JPH04370142A - Production of polyester composition - Google Patents
Production of polyester compositionInfo
- Publication number
- JPH04370142A JPH04370142A JP17461991A JP17461991A JPH04370142A JP H04370142 A JPH04370142 A JP H04370142A JP 17461991 A JP17461991 A JP 17461991A JP 17461991 A JP17461991 A JP 17461991A JP H04370142 A JPH04370142 A JP H04370142A
- Authority
- JP
- Japan
- Prior art keywords
- weight
- parts
- added
- polyester
- fine particles
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 48
- 229920000728 polyester Polymers 0.000 title claims abstract description 36
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 15
- 239000002245 particle Substances 0.000 claims abstract description 51
- -1 alkaline-earth metal salt Chemical class 0.000 claims abstract description 45
- 239000010419 fine particle Substances 0.000 claims abstract description 35
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 16
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 14
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 128
- 239000002253 acid Substances 0.000 claims description 8
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 7
- 150000002148 esters Chemical class 0.000 claims description 5
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 4
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 3
- 239000011574 phosphorus Substances 0.000 claims description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims 1
- 230000002776 aggregation Effects 0.000 abstract description 12
- 238000004220 aggregation Methods 0.000 abstract description 4
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 57
- 239000002002 slurry Substances 0.000 description 39
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 38
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 38
- 230000032050 esterification Effects 0.000 description 38
- 238000005886 esterification reaction Methods 0.000 description 38
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 34
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 description 22
- 239000011654 magnesium acetate Substances 0.000 description 22
- 235000011285 magnesium acetate Nutrition 0.000 description 22
- 229940069446 magnesium acetate Drugs 0.000 description 22
- 229920000642 polymer Polymers 0.000 description 22
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 21
- 239000011362 coarse particle Substances 0.000 description 20
- 229920000139 polyethylene terephthalate Polymers 0.000 description 20
- 239000005020 polyethylene terephthalate Substances 0.000 description 20
- 235000019832 sodium triphosphate Nutrition 0.000 description 19
- 229910000019 calcium carbonate Inorganic materials 0.000 description 17
- 238000011156 evaluation Methods 0.000 description 17
- 238000006068 polycondensation reaction Methods 0.000 description 17
- 229910052791 calcium Inorganic materials 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 12
- 238000003756 stirring Methods 0.000 description 10
- 238000000034 method Methods 0.000 description 9
- 238000005054 agglomeration Methods 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 230000002265 prevention Effects 0.000 description 3
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- 229920001283 Polyalkylene terephthalate Polymers 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
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 230000001588 bifunctional effect Effects 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 description 2
- 239000001639 calcium acetate Substances 0.000 description 2
- 235000011092 calcium acetate Nutrition 0.000 description 2
- 229960005147 calcium acetate Drugs 0.000 description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 2
- 239000000292 calcium oxide Substances 0.000 description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-N 0.000 description 1
- SWDVLAABQICXFS-UHFFFAOYSA-N 4-benzoylcyclohexa-2,4-diene-1,1-dicarboxylic acid Chemical compound C1=CC(C(=O)O)(C(O)=O)CC=C1C(=O)C1=CC=CC=C1 SWDVLAABQICXFS-UHFFFAOYSA-N 0.000 description 1
- LLLVZDVNHNWSDS-UHFFFAOYSA-N 4-methylidene-3,5-dioxabicyclo[5.2.2]undeca-1(9),7,10-triene-2,6-dione Chemical compound C1(C2=CC=C(C(=O)OC(=C)O1)C=C2)=O LLLVZDVNHNWSDS-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 229910052582 BN Inorganic materials 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- JYFHYPJRHGVZDY-UHFFFAOYSA-N Dibutyl phosphate Chemical compound CCCCOP(O)(=O)OCCCC JYFHYPJRHGVZDY-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 239000005083 Zinc sulfide 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
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- BNMJSBUIDQYHIN-UHFFFAOYSA-N butyl dihydrogen phosphate Chemical compound CCCCOP(O)(O)=O BNMJSBUIDQYHIN-UHFFFAOYSA-N 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 1
- 239000006059 cover glass Substances 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000010191 image analysis Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- OJURWUUOVGOHJZ-UHFFFAOYSA-N methyl 2-[(2-acetyloxyphenyl)methyl-[2-[(2-acetyloxyphenyl)methyl-(2-methoxy-2-oxoethyl)amino]ethyl]amino]acetate Chemical compound C=1C=CC=C(OC(C)=O)C=1CN(CC(=O)OC)CCN(CC(=O)OC)CC1=CC=CC=C1OC(C)=O OJURWUUOVGOHJZ-UHFFFAOYSA-N 0.000 description 1
- CAAULPUQFIIOTL-UHFFFAOYSA-N methyl dihydrogen phosphate Chemical compound COP(O)(O)=O CAAULPUQFIIOTL-UHFFFAOYSA-N 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 125000005487 naphthalate group Chemical group 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
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229920001281 polyalkylene Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 1
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 1
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Abstract
Description
【０００１】0001
【産業上の利用分野】本発明はポリエステル組成物、特
に磁気テープの製造に有用なポリエステル組成物の製造
方法に関し、さらに詳しくは芳香族ジカルボン酸を主と
する二官能性酸成分と少なくとも一種のグリコール成分
よりなるポリエステルと無機または有機性微粒子を含有
するエステル組成物を製造するに際し、該微粒子の凝集
を大幅に抑制するようにしたポリエステル組成物の製造
方法に関する。[Field of Industrial Application] The present invention relates to a method for producing a polyester composition, particularly a polyester composition useful for producing magnetic tapes, and more particularly, it relates to a method for producing a polyester composition useful for producing magnetic tapes, and more particularly, it relates to a method for producing a polyester composition useful for producing a magnetic tape, and more specifically, a method for producing a polyester composition useful for producing a magnetic tape. The present invention relates to a method for producing a polyester composition that significantly suppresses aggregation of the fine particles when producing an ester composition containing a polyester made of a glycol component and inorganic or organic fine particles.
【０００２】0002
【従来の技術】ポリエステル、特にポリエチレンテレフ
タレレートは優れた物理的、化学的特性を示しており、
繊維、フイルムその他の成形品として広く使用されてい
る。またこれらの組成物には、普通その用途に応じてさ
まざまな添加物が加えられており、更にその特性が向上
されている。[Prior Art] Polyesters, especially polyethylene terephthalate, exhibit excellent physical and chemical properties.
Widely used in fibers, films, and other molded products. Furthermore, various additives are usually added to these compositions depending on their intended use to further improve their properties.
【０００３】磁気テープフイルム製造用のポリエステル
組成物の場合、その滑り特性を改善するために通常滑剤
粒子と呼ばれる無機または有機性の微粒子がその組成物
に添加される。しかしながら、これらの微粒子はその粒
径が小さければ小さいほど凝集を起こしてしまうという
問題がある。そこで、それらの問題を改善するために以
前からさまざまな工夫がなされてきた。たとえば、無機
不活性微粒子を有機化合物で表面処理する方法（特開昭
４９−１３０４４８号、特開昭５６−２６９５８号など
）や分散剤をスラリーに添加する方法（特開昭５６−１
１０７２２、特開昭６０−１３９７５０など）などであ
る。しかしながら、これらの従来技術の方法をもってし
てもポリエステル中での該微粒子の凝集を抑制するには
不十分であった。In the case of polyester compositions for the production of magnetic tape films, inorganic or organic fine particles, called lubricant particles, are usually added to the composition in order to improve its sliding properties. However, there is a problem in that the smaller the particle size of these fine particles, the more they tend to aggregate. Therefore, various efforts have been made to improve these problems. For example, a method of surface treating inorganic inert fine particles with an organic compound (JP-A-49-130448, JP-A-56-26958, etc.) and a method of adding a dispersant to a slurry (JP-A-56-1
10722, JP-A-60-139750, etc.). However, even these prior art methods were insufficient to suppress agglomeration of the fine particles in polyester.
【０００４】0004
【発明が解決しようとする課題】本発明は、芳香族ジカ
ルボン酸を主とする二官能性酸成分と少なくとも一種の
グリコール成分よりなるポリエステルと無機または有機
性微粒子を含有する磁気テープ製造用ポリエステル組成
物を製造する際に起こる該微粒子の凝集を防止し、また
、それらを磁気テープ用ベースフイルムとして用いた場
合に、フイルムの欠点となるドロップアウトが非常に少
なくなるようなポリエステル組成物の製造方法を提供し
ようとするものである。Problem to be Solved by the Invention The present invention provides a polyester composition for manufacturing magnetic tapes containing a polyester consisting of a bifunctional acid component mainly consisting of an aromatic dicarboxylic acid and at least one glycol component, and inorganic or organic fine particles. A method for producing a polyester composition that prevents the agglomeration of the fine particles that occurs during the production of the product, and that when used as a base film for a magnetic tape, dropout, which is a drawback of the film, is extremely reduced. This is what we are trying to provide.
【０００５】[0005]
【課題を解決するための手段】即ち、本発明は芳香族ジ
カルボン酸を主とする二官能性酸成分と少なくとも一種
のグリコール成分よりなるポリエステルと平均粒径が０
．０１〜５．０μの無機または有機性微粒子を含有する
ポリエステル組成物を製造するに際して、該微粒子を添
加する前に、以下の式（１）および（２）を満足するア
ルカリ土類金属塩とリン酸及び／またはリン酸エステル
化合物とを、同時にまたは該アルカリ土類金属を添加後
、該リン酸及び／またはリン酸エステル化合物を添加す
る事を特徴とするポリエステル組成物の製造方法に関す
るものである。
１．２≦Ｍ／Ｐ≦１．８ （１
）Ｍ≦５
（２）（式中Ｍはアルカリ土類金属塩中
のアルカリ土類金属のポリエステル１０６ ｇ当たりの
総モル数、Ｐはリン酸またはそのエステル誘導体中にお
けるリンのポリエステル１０６ ｇ当たりの総モル数を
示す）[Means for Solving the Problems] That is, the present invention provides a polyester comprising a bifunctional acid component mainly consisting of an aromatic dicarboxylic acid and at least one glycol component, and an average particle size of 0.
．． When producing a polyester composition containing inorganic or organic fine particles of 01 to 5.0μ, before adding the fine particles, an alkaline earth metal salt and phosphorus that satisfy the following formulas (1) and (2) are added. The present invention relates to a method for producing a polyester composition, characterized in that the phosphoric acid and/or phosphoric ester compound is added at the same time or after the alkaline earth metal is added. . 1.2≦M/P≦1.8 (1
)M≦5
(2) (where M is the total number of moles of alkaline earth metal in the alkaline earth metal salt per 106 g of polyester, and P is the total number of moles of phosphorus per 106 g of polyester in phosphoric acid or its ester derivative. show)
【０００６】本発明に用いられるポリエステルとは芳香
族ジカルボン酸を主とする二官能性酸成分と少なくとも
一種のグリコール成分よりなるポリアルキレンテレフタ
レート、ポリアルキレンナフタレート等の結晶性ポリエ
ステルであり、特に限定はされないがとりわけポリアル
キレンテレフタレートが適しており、なかでもその繰り
返し単位の８０モル％以上がエチレンテレフタレートか
らなるものが好ましい。他の共重合成分としてはイソフ
タル酸、ｐ−β−オキシエトキシ安息香酸、２，６−ナ
フタレンジカルボン酸、４，４−ジカルボキシフエニー
ル、４，４−ジカルボキシルベンゾフエノン、ビス（４
−カルボキシルフエニール）エタン、アジピン酸、セバ
シン酸、５−ナトリウムスルホイソフタル酸、シクロヘ
キサン−１，４−ジカルボン酸等のジカルボン酸成分、
プロピレングリコール、ブタンジオール、ネオペンチル
グリコール、ジエチレングリコール、シクロヘキサンジ
メタノール、ビスフエノールＡのエチレンオキサイド付
加物、ポリエチレングリコール、ポリプロピレングリコ
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、ｐ−オキシ安息香酸などのオキシカルボン酸成分等
を任意に選択使用することができる。このほか共重合成
分として少量のアミド結合、ウレタン結合、エーテル結
合、カーボネート結合等含有する化合物を含んでいても
よい。The polyester used in the present invention is a crystalline polyester such as polyalkylene terephthalate or polyalkylene naphthalate, which is composed of a difunctional acid component mainly consisting of an aromatic dicarboxylic acid and at least one glycol component, and is particularly limited to Particularly suitable are polyalkylene terephthalates, although not limited thereto, and those in which 80 mol % or more of the repeating units are ethylene terephthalate are especially preferred. Other copolymerization components include isophthalic acid, p-β-oxyethoxybenzoic acid, 2,6-naphthalene dicarboxylic acid, 4,4-dicarboxyphenyl, 4,4-dicarboxylbenzophenone, bis(4
- dicarboxylic acid components such as carboxyl phenyl) ethane, adipic acid, sebacic acid, 5-sodium sulfoisophthalic acid, cyclohexane-1,4-dicarboxylic acid,
Glycol components such as propylene glycol, butanediol, neopentyl glycol, diethylene glycol, cyclohexanedimethanol, ethylene oxide adduct of bisphenol A, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, oxycarboxylic acids such as p-oxybenzoic acid Components etc. can be arbitrarily selected and used. In addition, compounds containing small amounts of amide bonds, urethane bonds, ether bonds, carbonate bonds, etc. may also be included as copolymerization components.
【０００７】本発明で使用する微粒子としては、乾式法
シリカ、湿式法シリカ、球状コロイダルシリカ、酸化チ
タン、酸化カルシウム、アルミナ、マグネシア、ゼオラ
イト、カオリン、炭酸カルシウム、硫酸バリウム、硫酸
カルシウム、酸化ジルコニウム、炭酸マグネシウム、硫
化亜鉛、炭化珪素、窒化珪素、窒化アルミニウム、窒化
ホウ素、タルク、等の無機微粒子やシリコン樹脂微粒子
、球状架橋アクリル微粒子、球状ポリスチレン微粒子等
の有機微粒子が列挙されるが特に炭酸カルシウム微粒子
、アルミナ微粒子に有効である。本発明で用いられる微
粒子は、平均粒径が０．０１μ以上５μｍ以下のもので
あるが、なかでも平均粒径が０．５μｍ以下の微粒子を
用いた場合に本発明による顕著な凝集防止効果を発現す
る事ができる。平均粒径が０．０１μｍより小さければ
本発明の方法をもってしても凝集を抑制する事ができず
、、また平均粒径が５μｍより大きければ凝集は抑制さ
れるが粒子が大きすぎて磁気テープ用のベースフイルム
には使用できない。なお、ここでいう平均粒径とは、ス
トークスの式に基づいて算出された等価球粒度分布の積
算５０％点における径を意味する。なおかかる微粒子は
、通常、ポリエステルに対して５００〜３００００ｐｐ
ｍの範囲で添加される。The fine particles used in the present invention include dry process silica, wet process silica, spherical colloidal silica, titanium oxide, calcium oxide, alumina, magnesia, zeolite, kaolin, calcium carbonate, barium sulfate, calcium sulfate, zirconium oxide, Examples include inorganic fine particles such as magnesium carbonate, zinc sulfide, silicon carbide, silicon nitride, aluminum nitride, boron nitride, talc, and organic fine particles such as silicone resin fine particles, spherical cross-linked acrylic fine particles, and spherical polystyrene fine particles, but especially calcium carbonate fine particles. , is effective for alumina fine particles. The fine particles used in the present invention have an average particle size of 0.01 μm or more and 5 μm or less, and in particular, when fine particles with an average particle size of 0.5 μm or less are used, the remarkable agglomeration prevention effect of the present invention can be obtained. It can be expressed. If the average particle size is smaller than 0.01 μm, agglomeration cannot be suppressed even with the method of the present invention, and if the average particle size is larger than 5 μm, aggregation can be suppressed, but the particles are too large to prevent magnetic tape. Cannot be used with base films for Note that the average particle diameter here means the diameter at the 50% cumulative point of the equivalent spherical particle size distribution calculated based on Stokes' equation. In addition, such fine particles usually have a content of 500 to 30,000 pp per polyester.
It is added within a range of m.
【０００８】本発明方法において添加されるリン酸また
はリン酸エステル化合物としては、リン酸、リン酸トリ
メチルエステル、リン酸トリエチルエステル、リン酸ト
リブチルエステル、リン酸トリフエニルエステル、リン
酸モノメチルエステル、リン酸ジメチルエステル、リン
酸モノブチルエステル、リン酸ジブチルエステル等があ
げられ、これらは単独で使用してもよく、また２種以上
を併用してもよい。リン酸、およびリン酸トリメチルエ
ステルの使用が特に好ましい。Examples of the phosphoric acid or phosphoric acid ester compound added in the method of the present invention include phosphoric acid, trimethyl phosphate, triethyl phosphate, tributyl phosphate, triphenyl phosphate, monomethyl phosphate, and phosphoric acid. Examples include acid dimethyl ester, phosphoric acid monobutyl ester, phosphoric acid dibutyl ester, etc., and these may be used alone or in combination of two or more. Particular preference is given to using phosphoric acid and phosphoric acid trimethyl ester.
【０００９】本発明方法において添加されるアルカリ土
類金属塩としては、たとえば水酸化カルシウム、水酸化
マグネシウム、酸化カルシウム、酸化マグネシウム、酢
酸カルシウム、酢酸マグネシウム、塩化カルシウム、酢
酸マグネシウム等があげられるが、なかでも酢酸マグネ
シウム、塩化マグネシウムが特に好ましい。Examples of the alkaline earth metal salts added in the method of the present invention include calcium hydroxide, magnesium hydroxide, calcium oxide, magnesium oxide, calcium acetate, magnesium acetate, calcium chloride, and magnesium acetate. Among them, magnesium acetate and magnesium chloride are particularly preferred.
【００１０】本発明方法で添加される上記リン酸または
リン酸エステル化合物とアルカリ土類金属塩が良好な凝
集防止効果を発揮するためには、アルカリ土類金属塩の
量をアルカリ土類金属としてポリエステルにたいして３
０ｐｐｍから４００ｐｐｍの範囲内、とりわけ５０ｐｐ
ｍから１５０ｐｐｍの範囲内になるよう添加する事が好
ましい。また、Ｍ／Ｐのモル比としては１．２から１．
８、とりわけ１．２５から１．６の範囲内にあることが
重要である。上記範囲を外れると良好な凝集防止効果を
発現する事ができずポリマー中に異物が発生したり、添
加剤が析出したり、また、フイルム製膜のときに重要な
静電密着性が得られなかったりする。In order for the above-mentioned phosphoric acid or phosphoric acid ester compound and alkaline earth metal salt added in the method of the present invention to exhibit a good agglomeration prevention effect, the amount of alkaline earth metal salt must be adjusted as the alkaline earth metal. 3 for polyester
In the range 0ppm to 400ppm, especially 50ppm
It is preferable to add it within the range of m to 150 ppm. Moreover, the molar ratio of M/P is 1.2 to 1.
8, especially in the range of 1.25 to 1.6. If it is outside the above range, a good agglomeration prevention effect cannot be achieved, foreign matter may occur in the polymer, additives may precipitate, and electrostatic adhesion, which is important during film production, may not be obtained. There may be none.
【００１１】本発明における上記リン酸及び／またはリ
ン酸エステル化合物とアルカリ土類金属塩の添加時期は
エステル化終了前が好ましいが、何れの場合でも共に上
記微粒子を添加する前に添加する事が重要である。該微
粒子と同時または該微粒子添加後では所望の凝集抑制効
果を発現する事ができない。また、アルカリ土類金属塩
はリン酸及び／またはリン酸エステル化合物の添加前ま
たは同時に添加する必要がある。Ｍｇ化合物はできる限
り重合初期に添加する必要があり加圧エステル化前がよ
り望ましい。リン酸及び／またはリン酸エステル化合物
は一括または分割添加するがアルカリ金属塩と同時また
は添加後添加する事が好ましく、更にアルカリ土類金属
塩添加後に添加することがより好ましい。何れの場合も
無機または有機性微粒子はその後に添加されなくてはな
らない。In the present invention, the phosphoric acid and/or phosphate ester compound and the alkaline earth metal salt are preferably added before the end of esterification, but in any case, they may be added before the fine particles are added. is important. If it is added at the same time as the fine particles or after the fine particles are added, the desired aggregation inhibiting effect cannot be achieved. Further, the alkaline earth metal salt needs to be added before or at the same time as the phosphoric acid and/or phosphoric acid ester compound. It is necessary to add the Mg compound as early as possible in the polymerization stage, and more preferably before pressure esterification. The phosphoric acid and/or phosphoric acid ester compound may be added all at once or in portions, but it is preferably added at the same time or after addition of the alkali metal salt, and more preferably after addition of the alkaline earth metal salt. In either case, inorganic or organic fine particles must be added afterwards.
【００１２】かかる方法により製造された、無機または
有機性微粒子を含有してなるポリエステル組成物は、該
微粒子の凝集度が大幅に改善されており、これらを用い
て磁気テープ用ベースフイルムを製膜した場合、フイル
ムの欠点となるドロップアウトが非常に少ないベースフ
イルムを得ることができる。[0012] The polyester composition containing inorganic or organic fine particles produced by this method has a greatly improved degree of agglomeration of the fine particles, and can be used to form a base film for magnetic tape. In this case, a base film with very little dropout, which is a drawback of film, can be obtained.
【００１３】[0013]
【実施例】次に本発明の実施例及び比較例を示すが、本
発明は以下の実施例に限定されるものではない。なお、
実施例中の部は特に断らない限りすべて重量部を意味す
る。[Examples] Next, examples and comparative examples of the present invention will be shown, but the present invention is not limited to the following examples. In addition,
All parts in the examples mean parts by weight unless otherwise specified.
【００１４】以下に実施例及び比較例において用いた測
定方法を示す。
（１） 平均粒径
島津製作所（株）製遠心沈降式粒度分布測定器（ＳＡ−
ＣＰ−３）によって得た等価球状分布における積算５０
％の点の値。
（２） ポリマーの粗大粒子数
ポリマーの少量を２枚のカバーグラスにはさんで２８０
℃で溶融プレスし、急冷した後位相差顕微鏡を用いて観
察し、画像解析処理装置ルーゼックス５００（日本レギ
ュレーター製）で画像内の粒子の最大長が５μｍ以上の
粒子数をカウントする。
優 ：５μ以上の粗大突起数１５未満良 ：５μ以
上の粗大突起数１５以上４０未満可 ：５μ以上の粗
大突起数４０以上１００未満不可：５μ以上の粗大突起
数１００以上（３） 極限粘度
フエノール：テトラクロロエタン＝３：２（重量比）の
混合溶媒中３０℃で求めた極限粘度。
（４） 溶融比抵抗
２７５℃で溶融したポリエステル中に２枚の電極板を置
き、１２０Ｖの電圧を印加したときの電流値（ｉＯ）を
測定し、比抵抗値（ρｉ）を次式により求める。
ρｉ（Ω・ｃｍ）＝（Ａ／ｌ）×（Ｖ／ｉＯ）Ａ＝電極
面積（ｃｍ２ ）、ｌ＝電極間距離Ｖ＝電圧（Ｖ）
良 ：０．３未満
可 ：０．３以上０．４５未満
不可：０．４５以上The measurement methods used in Examples and Comparative Examples are shown below. (1) Average particle size Centrifugal sedimentation type particle size distribution analyzer (SA-
Integration 50 in the equivalent spherical distribution obtained by CP-3)
Point value in %. (2) The number of coarse particles of the polymer is 280 by sandwiching a small amount of polymer between two cover glasses.
After melt-pressing at °C and quenching, it is observed using a phase contrast microscope, and the number of particles with a maximum length of 5 μm or more in the image is counted using an image analysis processing device Luzex 500 (manufactured by Nippon Regulator). Excellent: Number of coarse protrusions of 5 μ or more is less than 15 Good: Number of coarse protrusions of 5 μ or more is 15 or more and less than 40 Acceptable: Number of coarse protrusions of 5 μ or more is 40 or more and less than 100 Not allowed: Number of coarse protrusions of 5 μ or more is 100 or more (3) Intrinsic viscosity phenol : Intrinsic viscosity determined at 30°C in a mixed solvent of tetrachloroethane = 3:2 (weight ratio). (4) Melting specific resistance Place two electrode plates in polyester melted at 275°C, apply a voltage of 120 V, measure the current value (iO), and calculate the specific resistance value (ρi) using the following formula. . ρi (Ω・cm) = (A/l) × (V/iO) A = electrode area (cm2), l = distance between electrodes V = voltage (V) Good: Less than 0.3 possible: 0.3 or more 0 Not less than .45: 0.45 or more
【００１５】実施例 １
平均粒径０．６μｍの炭酸カルシウム粒子（丸尾カルシ
ウム（株）製）１．４８重量部、エチレングリコール１
４．８重量部、０．１ｍｏｌ／ｌのトリポリリン酸ナト
リウム０．００２９６重量部を混合し、ホモジナイザー
で撹はん処理し１６．３重量部のスラリーを得た。他方
テレフタル酸１００重量部とエチレングリコール７０．
７重量部及び三酸化アンチモン０．０６９７重量部とト
リエチルアミン０．２７１重量部、酢酸マグネシウム０
．０９３１重量部を加えて２．５Ｋｇ／ｃｍ２ ・２５
０℃で加圧エステル化を行った。加圧エステル化終了後
、トリメチルホスフエート０．０３２７重量部を加えて
常圧・２６０℃で撹はんを行い３０分後、先に調整した
スラリー１１．０重量部を加えてさらに３０分撹はんを
行った。その後、真空下で重縮合反応を行い（η）０．
６２のポリエチレンテレフタレート組成物を得た。
このポリマーの粗大粒子数の評価を行ったところ８個で
非常に良好であり、また溶融比抵抗の評価結果も０．２
８で非常に良好であった。Example 1 1.48 parts by weight of calcium carbonate particles with an average particle size of 0.6 μm (manufactured by Maruo Calcium Co., Ltd.), 1 part by weight of ethylene glycol
4.8 parts by weight and 0.00296 parts by weight of 0.1 mol/l sodium tripolyphosphate were mixed and stirred with a homogenizer to obtain 16.3 parts by weight of slurry. On the other hand, 100 parts by weight of terephthalic acid and 70 parts by weight of ethylene glycol.
7 parts by weight, 0.0697 parts by weight of antimony trioxide, 0.271 parts by weight of triethylamine, 0 parts by weight of magnesium acetate.
．． Add 0931 parts by weight to 2.5Kg/cm2 ・25
Pressure esterification was carried out at 0°C. After the pressure esterification was completed, 0.0327 parts by weight of trimethyl phosphate was added and stirred at normal pressure and 260°C for 30 minutes. After 30 minutes, 11.0 parts by weight of the slurry prepared earlier was added and stirred for another 30 minutes. I went to dinner. Thereafter, a polycondensation reaction is carried out under vacuum (η)0.
A polyethylene terephthalate composition of No. 62 was obtained. When the number of coarse particles of this polymer was evaluated, it was found to be 8, which was very good, and the evaluation result of melt specific resistance was also 0.2.
8, which was very good.
【００１６】比較例 １
平均粒径０．６μｍの炭酸カルシウム粒子（丸尾カルシ
ウム（株）製）１．４８重量部、エチレングリコール１
４．８重量部、０．１ｍｏｌ／ｌのトリポリリン酸ナト
リウム０．００２９６重量部を混合し、ホモジナイザー
で撹はん処理し１６．３重量部のスラリーを得た。他方
テレフタル酸１００重量部とエチレングリコール７０．
７重量部及び三酸化アンチモン０．０６９７重量部とト
リエチルアミン０．２７１重量部、酢酸マグネシウム０
．０９３１重量部を加えて２．５Ｋｇ／ｃｍ２ ・２５
０℃で加圧エステル化を行った。加圧エステル化終了後
、先に調整したスラリー１１．０重量部とトリメチルホ
スフエート０．０３２７重量部とを加え、常圧・２６０
℃で３０分撹はんを行った。その後、真空下で重縮合反
応を行い（η）０．６２のポリエチレンテレフタレート
組成物を得た。このポリマーの粗大粒子数の評価を行っ
たところ６４個で使用可能であった。溶融比抵抗の評価
結果は０．３４で使用可能であった。Comparative Example 1 1.48 parts by weight of calcium carbonate particles with an average particle size of 0.6 μm (manufactured by Maruo Calcium Co., Ltd.), 1 part by weight of ethylene glycol
4.8 parts by weight and 0.00296 parts by weight of 0.1 mol/l sodium tripolyphosphate were mixed and stirred with a homogenizer to obtain 16.3 parts by weight of slurry. On the other hand, 100 parts by weight of terephthalic acid and 70 parts by weight of ethylene glycol.
7 parts by weight, 0.0697 parts by weight of antimony trioxide, 0.271 parts by weight of triethylamine, 0 parts by weight of magnesium acetate.
．． Add 0931 parts by weight to 2.5Kg/cm2 ・25
Pressure esterification was carried out at 0°C. After the completion of pressure esterification, 11.0 parts by weight of the slurry prepared earlier and 0.0327 parts by weight of trimethyl phosphate were added, and the mixture was heated to 260 parts by weight at normal pressure.
Stirring was performed at ℃ for 30 minutes. Thereafter, a polycondensation reaction was carried out under vacuum to obtain a polyethylene terephthalate composition having an (η) of 0.62. When the number of coarse particles of this polymer was evaluated, it was found that 64 could be used. The evaluation result of melt specific resistance was 0.34, which was usable.
【００１７】実施例 ２
平均粒径０．５μｍの炭酸カルシウム粒子（丸尾カルシ
ウム（株）製）１．４８重量部、エチレングリコール１
４．８重量部、０．１ｍｏｌ／ｌのトリポリリン酸ナト
リウム０．００２９６重量部を混合し、ホモジナイザー
で撹はん処理し１６．３重量部のスラリーを得た。他方
テレフタル酸１００重量部とエチレングリコール７０．
７重量部及び三酸化アンチモン０．０６９７重量部とト
リエチルアミン０．２７１重量部、トリメチルホスフエ
ート０．０３２７重量部と酢酸マグネシウム０．０９３
１重量部を加えて２．５Ｋｇ／ｃｍ２ ・２５０℃で加
圧エステル化を行った。加圧エステル化終了後、先に調
整したスラリー１１．０重量部を加え常圧・２６０℃で
３０分撹はんを行った。その後、真空下・２８０℃で重
縮合反応を行い（η）０．６２のポリエチレンテレフタ
レート組成物を得た。このポリマーの粗大粒子数の評価
を行ったところ１個で非常に良好であり、また溶融比抵
抗の評価結果も０．３１で使用可能であった。Example 2 1.48 parts by weight of calcium carbonate particles with an average particle size of 0.5 μm (manufactured by Maruo Calcium Co., Ltd.), 1 part by weight of ethylene glycol
4.8 parts by weight and 0.00296 parts by weight of 0.1 mol/l sodium tripolyphosphate were mixed and stirred with a homogenizer to obtain 16.3 parts by weight of slurry. On the other hand, 100 parts by weight of terephthalic acid and 70 parts by weight of ethylene glycol.
7 parts by weight, 0.0697 parts by weight of antimony trioxide, 0.271 parts by weight of triethylamine, 0.0327 parts by weight of trimethyl phosphate, and 0.093 parts by weight of magnesium acetate.
1 part by weight was added to carry out pressure esterification at 2.5 Kg/cm2 and 250°C. After the pressure esterification was completed, 11.0 parts by weight of the previously prepared slurry was added and stirred at normal pressure and 260° C. for 30 minutes. Thereafter, a polycondensation reaction was carried out under vacuum at 280° C. to obtain a polyethylene terephthalate composition having an (η) of 0.62. When the number of coarse particles of this polymer was evaluated, it was found to be 1, which was very good, and the melt specific resistance was also evaluated as 0.31, indicating that it could be used.
【００１８】実施例 ３
平均粒径０．５μｍの炭酸カルシウム粒子（丸尾カルシ
ウム（株）製）１．４８重量部、エチレングリコール１
４．８重量部、０．１ｍｏｌ／ｌのトリポリリン酸ナト
リウム０．００２９６重量部を混合し、ホモジナイザー
で撹はん処理し１６．３重量部のスラリーを得た。他方
テレフタル酸１００重量部とエチレングリコール７０．
７重量部及び三酸化アンチモン０．０６９７重量部とト
リエチルアミン０．２７１重量部、酢酸マグネシウム０
．０９３１重量部を加えて２．５Ｋｇ／ｃｍ２ ・２５
０℃で加圧エステル化を行った。加圧エステル化終了後
、トリメチルホスフエート０．０３２７重量部を加えて
常圧・２６０℃で撹はんを行い３０分後、先に調整した
スラリー１１．０重量部を加えてさらに３０分撹はんを
行った。その後、真空下で重縮合反応を行い（η）０．
６２のポリエチレンテレフタレート組成物を得た。
このポリマーの粗大粒子数の評価を行ったところ１２個
で非常に良好であり、また溶融比抵抗の評価結果も０．
２９で非常に良好であった。Example 3 1.48 parts by weight of calcium carbonate particles with an average particle size of 0.5 μm (manufactured by Maruo Calcium Co., Ltd.), 1 part by weight of ethylene glycol
4.8 parts by weight and 0.00296 parts by weight of 0.1 mol/l sodium tripolyphosphate were mixed and stirred with a homogenizer to obtain 16.3 parts by weight of slurry. On the other hand, 100 parts by weight of terephthalic acid and 70 parts by weight of ethylene glycol.
7 parts by weight, 0.0697 parts by weight of antimony trioxide, 0.271 parts by weight of triethylamine, 0 parts by weight of magnesium acetate.
．． Add 0931 parts by weight to 2.5Kg/cm2 ・25
Pressure esterification was carried out at 0°C. After the pressure esterification was completed, 0.0327 parts by weight of trimethyl phosphate was added and stirred at normal pressure and 260°C for 30 minutes. After 30 minutes, 11.0 parts by weight of the slurry prepared earlier was added and stirred for another 30 minutes. I went to dinner. Thereafter, a polycondensation reaction is carried out under vacuum (η)0.
A polyethylene terephthalate composition of No. 62 was obtained. When the number of coarse particles of this polymer was evaluated, it was found to be 12, which was very good, and the evaluation result of melt specific resistance was also 0.
29, which was very good.
【００１９】比較例 ２
平均粒径０．５μｍの炭酸カルシウム粒子（丸尾カルシ
ウム（株）製）１．４８重量部、エチレングリコール１
４．８重量部、０．１ｍｏｌ／ｌのトリポリリン酸ナト
リウム０．００２９６重量部を混合し、ホモジナイザー
で撹はん処理し１６．３重量部のスラリーを得た。他方
テレフタル酸１００重量部とエチレングリコール７０．
７重量部及び三酸化アンチモン０．０６９７重量部とト
リエチルアミン０．２７１重量部、酢酸マグネシウム０
．０９３１重量部を加えて２．５Ｋｇ／ｃｍ２ ・２５
０℃で加圧エステル化を行った。加圧エステル化終了後
、先に調整したスラリー１１．０重量部とトリメチルホ
スフエート０．０３２７重量部とを加え、常圧・２６０
℃で３０分撹はんを行った。その後、真空下で重縮合反
応を行い（η）０．６２のポリエチレンテレフタレート
組成物を得た。このポリマーの粗大粒子数の評価を行っ
たところ６９個で使用可能であった。溶融比抵抗の評価
結果は０．３１で良好で使用可能であった。Comparative Example 2 1.48 parts by weight of calcium carbonate particles with an average particle size of 0.5 μm (manufactured by Maruo Calcium Co., Ltd.), 1 part by weight of ethylene glycol
4.8 parts by weight and 0.00296 parts by weight of 0.1 mol/l sodium tripolyphosphate were mixed and stirred with a homogenizer to obtain 16.3 parts by weight of slurry. On the other hand, 100 parts by weight of terephthalic acid and 70 parts by weight of ethylene glycol.
7 parts by weight, 0.0697 parts by weight of antimony trioxide, 0.271 parts by weight of triethylamine, 0 parts by weight of magnesium acetate.
．． Add 0931 parts by weight to 2.5Kg/cm2 ・25
Pressure esterification was carried out at 0°C. After the completion of pressure esterification, 11.0 parts by weight of the slurry prepared earlier and 0.0327 parts by weight of trimethyl phosphate were added, and the mixture was heated to 260 parts by weight at normal pressure.
Stirring was performed at ℃ for 30 minutes. Thereafter, a polycondensation reaction was carried out under vacuum to obtain a polyethylene terephthalate composition having an (η) of 0.62. When the number of coarse particles of this polymer was evaluated, it was found that 69 could be used. The evaluation result of melt specific resistance was 0.31, which was good and usable.
【００２０】比較例 ３
平均粒径０．５μｍの炭酸カルシウム粒子（丸尾カルシ
ウム（株）製）１．４８重量部、エチレングリコール１
４．８重量部、０．１ｍｏｌ／ｌのトリポリリン酸ナト
リウム０．００２９６重量部を混合し、ホモジナイザー
で撹はん処理し１６．３重量部のスラリーを得た。他方
テレフタル酸１００重量部とエチレングリコール７０．
７重量部及び三酸化アンチモン０．０６９７重量部とト
リエチルアミン０．２７１重量部、酢酸マグネシウム０
．０９３１重量部を加えて２．５Ｋｇ／ｃｍ２ ・２５
０℃で加圧エステル化を行った。加圧エステル化終了後
、先に調整したスラリー１１．０重量部を加え常圧・２
６０℃で撹はんを行い３０分後、トリメチルホスフエー
ト０．０３２７重量部を加え更に３０分撹はんを行った
。その後、真空下で重合を行い（η）０．６２のポリエ
チレンテレフタレート組成物を得た。このポリマーの粗
大粒子数の評価を行ったところ７０個で使用可能であっ
た。溶融比抵抗の評価結果は０．３１で使用可能であっ
た。Comparative Example 3 1.48 parts by weight of calcium carbonate particles with an average particle size of 0.5 μm (manufactured by Maruo Calcium Co., Ltd.), 1 part by weight of ethylene glycol
4.8 parts by weight and 0.00296 parts by weight of 0.1 mol/l sodium tripolyphosphate were mixed and stirred with a homogenizer to obtain 16.3 parts by weight of slurry. On the other hand, 100 parts by weight of terephthalic acid and 70 parts by weight of ethylene glycol.
7 parts by weight, 0.0697 parts by weight of antimony trioxide, 0.271 parts by weight of triethylamine, 0 parts by weight of magnesium acetate.
．． Add 0931 parts by weight to 2.5Kg/cm2 ・25
Pressure esterification was carried out at 0°C. After the pressure esterification was completed, 11.0 parts by weight of the previously prepared slurry was added and the mixture was heated at normal pressure to 2.
After stirring at 60° C. for 30 minutes, 0.0327 parts by weight of trimethyl phosphate was added and stirring was continued for an additional 30 minutes. Thereafter, polymerization was carried out under vacuum to obtain a polyethylene terephthalate composition having an (η) of 0.62. When the number of coarse particles of this polymer was evaluated, it was found that 70 particles were usable. The evaluation result of melt specific resistance was 0.31, which was usable.
【００２１】実施例 ４
平均粒径０．５μｍの炭酸カルシウム粒子（丸尾カルシ
ウム（株）製）１．４８重量部、エチレングリコール１
４．８重量部、０．１ｍｏｌ／ｌのトリポリリン酸ナト
リウム０．００２９６重量部を混合し、ホモジナイザー
で撹はん処理し１６．３重量部のスラリーを得た。他方
テレフタル酸１００重量部とエチレングリコール７０．
７重量部及び三酸化アンチモン０．０６９７重量部とト
リエチルアミン０．２７１重量部、酢酸マグネシウム０
．０９３１重量部を加えて２．５Ｋｇ／ｃｍ２ ・２５
０℃で加圧エステル化を行った。加圧エステル化終了後
、トリメチルホスフエート０．０２８９重量部を加えて
常圧・２６０℃で撹はんを行い３０分後、先に調整した
スラリー１１．０重量部を加えてさらに３０分撹はんを
行った。その後、真空下で重縮合反応を行い（η）０．
６２のポリエチレンテレフタレート組成物を得た。
このポリマーの粗大粒子数の評価を行ったところ３８個
で良好であり、また溶融比抵抗の評価結果も０．２７で
非常に良好であった。Example 4 1.48 parts by weight of calcium carbonate particles with an average particle size of 0.5 μm (manufactured by Maruo Calcium Co., Ltd.), 1 part by weight of ethylene glycol
4.8 parts by weight and 0.00296 parts by weight of 0.1 mol/l sodium tripolyphosphate were mixed and stirred with a homogenizer to obtain 16.3 parts by weight of slurry. On the other hand, 100 parts by weight of terephthalic acid and 70 parts by weight of ethylene glycol.
7 parts by weight, 0.0697 parts by weight of antimony trioxide, 0.271 parts by weight of triethylamine, 0 parts by weight of magnesium acetate.
．． Add 0931 parts by weight to 2.5Kg/cm2 ・25
Pressure esterification was carried out at 0°C. After the completion of pressure esterification, 0.0289 parts by weight of trimethyl phosphate was added and stirred at normal pressure and 260°C for 30 minutes. After 30 minutes, 11.0 parts by weight of the slurry prepared earlier was added and stirred for another 30 minutes. I went to dinner. Thereafter, a polycondensation reaction is carried out under vacuum (η)0.
A polyethylene terephthalate composition of No. 62 was obtained. When the number of coarse particles of this polymer was evaluated, it was found to be 38, which was good, and the evaluation result of melt specific resistance was also very good, which was 0.27.
【００２２】実施例 ５
平均粒径０．５μｍの炭酸カルシウム粒子（丸尾カルシ
ウム（株）製）１．４８重量部、エチレングリコール１
４．８重量部、０．１ｍｏｌ／ｌのトリポリリン酸ナト
リウム０．００２９６重量部を混合し、ホモジナイザー
で撹はん処理し１６．３重量部のスラリーを得た。他方
テレフタル酸１００重量部とエチレングリコール７０．
７重量部及び三酸化アンチモン０．０６９７重量部とト
リエチルアミン０．２７１重量部、酢酸マグネシウム０
．０９３１重量部を加えて２．５Ｋｇ／ｃｍ２ ・２５
０℃で加圧エステル化を行った。加圧エステル化終了後
、トリメチルホスフエート０．０２５０重量部を加えて
常圧・２６０℃で撹はんを行い３０分後、先に調整した
スラリー１１．０重量部を加えてさらに３０分撹はんを
行った。その後、真空下で重縮合反応を行い（η）０．
６２のポリエチレンテレフタレート組成物を得た。
このポリマーの粗大粒子数の評価を行ったところ５３個
で使用可能であり、また溶融比抵抗の評価結果も０．３
１で使用可能であった。Example 5 1.48 parts by weight of calcium carbonate particles with an average particle size of 0.5 μm (manufactured by Maruo Calcium Co., Ltd.), 1 part by weight of ethylene glycol
4.8 parts by weight and 0.00296 parts by weight of 0.1 mol/l sodium tripolyphosphate were mixed and stirred with a homogenizer to obtain 16.3 parts by weight of slurry. On the other hand, 100 parts by weight of terephthalic acid and 70 parts by weight of ethylene glycol.
7 parts by weight, 0.0697 parts by weight of antimony trioxide, 0.271 parts by weight of triethylamine, 0 parts by weight of magnesium acetate.
．． Add 0931 parts by weight to 2.5Kg/cm2 ・25
Pressure esterification was carried out at 0°C. After the pressure esterification was completed, 0.0250 parts by weight of trimethyl phosphate was added and stirred at normal pressure and 260°C for 30 minutes. After 30 minutes, 11.0 parts by weight of the slurry prepared earlier was added and stirred for another 30 minutes. I went to dinner. Thereafter, a polycondensation reaction is carried out under vacuum (η)0.
A polyethylene terephthalate composition of No. 62 was obtained. When the number of coarse particles of this polymer was evaluated, it was found that it was usable with 53 particles, and the evaluation result of melt specific resistance was also 0.3.
1 was usable.
【００２３】比較例 ４
平均粒径０．５μｍの炭酸カルシウム粒子（丸尾カルシ
ウム（株）製）１．４８重量部、エチレングリコール１
４．８重量部、０．１ｍｏｌ／ｌのトリポリリン酸ナト
リウム０．００２９６重量部を混合し、ホモジナイザー
で撹はん処理し１６．３重量部のスラリーを得た。他方
テレフタル酸１００重量部とエチレングリコール７０．
７重量部及び三酸化アンチモン０．０６９７重量部とト
リエチルアミン０．２７１重量部、酢酸マグネシウム０
．０９３１重量部を加えて２．５Ｋｇ／ｃｍ２ ・２５
０℃で加圧エステル化を行った。加圧エステル化終了後
、トリメチルホスフエート０．０１７３重量部を加えて
常圧・２６０℃で撹はんを行い３０分後、先に調整した
スラリー１１．０重量部を加えてさらに３０分撹はんを
行った。その後、真空下で重縮合反応を行い（η）０．
６２のポリエチレンテレフタレート組成物を得た。
このポリマーの粗大粒子数の評価を行ったところ１２個
で非常に良好であり、また溶融比抵抗の評価結果も０．
２９で非常に良好であった。Comparative Example 4 1.48 parts by weight of calcium carbonate particles with an average particle size of 0.5 μm (manufactured by Maruo Calcium Co., Ltd.), 1 part by weight of ethylene glycol
4.8 parts by weight and 0.00296 parts by weight of 0.1 mol/l sodium tripolyphosphate were mixed and stirred with a homogenizer to obtain 16.3 parts by weight of slurry. On the other hand, 100 parts by weight of terephthalic acid and 70 parts by weight of ethylene glycol.
7 parts by weight, 0.0697 parts by weight of antimony trioxide, 0.271 parts by weight of triethylamine, 0 parts by weight of magnesium acetate.
．． Add 0931 parts by weight to 2.5Kg/cm2 ・25
Pressure esterification was carried out at 0°C. After the pressure esterification was completed, 0.0173 parts by weight of trimethyl phosphate was added and stirred at normal pressure and 260°C for 30 minutes. After 30 minutes, 11.0 parts by weight of the slurry prepared earlier was added and stirred for another 30 minutes. I went to dinner. Thereafter, a polycondensation reaction is carried out under vacuum (η)0.
A polyethylene terephthalate composition of No. 62 was obtained. When the number of coarse particles of this polymer was evaluated, it was found to be 12, which was very good, and the evaluation result of melt specific resistance was also 0.
29, which was very good.
【００２４】比較例 ５
平均粒径０．５μｍの炭酸カルシウム粒子（丸尾カルシ
ウム（株）製）１．４８重量部、エチレングリコール１
４．８重量部、０．１ｍｏｌ／ｌのトリポリリン酸ナト
リウム０．００２９６重量部を混合し、ホモジナイザー
で撹はん処理し１６．３重量部のスラリーを得た。他方
テレフタル酸１００重量部とエチレングリコール７０．
７重量部及び三酸化アンチモン０．０６９７重量部とト
リエチルアミン０．２７１重量部、酢酸マグネシウム０
．０９３１重量部を加えて２．５Ｋｇ／ｃｍ２ ・２５
０℃で加圧エステル化を行った。加圧エステル化終了後
、トリメチルホスフエート０．０３８４重量部を加えて
常圧・２６０℃で撹はんを行い３０分後、先に調整した
スラリー１１．０重量部を加えてさらに３０分撹はんを
行った。その後、真空下で重縮合反応を行い（η）０．
６２のポリエチレンテレフタレート組成物を得た。
このポリマーの粗大粒子数の評価を行ったところ１２個
で非常に良好であり、また溶融比抵抗の評価結果も０．
２９で非常に良好であった。Comparative Example 5 1.48 parts by weight of calcium carbonate particles with an average particle size of 0.5 μm (manufactured by Maruo Calcium Co., Ltd.), 1 part by weight of ethylene glycol
4.8 parts by weight and 0.00296 parts by weight of 0.1 mol/l sodium tripolyphosphate were mixed and stirred with a homogenizer to obtain 16.3 parts by weight of slurry. On the other hand, 100 parts by weight of terephthalic acid and 70 parts by weight of ethylene glycol.
7 parts by weight, 0.0697 parts by weight of antimony trioxide, 0.271 parts by weight of triethylamine, 0 parts by weight of magnesium acetate.
．． Add 0931 parts by weight to 2.5Kg/cm2 ・25
Pressure esterification was carried out at 0°C. After the pressure esterification was completed, 0.0384 parts by weight of trimethyl phosphate was added and stirred at normal pressure and 260°C for 30 minutes. After 30 minutes, 11.0 parts by weight of the slurry prepared earlier was added and stirred for another 30 minutes. I went to dinner. Thereafter, a polycondensation reaction is carried out under vacuum (η)0.
A polyethylene terephthalate composition of No. 62 was obtained. When the number of coarse particles of this polymer was evaluated, it was found to be 12, which was very good, and the evaluation result of melt specific resistance was also 0.
29, which was very good.
【００２５】実施例 ６
平均粒径０．５μｍの炭酸カルシウム粒子（丸尾カルシ
ウム（株）製）１．４８重量部、エチレングリコール１
４．８重量部、０．１ｍｏｌ／ｌのトリポリリン酸ナト
リウム０．００２９６重量部を混合し、ホモジナイザー
で撹はん処理し１６．３重量部のスラリーを得た。他方
テレフタル酸１００重量部とエチレングリコール７０．
７重量部及び三酸化アンチモン０．０６９７重量部とト
リエチルアミン０．２７１重量部、酢酸カルシウム０．
０７６５重量部を加えて２．５Ｋｇ／ｃｍ２ ・２５０
℃で加圧エステル化を行った。加圧エステル化終了後、
トリメチルホスフエート０．０３２７重量部を加えて常
圧・２６０℃で撹はんを行い３０分後、先に調整したス
ラリー１１．０重量部を加えてさらに３０分撹はんを行
った。その後、真空下で重縮合反応を行い（η）０．６
２のポリエチレンテレフタレート組成物を得た。このポ
リマーの粗大粒子数の評価を行ったところ４７個で使用
可能であり、また溶融比抵抗の評価結果も０．３４で使
用可能であった。Example 6 1.48 parts by weight of calcium carbonate particles with an average particle size of 0.5 μm (manufactured by Maruo Calcium Co., Ltd.), 1 part by weight of ethylene glycol
4.8 parts by weight and 0.00296 parts by weight of 0.1 mol/l sodium tripolyphosphate were mixed and stirred with a homogenizer to obtain 16.3 parts by weight of slurry. On the other hand, 100 parts by weight of terephthalic acid and 70 parts by weight of ethylene glycol.
7 parts by weight, 0.0697 parts by weight of antimony trioxide, 0.271 parts by weight of triethylamine, and 0.0 parts by weight of calcium acetate.
Add 0765 parts by weight to 2.5Kg/cm2 ・250
Pressure esterification was carried out at °C. After pressure esterification,
0.0327 parts by weight of trimethyl phosphate was added and stirred at normal pressure and 260°C for 30 minutes. After 30 minutes, 11.0 parts by weight of the previously prepared slurry was added and stirred for an additional 30 minutes. After that, a polycondensation reaction was carried out under vacuum (η)0.6
A polyethylene terephthalate composition of No. 2 was obtained. When the number of coarse particles of this polymer was evaluated, it was found to be usable at 47, and the melt specific resistance was also evaluated at 0.34, which was usable.
【００２６】実施例 ７
平均粒径０．４μｍの炭酸カルシウム粒子（丸尾カルシ
ウム（株）製）１．４８重量部、エチレングリコール１
４．８重量部、０．１ｍｏｌ／ｌのトリポリリン酸ナト
リウム０．００２９６重量部を混合し、ホモジナイザー
で撹はん処理し１６．３重量部のスラリーを得た。他方
テレフタル酸１００重量部とエチレングリコール７０．
７重量部及び三酸化アンチモン０．０６９７重量部とト
リエチルアミン０．２７１重量部、酢酸マグネシウム０
．０９３１重量部を加えて２．５Ｋｇ／ｃｍ２ ・２５
０℃で加圧エステル化を行った。加圧エステル化終了後
、トリメチルホスフエート０．０３２７重量部を加えて
常圧・２６０℃で撹はんを行い３０分後、先に調整した
スラリー１１．０重量部を加えてさらに３０分撹はんを
行った。その後、真空下で重縮合反応を行い（η）０．
６２のポリエチレンテレフタレート組成物を得た。
このポリマーの粗大粒子数の評価を行ったところ２８個
で良好であり、また溶融比抵抗の評価結果も０．２７で
非常に良好であった。Example 7 1.48 parts by weight of calcium carbonate particles with an average particle size of 0.4 μm (manufactured by Maruo Calcium Co., Ltd.), 1 part by weight of ethylene glycol
4.8 parts by weight and 0.00296 parts by weight of 0.1 mol/l sodium tripolyphosphate were mixed and stirred with a homogenizer to obtain 16.3 parts by weight of slurry. On the other hand, 100 parts by weight of terephthalic acid and 70 parts by weight of ethylene glycol.
7 parts by weight, 0.0697 parts by weight of antimony trioxide, 0.271 parts by weight of triethylamine, 0 parts by weight of magnesium acetate.
．． Add 0931 parts by weight to 2.5Kg/cm2 ・25
Pressure esterification was carried out at 0°C. After the pressure esterification was completed, 0.0327 parts by weight of trimethyl phosphate was added and stirred at normal pressure and 260°C for 30 minutes. After 30 minutes, 11.0 parts by weight of the slurry prepared earlier was added and stirred for another 30 minutes. I went to dinner. Thereafter, a polycondensation reaction is carried out under vacuum (η)0.
A polyethylene terephthalate composition of No. 62 was obtained. When the number of coarse particles of this polymer was evaluated, it was found to be 28, which was good, and the evaluation result of melt specific resistance was also very good, which was 0.27.
【００２７】比較例 ６
平均粒径０．４μｍの炭酸カルシウム粒子（丸尾カルシ
ウム（株）製）１．４８重量部、エチレングリコール１
４．８重量部、０．１ｍｏｌ／ｌのトリポリリン酸ナト
リウム０．００２９６重量部を混合し、ホモジナイザー
で撹はん処理し１６．３重量部のスラリーを得た。他方
テレフタル酸１００重量部とエチレングリコール７０．
７重量部及び三酸化アンチモン０．０６９７重量部とト
リエチルアミン０．２７１重量部、酢酸マグネシウム０
．０９３１重量部を加えて２．５Ｋｇ／ｃｍ２ ・２５
０℃で加圧エステル化を行った。加圧エステル化終了後
、先に調整したスラリー１１．０重量部を加え常圧・２
６０℃で撹はんを行い３０分後、トリメチルホスフエー
ト０．０３２７重量部を加え更に３０分撹はんを行った
。その後真空下で重合を行い（η）０．６２のポリエチ
レンテレフタレート組成物を得た。このポリマーの粗大
粒子数の評価を行ったところ２８９個で不良であった。
溶融比抵抗の評価結果は０．３３で使用可能であった。Comparative Example 6 1.48 parts by weight of calcium carbonate particles with an average particle size of 0.4 μm (manufactured by Maruo Calcium Co., Ltd.), 1 part by weight of ethylene glycol
4.8 parts by weight and 0.00296 parts by weight of 0.1 mol/l sodium tripolyphosphate were mixed and stirred with a homogenizer to obtain 16.3 parts by weight of slurry. On the other hand, 100 parts by weight of terephthalic acid and 70 parts by weight of ethylene glycol.
7 parts by weight, 0.0697 parts by weight of antimony trioxide, 0.271 parts by weight of triethylamine, 0 parts by weight of magnesium acetate.
．． Add 0931 parts by weight to 2.5Kg/cm2 ・25
Pressure esterification was carried out at 0°C. After the pressure esterification was completed, 11.0 parts by weight of the previously prepared slurry was added and the mixture was heated at normal pressure to 2.
After stirring at 60° C. for 30 minutes, 0.0327 parts by weight of trimethyl phosphate was added and stirring was continued for an additional 30 minutes. Thereafter, polymerization was carried out under vacuum to obtain a polyethylene terephthalate composition having an (η) of 0.62. When the number of coarse particles of this polymer was evaluated, it was found to be 289, which was poor. The evaluation result of melt specific resistance was 0.33, which was usable.
【００２８】実施例 ８
平均粒径０．３μｍの炭酸カルシウム粒子（丸尾カルシ
ウム（株）製）１．４８重量部、エチレングリコール１
４．８重量部、０．１ｍｏｌ／ｌのトリポリリン酸ナト
リウム０．００２９６重量部を混合し、ホモジナイザー
で撹はん処理し１６．３重量部のスラリーを得た。他方
テレフタル酸１００重量部とエチレングリコール７０．
７重量部及び三酸化アンチモン０．０６９７重量部とト
リエチルアミン０．２７１重量部、酢酸マグネシウム０
．０９３１重量部を加えて２．５Ｋｇ／ｃｍ２ ・２５
０℃で加圧エステル化を行った。加圧エステル化終了後
、トリメチルホスフエート０．０３２７重量部を加えて
常圧・２６０℃で撹はんを行い３０分後、先に調整した
スラリー１１．０重量部を加えてさらに３０分撹はんを
行った。その後、真空下で重縮合反応を行い（η）０．
６２のポリエチレンテレフタレート組成物を得た。
このポリマーの粗大粒子数の評価を行ったところ２１個
で良好であり、また溶融比抵抗の評価結果も０．２９で
非常に良好であった。Example 8 Calcium carbonate particles with an average particle size of 0.3 μm (manufactured by Maruo Calcium Co., Ltd.) 1.48 parts by weight, 1 part of ethylene glycol
4.8 parts by weight and 0.00296 parts by weight of 0.1 mol/l sodium tripolyphosphate were mixed and stirred with a homogenizer to obtain 16.3 parts by weight of slurry. On the other hand, 100 parts by weight of terephthalic acid and 70 parts by weight of ethylene glycol.
7 parts by weight, 0.0697 parts by weight of antimony trioxide, 0.271 parts by weight of triethylamine, 0 parts by weight of magnesium acetate.
．． Add 0931 parts by weight to 2.5Kg/cm2 ・25
Pressure esterification was carried out at 0°C. After the pressure esterification was completed, 0.0327 parts by weight of trimethyl phosphate was added and stirred at normal pressure and 260°C for 30 minutes. After 30 minutes, 11.0 parts by weight of the slurry prepared earlier was added and stirred for another 30 minutes. I went to dinner. Thereafter, a polycondensation reaction is carried out under vacuum (η)0.
A polyethylene terephthalate composition of No. 62 was obtained. When the number of coarse particles of this polymer was evaluated, it was found to be 21, which was good, and the evaluation result of melt specific resistance was also very good, which was 0.29.
【００２９】比較例 ７
平均粒径０．３μｍの炭酸カルシウム粒子（丸尾カルシ
ウム（株）製）１．４８重量部、エチレングリコール１
４．８重量部、０．１ｍｏｌ／ｌのトリポリリン酸ナト
リウム０．００２９６重量部を混合し、ホモジナイザー
で撹はん処理し１６．３重量部のスラリーを得た。他方
テレフタル酸１００重量部とエチレングリコール７０．
７重量部及び三酸化アンチモン０．０６９７重量部とト
リエチルアミン０．２７１重量部、酢酸マグネシウム０
．０９３１重量部を加えて２．５Ｋｇ／ｃｍ２ ・２５
０℃で加圧エステル化を行った。加圧エステル化終了後
、先に調整したスラリー１１．０重量部を加え常圧・２
６０℃で撹はんを行い３０分後、トリメチルホスフエー
ト０．０３２７重量部を加え更に３０分撹はんを行った
。その後、真空下で重縮合反応を行い（η）０．６２の
ポリエチレンテレフタレート組成物を得た。このポリマ
ーの粗大粒子数の評価を行ったところ４２３個で不良で
あった。溶融比抵抗の評価結果は０．３８で使用可能で
あった。Comparative Example 7 1.48 parts by weight of calcium carbonate particles with an average particle size of 0.3 μm (manufactured by Maruo Calcium Co., Ltd.), 1 part by weight of ethylene glycol
4.8 parts by weight and 0.00296 parts by weight of 0.1 mol/l sodium tripolyphosphate were mixed and stirred with a homogenizer to obtain 16.3 parts by weight of slurry. On the other hand, 100 parts by weight of terephthalic acid and 70 parts by weight of ethylene glycol.
7 parts by weight, 0.0697 parts by weight of antimony trioxide, 0.271 parts by weight of triethylamine, 0 parts by weight of magnesium acetate.
．． Add 0931 parts by weight to 2.5Kg/cm2 ・25
Pressure esterification was carried out at 0°C. After the pressure esterification was completed, 11.0 parts by weight of the previously prepared slurry was added and the mixture was heated at normal pressure to 2.
After stirring at 60° C. for 30 minutes, 0.0327 parts by weight of trimethyl phosphate was added and stirring was continued for an additional 30 minutes. Thereafter, a polycondensation reaction was carried out under vacuum to obtain a polyethylene terephthalate composition having an (η) of 0.62. When the number of coarse particles of this polymer was evaluated, it was found to be 423, which was poor. The evaluation result of melt specific resistance was 0.38, which was usable.
【００３０】実施例 ９
平均粒径０．０５μｍのアルミナ粒子（バイコウスキー
社製）１．４８重量部、エチレングリコール１４．８重
量部、０．１ｍｏｌ／ｌのトリポリリン酸ナトリウム０
．００２９６重量部を混合し、ホモジナイザーで撹はん
処理し１６．３重量部のスラリーを得た。他方テレフタ
ル酸１００重量部とエチレングリコール７０．７重量部
及び三酸化アンチモン０．０６９７重量部とトリエチル
アミン０．２７１重量部、トリメチルホスフエート０．
０３２７重量部と酢酸マグネシウム０．０９３１重量部
を加えて２．５Ｋｇ／ｃｍ２ ・２５０℃で加圧エステ
ル化を行った。加圧エステル化終了後、先に調整したス
ラリー１１．０重量部を加え常圧・２６０℃で３０分撹
はんを行った。その後、真空下・２８０℃で重縮合反応
を行い（η）０．６２のポリエチレンテレフタレート組
成物を得た。このポリマーの粗大粒子数の評価を行った
ところ１１個で非常に良好であり、また溶融比抵抗の評
価結果も０．４２３で使用可能であった。Example 9 1.48 parts by weight of alumina particles with an average particle size of 0.05 μm (manufactured by Baikowski), 14.8 parts by weight of ethylene glycol, 0.1 mol/l of sodium tripolyphosphate
．． 00296 parts by weight were mixed and stirred with a homogenizer to obtain 16.3 parts by weight of slurry. On the other hand, 100 parts by weight of terephthalic acid, 70.7 parts by weight of ethylene glycol, 0.0697 parts by weight of antimony trioxide, 0.271 parts by weight of triethylamine, and 0.0 parts by weight of trimethyl phosphate.
0.0327 parts by weight of magnesium acetate and 0.0931 parts by weight of magnesium acetate were added to carry out pressure esterification at 2.5 Kg/cm2 and 250°C. After the pressure esterification was completed, 11.0 parts by weight of the previously prepared slurry was added and stirred at normal pressure and 260° C. for 30 minutes. Thereafter, a polycondensation reaction was carried out under vacuum at 280° C. to obtain a polyethylene terephthalate composition having an (η) of 0.62. When the number of coarse particles of this polymer was evaluated, it was found to be 11, which was very good, and the evaluation result of melt specific resistance was also 0.423, indicating that it could be used.
【００３１】比較例 ８
平均粒径０．０５μｍのＡｌ２０３（バイコウスキー社
製）１．４８重量部、エチレングリコール１４．８重量
部、０．１ｍｏｌ／ｌのトリポリリン酸ナトリウム０．
００２９６重量部を混合し、ホモジナイザーで撹はん処
理し１６．３重量部のスラリーを得た。他方テレフタル
酸１００重量部とエチレングリコール７０．７重量部及
び三酸化アンチモン０．０６９７重量部とトリエチルア
ミン０．２７１重量部、酢酸マグネシウム０．０９３１
重量部を加えて２．５Ｋｇ／ｃｍ２ ・２５０℃で加圧
エステル化を行った。加圧エステル化終了後、先に調整
したスラリー１１．０重量部とトリメチルホスフエート
０．０３２７重量部とを加え、常圧・２６０℃で３０分
撹はんを行った。その後、真空下で重縮合反応を行い（
η）０．６２のポリエチレンテレフタレート組成物を得
た。このポリマーの粗大粒子数の評価を行ったところ６
３０個で不良であった。また溶融比抵抗の評価結果も４
．３で不良であった。Comparative Example 8 1.48 parts by weight of Al203 (manufactured by Baikowski) with an average particle size of 0.05 μm, 14.8 parts by weight of ethylene glycol, 0.1 mol/l of sodium tripolyphosphate.
00296 parts by weight were mixed and stirred with a homogenizer to obtain 16.3 parts by weight of slurry. On the other hand, 100 parts by weight of terephthalic acid, 70.7 parts by weight of ethylene glycol, 0.0697 parts by weight of antimony trioxide, 0.271 parts by weight of triethylamine, and 0.0931 parts by weight of magnesium acetate.
Parts by weight were added to perform pressure esterification at 2.5 Kg/cm2 and 250°C. After the pressure esterification was completed, 11.0 parts by weight of the previously prepared slurry and 0.0327 parts by weight of trimethyl phosphate were added, followed by stirring at normal pressure and 260° C. for 30 minutes. After that, a polycondensation reaction is carried out under vacuum (
A polyethylene terephthalate composition with η) of 0.62 was obtained. When the number of coarse particles of this polymer was evaluated, it was found that 6
Thirty pieces were defective. Also, the evaluation result of melt specific resistance is 4
．． 3 was bad.
【００３２】実施例 １０
平均粒径０．３μｍのシリカ粒子（日本触媒（株）製）
１．４８重量部、エチレングリコール１４．８重量部、
０．１ｍｏｌ／ｌのトリポリリン酸ナトリウム０．００
２９６重量部を混合し、ホモジナイザーで撹はん処理し
１６．３重量部のスラリーを得た。他方テレフタル酸１
００重量部とエチレングリコール７０．７重量部及び三
酸化アンチモン０．０６９７重量部とトリエチルアミン
０．２７１重量部、酢酸マグネシウム０．０９３１重量
部を加えて２．５Ｋｇ／ｃｍ２ ・２５０℃で加圧エス
テル化を行った。加圧エステル化終了後、トリメチルホ
スフエート０．０３２７重量部を加えて常圧・２６０℃
で撹はんを行い３０分後、先に調整したスラリー１１．
０重量部を加えてさらに３０分撹はんを行った。その後
、真空下で重縮合反応を行い（η）０．６２のポリエチ
レンテレフタレート組成物を得た。このポリマーの粗大
粒子数の評価を行ったところ２９個で良好であり、また
溶融比抵抗の評価結果も０．２９で非常に良好であった
。Example 10 Silica particles with an average particle size of 0.3 μm (manufactured by Nippon Shokubai Co., Ltd.)
1.48 parts by weight, 14.8 parts by weight of ethylene glycol,
0.1 mol/l sodium tripolyphosphate 0.00
296 parts by weight were mixed and stirred using a homogenizer to obtain 16.3 parts by weight of slurry. On the other hand, terephthalic acid 1
00 parts by weight, 70.7 parts by weight of ethylene glycol, 0.0697 parts by weight of antimony trioxide, 0.271 parts by weight of triethylamine, and 0.0931 parts by weight of magnesium acetate to produce 2.5 Kg/cm2 ・Pressure ester at 250°C . After completion of pressure esterification, 0.0327 parts by weight of trimethyl phosphate was added and the mixture was heated at normal pressure and 260°C.
After stirring for 30 minutes, the slurry prepared earlier in step 11.
0 parts by weight was added and stirred for an additional 30 minutes. Thereafter, a polycondensation reaction was carried out under vacuum to obtain a polyethylene terephthalate composition having an (η) of 0.62. When the number of coarse particles of this polymer was evaluated, it was found to be 29, which was good, and the evaluation result of melt specific resistance was also very good, which was 0.29.
【００３３】比較例 ９
平均粒径０．３μｍのシリカ粒子（日本触媒（株）製）
１．４８重量部、エチレングリコール１４．８重量部、
０．１ｍｏｌ／ｌのトリポリリン酸ナトリウム０．００
２９６重量部を混合し、ホモジナイザーで撹はん処理し
１６．３重量部のスラリーを得た。他方テレフタル酸１
００重量部とエチレングリコール７０．７重量部及び三
酸化アンチモン０．０６９７重量部とトリエチルアミン
０．２７１重量部、酢酸マグネシウム０．０９３１重量
部を加えて２．５Ｋｇ／ｃｍ２ ・２５０℃で加圧エス
テル化を行った。加圧エステル化終了後、先に調整した
スラリー１１．０重量部とトリメチルホスフエート０．
０３２７重量部とを加え、常圧・２６０℃で３０分撹は
んを行った。その後、真空下で重縮合反応を行い（η）
０．６２のポリエチレンテレフタレート組成物を得た。
このポリマーの粗大粒子数の評価を行ったところ１２６
個で不良であった。溶融比抵抗の評価結果は０．３１で
使用可能であった。Comparative Example 9 Silica particles with an average particle size of 0.3 μm (manufactured by Nippon Shokubai Co., Ltd.)
1.48 parts by weight, 14.8 parts by weight of ethylene glycol,
0.1 mol/l sodium tripolyphosphate 0.00
296 parts by weight were mixed and stirred using a homogenizer to obtain 16.3 parts by weight of slurry. On the other hand, terephthalic acid 1
00 parts by weight, 70.7 parts by weight of ethylene glycol, 0.0697 parts by weight of antimony trioxide, 0.271 parts by weight of triethylamine, and 0.0931 parts by weight of magnesium acetate to produce 2.5 Kg/cm2 ・Pressure ester at 250°C . After completion of pressure esterification, 11.0 parts by weight of the slurry prepared previously and 0.0 parts by weight of trimethyl phosphate were added.
0327 parts by weight were added thereto, and the mixture was stirred at normal pressure and 260°C for 30 minutes. Then, a polycondensation reaction is performed under vacuum (η)
A polyethylene terephthalate composition of 0.62 was obtained. The number of coarse particles of this polymer was evaluated and was 126.
It was defective in 1 piece. The evaluation result of melt specific resistance was 0.31, which was usable.
【００３４】以上の実施例および比較例における主要デ
ータを整理して表示すると下記の表１および表２に示す
とおりである。The main data in the above Examples and Comparative Examples are summarized and shown in Tables 1 and 2 below.
【００３５】[0035]
【表１】[Table 1]
【００３６】[0036]
【表２】[Table 2]
【００３７】[0037]
【発明の効果】以上説明したように本発明によるときは
無機または有機性微粒子をポリエステルに添加したとき
に生起する該微粒子の凝集を防止することができ、かく
して磁気テープフイルムを製造するに好適な微粒子含有
ポリエステル組成物を得ることができる。As explained above, the present invention can prevent the agglomeration of inorganic or organic fine particles that occurs when they are added to polyester, and is thus suitable for producing magnetic tape films. A polyester composition containing fine particles can be obtained.
Claims (1)
性酸成分と少なくとも一種のグリコール成分よりなるポ
リエステルと平均粒径が０．０１〜５．０μの無機また
は有機性微粒子を含有するポリエステル組成物を製造す
るに際して、該微粒子を添加する前に、式（１）および
（２）を満足するアルカリ土類金属塩とリン酸及び／ま
たはリン酸エステル化合物とを、同時にまたは該アルカ
リ土類金属塩を添加後、該リン酸及び／またはリン酸エ
ステル化合物を添加することを特徴とするポリエステル
組成物の製造方法。 １．２≦Ｍ／Ｐ≦１．８ （１）Ｍ
≦５
（２）（式中Ｍはアルカリ土類金属塩中のアルカ
リ土類金属のポリエステル１０６ ｇ当たりの総モル数
、Ｐはリン酸またはそのエステル誘導体中におけるリン
のポリエステル１０６ ｇ当たりの総モル数を示す）Claim 1: A polyester composition comprising a polyester comprising a difunctional acid component mainly consisting of an aromatic dicarboxylic acid and at least one glycol component, and inorganic or organic fine particles having an average particle size of 0.01 to 5.0 μm. When producing a product, before adding the fine particles, an alkaline earth metal salt satisfying formulas (1) and (2) and a phosphoric acid and/or phosphoric acid ester compound are added simultaneously or together with the alkaline earth metal salt. A method for producing a polyester composition, which comprises adding the phosphoric acid and/or phosphoric ester compound after adding the salt. 1.2≦M/P≦1.8 (1)M
≦5
(2) (where M is the total number of moles of alkaline earth metal in the alkaline earth metal salt per 106 g of polyester, and P is the total number of moles of phosphorus per 106 g of polyester in phosphoric acid or its ester derivative. show)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3174619A JP2611059B2 (en) | 1991-06-18 | 1991-06-18 | Method for producing polyester composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3174619A JP2611059B2 (en) | 1991-06-18 | 1991-06-18 | Method for producing polyester composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04370142A true JPH04370142A (en) | 1992-12-22 |
| JP2611059B2 JP2611059B2 (en) | 1997-05-21 |
Family
ID=15981759
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3174619A Expired - Lifetime JP2611059B2 (en) | 1991-06-18 | 1991-06-18 | Method for producing polyester composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2611059B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012025930A (en) * | 2010-06-25 | 2012-02-09 | Vision Development Co Ltd | Method for producing polyester resin containing diamond fine particle and/or carbon nanotube |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5345396A (en) * | 1976-10-06 | 1978-04-24 | Toray Ind Inc | Preparation of polyester with high particle dispersibility |
| JPH0317123A (en) * | 1989-06-14 | 1991-01-25 | Toray Ind Inc | Production of particle-containing polyester |
| JPH03203953A (en) * | 1989-12-29 | 1991-09-05 | Toray Ind Inc | Polyester composition and production thereof |
-
1991
- 1991-06-18 JP JP3174619A patent/JP2611059B2/en not_active Expired - Lifetime
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5345396A (en) * | 1976-10-06 | 1978-04-24 | Toray Ind Inc | Preparation of polyester with high particle dispersibility |
| JPH0317123A (en) * | 1989-06-14 | 1991-01-25 | Toray Ind Inc | Production of particle-containing polyester |
| JPH03203953A (en) * | 1989-12-29 | 1991-09-05 | Toray Ind Inc | Polyester composition and production thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012025930A (en) * | 2010-06-25 | 2012-02-09 | Vision Development Co Ltd | Method for producing polyester resin containing diamond fine particle and/or carbon nanotube |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2611059B2 (en) | 1997-05-21 |
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