JP7400499B2 - polyester resin composition - Google Patents
polyester resin composition Download PDFInfo
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- JP7400499B2 JP7400499B2 JP2020012294A JP2020012294A JP7400499B2 JP 7400499 B2 JP7400499 B2 JP 7400499B2 JP 2020012294 A JP2020012294 A JP 2020012294A JP 2020012294 A JP2020012294 A JP 2020012294A JP 7400499 B2 JP7400499 B2 JP 7400499B2
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- JP
- Japan
- Prior art keywords
- ppm
- resin composition
- polyester resin
- acid
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- 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.)
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- 239000000203 mixture Substances 0.000 title claims description 78
- 229920001225 polyester resin Polymers 0.000 title claims description 57
- 239000004645 polyester resin Substances 0.000 title claims description 57
- 229910052698 phosphorus Inorganic materials 0.000 claims description 26
- 239000011574 phosphorus Substances 0.000 claims description 26
- 239000011777 magnesium Substances 0.000 claims description 25
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 17
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 17
- 229910052749 magnesium Inorganic materials 0.000 claims description 17
- 229920000728 polyester Polymers 0.000 claims description 17
- 239000011572 manganese Substances 0.000 claims description 15
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 12
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 12
- 230000009477 glass transition Effects 0.000 claims description 12
- 239000010936 titanium Substances 0.000 claims description 12
- 229910052719 titanium Inorganic materials 0.000 claims description 12
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 9
- 229910052783 alkali metal Inorganic materials 0.000 claims description 9
- 229910000318 alkali metal phosphate Inorganic materials 0.000 claims description 9
- 150000001340 alkali metals Chemical class 0.000 claims description 9
- 229910052748 manganese Inorganic materials 0.000 claims description 7
- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-N 0.000 claims description 6
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 6
- 125000002723 alicyclic group Chemical group 0.000 claims description 5
- 150000002009 diols Chemical class 0.000 claims description 5
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 claims description 3
- 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 3
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 239000000470 constituent Substances 0.000 claims description 2
- 238000000113 differential scanning calorimetry Methods 0.000 claims description 2
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 claims 2
- 125000002467 phosphate group Chemical class [H]OP(=O)(O[H])O[*] 0.000 claims 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 110
- 238000006116 polymerization reaction Methods 0.000 description 27
- 239000000243 solution Substances 0.000 description 24
- 239000010408 film Substances 0.000 description 20
- 238000000354 decomposition reaction Methods 0.000 description 19
- 238000005809 transesterification reaction Methods 0.000 description 19
- 229920000642 polymer Polymers 0.000 description 18
- -1 phosphorus compound Chemical class 0.000 description 17
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 14
- 238000005979 thermal decomposition reaction Methods 0.000 description 13
- 230000003287 optical effect Effects 0.000 description 12
- 239000007809 chemical reaction catalyst Substances 0.000 description 10
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 10
- 238000011156 evaluation Methods 0.000 description 10
- 238000005259 measurement Methods 0.000 description 10
- GGUBFICZYGKNTD-UHFFFAOYSA-N triethyl phosphonoacetate Chemical compound CCOC(=O)CP(=O)(OCC)OCC GGUBFICZYGKNTD-UHFFFAOYSA-N 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 239000002253 acid Substances 0.000 description 9
- 239000010410 layer Substances 0.000 description 9
- 229920000139 polyethylene terephthalate Polymers 0.000 description 9
- 239000005020 polyethylene terephthalate Substances 0.000 description 9
- 229940097364 magnesium acetate tetrahydrate Drugs 0.000 description 8
- XKPKPGCRSHFTKM-UHFFFAOYSA-L magnesium;diacetate;tetrahydrate Chemical compound O.O.O.O.[Mg+2].CC([O-])=O.CC([O-])=O XKPKPGCRSHFTKM-UHFFFAOYSA-L 0.000 description 8
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 description 6
- 230000004927 fusion Effects 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000004132 cross linking Methods 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
- 229940082328 manganese acetate tetrahydrate Drugs 0.000 description 4
- 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 4
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 4
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 4
- 239000002904 solvent Substances 0.000 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 description 3
- 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
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical group OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- 125000004036 acetal group Chemical group 0.000 description 3
- 125000003545 alkoxy group Chemical group 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical group OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000003111 delayed effect Effects 0.000 description 3
- LNGAGQAGYITKCW-UHFFFAOYSA-N dimethyl cyclohexane-1,4-dicarboxylate Chemical compound COC(=O)C1CCC(C(=O)OC)CC1 LNGAGQAGYITKCW-UHFFFAOYSA-N 0.000 description 3
- 238000010030 laminating Methods 0.000 description 3
- 150000002681 magnesium compounds Chemical class 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000001579 optical reflectometry Methods 0.000 description 3
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- GNSKLFRGEWLPPA-UHFFFAOYSA-M potassium dihydrogen phosphate Chemical compound [K+].OP(O)([O-])=O GNSKLFRGEWLPPA-UHFFFAOYSA-M 0.000 description 3
- 238000011002 quantification Methods 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 150000003609 titanium compounds Chemical class 0.000 description 3
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 3
- 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 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical group OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical group CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 239000012298 atmosphere Substances 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
- 238000004040 coloring Methods 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-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
- 238000010438 heat treatment Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical group CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 238000003475 lamination Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 150000002697 manganese compounds Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical group OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000002685 polymerization catalyst Substances 0.000 description 2
- 239000002244 precipitate Substances 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
- 239000000376 reactant Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 239000011342 resin composition Substances 0.000 description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical group OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid group Chemical group C(CCCCCCCCC(=O)O)(=O)O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Chemical group OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-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
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 2
- FSJPQPQXDUGPFV-UHFFFAOYSA-N (2-ethoxy-2-oxoethyl)phosphonic acid Chemical compound CCOC(=O)CP(O)(O)=O FSJPQPQXDUGPFV-UHFFFAOYSA-N 0.000 description 1
- MQYFWRJEFAZXHE-UHFFFAOYSA-N (2-phenylphenyl)phosphonic acid Chemical compound OP(O)(=O)C1=CC=CC=C1C1=CC=CC=C1 MQYFWRJEFAZXHE-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
- AATNZNJRDOVKDD-UHFFFAOYSA-N 1-[ethoxy(ethyl)phosphoryl]oxyethane Chemical compound CCOP(=O)(CC)OCC AATNZNJRDOVKDD-UHFFFAOYSA-N 0.000 description 1
- NYYLZXREFNYPKB-UHFFFAOYSA-N 1-[ethoxy(methyl)phosphoryl]oxyethane Chemical compound CCOP(C)(=O)OCC NYYLZXREFNYPKB-UHFFFAOYSA-N 0.000 description 1
- YHQMSHVVGOSZEW-UHFFFAOYSA-N 1-dimethoxyphosphorylethane Chemical compound CCP(=O)(OC)OC YHQMSHVVGOSZEW-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
- KDRBAEZRIDZKRP-UHFFFAOYSA-N 2,2-bis[3-(aziridin-1-yl)propanoyloxymethyl]butyl 3-(aziridin-1-yl)propanoate Chemical compound C1CN1CCC(=O)OCC(COC(=O)CCN1CC1)(CC)COC(=O)CCN1CC1 KDRBAEZRIDZKRP-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
- DVQMPWOLBFKUMM-UHFFFAOYSA-M 2-diethoxyphosphorylacetate Chemical compound CCOP(=O)(CC([O-])=O)OCC DVQMPWOLBFKUMM-UHFFFAOYSA-M 0.000 description 1
- WWNZUHFWZPYTBX-UHFFFAOYSA-N 2-phosphonobenzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(P(O)(O)=O)C(C(O)=O)=C1 WWNZUHFWZPYTBX-UHFFFAOYSA-N 0.000 description 1
- VAHAOUZUOJVJNC-UHFFFAOYSA-N 2-phosphonobenzene-1,3-dicarboxylic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1P(O)(O)=O VAHAOUZUOJVJNC-UHFFFAOYSA-N 0.000 description 1
- DQULYJXGTXMNTM-UHFFFAOYSA-N 2-phosphonobenzoic acid Chemical compound OC(=O)C1=CC=CC=C1P(O)(O)=O DQULYJXGTXMNTM-UHFFFAOYSA-N 0.000 description 1
- LSGSSTRMKJNXRE-UHFFFAOYSA-N 2-phosphonoterephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(P(O)(O)=O)=C1 LSGSSTRMKJNXRE-UHFFFAOYSA-N 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
- 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
- TXVJDPRWVLBNQI-UHFFFAOYSA-N 3-phosphonobenzene-1,2,4-tricarboxylic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(P(O)(O)=O)=C1C(O)=O TXVJDPRWVLBNQI-UHFFFAOYSA-N 0.000 description 1
- ZKKXCRILZNBJJM-UHFFFAOYSA-N 3-phosphonobenzoic acid Chemical compound OC(=O)C1=CC=CC(P(O)(O)=O)=C1 ZKKXCRILZNBJJM-UHFFFAOYSA-N 0.000 description 1
- GCVZZYGDTUQTSF-UHFFFAOYSA-N 3-phosphonophthalic acid Chemical compound OC(=O)C1=CC=CC(P(O)(O)=O)=C1C(O)=O GCVZZYGDTUQTSF-UHFFFAOYSA-N 0.000 description 1
- YISPNHJOGNWBMB-UHFFFAOYSA-N 4-phosphonobenzene-1,2,3-tricarboxylic acid Chemical compound OC(=O)C1=CC=C(P(O)(O)=O)C(C(O)=O)=C1C(O)=O YISPNHJOGNWBMB-UHFFFAOYSA-N 0.000 description 1
- GYDIOHSAKOKUSU-UHFFFAOYSA-N 4-phosphonobenzene-1,3-dicarboxylic acid Chemical compound OC(=O)C1=CC=C(P(O)(O)=O)C(C(O)=O)=C1 GYDIOHSAKOKUSU-UHFFFAOYSA-N 0.000 description 1
- IEQICHVXWFGDAN-UHFFFAOYSA-N 4-phosphonobenzoic acid Chemical compound OC(=O)C1=CC=C(P(O)(O)=O)C=C1 IEQICHVXWFGDAN-UHFFFAOYSA-N 0.000 description 1
- JRGIIBCBZMLCFD-UHFFFAOYSA-N 4-phosphonophthalic acid Chemical compound OC(=O)C1=CC=C(P(O)(O)=O)C=C1C(O)=O JRGIIBCBZMLCFD-UHFFFAOYSA-N 0.000 description 1
- ZCDDUQKDPBQFMN-UHFFFAOYSA-N 5-phosphonobenzene-1,2,4-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(P(O)(O)=O)C=C1C(O)=O ZCDDUQKDPBQFMN-UHFFFAOYSA-N 0.000 description 1
- INJNMXHKFWFNLW-UHFFFAOYSA-N 5-phosphonobenzene-1,3-dicarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(P(O)(O)=O)=C1 INJNMXHKFWFNLW-UHFFFAOYSA-N 0.000 description 1
- VVRIRTUTAWGRNK-UHFFFAOYSA-N 6-phosphonobenzene-1,2,4-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C(P(O)(O)=O)=C1 VVRIRTUTAWGRNK-UHFFFAOYSA-N 0.000 description 1
- OGBVRMYSNSKIEF-UHFFFAOYSA-N Benzylphosphonic acid Chemical compound OP(O)(=O)CC1=CC=CC=C1 OGBVRMYSNSKIEF-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-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
- 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 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
- 229910019142 PO4 Inorganic materials 0.000 description 1
- QLZHNIAADXEJJP-UHFFFAOYSA-N Phenylphosphonic acid Chemical compound OP(O)(=O)C1=CC=CC=C1 QLZHNIAADXEJJP-UHFFFAOYSA-N 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 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
- UKQZIZWJJVPSNV-UHFFFAOYSA-J [Mg+2].[Mg+2].CCC(P([O-])([O-])=O)C1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1.CCC(P([O-])([O-])=O)C1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 Chemical compound [Mg+2].[Mg+2].CCC(P([O-])([O-])=O)C1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1.CCC(P([O-])([O-])=O)C1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 UKQZIZWJJVPSNV-UHFFFAOYSA-J 0.000 description 1
- CDOMXXVCZQOOMT-UHFFFAOYSA-N [phenoxy(phenyl)phosphoryl]oxybenzene Chemical compound C=1C=CC=CC=1OP(C=1C=CC=CC=1)(=O)OC1=CC=CC=C1 CDOMXXVCZQOOMT-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 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
- 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
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000001479 atomic absorption spectroscopy Methods 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
- UOKRBSXOBUKDGE-UHFFFAOYSA-N butylphosphonic acid Chemical compound CCCCP(O)(O)=O UOKRBSXOBUKDGE-UHFFFAOYSA-N 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229940043430 calcium compound Drugs 0.000 description 1
- 150000001674 calcium compounds Chemical class 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical group 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 150000001869 cobalt compounds Chemical class 0.000 description 1
- 238000005094 computer simulation Methods 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- VZEGPPPCKHRYGO-UHFFFAOYSA-N diethoxyphosphorylbenzene Chemical compound CCOP(=O)(OCC)C1=CC=CC=C1 VZEGPPPCKHRYGO-UHFFFAOYSA-N 0.000 description 1
- AIPRAPZUGUTQKX-UHFFFAOYSA-N diethoxyphosphorylmethylbenzene Chemical compound CCOP(=O)(OCC)CC1=CC=CC=C1 AIPRAPZUGUTQKX-UHFFFAOYSA-N 0.000 description 1
- PAGBSTCJQYFPLU-UHFFFAOYSA-L dilithium 2,6-ditert-butyl-4-(1-phosphonatopropyl)phenol Chemical compound C(C)C(C1=CC(=C(C(=C1)C(C)(C)C)O)C(C)(C)C)P([O-])([O-])=O.[Li+].[Li+] PAGBSTCJQYFPLU-UHFFFAOYSA-L 0.000 description 1
- REKWWOFUJAJBCL-UHFFFAOYSA-L dilithium;hydrogen phosphate Chemical compound [Li+].[Li+].OP([O-])([O-])=O REKWWOFUJAJBCL-UHFFFAOYSA-L 0.000 description 1
- QLNYTKJCHFEIDA-UHFFFAOYSA-N dimethoxyphosphorylmethylbenzene Chemical compound COP(=O)(OC)CC1=CC=CC=C1 QLNYTKJCHFEIDA-UHFFFAOYSA-N 0.000 description 1
- VONWDASPFIQPDY-UHFFFAOYSA-N dimethyl methylphosphonate Chemical compound COP(C)(=O)OC VONWDASPFIQPDY-UHFFFAOYSA-N 0.000 description 1
- BTVWZWFKMIUSGS-UHFFFAOYSA-N dimethylethyleneglycol Natural products CC(C)(O)CO BTVWZWFKMIUSGS-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- KTKSQHLURDTACB-UHFFFAOYSA-N diphenoxyphosphorylmethylbenzene Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)CC1=CC=CC=C1 KTKSQHLURDTACB-UHFFFAOYSA-N 0.000 description 1
- GGTJZPPHIMQXDL-UHFFFAOYSA-L disodium 2,6-ditert-butyl-4-(1-phosphonatopropyl)phenol Chemical compound C(C)C(C1=CC(=C(C(=C1)C(C)(C)C)O)C(C)(C)C)P([O-])([O-])=O.[Na+].[Na+] GGTJZPPHIMQXDL-UHFFFAOYSA-L 0.000 description 1
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical group CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 1
- GATNOFPXSDHULC-UHFFFAOYSA-N ethylphosphonic acid Chemical compound CCP(O)(O)=O GATNOFPXSDHULC-UHFFFAOYSA-N 0.000 description 1
- 239000001530 fumaric acid Chemical group 0.000 description 1
- 229920002100 high-refractive-index polymer Polymers 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 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
- 229960002479 isosorbide Drugs 0.000 description 1
- 150000003893 lactate salts Chemical group 0.000 description 1
- 239000004310 lactic acid Chemical group 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 239000005001 laminate film Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 150000002642 lithium compounds Chemical class 0.000 description 1
- SNKMVYBWZDHJHE-UHFFFAOYSA-M lithium;dihydrogen phosphate Chemical compound [Li+].OP(O)([O-])=O SNKMVYBWZDHJHE-UHFFFAOYSA-M 0.000 description 1
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 description 1
- 229940069446 magnesium acetate Drugs 0.000 description 1
- 239000011654 magnesium acetate Substances 0.000 description 1
- 235000011285 magnesium acetate Nutrition 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical group OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Chemical group 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- CTSAXXHOGZNKJR-UHFFFAOYSA-N methyl 2-diethoxyphosphorylacetate Chemical compound CCOP(=O)(OCC)CC(=O)OC CTSAXXHOGZNKJR-UHFFFAOYSA-N 0.000 description 1
- YACKEPLHDIMKIO-UHFFFAOYSA-N methylphosphonic acid Chemical compound CP(O)(O)=O YACKEPLHDIMKIO-UHFFFAOYSA-N 0.000 description 1
- YOOYVODKUBZAPO-UHFFFAOYSA-N naphthalen-1-ylphosphonic acid Chemical compound C1=CC=C2C(P(O)(=O)O)=CC=CC2=C1 YOOYVODKUBZAPO-UHFFFAOYSA-N 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical group CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- 239000012788 optical film Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 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
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical class [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 1
- 150000003009 phosphonic acids Chemical class 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 238000005375 photometry Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- OGHBATFHNDZKSO-UHFFFAOYSA-N propan-2-olate Chemical compound CC(C)[O-] OGHBATFHNDZKSO-UHFFFAOYSA-N 0.000 description 1
- ATLPLEZDTSBZQG-UHFFFAOYSA-N propan-2-ylphosphonic acid Chemical compound CC(C)P(O)(O)=O ATLPLEZDTSBZQG-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
- 235000019260 propionic acid Nutrition 0.000 description 1
- NSETWVJZUWGCKE-UHFFFAOYSA-N propylphosphonic acid Chemical compound CCCP(O)(O)=O NSETWVJZUWGCKE-UHFFFAOYSA-N 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000002310 reflectometry Methods 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- YXTFRJVQOWZDPP-UHFFFAOYSA-M sodium;3,5-dicarboxybenzenesulfonate Chemical compound [Na+].OC(=O)C1=CC(C(O)=O)=CC(S([O-])(=O)=O)=C1 YXTFRJVQOWZDPP-UHFFFAOYSA-M 0.000 description 1
- 239000002344 surface layer Substances 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
- 238000012546 transfer Methods 0.000 description 1
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 1
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 description 1
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 1
- 229910000404 tripotassium phosphate Inorganic materials 0.000 description 1
- 235000019798 tripotassium phosphate Nutrition 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 229910000406 trisodium phosphate Inorganic materials 0.000 description 1
- 235000019801 trisodium phosphate Nutrition 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Description
本発明は非晶性ポリエステル樹脂組成物に関する。 The present invention relates to an amorphous polyester resin composition.
屈折率の異なるポリマーを交互に積層したフィルムは、特定の波長の光を効率良く反射させることができ、光フィルタや反射体として利用されている。その中でも特に中間層に用いられるポリマーには層間密着性や配向による光学特性変化の点から非晶性ポリエステル樹脂組成物であることが好ましい。また、光学フィルムに用いる際に、透明性などの光学特性は非常に重要な要素であり、様々な用途に用いられる際に耐熱分解性といった特性も重要視される。一般に組成物としての共重合成分の変更なく、光学特性、耐熱分解性などのポリマー特性を向上させるためには、触媒や添加物の組み合わせを最適化することが必要である。 Films made by alternately laminating polymers with different refractive indexes can efficiently reflect light of specific wavelengths, and are used as optical filters and reflectors. Among these, an amorphous polyester resin composition is particularly preferable for the polymer used in the intermediate layer from the viewpoint of interlayer adhesion and changes in optical properties due to orientation. Furthermore, optical properties such as transparency are very important factors when used in optical films, and properties such as heat decomposition resistance are also considered important when used in various applications. In general, in order to improve polymer properties such as optical properties and thermal decomposition resistance without changing the copolymerized components of the composition, it is necessary to optimize the combination of catalysts and additives.
これに対し特許文献１では非晶性、透明性、耐熱分解性が揃ったポリエステル樹脂組成物が提案されているが、本用途において十分な耐熱分解性は達成できない。 On the other hand, Patent Document 1 proposes a polyester resin composition having amorphous properties, transparency, and heat decomposition resistance, but sufficient heat decomposition resistance cannot be achieved for this purpose.
続いて、特許文献２では光学特性に優れた非晶性ポリエステル樹脂組成物が提案されているが、こちらも同様に本用途における十分な耐熱分解性を達成できない。 Subsequently, Patent Document 2 proposes an amorphous polyester resin composition with excellent optical properties, but this similarly cannot achieve sufficient heat decomposition resistance for this purpose.
また、特許文献３では耐加水分解性、機械特性に優れたポリエステル樹脂組成物が提案されているが、結晶性のポリエステル樹脂組成物であるため、フィルムとして積層する際の層間密着性の悪化、配向による光学特性の変化が起こり不適当である。 In addition, Patent Document 3 proposes a polyester resin composition with excellent hydrolysis resistance and mechanical properties, but since it is a crystalline polyester resin composition, interlayer adhesion deteriorates when laminated as a film. This is inappropriate because optical properties change due to orientation.
本発明の目的は、これら従来の欠点を解消せしめ、特に透明性、耐熱分解性に優れたポリエステル樹脂組成物を提供することにある。 An object of the present invention is to eliminate these conventional drawbacks and provide a polyester resin composition particularly excellent in transparency and heat decomposition resistance.
すなわち本発明の目的は、非晶性組成物に、リン酸アルカリ金属塩を含有し、
アルカリ金属の含有量が組成物との重量比として１０ｐｐｍ以上２００ｐｐｍ以下、
チタンの含有量が得られる組成物との重量比として５ｐｐｍ以上１００ｐｐｍ以下、
リン含有量が７０ｐｐｍ以上３００ｐｐｍ以下、
マグネシウムとマンガンの総含有量が得られる組成物との重量比として３０ｐｐｍ以上１００ｐｐｍであって、
マグネシウム（Ｍｇ）とマンガン（Ｍｎ）のモル比として下記式（１）を満たすことで透明性、耐熱分解性に優れたポリエステル樹脂組成物を提供することにより達成される。
０．０５≦Ｍｎ／Ｍｇ≦０．４３・・・（１）
That is, the object of the present invention is to contain an alkali metal phosphate salt in an amorphous composition,
The content of alkali metal is 10 ppm or more and 200 ppm or less as a weight ratio to the composition,
The weight ratio of titanium to the composition obtained is 5 ppm or more and 100 ppm or less,
Phosphorus content is 70 ppm or more and 300 ppm or less,
The total content of magnesium and manganese is 30 ppm or more and 100 ppm as a weight ratio of the composition obtained,
This is achieved by providing a polyester resin composition with excellent transparency and heat decomposition resistance by satisfying the following formula (1) as the molar ratio of magnesium (Mg) and manganese (Mn).
0.05≦Mn/Mg≦0.43...(1)
本発明によれば、透明性、耐熱分解性に優れた非晶性のポリエステル樹脂組成物を提供することができる。また、本発明のポリエステル樹脂組成物を二軸延伸することにより液晶ディスプレイなどの光学反射板用途に適用することができ、特に、屈折率を制御した多層積層フィルムとすることにより全光線反射フィルム、熱線反射フィルムなどの用途に安定して提供することができる。 According to the present invention, it is possible to provide an amorphous polyester resin composition having excellent transparency and heat decomposition resistance. In addition, by biaxially stretching the polyester resin composition of the present invention, it can be applied to optical reflector applications such as liquid crystal displays, and in particular, by forming a multilayer laminated film with a controlled refractive index, a total light reflection film, It can be stably provided for applications such as heat ray reflective films.
本発明におけるポリエステル樹脂組成物は、多層積層フィルムとした場合の層間剥離や配向による光学特性の変化を抑制するため非晶性である必要がある。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ける延伸工程での配向が起こらないため、その光学特性が変化しにくく好ましい。 The polyester resin composition in the present invention needs to be amorphous in order to suppress changes in optical properties due to delamination and orientation when formed into a multilayer laminate film. 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 orientation does not occur during the stretching process in film production, so that its optical properties are less likely to change.
また、本発明におけるポリエステル樹脂組成物は、耐熱分解性の点からリン酸アルカリ金属塩を含有する必要がある。本発明におけるリン酸アルカリ金属塩とは、リン酸塩の正塩、水素塩の中でもアルカリ金属を含むリン化合物のことを指している。このような化合物として、例えばリン酸三ナトリウム、リン酸一水素二ナトリウム、リン酸二水素一ナトリウム、リン酸三カリウム、リン酸一水素二カリウム、リン酸二水素一カリウム、リン酸三リチウム、リン酸一水素二リチウム、リン酸二水素一リチウムなどが挙げられ、中でもリン酸二水素一ナトリウム、リン酸二水素一カリウム、リン酸一水素二カリウムが耐熱分解性の点から好ましい。 Moreover, the polyester resin composition in the present invention needs to contain an alkali metal phosphate salt from the viewpoint of heat decomposition resistance. The alkali metal phosphate salt in the present invention refers to a phosphorus compound containing an alkali metal among normal salts and hydrogen salts of phosphate. Examples of such compounds include trisodium phosphate, disodium monohydrogen phosphate, monosodium dihydrogen phosphate, tripotassium phosphate, dipotassium monohydrogen phosphate, monopotassium dihydrogen phosphate, trilithium phosphate, Examples include dilithium monohydrogen phosphate and monolithium dihydrogen phosphate, among which monosodium dihydrogen phosphate, monopotassium dihydrogen phosphate, and dipotassium monohydrogen phosphate are preferred from the viewpoint of heat decomposition resistance.
本発明におけるポリエステル樹脂組成物は、耐熱分解性および透明性、ポリマーの色調の点からアルカリ金属の含有量が得られる組成物との重量比として１０ｐｐｍ以上３００ｐｐｍ以下であることが好ましく、さらには３０ｐｐｍ以上２００ｐｐｍ以下であることが好ましい。アルカリ金属含有量が１０ｐｐｍ未満では、本発明における耐熱分解性が不足する。一方、３００ｐｐｍを超えると異物化およびポリマーへの着色が起こりやすくなる。 The polyester resin composition of the present invention preferably has an alkali metal content of 10 ppm or more and 300 ppm or less, more preferably 30 ppm or less, in terms of heat decomposition resistance, transparency, and color tone of the polymer. The content is preferably 200 ppm or less. When the alkali metal content is less than 10 ppm, the heat decomposition resistance in the present invention is insufficient. On the other hand, if it exceeds 300 ppm, foreign matter formation and coloring of the polymer tend to occur.
本発明における耐熱分解性とは３００℃窒素雰囲気下で１時間溶融した場合の固有粘度低下幅のことを指し、本発明のポリエステル樹脂組成物は、耐熱分解性の点から、この固有粘度低下幅が０．１以下であることが好ましい。 Thermal decomposition resistance in the present invention refers to the range of decrease in intrinsic viscosity when melted for 1 hour at 300°C in a nitrogen atmosphere. is preferably 0.1 or less.
本発明のポリエステル樹脂組成物は、エステル交換反応触媒に用いる金属化合物としてマグネシウム化合物、マンガン化合物、コバルト化合物、リチウム化合物、チタン化合物、カルシウム化合物などを挙げることができるが、透明性、ポリマー色調の点からマグネシウム化合物を用いることが好ましい。また、マグネシウムの含有量は得られる組成物との重量比として３０ｐｐｍ以上１００ｐｐｍ以下であることが好ましく、さらには４０ｐｐｍ以上９０ｐｐｍ以下であることが好ましい。マグネシウムの含有量が３０ｐｐｍ未満では、エステル交換反応性が不十分であり、１００ｐｐｍを超えるとポリマーへの黄着色が起こりやすくなる。 In the polyester resin composition of the present invention, magnesium compounds, manganese compounds, cobalt compounds, lithium compounds, titanium compounds, calcium compounds, etc. can be used as metal compounds for use as transesterification reaction catalysts, but in terms of transparency and polymer color tone. It is preferable to use a magnesium compound from. Further, the content of magnesium is preferably 30 ppm or more and 100 ppm or less, more preferably 40 ppm or more and 90 ppm or less, as a weight ratio to the resulting composition. When the magnesium content is less than 30 ppm, the transesterification reactivity is insufficient, and when it exceeds 100 ppm, yellowing of the polymer tends to occur.
本発明のポリエステル樹脂組成物は、エステル交換反応および重合反応にて留出するエチレングリコールの回収性の点から、エステル交換反応触媒に用いる金属化合物としてマグネシウム化合物とマンガン化合物を併用することが好ましく、マグネシウム元素とマンガン元素の総含有量が得られるポリエステル組成物との重量比として３０ｐｐｍ以上１００ｐｐｍであって、マグネシウム元素（Ｍｇ）とマンガン元素（Ｍｎ）のモル比として下記式（１）を満たすことが好ましい。
０．０５≦Ｍｎ／Ｍｇ≦０．４３・・・（１）
Ｍｎ／Ｍｇが０．０５未満である場合、エステル交換反応で反応しきれなかった未反応物が留出エチレングリコールに含有される可能性があり、回収性が十分でなくなる。また、Ｍｎ／Ｍｇが０．４３を超える場合は、溶液ヘイズが高くなり、本発明の用途に不適となる可能性がある。
In the polyester resin composition of the present invention, from the viewpoint of recovery of ethylene glycol distilled out in the transesterification reaction and polymerization reaction, it is preferable to use a magnesium compound and a manganese compound together as the metal compound used in the transesterification reaction catalyst. The weight ratio of the polyester composition from which the total content of magnesium element and manganese element is obtained is 30 ppm or more and 100 ppm, and the molar ratio of magnesium element (Mg) and manganese element (Mn) satisfies the following formula (1). is preferred.
0.05≦Mn/Mg≦0.43...(1)
If Mn/Mg is less than 0.05, there is a possibility that unreacted substances that have not been completely reacted in the transesterification reaction will be contained in the distilled ethylene glycol, resulting in insufficient recovery. Moreover, when Mn/Mg exceeds 0.43, the solution haze becomes high and there is a possibility that the solution becomes unsuitable for the use of the present invention.
本発明のポリエステル樹脂組成物は、結晶特性、透明性の観点から、構成成分として、芳香族ジカルボン酸成分、脂環族ジカルボン酸成分、脂肪族ジオール、アセタール環を有するジオールを含有することが好ましい。ポリエチレンテレフタレートからなる樹脂組成物は高い結晶性を持つため、フィルムに応力を加えた際に配向し、光学特性が変化してしまう。そこで、共重合成分として一部を脂環族ジカルボン酸成分やアセタール環を有するジオールに置換することによって、ガラス転移点、屈折率のバランスを保ちつつ非晶化させることができる。 From the viewpoint of crystal properties and transparency, the polyester resin composition of the present invention preferably contains an aromatic dicarboxylic acid component, an alicyclic dicarboxylic acid component, an aliphatic diol, and a diol having an acetal ring as constituent components. . Since the resin composition made of polyethylene terephthalate has high crystallinity, when stress is applied to the film, it becomes oriented and its optical properties change. Therefore, by partially substituting an alicyclic dicarboxylic acid component or a diol having an acetal ring as a copolymerization component, it is possible to amorphize the material while maintaining the balance between the glass transition point and the refractive index.
本発明における芳香族ジカルボン酸成分としては、テレフタル酸成分、イソフタル酸成分、２，６－ナフタレンジカルボン酸成分、５スルホイソフタル酸ナトリウム成分などを挙げることができ、耐熱分解性の点からテレフタル酸成分、２，６－ナフタレンジカルボン酸成分であることが好ましい。また、これらは１種だけでなく２種以上併用することも可能である。 Examples of the aromatic dicarboxylic acid component in the present invention include a terephthalic acid component, an isophthalic acid component, a 2,6-naphthalenedicarboxylic acid component, and a sodium 5-sulfoisophthalate component. , 2,6-naphthalene dicarboxylic acid component. Moreover, these can be used not only alone but also in combination of two or more kinds.
脂環族ジカルボン酸成分としては、１，４－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が挙げられ、光学特性の点から１，４－シクロヘキサンジカルボン酸成分が好ましい。また、１，４－シクロヘキサンジカルボン酸成分は、一般にシス体、トランス体の混合物であるが、トランス体の比率が４０％以下であることが好ましい。トランス体は、得られたポリエステル組成物の結晶性に影響しやすく、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。 Examples of the alicyclic dicarboxylic acid component include a 1,4-cyclohexanedicarboxylic acid component and a decalindicarboxylic acid component, with the 1,4-cyclohexanedicarboxylic acid component being preferred from the viewpoint of optical properties. Furthermore, the 1,4-cyclohexanedicarboxylic acid component is generally a mixture of cis and trans forms, but it is preferable that the ratio of trans forms is 40% or less. The trans isomer tends to affect the crystallinity of the obtained polyester composition, and the trans isomer ratio is preferably 35% or less, more preferably 30% or less.
本発明における脂肪族ジオール成分は、エチレングリコール、プロパンジオール、ブタンジオール、ネオペンチルグリコールなどが挙げられ、耐熱分解性の点からエチレングリコールであることが好ましい。 Examples of the aliphatic diol component in the present invention include ethylene glycol, propanediol, butanediol, neopentyl glycol, etc., and ethylene glycol is preferred from the viewpoint of heat decomposition resistance.
本発明におけるアセタール環を有するジオール成分は、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耐熱分解性、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。 The diol component having an acetal ring in the present invention is preferably a spiroglycol component or an isosorbide component, and a spiroglycol component is particularly preferred from the viewpoint of heat decomposition resistance and color tone of the obtained polyester. Here, spiroglycol refers to 3,9-bis(2-hydroxy-1,1-dimethylethyl)-2,4,8,10-tetraoxaspiro[5,5]undecane.
本発明のポリエステル樹脂組成物は、重合反応触媒として従来公知の化合物を使用することができるが、耐熱分解性、重合反応性の点からチタン化合物を用いることが好ましい。また、チタンの含有量は得られる組成物との重量比として５ｐｐｍ以上１００ｐｐｍ以下であることが好ましく、さらには８ｐｐｍ以上９０ｐｐｍ以上であることが好ましい。チタン量が５ｐｐｍ未満では、重合反応が十分に進行せず、長時間高温下に滞留することになってしまうため、耐熱分解性、色調が悪化する。一方、１００ｐｐｍを超えると含有する金属量が増え、熱分解も促進するため耐熱分解性が悪化し、またポリマーへの着色も起こりやすくなる。 In the polyester resin composition of the present invention, conventionally known compounds can be used as polymerization reaction catalysts, but titanium compounds are preferably used from the viewpoint of heat decomposition resistance and polymerization reactivity. Further, the content of titanium is preferably from 5 ppm to 100 ppm, more preferably from 8 ppm to 90 ppm, as a weight ratio to the resulting composition. If the amount of titanium is less than 5 ppm, the polymerization reaction will not proceed sufficiently and the resin will remain at high temperature for a long time, resulting in poor thermal decomposition resistance and poor color tone. On the other hand, if it exceeds 100 ppm, the amount of metals contained will increase and thermal decomposition will be promoted, resulting in poor thermal decomposition resistance and coloring of the polymer.
本発明のポリエステル樹脂組成物において、好適なチタン触媒としては、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, as a suitable titanium catalyst, a titanium compound whose substituent 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、１，４－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 titanium tetraalkoxides such as tetraethoxide, tetrapropoxide, tetraisopropoxide, tetrabutoxide, and tetra-2-ethylhexoxide, β-diketone functional groups such as acetylacetone, lactic acid, Examples include hydroxy polycarboxylic acid functional groups such as malic acid, tartaric acid, salicylic acid, and citric acid, and ketoester functional groups such as methyl acetoacetate and ethyl acetoacetate, with aliphatic alkoxy groups being particularly preferred. Furthermore, examples of the phenoxy group include phenoxy, crecylate, and the like. In addition, 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, and adipic acid. , polyvalent carboxylic acid functional groups such as sebacic acid, maleic acid, fumaric acid, 1,4-cyclohexanedicarboxylic acid or their anhydrides, ethylenediaminetetraacetic acid, nitrilotripropionic acid, carboxyiminodiacetic acid, carboxymethyliminodiacetic acid, etc. Nitrogen-containing polyvalent carboxylic acids such as propionic acid, diethylenetriaminopentaacetic acid, triethylenetetraminohexaacetic acid, iminodiacetic acid, iminodipropionic acid, hydroxyethyliminodiacetic acid, hydroxyethyliminodipropionic acid, methoxyethyliminodiacetic acid, etc. Examples include functional groups, with aliphatic acylate groups being particularly preferred. Further, examples of the amino group include aniline, phenylamine, diphenylamine, and the like. Further, diisopropoxybisacetylacetone, triethanolaminate isopropoxide, etc. containing two types of these substituents can be mentioned.
本発明のポリエステル樹脂組成物は、耐熱分解性、着色防止の点からリン化合物を含有することが好ましい。また、リンの含有量は得られる組成物との重量比として７０ｐｐｍ以上３００ｐｐｍ以下であることが好ましく、さらには９０ｐｐｍ以上２５０ｐｐｍ以下であることが好ましい。リン量が７０ｐｐｍ未満では耐熱分解性が不足してしまい、３００ｐｐｍを超えると重合反応触媒が触媒活性を失い、重合反応が進行しなくなる。 The polyester resin composition of the present invention preferably contains a phosphorus compound from the viewpoint of heat decomposition resistance and coloration prevention. Further, the content of phosphorus is preferably 70 ppm or more and 300 ppm or less, more preferably 90 ppm or more and 250 ppm or less, as a weight ratio to the resulting composition. If the amount of phosphorus is less than 70 ppm, heat decomposition resistance will be insufficient, and if it exceeds 300 ppm, the polymerization reaction catalyst will lose catalytic activity and the polymerization reaction will not proceed.
本発明におけるリン化合物としては、５価のリン化合物であることが、透明性の点から好ましい。例えばリン酸系、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好ましく使用される。 As the phosphorus compound in the present invention, a pentavalent phosphorus compound is preferable from the viewpoint of transparency. Examples include phosphoric acid-based, phosphonic acid-based, and phosphinic acid-based compounds, among which ester compounds of these are preferably used.
具体的な５価のリン化合物には、リン酸、リン酸トリメチル、リン酸トリエチル等のリン酸系、リン酸トリフェニル、メチルホスホン酸、エチルホスホン酸、プロピルホスホン酸、イソプロピルホスホン酸、ブチルホスホン酸、フェニルホスホン酸、ベンジルホスホン酸、トリルホスホン酸、キシリルホスホン酸、ビフェニルホスホン酸、ナフチルホスホン酸、アントリルホスホン酸、２－カルボキシフェニルホスホン酸、３－カルボキシフェニルホスホン酸、４－カルボキシフェニルホスホン酸、２，３－ジカルボキシフェニルホスホン酸、２，４－ジカルボキシフェニルホスホン酸、２，５－ジカルボキシフェニルホスホン酸、２，６－ジカルボキシフェニルホスホン酸、３，４－ジカルボキシフェニルホスホン酸、３，５－ジカルボキシフェニルホスホン酸、２，３，４－トリカルボキシフェニルホスホン酸、２，３，５－トリカルボキシフェニルホスホン酸、２，３，６－トリカルボキシフェニルホスホン酸、２，４，５－トリカルボキシフェニルホスホン酸、２，４，６－トリカルボキシフェニルホスホン酸、メチルホスホン酸ジメチルエステル、メチルホスホン酸ジエチルエステル、エチルホスホン酸ジメチルエステル、エチルホスホン酸ジエチルエステル、フェニルホスホン酸ジメチルエステル、フェニルホスホン酸ジエチルエステル、フェニルホスホン酸ジフェニルエステル、ベンジルホスホン酸ジメチルエステル、ベンジルホスホン酸ジエチルエステル、ベンジルホスホン酸ジフェニルエステル、リチウム（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシベンジルホスホン酸エチル）、ナトリウム（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシベンジルホスホン酸エチル）、マグネシウムビス（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシベンジルホスホン酸エチル）、カルシウムビス（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシベンジルホスホン酸エチル）、ジエチルホスホノ酢酸エチル、ジエチルホスホノ酢酸メチル等のホスホン酸系化合物が挙げられる。 Specific pentavalent phosphorus compounds include phosphoric acid, trimethyl phosphate, triethyl phosphate, etc., triphenyl phosphate, methylphosphonic acid, ethylphosphonic acid, propylphosphonic acid, isopropylphosphonic acid, butylphosphonic acid. , phenylphosphonic acid, benzylphosphonic acid, tolylphosphonic acid, xylylphosphonic acid, biphenylphosphonic acid, naphthylphosphonic acid, anthrylphosphonic acid, 2-carboxyphenylphosphonic acid, 3-carboxyphenylphosphonic acid, 4-carboxyphenylphosphonic acid acid, 2,3-dicarboxyphenylphosphonic acid, 2,4-dicarboxyphenylphosphonic acid, 2,5-dicarboxyphenylphosphonic acid, 2,6-dicarboxyphenylphosphonic acid, 3,4-dicarboxyphenylphosphonic acid acid, 3,5-dicarboxyphenylphosphonic acid, 2,3,4-tricarboxyphenylphosphonic acid, 2,3,5-tricarboxyphenylphosphonic acid, 2,3,6-tricarboxyphenylphosphonic acid, 2, 4,5-tricarboxyphenylphosphonic acid, 2,4,6-tricarboxyphenylphosphonic acid, methylphosphonic acid dimethyl ester, methylphosphonic acid diethyl ester, ethylphosphonic acid dimethyl ester, ethylphosphonic acid diethyl ester, phenylphosphonic acid dimethyl ester, Phenylphosphonic acid diethyl ester, phenylphosphonic acid diphenyl ester, benzylphosphonic acid dimethyl ester, benzylphosphonic acid diethyl ester, benzylphosphonic acid diphenyl ester, lithium (ethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate) , sodium (ethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate), magnesium bis(ethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate), calcium bis(3,5 Examples include phosphonic acid compounds such as ethyl -di-tert-butyl-4-hydroxybenzylphosphonate), ethyl diethylphosphonoacetate, and methyl diethylphosphonoacetate.
本発明のポリエステル樹脂組成物の屈折率は、１．５００以上１．５７０以下の範囲にあることが好ましく、さらには１．５１０以上１．５６０以下の範囲であることが好ましい。屈折率を１．５１０未満とすることはポリエステル樹脂の耐熱性が悪化する組成となり、１．５７０を超える場合には、積層フィルムとした場合の高屈折率ポリマーとの屈折率差が小さくなり、得られる積層フィルムの光反射性が小さくなるため、本発明の用途に適さない。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。 The refractive index of the polyester resin composition of the present invention is preferably in the range of 1.500 or more and 1.570 or less, and more preferably in the range of 1.510 or more and 1.560 or less. If the refractive index is less than 1.510, the heat resistance of the polyester resin will deteriorate, and if it exceeds 1.570, the difference in refractive index with the high refractive index polymer will become small when used as a laminated film. Since the resulting laminated film has low light reflectivity, it is not suitable for use in the present invention. Note that the refractive index in the present invention refers to a refractive index measured using a sodium D line at 23°C.
本発明のポリエステル樹脂組成物は、製膜安定性、耐熱分解性の点から示差走査熱量測定によるガラス転移温度の中間点（Ｔｇ）が６５℃以上９０℃以下であることが好ましく、さらには７０℃以上８５℃以下であることが好ましい。Ｔｇが６５℃未満の場合、耐熱分解性の不足やＰＥＴ等を積層する際のＴｇ差が大きくなりすぎるため、積層ムラ等が発生してしまい、またＴｇが９０℃を超える場合にも同様に、積層ムラ等が発生するため、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る。 The polyester resin composition of the present invention preferably has a glass transition temperature midpoint (Tg) measured by differential scanning calorimetry of 65°C or more and 90°C or less, more preferably 70°C or less, from the viewpoint of film forming stability and thermal decomposition resistance. It is preferable that the temperature is not less than 0.degree. C. and not more than 85.degree. If the Tg is less than 65℃, the thermal decomposition resistance is insufficient and the Tg difference when laminating PET etc. becomes too large, resulting in uneven lamination, etc.If the Tg exceeds 90℃, the same problem occurs. , lamination unevenness, etc. occur, which impairs film formation stability and makes it difficult to lower the refractive index of the polyester resin.
以下に本発明のポリエステル樹脂組成物の具体的な製造方法について述べるがこれに限定するものではない。 A specific method for producing the polyester resin composition of the present invention will be described below, but the method is not limited thereto.
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、１，４－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エステル交換反応槽へ仕込む。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１．７～２．７モル倍添加すれば反応性が良好となる。本発明のポリエステル樹脂組成物を積層フィルムとする場合、本発明のポリエステル樹脂組成物のＴｇ（ガラス転移点）をもう一方の積層ポリマーの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組成物の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。ガラス転移点を制御するには、例えば、テレフタル酸ジメチル、１，４－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、スピログリコールの共重合の場合、スピログリコール量および／またはテレフタル酸ジメチルの割合を高くすることでガラス転移点が高くなり、エチレングリコールおよび／または１，４－シクロヘキサンジカルボン酸ジメチルの割合を高くすると、ガラス転移点は低くなる。
これらを１５０℃程度で溶融したのち酢酸マグネシウム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、得られた低重合体を重合反応槽へ移送する。
重合反応槽へ移送が完了したのち、攪拌しながらリン酸二水素一ナトリウムなどのリン酸アルカリ金属塩および／またはエチルジエチルホスホノアセテート等のリン化合物を添加する。リン化合物は重合反応中に飛散するため、飛散量を見込んだ量を添加する必要がある。
In the case of the transesterification method, raw materials such as dimethyl terephthalate, dimethyl 1,4-cyclohexanedicarboxylate, ethylene glycol, and spiroglycol are charged into a transesterification reactor so as to have a predetermined polymer composition. At this time, good reactivity can be achieved by adding ethylene glycol in 1.7 to 2.7 moles of the total dicarboxylic acid components. When the polyester resin composition of the present invention is used as a laminated film, it is preferable that the Tg (glass transition point) of the polyester resin composition of the present invention match the Tg of the other laminated polymer, and the Tg (Tg1) of the laminated polymer It is preferable that the difference (|Tg1−Tg2|) between Tg (Tg2) and the polyester resin composition in the present invention is within 10°C, more preferably within 5°C. To control the glass transition point, for example, in the case of copolymerization of dimethyl terephthalate, dimethyl 1,4-cyclohexanedicarboxylate, ethylene glycol, and spiroglycol, the amount of spiroglycol and/or the proportion of dimethyl terephthalate may be increased. The glass transition point becomes high, and when the proportion of ethylene glycol and/or dimethyl 1,4-cyclohexanedicarboxylate is increased, the glass transition point becomes low.
After melting these at about 150° C., magnesium acetate or the like is added as a transesterification reaction catalyst. At 150°C, these monomer components become a homogeneous molten liquid. Next, methanol is distilled off while the temperature inside the reaction vessel is raised to 235° C., and a transesterification reaction is carried out. After the transesterification reaction is completed in this way, the obtained low polymer is transferred to a polymerization reaction tank.
After the transfer to the polymerization reactor is completed, an alkali metal phosphate such as monosodium dihydrogen phosphate and/or a phosphorus compound such as ethyldiethylphosphonoacetate is added while stirring. Since the phosphorus compound scatters during the polymerization reaction, it is necessary to add an amount that takes into account the amount of scattering.
リン化合物添加から１０分以上２５分以内でテトラブチルチタネート等の重合触媒を添加する。 A polymerization catalyst such as tetrabutyl titanate is added within 10 minutes or more and within 25 minutes after the addition of the phosphorus compound.
重合触媒の添加が終了したら装置内温度をゆっくり２８０℃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。反応物の撹拌トルク増加値が重合終了目標に到達した時点で反応を終了し、重合反応槽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され、カッターでチップとする。 When the addition of the polymerization catalyst is completed, the temperature inside the device is slowly raised to 280° C. while the pressure inside the device is reduced from normal pressure to 133 Pa or less. As the polymerization reaction progresses, the viscosity of the reactant increases. The reaction is terminated when the stirring torque increase value of the reactants reaches the polymerization completion target, and the polyester is discharged from the polymerization reaction tank into the water tank. The discharged polyester is rapidly cooled in a water tank and cut into chips using 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 just an example, and the monomers, catalysts, and polymerization conditions are not limited thereto.
このようにして得られた非晶性のポリエステル樹脂組成物は、透明性、耐熱分解性に優れ、ＰＥＴ等を交互に積層したフィルムは光反射性、熱線反射性に優れ、反射材用途などに好適である。 The amorphous polyester resin composition obtained in this way has excellent transparency and thermal decomposition resistance, and the film made by alternately laminating PET etc. has excellent light reflectivity and heat ray reflectivity, and can be used as a reflective material. suitable.
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 explained in more detail with reference to Examples below.
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。 The physical properties were measured and the effects evaluated according to the following methods.
（１）ポリエステルの熱特性（ガラス転移点、結晶特性）
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（ティー・エイ・インスツルメント・ジャパン製：ＤＳＣ２５０）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度目の昇温過程で得られるガラス転移点の中間点を測定した。
(1) Thermal properties of polyester (glass transition point, crystal properties)
About 10 mg of the sample to be measured was weighed, sealed using an aluminum pan and a pan cover, and measured using a differential scanning calorimeter (manufactured by TA Instruments Japan: DSC250). 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 using liquid nitrogen, and then again from 20°C to 285°C at a rate of 16°C/min in a nitrogen atmosphere. Increase temperature. The midpoint of the glass transition point obtained during this second heating process was measured.
また、上記測定において２度目の昇温過程で得られる融解熱量が４Ｊ／ｇ以下である樹脂組成物を本発明における非晶性と定義した。 Further, in the above measurement, a resin composition in which the heat of fusion obtained in the second heating process was 4 J/g or less was defined as amorphous in the present invention.
（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。
(2) Refractive index of polyester An unstretched sheet with a thickness of 100 μm is obtained by melt-extruding a polyester resin composition. Then, the refractive index was measured using an "Abbe refractometer NAR-4T" manufactured by Atago Co., Ltd. at a temperature of 23° C. using sodium D line as a light source.
（３）ポリエステルの固有粘度
オルトクロロフェノール１０ｍｌに、測定試料を１００℃で溶解させ（溶液濃度Ｃ（測定試料重量／溶液体積）＝０．０８ｇ／ｍＬ）、粘度計を用いてその溶液の２５℃での粘度を測定した。また、同様に溶媒の粘度を測定した。得られた溶液粘度、溶媒粘度を用いて、下記式（α）により、［η］を算出し、得られた値をもって固有粘度とした。
ηｓｐ／Ｃ＝［η］＋Ｋ［η］２・Ｃ （α）
（ここで、ηｓｐ＝（溶液粘度／溶媒粘度）－１、Ｋはハギンス定数（０．３４３とする）である。）
なお、測定試料を溶解させた溶液に無機粒子などの不溶物がある場合は、以下の（ｉ）～（ｉｖ）の方法を用いて測定を行った。
（ｉ）オルトクロロフェノール１０ｍＬに測定試料を溶解させ、溶液濃度が０．０８ｇ／ｍＬよりも濃い溶液を作成する。ここで、オルトクロロフェノールに供した測定試料の重量を測定試料重量とする。
（ｉｉ）次に、不溶物を含む溶液を濾過し、不溶物の重量測定と、濾過後の濾液の体積測定を行う。
（ｉｉｉ）濾過後の濾液にオルトクロロフェノールを追加して、（測定試料重量（ｇ）－不溶物の重量（ｇ））／（濾過後の濾液の体積（ｍＬ）＋追加したオルトクロロフェノールの体積（ｍＬ））が、０．０８ｇ／ｍＬとなるように調整する。
(3) Intrinsic viscosity of polyester Dissolve the sample to be measured in 10 ml of orthochlorophenol at 100°C (solution concentration C (measured sample weight/solution volume) = 0.08 g/mL), and use a viscometer to measure the The viscosity at °C was measured. In addition, the viscosity of the solvent was measured in the same manner. Using the obtained solution viscosity and solvent viscosity, [η] was calculated by the following formula (α), and the obtained value was taken as the intrinsic viscosity.
ηsp/C=[η]+K[η]2・C (α)
(Here, ηsp=(solution viscosity/solvent viscosity)-1, K is Huggins constant (set to 0.343).)
Note that when there were insoluble substances such as inorganic particles in the solution in which the measurement sample was dissolved, measurements were performed using the following methods (i) to (iv).
(i) Dissolve the measurement sample in 10 mL of orthochlorophenol to create a solution with a concentration higher than 0.08 g/mL. Here, the weight of the measurement sample subjected to orthochlorophenol is defined as the measurement sample weight.
(ii) Next, the solution containing insoluble matter is filtered, and the weight of the insoluble matter and the volume of the filtrate after filtration are measured.
(iii) Add orthochlorophenol to the filtrate after filtration, (measured sample weight (g) - weight of insoluble matter (g)) / (volume of filtrate after filtration (mL) + added orthochlorophenol) Adjust the volume (mL) to 0.08 g/mL.
（例えば、測定試料重量１．００ｇ／溶液体積１０ｍＬの濃厚溶液を作成したときに、該溶液を濾過したときの不溶物の重量が０．０２ｇ、濾過後の濾液の体積が９．９ｍＬであった場合は、オルトクロロフェノールを５．１ｍＬ追加する調整を実施する。（（１．００ｇ－０．２０ｇ）／（９．９ｍＬ＋０．１ｍＬ）＝０．０８ｇ／ｍＬ））
（ｉｖ）粘度計を用いて（ｉｉｉ）で得られた溶液の２５℃での粘度を測定し、得られた溶液粘度、溶媒粘度を用いて、上記式（α）により、［η］を算出し、得られた値をもって固有粘度とする。
(For example, when a concentrated solution with a measurement sample weight of 1.00 g/solution volume of 10 mL is created, the weight of insoluble matter when the solution is filtered is 0.02 g, and the volume of the filtrate after filtration is 9.9 mL. If so, add 5.1 mL of orthochlorophenol. ((1.00 g - 0.20 g) / (9.9 mL + 0.1 mL) = 0.08 g/mL))
(iv) Measure the viscosity of the solution obtained in (iii) at 25°C using a viscometer, and use the obtained solution viscosity and solvent viscosity to calculate [η] using the above formula (α). The obtained value is taken as the intrinsic viscosity.
なお、粘度計は（株）離合社製の自動粘度計装置（ＶＭＲ－０５２ＵＰＣ・Ｆ１０）を使用した。 As the viscometer, an automatic viscometer (VMR-052UPC/F10) manufactured by Rigosha Co., Ltd. was used.
（４）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（ｂ値）として測定し、ｂ値が１２以下である場合を◎、１５以下かつ１２を超える場合を〇、１５を超える場合を×として、○、◎である場合のみを合格として判定した。
(4) Color tone of polyester Polyester chips are measured as Hunter value (b value) using a color difference meter (manufactured by Suga Test Instruments Co., Ltd., SM color computer model SM-T45), and if the b value is 12 or less, ◎ , 15 or less and more than 12 were rated as ○, and those in excess of 15 were rated as ×, and only ◎ and ◎ were judged as passing.
（５）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、２．５％以下である場合のみを合格とした。
(5) Haze value of polymer Dissolve 2 g of polyester chips in 20 ml of o-chlorophenol, and measure by integrating sphere photoelectric photometry using a quartz cell with an optical path length of 20 mm and a haze meter (HGM-2DP type, manufactured by Suga Test Instruments Co., Ltd.). The haze value of the solution was measured, and only those cases where the haze value was 2.5% or less were considered to be passed.
（６）ポリエステル樹脂組成物中のリン、および金属の定量
堀場製作所製蛍光Ｘ線装置（型番ＭＥＳＡ－５００Ｗ）を用い、ポリマーの蛍光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。
(6) Quantification of phosphorus and metal in polyester resin composition The intensity of fluorescent X-rays of the polymer was measured using a fluorescent X-ray device manufactured by Horiba, Ltd. (model number MESA-500W). This value was converted into metal content using a calibration curve prepared in advance using samples with known contents.
（７）ポリエステル樹脂組成物中のアルカリ金属の定量
試料１ｇを白金皿にとり、７００℃にて１．５ｈｒかけて完全に灰化させ、つぎに灰化物を０．２５Ｎ塩酸水溶液２０ｍＬに溶かし、０．１Ｎ塩酸水溶液となるように純水を加え測定試料とし、原子吸光分析法（フレーム：アセチレン－空気）にて定量を行った。測定吸光度が１．０を超える場合、０．１Ｎ塩酸水溶液を用いて希釈して、測定吸光度が１．０を超えない濃度で定量を行った。
なお、装置は島津製作所製の原子吸光分光光度計（ＡＡ－６３００）を用いた。
(7) Quantification of alkali metal in polyester resin composition Take 1 g of sample in a platinum dish, completely incinerate at 700°C for 1.5 hr, then dissolve the ash in 20 mL of 0.25N hydrochloric acid aqueous solution, Pure water was added to make a .1N aqueous hydrochloric acid solution to prepare a measurement sample, and quantification was performed using atomic absorption spectrometry (frame: acetylene-air). When the measured absorbance exceeded 1.0, it was diluted with a 0.1N aqueous hydrochloric acid solution and quantified at a concentration at which the measured absorbance did not exceed 1.0.
The apparatus used was an atomic absorption spectrophotometer (AA-6300) manufactured by Shimadzu Corporation.
（８）ポリマーの耐熱分解性評価
十分に乾燥させたポリエステルチップを３００℃窒素雰囲気下で１時間溶融した際の固有粘度と、未処理のポリエステルチップの固有粘度の差を比較し、０．１以下である場合のみを合格とした。
(8) Evaluation of thermal decomposition resistance of polymer Compare the intrinsic viscosity of sufficiently dried polyester chips by melting them in a nitrogen atmosphere at 300°C for 1 hour and the difference in the intrinsic viscosity of untreated polyester chips. Only the following cases were considered to have passed.
（９）エチレングリコールの回収性評価
重合反応時に留出する余剰エチレングリコール１５０ｍｌを撹拌しながら常圧で１９５℃から２０５℃で留出させ、初留２０ｍｌを廃棄したのち中留３０ｍｌを採取する。得られた中留を撹拌しながら１２０ｍｌのイオン交換水にて希釈し、析出物が確認されなかった場合を○、析出物が確認された場合を×として判定した。
(9) Evaluation of recoverability of ethylene glycol 150 ml of excess ethylene glycol distilled out during the polymerization reaction is distilled at normal pressure from 195° C. to 205° C. while stirring, and after discarding 20 ml of the initial distillate, 30 ml of the middle distillate is collected. The obtained middle distillate was diluted with 120 ml of ion-exchanged water while stirring, and the case where no precipitate was observed was evaluated as ◯, and the case where precipitate was observed was evaluated as ×.
実施例１（以下において、実施例１～１３を参考例１～１３と読み替える）
（ポリエステルの合成）
テレフタル酸ジメチルを５６．３重量部、１，４－シクロヘキサンジカルボン酸を２３．７重量部、エチレングリコールを５０．１重量部、スピログリコール２６．１重量部、水酸化カリウム０．００５重量部をそれぞれ計量し、エステル交換反応槽に仕込んだ。内容物を１５０℃で溶解させて撹拌した。酢酸マグネシウム４水和物０．０５３重量部を添加し、エステル交換反応をスタートした。
Example 1 (Hereinafter, Examples 1 to 13 will be read as Reference Examples 1 to 13)
(Synthesis of polyester)
56.3 parts by weight of dimethyl terephthalate, 23.7 parts by weight of 1,4-cyclohexanedicarboxylic acid, 50.1 parts by weight of ethylene glycol, 26.1 parts by weight of spiroglycol, and 0.005 parts by weight of potassium hydroxide. Each was weighed and charged into a transesterification reactor. The contents were dissolved and stirred at 150°C. 0.053 parts by weight of magnesium acetate tetrahydrate was added to start the transesterification reaction.
撹拌しながら反応内容物の温度を２２０℃まで規定の昇温プログラムにて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、余剰のエチレングリコールを留出させながら３０分間で２３０℃まで昇温を行った。その後、２１０Ｔｏｒｒで２０分間初期重合を行い、エチレングリコールを留出させ、低重合体を得た。 Methanol was distilled off while stirring and raising the temperature of the reaction contents to 220° C. according to a prescribed heating program. After a predetermined amount of methanol had been distilled off, the temperature was raised to 230° C. for 30 minutes while distilling off excess ethylene glycol. Thereafter, initial polymerization was performed at 210 Torr for 20 minutes, and ethylene glycol was distilled off to obtain a low polymer.
得られた低重合体を重合反応槽へ移行した後、攪拌しながらリン化合物であるジエチルホスホノ酢酸エチル０．０４３重量部およびリン酸アルカリ金属塩であるリン酸一水素二カリウムを０．０３０重量部添加し、１５分後にテトラブトキシチタンを０．０２１重量部添加、その５分後から２８５℃まで徐々に昇温、および減圧を行い、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。最終圧力は０．１Ｔｏｒｒであった。 After transferring the obtained low polymer to a polymerization reaction tank, 0.043 parts by weight of ethyl diethylphosphonoacetate, which is a phosphorus compound, and 0.030 parts by weight of dipotassium monohydrogen phosphate, which is an alkali metal phosphate salt, were added while stirring. After 15 minutes, 0.021 parts by weight of tetrabutoxytitanium was added, and after 5 minutes, the temperature was gradually raised to 285° C. and the pressure was reduced to carry out polymerization while distilling ethylene glycol. The final pressure was 0.1 Torr.
重合装置の撹拌トルクが所定の値に達したら重合反応槽内を窒素ガスにて常圧へ戻し、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、ポリエステル樹脂組成物Ａを得た。 When the stirring torque of the polymerization apparatus reached a predetermined value, the inside of the polymerization reaction tank was returned to normal pressure with nitrogen gas, and the gut-shaped polymer was discharged into a water tank. The polyester gut cooled in the water tank was cut with a cutter to obtain polyester resin composition A.
得られたポリエステル樹脂組成物は、屈折率１．５４５、ガラス転移点７８℃、融解熱量０Ｊ／ｇ、固有粘度０．７０、ｂ値１１．０、溶液ヘイズ０．８％であり、３００℃窒素雰囲気下で１時間溶融した際の固有粘度は０．６６と、固有粘度差は０．０４であった。また、エチレングリコールの回収性は×であった。 The obtained polyester resin composition had a refractive index of 1.545, a glass transition point of 78°C, a heat of fusion of 0 J/g, an intrinsic viscosity of 0.70, a b value of 11.0, a solution haze of 0.8%, and a temperature of 300°C. The intrinsic viscosity when melted for 1 hour in a nitrogen atmosphere was 0.66, and the intrinsic viscosity difference was 0.04. Moreover, the recoverability of ethylene glycol was poor.
（積層ポリエステルフィルムの製膜）
前記ポリエステル樹脂組成物ＡおよびＰＥＴ樹脂をそれぞれ真空乾燥した後、２台の押出機にそれぞれ供給した。
(Formation of laminated polyester film)
After drying the polyester resin composition A and the PET resin in vacuum, they were each supplied to two extruders.
ポリエステル樹脂組成物ＡおよびＰＥＴ樹脂は、それぞれ、押出機にて２８０℃の溶融状態とし、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樹脂組成物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樹脂組成物Ａ層は５０層、ＰＥＴ層は５１層となるように交互に積層した。 Polyester resin composition A and PET resin were melted at 280° C. in an extruder, passed through a gear pump and a filter, and then merged in 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 layers were alternately laminated so that the laminated thickness was 1/2 of polyester resin composition A layer/PET resin layer. That is, 50 polyester resin composition A layers and 51 PET layers were alternately laminated.
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 thus obtained laminate consisting of 101 layers was supplied to a die, extruded into a sheet, and rapidly solidified on a casting drum whose surface temperature was maintained at 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。本発明のポリエステル組成物は屈折率が低いため、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 obtained cast film was introduced into a roll-type longitudinal stretching machine, heated by a group of rolls heated to 90° C., and stretched three times in the longitudinal direction between rolls having different circumferential speeds. The film that had been stretched in the longitudinal direction was then introduced into a tenter type transverse stretching machine. The film was preheated in a tenter with hot air at 100°C and stretched 3.3 times in the transverse direction. The stretched film was heat-treated as it was in a tenter with hot air at 200°C. In this way, a film with a thickness of 50 μm could be obtained. Since the polyester composition of the present invention had a low refractive index, it had excellent light reflectivity when formed into a laminated film.
実施例２
リン酸アルカリ金属塩をリン酸二水素一カリウムに変更する以外は実施例１と同様にしてポリエステル樹脂組成物を得た。
Example 2
A polyester resin composition was obtained in the same manner as in Example 1 except that the alkali metal phosphate was changed to monopotassium dihydrogen phosphate.
得られたポリエステル樹脂組成物は屈折率１．５４５、ガラス転移点７８℃、融解熱量０Ｊ／ｇ、固有粘度０．７１、ｂ値１１．２、溶液ヘイズ０．７％であり、３００℃窒素雰囲気下で１時間溶融した際の固有粘度は０．６７と、固有粘度差は０．０５であった。また、エチレングリコールの回収性は×であった。 The obtained polyester resin composition had a refractive index of 1.545, a glass transition point of 78°C, a heat of fusion of 0 J/g, an intrinsic viscosity of 0.71, a b value of 11.2, and a solution haze of 0.7%. The intrinsic viscosity when melted in an atmosphere for 1 hour was 0.67, and the intrinsic viscosity difference was 0.05. Moreover, the recoverability of ethylene glycol was poor.
実施例３
リン酸アルカリ金属塩をリン酸二水素一ナトリウムに変更する以外は実施例１と同様にしてポリエステル樹脂組成物を得た。
Example 3
A polyester resin composition was obtained in the same manner as in Example 1 except that the alkali metal phosphate was changed to monosodium dihydrogen phosphate.
得られたポリエステル樹脂組成物は屈折率１．５４５、ガラス転移点７８℃、融解熱量０Ｊ／ｇ、固有粘度０．７１、色調ｂ値１１．０、溶液ヘイズ０．８であり、３００℃窒素雰囲気下で１時間溶融した際の固有粘度は０．６６と、固有粘度差は０．０６であった。また、エチレングリコールの回収性は×であった。 The obtained polyester resin composition had a refractive index of 1.545, a glass transition point of 78°C, a heat of fusion of 0 J/g, an intrinsic viscosity of 0.71, a color b value of 11.0, and a solution haze of 0.8. The intrinsic viscosity when melted in an atmosphere for 1 hour was 0.66, and the intrinsic viscosity difference was 0.06. Moreover, the recoverability of ethylene glycol was poor.
実施例４、５、比較例３、４
添加するアルカリ金属量を変更する以外は実施例１と同様にしてポリエステル樹脂組成物を得た。
Examples 4 and 5, Comparative Examples 3 and 4
A polyester resin composition was obtained in the same manner as in Example 1 except that the amount of alkali metal added was changed.
実施例４においては、リン酸一水素二カトリウムをカリウム量として５ｐｐｍ、水酸化カリウムをカリウム量として５ｐｐｍとし、実施例１の総リン量と合わせるためにジエチルホスホノ酢酸エチルをリン量として１１３ｐｐｍとした結果、得られた組成物の耐熱分解性評価結果が０．０９と実施例１に対して悪化傾向にあったが、本発明の合格範囲内であった。また、エチレングリコールの回収性は×であった。 In Example 4, dipotassium monohydrogen phosphate was used as a potassium amount of 5 ppm, potassium hydroxide was used as a potassium amount of 5 ppm, and in order to match the total phosphorus amount of Example 1, ethyl phosphonoacetate was used as a phosphorus amount of 113 ppm. As a result, the thermal decomposition resistance evaluation result of the obtained composition was 0.09, which was a tendency to deteriorate compared to Example 1, but was within the acceptable range of the present invention. Moreover, the recoverability of ethylene glycol was poor.
実施例５においては、リン酸一水素ニカリウムをカリウム量として１００ｐｐｍ、水酸化カリウムをカリウム量として１００ｐｐｍとし、ジエチルホスホノ酢酸エチルの添加をなくした結果、溶液ヘイズが１．８％、色調Ｌ値が６１．５、ｂ値１３．４とそれぞれ悪化傾向にあったが、本発明の合格範囲内であった。また、エチレングリコールの回収性は×であった。 In Example 5, the amount of potassium dipotassium hydrogen phosphate was 100 ppm, the amount of potassium hydroxide was 100 ppm, and the addition of ethyl diethylphosphonoacetate was eliminated, resulting in a solution haze of 1.8% and a color tone L value. The b value was 61.5, and the b value was 13.4, which were both on a deteriorating trend, but were within the acceptable range of the present invention. Moreover, the recoverability of ethylene glycol was poor.
比較例３においては、リン酸一水素ニカリウムをカリウム量として５ｐｐｍ、水酸化カリウムの添加をなくし、ジエチルホスホノ酢酸エチルをリン量として１１３ｐｐｍとすることにより、アルカリ金属量を好ましい範囲の下限である１０ｐｐｍより少なくした結果、重合反応中に架橋反応が起こり、組成物を得ることができなかった。 In Comparative Example 3, the amount of alkali metal is at the lower limit of the preferable range by using dipotassium monohydrogen phosphate as a potassium amount of 5 ppm, eliminating the addition of potassium hydroxide, and using diethylphosphonoacetate as a phosphorus amount of 113 ppm. When the amount was less than 10 ppm, a crosslinking reaction occurred during the polymerization reaction, making it impossible to obtain a composition.
比較例４においては、水酸化カリウムをカリウム量として２００ｐｐｍとすることにより、アルカリ金属量を好ましい範囲の上限である２００ｐｐｍより多くした結果、耐熱分解性評価結果は０．０９と合格値であったが、ヘイズ値が３．８、色調Ｌ値が５５．８、ｂ値が１８．７と合格範囲外であり、本発明の用途へは適用不可であった。また、エチレングリコールの回収性は×であった。 In Comparative Example 4, the amount of alkali metal was increased from the upper limit of the preferred range of 200 ppm by setting the amount of potassium hydroxide to 200 ppm, and as a result, the thermal decomposition resistance evaluation result was 0.09, which was a passing value. However, the haze value was 3.8, the color tone L value was 55.8, and the b value was 18.7, which were outside the acceptable range and could not be applied to the purpose of the present invention. Moreover, the recoverability of ethylene glycol was poor.
実施例６～８、１４～１６比較例５、６
エステル交換反応触媒量、エステル交換反応触媒種を変更する以外は実施例１と同様にしてポリエステル樹脂組成物を得た。
Examples 6-8, 14-16 Comparative Examples 5, 6
A polyester resin composition was obtained in the same manner as in Example 1 except that the amount of the transesterification catalyst and the species of the transesterification catalyst were changed.
実施例６においては、酢酸マグネシウム４水和物をマグネシウムとして３０ｐｐｍとした結果、実施例１と比較して若干の重合反応遅延が起こったが、問題のないレベルであった。また、エチレングリコールの回収性は×であった。 In Example 6, the magnesium acetate tetrahydrate was adjusted to 30 ppm as magnesium, and as a result, the polymerization reaction was slightly delayed compared to Example 1, but it was at a level that caused no problems. Moreover, the recoverability of ethylene glycol was poor.
実施例７においては、酢酸マグネシウム４水和物をマグネシウムとして１００ｐｐｍとした結果、耐熱分解性評価結果が０．０８、色調ｂ値が１４．４と実施例１と比較して悪化傾向にあったが、いずれも本発明の合格範囲内であった。また、エチレングリコールの回収性は×であった。 In Example 7, as a result of setting magnesium acetate tetrahydrate to 100 ppm as magnesium, the heat decomposition resistance evaluation result was 0.08, and the color tone b value was 14.4, which tended to deteriorate compared to Example 1. However, all of them were within the acceptable range of the present invention. Moreover, the recoverability of ethylene glycol was poor.
実施例８においては、エステル交換反応触媒を酢酸マンガン４水和物とした結果、ヘイズ値が２．５％、色調Ｌ値が６０．７と実施例１と比較して悪化傾向にあったが、いずれも本発明の合格範囲内であった。また、エチレングリコールの回収性は○であった。 In Example 8, as a result of using manganese acetate tetrahydrate as the transesterification reaction catalyst, the haze value was 2.5% and the color L value was 60.7, which tended to be worse compared to Example 1. , all were within the acceptable range of the present invention. Moreover, the recoverability of ethylene glycol was rated as ○.
実施例１４においては、エステル交換反応触媒として酢酸マグネシウム４水和物をマグネシウムとして５７ｐｐｍ、酢酸マンガン４水和物をマンガンとして３ｐｐｍとした結果、溶液ヘイズが実施例１と比較して悪化傾向にあったが、本発明の合格範囲であった。また、エチレングリコールの回収性は○であった。 In Example 14, as a transesterification reaction catalyst, magnesium acetate tetrahydrate was used as magnesium at 57 ppm, and manganese acetate tetrahydrate was used as manganese at 3 ppm, and as a result, the solution haze tended to worsen compared to Example 1. However, it was within the acceptable range of the present invention. Moreover, the recoverability of ethylene glycol was rated as ○.
実施例１５においては、エステル交換反応触媒として酢酸マグネシウム４水和物をマグネシウムとして５４ｐｐｍ、酢酸マンガン４水和物をマンガンとして６ｐｐｍとした結果、溶液ヘイズが実施例１と比較して悪化傾向にあったが、本発明の合格範囲であった。また、エチレングリコールの回収性は○であった。 In Example 15, as a transesterification reaction catalyst, magnesium acetate tetrahydrate was used as magnesium at 54 ppm, and manganese acetate tetrahydrate was used as manganese at 6 ppm, and as a result, the solution haze tended to worsen compared to Example 1. However, it was within the acceptable range of the present invention. Moreover, the recoverability of ethylene glycol was rated as ○.
実施例１６においては、エステル交換反応触媒として酢酸マグネシウム４水和物をマグネシウムとして４２ｐｐｍ、酢酸マンガン４水和物をマンガンとして１８ｐｐｍとした結果、溶液ヘイズが実施例１と比較して悪化傾向にあったが、本発明の合格範囲であった。また、エチレングリコールの回収性は○であった。 In Example 16, as a transesterification reaction catalyst, magnesium acetate tetrahydrate was used as magnesium at 42 ppm, and manganese acetate tetrahydrate was used as manganese at 18 ppm, and as a result, the solution haze tended to worsen compared to Example 1. However, it was within the acceptable range of the present invention. Moreover, the recoverability of ethylene glycol was rated as ○.
比較例５においては、酢酸マグネシウム４水和物をマグネシウムとして１０ｐｐｍとすることにより、マグネシウム量を好ましい範囲の下限である３０ｐｐｍより少なくした結果、エステル交換反応が不十分となり、重合反応が進行せず、組成物を得ることができなかった。 In Comparative Example 5, magnesium acetate tetrahydrate was adjusted to 10 ppm as magnesium, thereby reducing the amount of magnesium below the preferable lower limit of 30 ppm, resulting in insufficient transesterification and the polymerization reaction not proceeding. , the composition could not be obtained.
比較例６においては、酢酸マグネシウム４水和物をマグネシウムとして１５０ｐｐｍとすることにより、マグネシウム量を好ましい範囲の上限である１００ｐｐｍより少なくした結果、耐熱分解性評価結果が０．１２、色調ｂ値が１６．９と合格範囲外であり、本発明の用途へは適用不可であった。また、エチレングリコールの回収性は×であった。 In Comparative Example 6, magnesium acetate tetrahydrate was adjusted to 150 ppm as magnesium, thereby reducing the amount of magnesium below the upper limit of the preferred range of 100 ppm, resulting in a heat decomposition resistance evaluation result of 0.12 and a color tone b value of 150 ppm. 16.9, which was outside the acceptable range, and could not be applied to the purpose of the present invention. Moreover, the recoverability of ethylene glycol was poor.
実施例９、１０、比較例７、８
重合反応触媒量を変更する以外は実施例１と同様にしてポリエステル樹脂組成物を得た。
Examples 9 and 10, Comparative Examples 7 and 8
A polyester resin composition was obtained in the same manner as in Example 1 except that the amount of polymerization reaction catalyst was changed.
実施例９においては、テトラブトキシチタンをチタン量として５ｐｐｍとした結果、実施例１と比較して重合反応遅延が起こったが、問題のないレベルであった。また、エチレングリコールの回収性は×であった。 In Example 9, as a result of using tetrabutoxytitanium as a titanium amount of 5 ppm, the polymerization reaction was delayed compared to Example 1, but it was at a level that caused no problem. Moreover, the recoverability of ethylene glycol was poor.
実施例１０においては、テトラブトキシチタンをチタン量として１００ｐｐｍとした結果、若干の架橋反応と、色調ｂ値が１４．８と悪化傾向にあったが、本発明の合格範囲内であった。また、エチレングリコールの回収性は×であった。 In Example 10, as a result of setting the titanium content to 100 ppm using tetrabutoxytitanium, there was a slight crosslinking reaction and the color tone b value was 14.8, which tended to deteriorate, but was within the acceptable range of the present invention. Moreover, the recoverability of ethylene glycol was poor.
比較例７においては、テトラブトキシチタンをチタン量として１ｐｐｍとすることにより、チタン量を好ましい範囲の下限である５ｐｐｍより少なくした結果、重合反応が進行せず、組成物を得ることができなかった。 In Comparative Example 7, by setting the amount of titanium in tetrabutoxytitanium to 1 ppm, the amount of titanium was reduced to less than 5 ppm, which is the lower limit of the preferable range, and as a result, the polymerization reaction did not proceed and a composition could not be obtained. .
比較例８においては、テトラブトキシチタンをチタン量として１５０ｐｐｍとすることにより、チタン量を好ましい範囲の上限である１００ｐｐｍより多くした結果、若干の架橋反応と、耐熱分解性評価結果が０．１１、色調ｂ値が１９．４と合格範囲外であり、本発明の用途へは適用不可であった。また、エチレングリコールの回収性は×であった。 In Comparative Example 8, by setting the titanium amount of tetrabutoxytitanium to 150 ppm, the titanium amount was increased from 100 ppm, which is the upper limit of the preferable range, and as a result, a slight crosslinking reaction and a thermal decomposition resistance evaluation result of 0.11, The color tone b value was 19.4, which was outside the acceptable range, and could not be applied to the purpose of the present invention. Moreover, the recoverability of ethylene glycol was poor.
実施例１１～１３、比較例９、１０
総リン量、リン化合物量を変更する以外は実施例１と同様にしてポリエステル樹脂組成物を得た。
Examples 11 to 13, Comparative Examples 9 and 10
A polyester resin composition was obtained in the same manner as in Example 1 except that the total amount of phosphorus and the amount of phosphorus compound were changed.
実施例１１においては、ジエチルホスホノ酢酸エチルをリン量として１０ｐｐｍとした結果、耐熱分解性評価結果が０．０９、色調ｂ値が１３．９と実施例１と比較して悪化傾向にあったが、本発明の合格範囲内であった。また、エチレングリコールの回収性は×であった。 In Example 11, as a result of setting the phosphorus content of ethyl diethylphosphonoacetate to 10 ppm, the heat decomposition resistance evaluation result was 0.09, and the color tone b value was 13.9, which tended to deteriorate compared to Example 1. was within the acceptable range of the present invention. Moreover, the recoverability of ethylene glycol was poor.
実施例１２においては、ジエチルホスホノ酢酸エチルをリン量として２４０ｐｐｍとした結果、実施例１と比較して重合反応遅延が起こり、ヘイズ値も２．１と悪化傾向にあったが、本発明の合格範囲内であった。また、エチレングリコールの回収性は×であった。 In Example 12, as a result of setting the phosphorus content of ethyl diethylphosphonoacetate to 240 ppm, the polymerization reaction was delayed compared to Example 1, and the haze value also tended to deteriorate to 2.1. It was within the passing range. Moreover, the recoverability of ethylene glycol was poor.
実施例１３においては、ジエチルホスホノ酢酸エチルをリン酸トリメチルに変更し、リン量として６０ｐｐｍ添加した結果、特に問題なく本発明の合格範囲内であった。また、エチレングリコールの回収性は×であった。 In Example 13, ethyl diethylphosphonoacetate was replaced with trimethyl phosphate and the amount of phosphorus added was 60 ppm, which was within the acceptable range of the present invention without any particular problem. Moreover, the recoverability of ethylene glycol was poor.
比較例９においては、リン酸一水素二カリウムをリン量として５０ｐｐｍとし、ジエチルホスホノ酢酸エチルの添加をなくすことにより、リン量を好ましい範囲の下限である７０ｐｐｍより少なくした結果、若干の架橋反応が起こり、耐熱分解性評価結果が０．１５、色調ｂ値が１７．６と合格範囲外であり、本発明の用途へは適用不可であった。また、エチレングリコールの回収性は×であった。 In Comparative Example 9, the amount of phosphorus in dipotassium monohydrogen phosphate was set at 50 ppm, and the addition of ethyl diethylphosphonoacetate was made to reduce the amount of phosphorus to less than 70 ppm, which is the lower limit of the preferable range, resulting in a slight crosslinking reaction. occurred, the thermal decomposition resistance evaluation result was 0.15, and the color tone b value was 17.6, which were outside the acceptable range, and could not be applied to the uses of the present invention. Moreover, the recoverability of ethylene glycol was poor.
比較例１０においては、ジエチルホスホノ酢酸エチルをリンとして２９０ｐｐｍとすることにより、リン量を好ましい範囲の上限である３００ｐｐｍより多くした結果、重合反応が進行せず、組成物を得ることができなかった。 In Comparative Example 10, as a result of increasing the amount of phosphorus from 300 ppm, which is the upper limit of the preferable range, by setting the amount of phosphorus in ethyl diethylphosphonoacetate to 290 ppm, the polymerization reaction did not proceed and a composition could not be obtained. Ta.
比較例１
テレフタル酸ジメチルおよびエチレングリコールのみを用いたポリエチレンテレフタレート組成にて実施例１と同様の触媒、添加物のポリエステル樹脂組成物を得た結果、得られた組成物は融解熱量３４Ｊ／ｇと結晶性であり、本発明の用途への適用は不可であった。また、エチレングリコールの回収性は×であった。
Comparative example 1
A polyester resin composition with the same catalyst and additives as in Example 1 was obtained using a polyethylene terephthalate composition using only dimethyl terephthalate and ethylene glycol. The resulting composition had a heat of fusion of 34 J/g and was crystalline. Therefore, application to the purpose of the present invention was not possible. Moreover, the recoverability of ethylene glycol was poor.
比較例２
リン酸アルカリ金属塩の添加を行わず、ジエチルホスホノ酢酸エチルを実施例１の総リン量に合わせて１２０ｐｐｍとする以外は実施例１と同様にしてポリエステル樹脂組成物を得た結果、耐熱分解性評価結果が０．１４と合格範囲外であり、本発明の用途への適用は不可であった。また、エチレングリコールの回収性は×であった。
Comparative example 2
A polyester resin composition was obtained in the same manner as in Example 1, except that no alkali metal phosphate was added and ethyl diethylphosphonoacetate was adjusted to 120 ppm to match the total phosphorus amount in Example 1. The performance evaluation result was 0.14, which was outside the acceptable range, and the product could not be applied to the purposes of the present invention. Moreover, the recoverability of ethylene glycol was poor.
Claims (7)
アルカリ金属の含有量が組成物との重量比として１０ｐｐｍ以上２００ｐｐｍ以下、
チタンの含有量が得られる組成物との重量比として５ｐｐｍ以上１００ｐｐｍ以下、
リン含有量が７０ｐｐｍ以上３００ｐｐｍ以下、
マグネシウムとマンガンの総含有量が得られる組成物との重量比として３０ｐｐｍ以上１００ｐｐｍであって、
マグネシウム（Ｍｇ）とマンガン（Ｍｎ）のモル比として下記式（１）を満たすポリエステル樹脂組成物。
０．０５≦Ｍｎ／Ｍｇ≦０．４３・・・（１） Contains amorphous and alkali metal phosphate salt,
The content of alkali metal is 10 ppm or more and 200 ppm or less as a weight ratio to the composition,
The weight ratio of titanium to the composition obtained is 5 ppm or more and 100 ppm or less,
Phosphorus content is 70 ppm or more and 300 ppm or less,
The total content of magnesium and manganese is 30 ppm or more and 100 ppm as a weight ratio of the composition obtained,
A polyester resin composition that satisfies the following formula (1) as a molar ratio of magnesium (Mg) and manganese (Mn).
0.05≦Mn/Mg≦0.43...(1)
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2006176556A (en) | 2004-12-21 | 2006-07-06 | Daicel Chem Ind Ltd | Transparent polyester resin composition |
| JP2009001656A (en) | 2007-06-21 | 2009-01-08 | Toray Ind Inc | Method of manufacturing polyester, and film formed using the same |
| JP2018100339A (en) | 2016-12-20 | 2018-06-28 | 東レ株式会社 | Polyester composition and biaxially stretched polyester film of the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2006176556A (en) | 2004-12-21 | 2006-07-06 | Daicel Chem Ind Ltd | Transparent polyester resin composition |
| JP2009001656A (en) | 2007-06-21 | 2009-01-08 | Toray Ind Inc | Method of manufacturing polyester, and film formed using the same |
| JP2018100339A (en) | 2016-12-20 | 2018-06-28 | 東レ株式会社 | Polyester composition and biaxially stretched polyester film of the same |
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