JPH02219854A - Polyester composition - Google Patents
Polyester compositionInfo
- Publication number
- JPH02219854A JPH02219854A JP4107689A JP4107689A JPH02219854A JP H02219854 A JPH02219854 A JP H02219854A JP 4107689 A JP4107689 A JP 4107689A JP 4107689 A JP4107689 A JP 4107689A JP H02219854 A JPH02219854 A JP H02219854A
- Authority
- JP
- Japan
- Prior art keywords
- polyester
- particles
- weight
- precipitated
- parts
- 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
- 229920000728 polyester Polymers 0.000 title claims abstract description 64
- 239000000203 mixture Substances 0.000 title claims abstract description 17
- 239000002245 particle Substances 0.000 claims abstract description 50
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 13
- 229910052751 metal Inorganic materials 0.000 claims abstract description 12
- 239000002184 metal Substances 0.000 claims abstract description 12
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 7
- 239000011574 phosphorus Substances 0.000 claims description 11
- 150000003839 salts Chemical class 0.000 claims description 8
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 7
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 7
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 7
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 7
- -1 polyethylene terephthalate Polymers 0.000 abstract description 8
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 238000006243 chemical reaction Methods 0.000 abstract description 4
- 229910052744 lithium Inorganic materials 0.000 abstract description 4
- 229910052791 calcium Inorganic materials 0.000 abstract description 3
- 238000002156 mixing Methods 0.000 abstract description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 abstract description 2
- 239000005020 polyethylene terephthalate Substances 0.000 abstract description 2
- 229910052783 alkali metal Inorganic materials 0.000 abstract 2
- 150000001340 alkali metals Chemical class 0.000 abstract 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 abstract 2
- 150000001342 alkaline earth metals Chemical class 0.000 abstract 2
- 125000000217 alkyl group Chemical group 0.000 abstract 1
- 125000003710 aryl alkyl group Chemical group 0.000 abstract 1
- 230000001788 irregular Effects 0.000 abstract 1
- 229920001225 polyester resin Polymers 0.000 abstract 1
- 239000004645 polyester resin Substances 0.000 abstract 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 abstract 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 22
- 238000000034 method Methods 0.000 description 11
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 8
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000005809 transesterification reaction Methods 0.000 description 5
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 4
- XQKKWWCELHKGKB-UHFFFAOYSA-L calcium acetate monohydrate Chemical compound O.[Ca+2].CC([O-])=O.CC([O-])=O XQKKWWCELHKGKB-UHFFFAOYSA-L 0.000 description 4
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 4
- 238000006068 polycondensation reaction Methods 0.000 description 4
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 4
- 229940067460 calcium acetate monohydrate Drugs 0.000 description 3
- 229940043430 calcium compound Drugs 0.000 description 3
- 150000001674 calcium compounds Chemical class 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- 150000002642 lithium compounds Chemical class 0.000 description 3
- 235000011007 phosphoric acid Nutrition 0.000 description 3
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- IAQLJCYTGRMXMA-UHFFFAOYSA-M lithium;acetate;dihydrate Chemical compound [Li+].O.O.CC([O-])=O IAQLJCYTGRMXMA-UHFFFAOYSA-M 0.000 description 2
- 150000003016 phosphoric acids Chemical class 0.000 description 2
- 229920006267 polyester film Polymers 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical class CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 description 1
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical class CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 description 1
- WHKKNVAGWPTSRS-UHFFFAOYSA-N 2-dodecylnaphthalene-1-sulfonic acid Chemical class C1=CC=CC2=C(S(O)(=O)=O)C(CCCCCCCCCCCC)=CC=C21 WHKKNVAGWPTSRS-UHFFFAOYSA-N 0.000 description 1
- AQQPJNOXVZFTGE-UHFFFAOYSA-N 2-octadecylbenzenesulfonic acid Chemical class CCCCCCCCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O AQQPJNOXVZFTGE-UHFFFAOYSA-N 0.000 description 1
- QWHHBVWZZLQUIH-UHFFFAOYSA-N 2-octylbenzenesulfonic acid Chemical class CCCCCCCCC1=CC=CC=C1S(O)(=O)=O QWHHBVWZZLQUIH-UHFFFAOYSA-N 0.000 description 1
- MMINFSMURORWKH-UHFFFAOYSA-N 3,6-dioxabicyclo[6.2.2]dodeca-1(10),8,11-triene-2,7-dione Chemical group O=C1OCCOC(=O)C2=CC=C1C=C2 MMINFSMURORWKH-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
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 241001422033 Thestylus Species 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- QEZIKGQWAWNWIR-UHFFFAOYSA-N antimony(3+) antimony(5+) oxygen(2-) Chemical compound [O--].[O--].[O--].[O--].[Sb+3].[Sb+5] QEZIKGQWAWNWIR-UHFFFAOYSA-N 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical class OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 229940092714 benzenesulfonic acid Drugs 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229960005147 calcium acetate Drugs 0.000 description 1
- 239000001639 calcium acetate Substances 0.000 description 1
- 235000011092 calcium acetate Nutrition 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 150000003841 chloride salts Chemical class 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- BTVWZWFKMIUSGS-UHFFFAOYSA-N dimethylethyleneglycol Natural products CC(C)(O)CO BTVWZWFKMIUSGS-UHFFFAOYSA-N 0.000 description 1
- 229940060296 dodecylbenzenesulfonic acid Drugs 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000010954 inorganic particle Substances 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
- 238000004898 kneading Methods 0.000 description 1
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- MXXDSLLVYZMTFA-UHFFFAOYSA-N octadecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 MXXDSLLVYZMTFA-UHFFFAOYSA-N 0.000 description 1
- 239000011146 organic particle Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 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
- 238000002834 transmittance Methods 0.000 description 1
Landscapes
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野コ
本発明はポリエステル組成物に関し、更に詳しくは微細
な析出粒子を含有し、帯電防止性を有するポリエステル
組成物に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a polyester composition, and more particularly to a polyester composition containing fine precipitated particles and having antistatic properties.
［従来の技術］
ポリエステル、とりわけポリエチレンテレフタレートの
二軸配向フィルムは機械特性、電気的特性、耐薬品性、
寸法安定性等の点で優れていることから、磁気テープ用
、コンデンサー用、包装用、製版用、電気絶縁用、写真
フィルム用等多くの分野で基材として用いられている。[Prior Art] Biaxially oriented films of polyester, especially polyethylene terephthalate, have excellent mechanical properties, electrical properties, chemical resistance,
Due to its excellent dimensional stability, it is used as a base material in many fields such as magnetic tape, capacitors, packaging, plate making, electrical insulation, and photographic film.
ポリエステルフィルムは各用途に応じ、その要求特性は
異なるが、普遍的に望まれる特性は滑り性のよいことで
ある。The properties required for polyester films vary depending on their use, but the universally desired property is good slipperiness.
滑り性をよくするためには、ポリエステル中に粒子を存
在させ、フィルム表面に凹凸を形成させればよいことが
よく知られている。この粒子には大きく２つの種類があ
る。一つは外部粒子と呼ばれるものであり、いま一つは
内部粒子（析出粒子）と呼ばれるものである。It is well known that in order to improve slipperiness, particles may be present in polyester to form irregularities on the surface of the film. There are two main types of these particles. One is called an external particle, and the other is an internal particle (precipitated particle).
内部粒子は、触媒として用いた金属化合物やリン化合物
等がポリエステル合成反応系で反応して析出してできた
粒子であり、ポリエステルとの親和性がよいという特長
をもっている。しかし、内部粒子は、金属種、リン化合
物の種類およびその量によって一元的に径が定まってし
まう欠点がある。The internal particles are particles formed by the reaction and precipitation of metal compounds, phosphorus compounds, etc. used as catalysts in the polyester synthesis reaction system, and have a characteristic of having good affinity with polyester. However, the internal particles have a drawback that the diameter is uniformly determined by the type of metal, the type of phosphorus compound, and the amount thereof.
それぞれの用途に応じて望まれるフィルムの表面凹凸の
度合は異なるが、いずれの用途においても、フィルムの
走行性、高品質化の要求が高まり、そのなめますます微
細な凹凸が要求されるようになっている。微細な凹凸の
要求は必然的に微細な粒子の必要を意味する。The desired degree of surface unevenness of the film differs depending on the application, but in all applications, there is an increasing demand for film runnability and high quality, and as a result, increasingly finer unevenness is required. It has become. The requirement for fine irregularities necessarily means the necessity for fine particles.
前記内部粒子は、ポリエステルとの親和性がよいという
特長を有しているため、微細化したものが得られればそ
の利用価値は極めて大きい。The internal particles have a good affinity with polyester, so if they can be made into fine particles, their utility value is extremely high.
従来は、カルシウム元素を含有する内部粒子（特公昭３
４−５１４４号公報）、リチウム元素を含有する内部粒
子（特開昭４８−６１５５６号公報）、リチウム元素、
カルシウム元素およびリン元素を含有する内部粒子（特
開昭５１−１１２８６０号公報）等が知られているが、
さらに微細化された内部粒子が望まれている。Conventionally, internal particles containing calcium element (Tokuko Kosho 3)
4-5144), internal particles containing lithium element (JP-A-48-61556), lithium element,
Internal particles containing calcium element and phosphorus element (Japanese Unexamined Patent Publication No. 112860/1983) are known, but
Even finer internal particles are desired.
また、ポリエステルは、帯電しやすい欠点があり、さま
ざまなトラブルが起こる。例えばフィルムに加工した場
合、製膜加工工程でのロールへの巻きつき、作業者への
電撃、ゴミやほこりの吸引によるフィルム面の汚れ、印
刷不良、フィルム同志のまつわりつきなどのトラブルが
起こり、また糸の場合にも、糸乱れ、毛羽立ちやもつれ
、また加工後着用時の密着、巻きつきによる不快感など
を生じる。このなめ、帯電防止性を有するポリエステル
が望まれていた。Polyester also has the disadvantage of being easily charged with electricity, which can cause various problems. For example, when processed into a film, problems such as wrapping around rolls during the film forming process, electric shock to workers, dirt on the film surface due to dust and dust absorption, printing defects, and clinging between films may occur. In the case of yarn, it also causes discomfort due to yarn disorder, fuzzing, tangles, and sticking and wrapping when worn after processing. For this reason, a polyester having antistatic properties has been desired.
［発明が解決しようとする課題］
本発明の目的は、上記従来技術の欠点を解消することに
あり、特に微細な表面凹凸を形成することができるＩＲ
絹な内部粒子を含有し、かつ帯電防止性能にも優れたポ
リエステル組成物を提供することにある。[Problems to be Solved by the Invention] An object of the present invention is to eliminate the drawbacks of the above-mentioned prior art, and in particular, to solve the problem of IR which can form fine surface irregularities.
An object of the present invention is to provide a polyester composition containing silky internal particles and having excellent antistatic performance.
［課題を解決するための手段］
上記本発明の目的は、ポリエステル１００重量部に対し
て、リチウム元素、カルシウム元素およびリン元素を含
むポリエステル重合系で析出しな粒子０１０１〜３重景
部およ重量機スルホン酸金属塩０．１〜５重量部を含有
してなるポリエステル組成物により達成される。[Means for Solving the Problems] The object of the present invention is to produce particles 0101 to 3-layered parts and particles that do not precipitate in a polyester polymerization system containing a lithium element, a calcium element, and a phosphorus element, based on 100 parts by weight of polyester. This is achieved by a polyester composition containing 0.1 to 5 parts by weight of a heavy metal sulfonic acid salt.
本発明におけるポリエステルとは、エチレンテレフタレ
ートを主なる構成成分とするポリエステルであり、具体
的にはテレフタル酸を主なる酸成分としエチレングリコ
ールを主なるグリコール成分として得られるものである
。もちろんこれら原料の一部を他の酸成分またはグリコ
ール成分で置換してもよいが、いず九にしても本発明で
いうポリエステルとはその８０モル％以上がエチレンテ
レフタレート単位であるポリエステルをいう。The polyester in the present invention is a polyester containing ethylene terephthalate as a main component, and specifically, it is obtained using terephthalic acid as a main acid component and ethylene glycol as a main glycol component. Of course, some of these raw materials may be replaced with other acid components or glycol components, but in any case, the term "polyester" as used in the present invention refers to a polyester in which 80 mol% or more of the polyester is ethylene terephthalate units.
本発明のポリエステル重合系で析出した粒子とは、ポリ
エステルの製造過程で反応系に不溶化し析出したもので
、公知の方法でポリエステルから分離されるものである
。すなわち、０−クロルフェノールにポリエステルを約
１００’Ｃで溶解させた溶液をグラスフィルターで戸別
し、該液を超遠心分離機を用い、分離液の３７５ｍμで
の光透過率が一定値となるまで遠心分離して粒子を分離
し、さらに該遠心分離操作を走査型差動熱量計により前
記粒子からポリエステルの融解ピークが検出できなくな
るまで繰返した後、１２０℃、１６時間真空乾燥して得
られる粒子をいう。析出粒子の量は、ポリエステルに対
して好ましくは、０．０１〜３重量％、特に好ましくは
０．０５〜１重量％である。なお、ポリエステル組成物
中にこのような析出粒子とともに少量の外部粒子をも含
有しているときは、前記粒子分離操作で得られた粒子ｉ
から、外部粒子の量を除いた分を析出粒子の量とする。The particles precipitated in the polyester polymerization system of the present invention are particles that are insolubilized and precipitated in the reaction system during the polyester production process, and are separated from the polyester by a known method. That is, a solution in which polyester is dissolved in 0-chlorophenol at about 100'C is separated from door to door through a glass filter, and the liquid is heated using an ultracentrifuge until the light transmittance of the separated liquid at 375 mμ reaches a constant value. The particles are separated by centrifugation, and the centrifugation operation is repeated until the melting peak of polyester can no longer be detected from the particles using a scanning differential calorimeter, and then vacuum dried at 120° C. for 16 hours to obtain particles. means. The amount of precipitated particles is preferably from 0.01 to 3% by weight, particularly preferably from 0.05 to 1% by weight, based on the polyester. In addition, when the polyester composition also contains a small amount of external particles together with such precipitated particles, the particles i obtained in the particle separation operation
The amount of precipitated particles is determined by subtracting the amount of external particles.
本発明においてポリエステル重合系で析出した粒子は、
リチウム元素、カルシウム元素およびリン元素を含有し
てなるものである。析出粒子中の各元素の好ましい含有
量は、析出粒子全量に対して、リチウム元素０．１〜１
０重量％カルシウム元素０．１〜１０重量％およびリン
元素０．１〜１０重量％である。なお、ここで析出粒子
中の各元素の含有量とは、ポリエステル組成物の中の個
々の粒子についてではなくボリエステル組成物から前記
分離操作で分離された析出粒子全体についての平均値を
いう。In the present invention, the particles precipitated in the polyester polymerization system are
It contains lithium element, calcium element and phosphorus element. The preferable content of each element in the precipitated particles is 0.1 to 1 lithium element based on the total amount of the precipitated particles.
0% by weight calcium element 0.1-10% by weight and phosphorus element 0.1-10% by weight. Note that the content of each element in the precipitated particles herein refers to an average value not for each individual particle in the polyester composition but for the entire precipitated particles separated from the polyester composition in the separation operation.
本発明の有機スルホン酸金属塩としては下記−最大（Ｉ
＞で表わされる化合物である。As the organic sulfonic acid metal salt of the present invention, the following maximum (I
It is a compound represented by >.
（Ｒ８Ｏ３）ｎＭ ＝ （１）
具体的には、ベンゼンスルホン酸、トルエンスルホン酸
、オクチルベンゼンスルホン酸、ドデシルベンゼンスル
ホン酸、オクタデシルベンゼンスルホン酸、ドデシルナ
フタレンスルホン酸の金属塩を挙げることができる。金
属種としては、リチウム、ナトリウム、カリウム、マグ
ネシウムが好ましい。(R8O3)nM = (1) Specifically, metal salts of benzenesulfonic acid, toluenesulfonic acid, octylbenzenesulfonic acid, dodecylbenzenesulfonic acid, octadecylbenzenesulfonic acid, and dodecylnaphthalenesulfonic acid can be mentioned. As the metal species, lithium, sodium, potassium, and magnesium are preferred.
有機スルホン酸金属塩の量はポリエステルに対して０．
１〜５重量％の範囲である。好ましくは０．２〜３重量
部である。０．１重量部未満の場合には、実質的に析出
粒子の径の微細化はおこらないなめ好ましくない。また
５重量部より多くしても析出粒子の径の変化、帯電防止
性は飽和に達し、かえって得られるポリエステル組成物
の物性が低下する。The amount of organic sulfonic acid metal salt is 0.0% based on the polyester.
It ranges from 1 to 5% by weight. Preferably it is 0.2 to 3 parts by weight. If the amount is less than 0.1 part by weight, the diameter of the precipitated particles will not be substantially reduced, which is not preferable. Even if the amount exceeds 5 parts by weight, the change in the diameter of the precipitated particles and the antistatic properties will reach saturation, and the physical properties of the resulting polyester composition will deteriorate.
本発明のポリエステルは、従来公知の方法によって製造
される。たとえばテレフタル酸とエチレングリコールと
を直接エステル化反応させるか、テレフタル酸ジメチル
とエチレングリコールとをエステル交換反応させるかし
てテレフタル酸のグリコールエステルまたはその低重合
体を生成する第１段階の反応と、この反応生成物を重縮
合反応させる第２段階とによって製造されるのが最も一
最的である。The polyester of the present invention is produced by a conventionally known method. For example, a first step reaction of producing a glycol ester of terephthalic acid or a low polymer thereof by directly esterifying terephthalic acid and ethylene glycol or transesterifying dimethyl terephthalate and ethylene glycol; Most optimally, it is produced by a second step in which this reaction product undergoes a polycondensation reaction.
本発明のポリエステル組成物は、このポリエステル製造
工程もしくはフィルム、繊維、その他成形品にいたる過
程で、リチウム化合物、カルシウム化合物、リン化合物
および有機スルホン酸金属塩を添加することにより製造
することができる。The polyester composition of the present invention can be produced by adding a lithium compound, a calcium compound, a phosphorus compound, and an organic sulfonic acid metal salt during the polyester production process or the process leading to films, fibers, and other molded products.
リチウム化合物、カルシウム化合物としては、水素化物
、アルコラード、塩化物、水酸化物、酢酸塩などのグリ
コール可溶性化合物が挙げられ、特に酢酸リチウム、酢
酸カルシウムが好ましい。Examples of the lithium compound and calcium compound include glycol-soluble compounds such as hydrides, alcoholades, chlorides, hydroxides, and acetates, with lithium acetate and calcium acetate being particularly preferred.
また、リン化合物としては、リン酸、亜リン酸、ホスホ
ン酸などのリン酸およびこれらのリンの酸のエステルな
どから選ばれた化合物の１種または２種以上が用いられ
る。As the phosphorus compound, one or more compounds selected from phosphoric acids such as phosphoric acid, phosphorous acid, and phosphonic acid, and esters of these phosphoric acids are used.
リチウム化合物、カルシウム化合物は、ポリエステルの
固有粘度が０．２を越えない任意の時期に添加すること
ができ、エステル交換反応またはエステル化反応触媒と
して使用してもよい。The lithium compound and the calcium compound can be added at any time when the intrinsic viscosity of the polyester does not exceed 0.2, and may be used as a transesterification or esterification reaction catalyst.
またリン化合物は、エステル交換反応またはエステル化
反応終了後からポリエステルの固有粘度が０．２を越え
ないまでの間の任意の時期に加えられる。Further, the phosphorus compound is added at any time after the end of the transesterification or esterification reaction until the intrinsic viscosity of the polyester does not exceed 0.2.
有機スルホン酸金属塩の配合には、任意の方法が採用さ
れる。Any method can be used for blending the organic sulfonic acid metal salt.
即ち、ポリエステル重合反応中に添加反応させる方法や
、エクストルーダーで混練する方法が採用できる。また
予め、実質的に析出粒子を含有せず、有機スルホン酸金
属塩を高濃度に含有するマスタポリマを作り、これをリ
チウム元素およびカルシウム元素ならびにリン元素を含
む析出粒子を含有するポリエステルに配合する方法を用
いることができる。各用途に応じた濃度に容易に対応で
きる点から前記のマスタポリマ方式が好ましい。That is, a method of addition reaction during the polyester polymerization reaction or a method of kneading with an extruder can be adopted. Alternatively, a master polymer containing substantially no precipitated particles and a high concentration of organic sulfonic acid metal salt is prepared in advance, and this is blended into a polyester containing precipitated particles containing lithium elements, calcium elements, and phosphorus elements. can be used. The master polymer method described above is preferable because it can easily adjust the concentration according to each application.
なお、本発明のポリエステル組成物には、本発明の要件
を満たす範囲内において難燃剤、制電剤、耐熱剤、耐候
剤などの各種の改質剤が含まれていてもよい。また、少
量であれば、炭カル、酸化チタン、シリカ、カオリン、
タルク、アルミナ等の無機粒子や有機粒子といった外部
粒子を併用してもよい。The polyester composition of the present invention may contain various modifiers such as a flame retardant, an antistatic agent, a heat resistant agent, and a weathering agent within a range that satisfies the requirements of the present invention. In addition, in small amounts, charcoal, titanium oxide, silica, kaolin,
External particles such as inorganic particles such as talc and alumina or organic particles may be used in combination.
［実施例］
以下本発明を実施例により、さらに詳細に説明する。な
お、各特性の測定値は下記の方法によるものである。[Examples] The present invention will be explained in more detail below using Examples. In addition, the measured values of each characteristic are based on the following method.
Ａ、ポリマの極限粘度は、０−クロロフェノールを溶媒
とし２５℃にて測定した。A. The intrinsic viscosity of the polymer was measured at 25°C using 0-chlorophenol as a solvent.
Ｂ９粒子径は、ポリマから超薄切片をつくり、透過型電
子顕微鏡にて観察し、長径と短径の平均値から算出した
。The B9 particle diameter was calculated from the average value of the major axis and minor axis after making an ultrathin section from the polymer and observing it with a transmission electron microscope.
Ｃ，フィルムの摩擦係数は、スリップテスターを用いＡ
ＳＴＭ Ｄ １８９４Ｂ法に従って測定した。なお
フィルムの易滑性の目安として静摩擦係数を用いた。１
以下が好ましいものである。C. The coefficient of friction of the film was determined using a slip tester.
Measured according to STM D 1894B method. The coefficient of static friction was used as a measure of the slipperiness of the film. 1
The following are preferred.
Ｄ、フィルムの表面粗さは、フィルム表面を顕微光波干
渉計により観測し、得られた表面凹凸の最高部と最低部
の差をμ単位で表わした。D. The surface roughness of the film was measured by observing the film surface using a microscopic light wave interferometer, and the difference between the highest and lowest parts of the surface irregularities obtained was expressed in μ units.
０．２μ以下が好ましいものである。The thickness is preferably 0.2μ or less.
Ｅ、フィルム表面凹凸の密度は、触針法で１１１１ｍ中
の山の個数をかぞえ個／ｌｌｌｌ１１単位で表わす。E. The density of the unevenness on the film surface is expressed by counting the number of peaks in 1111 m using the stylus method in units of peaks/llll11.
Ｆ、帯電防止性はフィルムを超絶縁計（Ｒ−５０３型■
川日電気製作所製）により印加電圧１０００Ｖ、２３℃
、６０％ＲＨの条件で測定した。F. For antistatic properties, measure the film with a super megohmmeter (R-503 type■
(manufactured by Kawahi Electric Works), applied voltage 1000V, 23℃
, 60% RH.
表面抵抗１０１４Ω以下が好ましいものである。A surface resistance of 1014Ω or less is preferable.
実施例１．２比較例１〜５
（１） ポリエステルＡの製造
テレフタル酸ジメチル１００重量部とエチレングリコー
ル７０重量部に、酢酸カルシウム１水和物０．１重量部
および三酸化アンチモン０．０４重量部を添加し、常法
によりエステル交換反応を行なった。得られた生成物に
酢酸リチウム２水和物０．１７重量部およびリン酸トリ
メチルエステル０．１５ｔｌＬ部を添加した後、重縮合
反応を行ない固有粘度０．６２１のポリエステルＡを得
た。Example 1.2 Comparative Examples 1 to 5 (1) Production of Polyester A To 100 parts by weight of dimethyl terephthalate and 70 parts by weight of ethylene glycol, 0.1 part by weight of calcium acetate monohydrate and 0.04 part by weight of antimony trioxide. A transesterification reaction was carried out by a conventional method. After adding 0.17 parts by weight of lithium acetate dihydrate and 0.15 tlL part of trimethyl phosphate to the obtained product, a polycondensation reaction was carried out to obtain polyester A having an intrinsic viscosity of 0.621.
（２） ポリエステルＢの製造
テレフタル酸ジメチル１００重量部とエチレングリコー
ル７０重量部に、酢酸カルシウム１水和物０．１重量部
および二酸化アンチモン０５０３重量部を添加し、常法
によりエステル交換反応を行なった。得られた生成物に
リン酸トリメチルエステル０．０５重量部を添加し、次
いでドデシルベンゼンスルホン酸ナトリウム１０重量部
を添加して重縮合反応を行ない固有粘度０．６１８のポ
リエステルＢを得た。(2) Production of Polyester B 0.1 parts by weight of calcium acetate monohydrate and 0503 parts by weight of antimony dioxide were added to 100 parts by weight of dimethyl terephthalate and 70 parts by weight of ethylene glycol, and a transesterification reaction was carried out by a conventional method. Ta. To the obtained product, 0.05 parts by weight of trimethyl phosphate was added, and then 10 parts by weight of sodium dodecylbenzenesulfonate were added to carry out a polycondensation reaction to obtain polyester B having an intrinsic viscosity of 0.618.
（３） ポリエステルＣの製造
ドデシルベンゼンスルホン酸ナトリウムを添加しないこ
と以外はポリエステルＢの製造と同様に行ない固有粘度
０．６１８のポリエステル（ポリエステルＣ）を得た。(3) Production of Polyester C Polyester (Polyester C) having an intrinsic viscosity of 0.618 was obtained in the same manner as in the production of Polyester B except that sodium dodecylbenzenesulfonate was not added.
（４）製膜
上記ポリエステルＡ、ＢおよびＣを表１に示すような割
合で用いて２９０℃で溶融押出しし、未延伸シートを作
成した。次いで、縦方向に３．２倍延伸し、更に横方向
に３．５倍延伸した後２００℃で熱処理して厚さ３０μ
の２軸延伸フイルムを得た。(4) Film Formation The polyesters A, B, and C described above were melt-extruded at 290° C. in the proportions shown in Table 1 to prepare unstretched sheets. Next, it was stretched 3.2 times in the machine direction, further stretched 3.5 times in the cross direction, and then heat-treated at 200°C to a thickness of 30 μm.
A biaxially stretched film was obtained.
該フィルムの特性値を併わせで表１に示した。The characteristic values of the film are also shown in Table 1.
表１から明らかなように本発明で規定した範囲にあるポ
リエステルフィルムは析出粒子が微細化し、滑り性を維
持しながらも表面が平坦化していることがわかる。また
帯電防止性も優れる。As is clear from Table 1, the polyester film within the range specified by the present invention has finer precipitated particles and a flattened surface while maintaining slipperiness. It also has excellent antistatic properties.
一方、本発明の範囲外であると滑り性、表面の平担性あ
るいは帯電防止性が不十分であることがわかる。On the other hand, if it is outside the scope of the present invention, it can be seen that the slip properties, surface flatness, or antistatic properties are insufficient.
実施例３
テレフタル酸ジメチル１００重量部、エチレングリコー
ルの７０重量部に、酢酸カルシウム１水和物０．１重量
部および三酸化アンチモン０．０４重量部を添加し、常
法によりエステル交換反応を行なった。得られた生成物
に酢酸リチウム２水和物０．１７重量部、リン酸トリメ
チルエステル０．１５重量部、亜リン酸０．０２重量部
およびドデシルベンゼンスルホン酸ナトリウム１．０重
量部を添加し、重縮合反応を行ない固有粘度０．６２２
のポリエステルを得た。Example 3 0.1 part by weight of calcium acetate monohydrate and 0.04 part by weight of antimony trioxide were added to 100 parts by weight of dimethyl terephthalate and 70 parts by weight of ethylene glycol, and a transesterification reaction was carried out by a conventional method. Ta. To the obtained product were added 0.17 parts by weight of lithium acetate dihydrate, 0.15 parts by weight of trimethyl phosphate, 0.02 parts by weight of phosphorous acid, and 1.0 parts by weight of sodium dodecylbenzenesulfonate. , conducts polycondensation reaction and has an intrinsic viscosity of 0.622.
of polyester was obtained.
次いで該ポリエステルを用いて、実施例１と同様に製膜
を行ない厚さ３０μの二軸延伸フィルムを得た。Next, a film was formed using the polyester in the same manner as in Example 1 to obtain a biaxially stretched film with a thickness of 30 μm.
該二軸延伸フィルムは、表２に示したように、微細な析
出粒子を含有し、滑り性を維持しながらも表面の平坦性
が優れ、また帯電防止性にも優れることがわかる。As shown in Table 2, the biaxially stretched film contains fine precipitated particles, has excellent surface flatness while maintaining slipperiness, and is also excellent in antistatic properties.
実施例４
ドデシルベンゼンスルホン酸ナトリウム１゜０重重部の
かわりにオクタデシルベンゼンスルホン酸ナトリウム１
．２重量部を用いること以外は実施例３と同様にポリエ
ステルの製造、製膜を行ない厚さ３０μの二軸延伸フィ
ルムを得た。Example 4 Sodium octadecylbenzenesulfonate 1 in place of 1°0 parts of sodium dodecylbenzenesulfonate
．． Polyester was produced and film formed in the same manner as in Example 3, except that 2 parts by weight was used, and a biaxially stretched film with a thickness of 30 μm was obtained.
表２に示したように該二軸延伸フィルムは、良好な滑り
性、表面の平担性、帯電防止性を有することがわかる。As shown in Table 2, it can be seen that the biaxially stretched film has good slip properties, flat surface properties, and antistatic properties.
［発明の効果］
本発明のポリエステル組成物は、有機スルホン酸金属塩
の共存により、極めて微細でポリエステルと親和性のあ
る析出粒子を含有し、滑り性を保持しながら表面の平担
性も良好である。[Effects of the Invention] Due to the coexistence of the organic sulfonic acid metal salt, the polyester composition of the present invention contains extremely fine precipitated particles that have an affinity for polyester, and has good surface flatness while maintaining slipperiness. It is.
また、帯電防止性をも満足させることができる。Moreover, antistatic properties can also be satisfied.
したがって本発明のポリエステル組成物は、繊維、フィ
ルムその他成形品として有効に用いられ、特に表面の平
担性への要求が厳しい磁気テープの高級用途に用いると
その効果が一層顕著に発現される。Therefore, the polyester composition of the present invention can be effectively used as fibers, films, and other molded products, and its effects are particularly pronounced when used in high-grade applications such as magnetic tapes, which require strict surface flatness.
Claims (2)
素、カルシウム元素およびリン元素を含むポリエステル
重合系で析出した粒子０．０１〜３重量部および有機ス
ルホン酸金属塩０．１〜５重量部を含有してなるポリエ
ステル組成物。(1) Contains 0.01 to 3 parts by weight of particles precipitated by a polyester polymerization system containing lithium element, calcium element, and phosphorus element and 0.1 to 5 parts by weight of organic sulfonic acid metal salt per 100 parts by weight of polyester. A polyester composition made of
元素、カルシウム元素およびリン元素含有量が析出粒子
全量に対して、それぞれ０．１〜１０重量％である請求
項（１）記載のポリエステル組成物。(2) The polyester composition according to claim (1), wherein the contents of lithium element, calcium element, and phosphorus element in the particles precipitated by the polyester polymerization system are each 0.1 to 10% by weight based on the total amount of the precipitated particles. .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4107689A JP2682108B2 (en) | 1989-02-21 | 1989-02-21 | Polyester composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4107689A JP2682108B2 (en) | 1989-02-21 | 1989-02-21 | Polyester composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02219854A true JPH02219854A (en) | 1990-09-03 |
| JP2682108B2 JP2682108B2 (en) | 1997-11-26 |
Family
ID=12598366
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4107689A Expired - Lifetime JP2682108B2 (en) | 1989-02-21 | 1989-02-21 | Polyester composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2682108B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013018802A (en) * | 2011-07-07 | 2013-01-31 | Mitsubishi Rayon Textile Co Ltd | Polyester resin composition, method for producing the same, polyester fiber composed of the same, and fiber product of the polyester fiber |
-
1989
- 1989-02-21 JP JP4107689A patent/JP2682108B2/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013018802A (en) * | 2011-07-07 | 2013-01-31 | Mitsubishi Rayon Textile Co Ltd | Polyester resin composition, method for producing the same, polyester fiber composed of the same, and fiber product of the polyester fiber |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2682108B2 (en) | 1997-11-26 |
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