
１．５００≦ナトリウムＤ線での屈折率≦１．５７０・・・（２）
０．５≦チタン元素≦５０ｐｐｍ・・・（３）
２０７≦リン元素≦１０００ｐｐｍ・・・（４） In producing a polyester resin composition satisfying the following formulas (1) to (4) containing at least an alicyclic dicarboxylic acid component and an alicyclic diol component, a titanium compound as a polycondensation catalyst, and a trivalent as an antioxidant A method for producing a polyester resin composition, comprising a polycondensation reaction containing a phosphorus compound, and further kneading a trivalent phosphorus compound after the polycondensation reaction is completed.
65 ° C. ≦ Glass transition temperature by differential scanning calorimetry ≦ 86 ° C. (1)
1.500 ≦ refractive index at sodium D line ≦ 1.570 (2)
0.5 ≦ Titanium element ≦ 50 ppm (3)
207 ≦ Phosphorus Element ≦ 1000 ppm (4)
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