JP6919258B2 - Method for manufacturing polyester resin composition - Google Patents
Method for manufacturing polyester resin composition Download PDFInfo
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- JP6919258B2 JP6919258B2 JP2017057786A JP2017057786A JP6919258B2 JP 6919258 B2 JP6919258 B2 JP 6919258B2 JP 2017057786 A JP2017057786 A JP 2017057786A JP 2017057786 A JP2017057786 A JP 2017057786A JP 6919258 B2 JP6919258 B2 JP 6919258B2
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- polyester resin
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- 229920001225 polyester resin Polymers 0.000 title claims description 75
- 239000004645 polyester resin Substances 0.000 title claims description 75
- 239000000203 mixture Substances 0.000 title claims description 45
- 238000000034 method Methods 0.000 title claims description 19
- 238000004519 manufacturing process Methods 0.000 title claims description 18
- 239000010954 inorganic particle Substances 0.000 claims description 76
- 239000002245 particle Substances 0.000 claims description 42
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 21
- 238000004898 kneading Methods 0.000 claims description 9
- 238000000691 measurement method Methods 0.000 claims description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 239000000523 sample Substances 0.000 description 9
- 238000010304 firing Methods 0.000 description 7
- 239000002002 slurry Substances 0.000 description 7
- 239000007788 liquid Substances 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- 229920000728 polyester Polymers 0.000 description 5
- 239000003985 ceramic capacitor Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 238000010008 shearing Methods 0.000 description 4
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 239000012488 sample solution Substances 0.000 description 3
- 239000002904 solvent Substances 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
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid 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
- 238000000635 electron micrograph Methods 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
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 125000005372 silanol group Chemical group 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 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
- 239000005995 Aluminium silicate Substances 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000012777 electrically insulating material Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity 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
- -1 magnetic tapes Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000002156 mixing Methods 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
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
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- Processes Of Treating Macromolecular Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
本発明はポリエステル樹脂組成物の製造方法に関する。詳しくは無機粒子を含有したポリエステル樹脂組成物の製造方法に関する。 The present invention relates to a method for producing a polyester resin composition. More specifically, the present invention relates to a method for producing a polyester resin composition containing inorganic particles.
ポリエステルフィルムは優れた透明性、機械的性質、耐熱性、耐薬品性等を有するため、多層セラミックキャパシタ、磁気テープ、電気絶縁材料、写真フィルム、包装材などのフィルム用途に広く用いられている。 Since polyester films have excellent transparency, mechanical properties, heat resistance, chemical resistance, etc., they are widely used in film applications such as multilayer ceramic capacitors, magnetic tapes, electrically insulating materials, photographic films, and packaging materials.
特に多層セラミックキャパシタの離型フィルムなどに用いる場合、フィルム表面の平坦性とフィルム取扱い時の作業性改善、すなわち摩擦係数の低減及び摩耗特性の向上が要求されている。フィルム表面の平坦性、フィルムの摩擦係数の低減及び摩耗特性の向上を達成するためにはポリエステルに不活性粒子を添加し、該不活性粒子をポリエステル中に均一に分散させることが必要である。 In particular, when it is used for a release film of a multilayer ceramic capacitor, it is required that the flatness of the film surface and the workability at the time of handling the film are improved, that is, the friction coefficient is reduced and the wear characteristics are improved. In order to achieve flatness of the film surface, reduction of the coefficient of friction of the film and improvement of wear characteristics, it is necessary to add inert particles to the polyester and uniformly disperse the inert particles in the polyester.
特許文献１にはベント式二軸混練押出機を用い、シリカ等の無機粒子をスラリー状態でポリエステル樹脂に添加、混練することが記載されている。特許文献２にはベント式二軸混練押出機を用い、同一の原料供給口からポリエステルと無機粒子のスラリーを供給し、吐出量Ｑの該ベント式２軸押出機のスクリュー回転数Ｎに対する比（Ｑ／Ｎ）を特定の範囲とすることが記載されている。 Patent Document 1 describes that an inorganic particle such as silica is added to a polyester resin in a slurry state and kneaded by using a bent type twin-screw kneading extruder. In Patent Document 2, a vent-type twin-screw extruder is used to supply a slurry of polyester and inorganic particles from the same raw material supply port, and the ratio of the discharge amount Q to the screw rotation speed N of the vent-type twin-screw extruder ( It is stated that Q / N) is set to a specific range.
しかしながら、これら従前知られたポリエステル樹脂組成物の製造方法では、無機粒子をスラリー状態とした後に、ベント式二軸押出機でポリエステルと混練しているため、無機粒子をスラリーとする工程が必要であること、製造されたポリエステル樹脂組成物中に、スラリーに用いた媒体が残存し、ポリエステル樹脂組成物の品質が悪化するという問題があった。 However, in these conventionally known methods for producing polyester resin compositions, since the inorganic particles are made into a slurry state and then kneaded with the polyester by a vent type twin-screw extruder, a step of making the inorganic particles into a slurry is required. There is a problem that the medium used for the slurry remains in the produced polyester resin composition and the quality of the polyester resin composition deteriorates.
本発明は上記問題点を解決するためになされたものであり、本発明の目的は、簡便な方法により、無機粒子をポリエステル中に高分散化することができるポリエステル樹脂組成物の製造方法を提供することである。 The present invention has been made to solve the above problems, and an object of the present invention is to provide a method for producing a polyester resin composition capable of highly dispersing inorganic particles in polyester by a simple method. It is to be.
本発明者は上記課題を解決すべく検討した結果、ポリエステル樹脂１００重量部と、無機粒子０．５〜２．５重量部とを、二軸押出機により溶融混練する無機粒子含有ポリエステル樹脂組成物の製造方法であって、該ポリエステル樹脂の固有粘度が０．７０ｄＬ／ｇ以上であり、該無機粒子の温度２５℃、湿度５０％における流動表面角と、該無機粒子の温度２５℃、湿度８０％における流動表面角との差が３°以下であり、該二軸押出機の運転条件を特定範囲とすることにより含有する無機粒子が高分散化されたポリエステル樹脂組成物とすることができることを見出した。
本発明はこのような知見に基づいて達成されたものであり、以下を要旨とする。
［１］ ポリエステル樹脂と、該ポリエステル樹脂１００重量部に対し、無機粒子０．５重量部以上２．５重量部以下とを、二軸押出機により溶融混練することによるポリエステル樹脂組成物の製造方法であって、
該ポリエステル樹脂の固有粘度が０．７０ｄＬ／ｇ以上であり、
該無機粒子の温度２５℃、湿度５０％における流動表面角と、該無機粒子の温度２５℃、湿度８０％における流動表面角との差が３°以下であり、
該二軸押出機の運転条件が下記式（１）、（２）及び（３）を満たすポリエステル樹脂組成物の製造方法。
（無機粒子の流動表面角の測定法）
恒温恒湿室にて５時間、規定の温度及び規定の湿度に調整した無機粒子３００ｇを円筒回転法流動表面角測定器ＦＳＡ−１００（筒井理化学器械株式会社製）の円筒型試料容器に入れ、該円筒型試料容器を毎分１０回転で回転させ、定常状態となったのちに、円筒型試料容器に内在する無機粒子の最低点と最高点とを直線で結び、該直線と水平線との為す角度を流動表面角とする。
０．６２≦Ｑ／Ｎ≦０．７５ （１）
８０≦Ｑ≦２００ （２）
４０≦Ｄ≦１３０ （３）
（式中、Ｑは二軸押出機の吐出量（ｋｇ／ｈ）であり、Ｎは二軸押出機のスクリュー回転数（ｒｐｍ）であり、Ｄは二軸押出機のバレル径（ｍｍ）である。）
［２］ 前記無機粒子がシリカ粒子である［１］に記載のポリエステル樹脂組成物の製造方法。
［３］ 前記無機粒子の球形比が０．９以上１．０以下である、［１］又は［２］に記載のポリエステル樹脂組成物の製造方法。
［４］ 前記無機粒子の平均粒子径が０．１μｍ以上１．０μｍ以下である、［１］乃至［３］のいずれかに記載のポリエステル樹脂組成物の製造方法。
［５］ 前記ポリエステル樹脂の固有粘度と、前記ポリエステル樹脂組成物の固有粘度との差が０．０５ｄＬ／ｇ以上０．２０ｄＬ／ｇ以下である、［１］乃至［４］のいずれかに記載のポリエステル樹脂組成物の製造方法。
As a result of studies to solve the above problems, the present inventor has made an inorganic particle-containing polyester resin composition in which 100 parts by weight of a polyester resin and 0.5 to 2.5 parts by weight of inorganic particles are melt-kneaded by a twin-screw extruder. The specific viscosity of the polyester resin is 0.70 dL / g or more, the flow surface angle of the inorganic particles at a temperature of 25 ° C. and a humidity of 50%, and the temperature of the inorganic particles of 25 ° C. and a humidity of 80. The difference from the flow surface angle in% is 3 ° or less, and the inorganic particles contained in the twin-screw extruder can be made into a highly dispersed polyester resin composition by setting the operating conditions in a specific range. I found it.
The present invention has been achieved based on such findings, and the gist of the present invention is as follows.
[1] A method for producing a polyester resin composition by melt-kneading a polyester resin and 0.5 parts by weight or more and 2.5 parts by weight or less of inorganic particles with respect to 100 parts by weight of the polyester resin by a twin-screw extruder. And
The intrinsic viscosity of the polyester resin is 0.70 dL / g or more.
The difference between the fluidized surface angle of the inorganic particles at a temperature of 25 ° C. and a humidity of 50% and the fluidized surface angle of the inorganic particles at a temperature of 25 ° C. and a humidity of 80% is 3 ° or less.
A method for producing a polyester resin composition, wherein the operating conditions of the twin-screw extruder satisfy the following formulas (1), (2) and (3).
(Measurement method of flow surface angle of inorganic particles)
300 g of inorganic particles adjusted to the specified temperature and specified humidity in a constant temperature and humidity chamber were placed in a cylindrical sample container of the cylindrical rotation method flow surface angle measuring device FSA-100 (manufactured by Tsutsui Rikagaku Kikai Co., Ltd.) for 5 hours. The cylindrical sample container is rotated at 10 rpm, and after a steady state is established, the lowest point and the highest point of the inorganic particles contained in the cylindrical sample container are connected by a straight line, and the straight line and the horizontal line are formed. Let the angle be the flow surface angle.
0.62 ≤ Q / N ≤ 0.75 (1)
80 ≦ Q ≦ 200 (2)
40 ≦ D ≦ 130 (3)
(In the formula, Q is the discharge amount (kg / h) of the twin-screw extruder, N is the screw rotation speed (rpm) of the twin-screw extruder, and D is the barrel diameter (mm) of the twin-screw extruder. be.)
[2] The method for producing a polyester resin composition according to [1], wherein the inorganic particles are silica particles.
[3] The method for producing a polyester resin composition according to [1] or [2], wherein the spherical ratio of the inorganic particles is 0.9 or more and 1.0 or less.
[4] The method for producing a polyester resin composition according to any one of [1] to [3], wherein the average particle size of the inorganic particles is 0.1 μm or more and 1.0 μm or less.
[5] Described in any one of [1] to [4], wherein the difference between the intrinsic viscosity of the polyester resin and the intrinsic viscosity of the polyester resin composition is 0.05 dL / g or more and 0.20 dL / g or less. Method for producing polyester resin composition.
本発明の製造方法によれば、媒体を使用し無機粒子のスラリー化を行う等、煩雑な工程もなく、製造されたポリエステル樹脂組成物は、残存する媒体による品質劣化がなく、無機粒子の分散性が良好なポリエステル樹脂組成物とすることができることより、多層セラミックキャパシタの離型フィルムなどに適用することができる。 According to the production method of the present invention, the produced polyester resin composition does not have complicated steps such as slurrying inorganic particles using a medium, and the produced polyester resin composition does not deteriorate in quality due to the remaining medium, and the inorganic particles are dispersed. Since the polyester resin composition having good properties can be obtained, it can be applied to a release film of a multilayer ceramic capacitor or the like.
以下、本発明を詳細に説明するが、以下に記載する構成要件の説明は、本発明の実施態様の一例であり、これらの内容に限定されるものではない。 Hereinafter, the present invention will be described in detail, but the description of the constituent requirements described below is an example of an embodiment of the present invention, and is not limited to these contents.
本発明は、ポリエステル樹脂と、無機粒子とを、二軸押出機により溶融混練することによる無機粒子含有ポリエステル樹脂組成物の製造方法である。 The present invention is a method for producing an inorganic particle-containing polyester resin composition by melt-kneading a polyester resin and inorganic particles with a twin-screw extruder.
前記ポリエステル樹脂は、テレフタル酸またはそのエステルと、エチレングリコールを主たる出発原料として得られるポリエステル樹脂を指すが、他の第三成分を含有しても構わない。この場合、ジカルボン酸成分として、例えばイソフタル酸、フタル酸、２，６−ナフタレンジカルボン酸、アジピン酸、セバシン酸、およびオキシカルボン酸成分、例えばｐ−オキシエトキシ安息香酸等の一種または二種以上を用いることができる。グリコール成分としては、プロピレングリコール、ブタンジオール、１，４−シクロヘキサンジメタノール、ネオペンチルグリコール等の一種または二種以上を用いることができる。いずれにしても該ポリエステル樹脂は繰り返し構造単位の８０％以上がエチレンテレフタレー
ト単位を有するポリエステル樹脂であることが好ましい。
又、該ポリエステル樹脂の固有粘度は０．７０ｄｌ／ｇ以上であり、好ましくは０．７５ｄｌ／ｇ以上であり、更に好ましくは０．８０ｄｌ／ｇ以上である。前記範囲であることにより、ポリエステル樹脂と無機粒子とを二軸押出機で溶融混練する時に、溶融粘度を高く保つことが可能となり、製造されたポリエステル樹脂組成物中の無機粒子が高分散化する可能性がある。
The polyester resin refers to a polyester resin obtained by using terephthalic acid or an ester thereof and ethylene glycol as a main starting material, but may contain another third component. In this case, as the dicarboxylic acid component, for example, one or more of isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, adipic acid, sebacic acid, and an oxycarboxylic acid component, for example, p-oxyethoxybenzoic acid, etc. Can be used. As the glycol component, one or more of propylene glycol, butanediol, 1,4-cyclohexanedimethanol, neopentyl glycol and the like can be used. In any case, the polyester resin is preferably a polyester resin in which 80% or more of the repeating structural units have ethylene terephthalate units.
The intrinsic viscosity of the polyester resin is 0.70 dl / g or more, preferably 0.75 dl / g or more, and more preferably 0.80 dl / g or more. Within the above range, when the polyester resin and the inorganic particles are melt-kneaded by a twin-screw extruder, the melt viscosity can be kept high, and the inorganic particles in the produced polyester resin composition are highly dispersed. there is a possibility.
前記無機粒子は、シリカ粒子、炭酸カルシウム粒子、酸化チタン粒子、酸化アルミニウム粒子、硫酸バリウム粒子、フッ化リチウム粒子、カオリン粒子、酸化鉄等が挙げられが、形状の均一性よりシリカ粒子が好ましい。
又、該無機粒子は温度２５℃、湿度５０％における流動表面角と、該無機粒子の温度２５℃、湿度８０％における流動表面角との差が３°以下であり、好ましくは２°以下であり、より好ましくは１°以下である。前記範囲であることにより、製造されたポリエステル樹脂組成物中の無機粒子が高分散化する可能性がある。とりわけ、長期間、二軸押出機によりポリエステル樹脂組成物を製造するときに、温度変化又は湿度変化等が生じる場合や、短期間であっても高温、高湿度等の厳しい外的環境で二軸押出機によりポリエステル樹脂組成物を製造する場合においても、安定して、無機粒子が高分散化したポリエステル樹脂組成物とすることができる。尚、該無機粒子の表面流動角の測定は、恒温恒湿室にて５時間、規定の温度及び規定の湿度に調整した無機粒子３００ｇを円筒回転法流動表面角測定器ＦＳＡ−１００（筒井理化学器械株式会社製）の円筒型試料容器に入れ、該円筒型試料容器を毎分１０回転で回転させ、定常状態となったのちに、円筒型試料容器に内在する無機粒子の最低点と最高点とを直線で結び、該直線と水平線との為す角度を流動表面角とすることができる。
Examples of the inorganic particles include silica particles, calcium carbonate particles, titanium oxide particles, aluminum oxide particles, barium sulfate particles, lithium fluoride particles, kaolin particles, iron oxide and the like, and silica particles are preferable from the viewpoint of shape uniformity.
Further, the difference between the fluidized surface angle of the inorganic particles at a temperature of 25 ° C. and a humidity of 50% and the fluidized surface angle of the inorganic particles at a temperature of 25 ° C. and a humidity of 80% is 3 ° or less, preferably 2 ° or less. Yes, more preferably 1 ° or less. Within the above range, the inorganic particles in the produced polyester resin composition may be highly dispersed. In particular, when a polyester resin composition is produced by a twin-screw extruder for a long period of time, temperature changes or humidity changes occur, or even for a short period of time, the twin-screw is used in a severe external environment such as high temperature and high humidity. Even when the polyester resin composition is produced by an extruder, the polyester resin composition can be stably obtained with highly dispersed inorganic particles. The surface flow angle of the inorganic particles was measured in a constant temperature and humidity chamber for 5 hours by using 300 g of the inorganic particles adjusted to a specified temperature and a specified humidity with a cylindrical rotation method flow surface angle measuring device FSA-100 (Tsutsui Rikagaku). Put it in a cylindrical sample container (manufactured by Kikai Co., Ltd.), rotate the cylindrical sample container at 10 rpm, and after it reaches a steady state, the lowest and highest points of the inorganic particles contained in the cylindrical sample container. Can be connected by a straight line, and the angle formed by the straight line and the horizontal line can be used as the flow surface angle.
無機粒子がシリカ粒子である場合、該シリカ粒子は例えば、テトラアルコキシシランを加水分解・重縮合するアルコキシド法や、ケイ酸ソーダを原料として加水分解・重縮合する水ガラス法やゲル法により得ることができる。なお、シリカ粒子中のケイ素元素及び酸素元素の含有量は合計して９９重量％以上であることが好ましい。なおこれらの方法で得られた球状シリカ粒子は、必要に応じ乾燥後 焼成処理を施してもよい。焼成処理は通常
８００℃〜１，３００℃程度で行う。焼成処理により、表面に存在していたシラノール基が縮合・脱水され、シラノール基含有量の少ない球状シリカ粒子となる。更に、不純物を除去することができるため、異物の少ないポリエステル樹脂組成物を得ることができる。
When the inorganic particles are silica particles, the silica particles can be obtained by, for example, an alkoxide method in which tetraalkoxysilane is hydrolyzed / polycondensed, a water glass method in which sodium silicate is hydrolyzed / polycondensed, or a gel method. Can be done. The total content of silicon element and oxygen element in the silica particles is preferably 99% by weight or more. The spherical silica particles obtained by these methods may be subjected to a firing treatment after drying, if necessary. The firing treatment is usually performed at about 800 ° C. to 1,300 ° C. By the firing treatment, the silanol groups existing on the surface are condensed and dehydrated to become spherical silica particles having a low silanol group content. Further, since impurities can be removed, a polyester resin composition having less foreign matter can be obtained.
前記二軸押出機において溶融混練する無機粒子の量は、ポリエステル樹脂１００重量部に対して、０．５重量部以上２．５重量部以下であり、好ましくは１．０重量部以上１．５重量部以下である。無機粒子の量が前記範囲であることにより、二軸押出機で溶融混練する際に適度なせん断力が加わることとなり、製造されたポリエステル樹脂組成物中の無機粒子が高分散する可能性がある。 The amount of inorganic particles melt-kneaded in the twin-screw extruder is 0.5 parts by weight or more and 2.5 parts by weight or less, preferably 1.0 parts by weight or more and 1.5 parts by weight, based on 100 parts by weight of the polyester resin. It is less than a part by weight. When the amount of the inorganic particles is within the above range, an appropriate shearing force is applied when melt-kneading with the twin-screw extruder, and the inorganic particles in the produced polyester resin composition may be highly dispersed. ..
前記二軸押出機によるポリエステル樹脂と無機粒子を溶融混練する運転条件は下記式（１）（２）及び（３）を満たす。
０．６２≦Ｑ／Ｎ≦０．７５ （１）
８０≦Ｑ≦２００ （２）
４０≦Ｄ≦１３０ （３）
（式中、Ｑは二軸押出機の吐出量（ｋｇ／ｈ）であり、Ｎは二軸押出機のスクリュー回転数（ｒｐｍ）であり、Ｄは二軸押出機のバレル径（ｍｍ）である。）
Ｑ／Ｎを上記式（１）の範囲内で二軸押出機を運転することにより無機粒子が分散されたポリエステル樹脂組成物とすることが可能となる。尚、Ｑ／Ｎの下限は０．６３が好ましく、上限は０．７４が好ましい。
Ｑは上記式（２）の範囲内で二軸押出機を運転することにより安定した生産性と無機粒
子の分散性を両立することができる、尚、Ｑの下限は８５が好ましく、９０がより好ましい。又、Ｑの上限は１９０が好ましく、１８０がより好ましい。
Ｄは上記式（３）の範囲内で二軸押出機を運転することにより安定した生産性と無機粒子の分散性を両立することができる、尚、Ｄの下限は５０が好ましく、６０がより好ましい。又、Ｄの上限は１２０が好ましく、１１０がより好ましい。
The operating conditions for melt-kneading the polyester resin and the inorganic particles by the twin-screw extruder satisfy the following formulas (1), (2) and (3).
0.62 ≤ Q / N ≤ 0.75 (1)
80 ≦ Q ≦ 200 (2)
40 ≦ D ≦ 130 (3)
(In the formula, Q is the discharge amount (kg / h) of the twin-screw extruder, N is the screw rotation speed (rpm) of the twin-screw extruder, and D is the barrel diameter (mm) of the twin-screw extruder. be.)
By operating the twin-screw extruder within the range of the above formula (1) for Q / N, it becomes possible to obtain a polyester resin composition in which inorganic particles are dispersed. The lower limit of Q / N is preferably 0.63, and the upper limit is preferably 0.74.
By operating the twin-screw extruder within the range of the above formula (2), Q can achieve both stable productivity and dispersibility of inorganic particles. The lower limit of Q is preferably 85, and 90 is more. preferable. Further, the upper limit of Q is preferably 190, more preferably 180.
By operating the twin-screw extruder within the range of the above formula (3), D can achieve both stable productivity and dispersibility of inorganic particles. The lower limit of D is preferably 50, more preferably 60. preferable. Further, the upper limit of D is preferably 120, more preferably 110.
本発明において、二軸押出機にポリエステル樹脂及び無機粒子を供給する方法は、例えば、事前にポリエステル樹脂と無機粒子を混合させたのちに二軸押出機に供給する方法、ポリエステル樹脂を溶融させた後に無機粒子を供給する方法が挙げられる。 In the present invention, the method of supplying the polyester resin and the inorganic particles to the twin-screw extruder is, for example, a method of mixing the polyester resin and the inorganic particles in advance and then supplying the polyester resin and the inorganic particles to the twin-screw extruder, or melting the polyester resin. Later, a method of supplying inorganic particles can be mentioned.
前記二軸押出機によるポリエステル樹脂と無機粒子との溶融混練においては、揮発分、水分及びポリエステル樹脂や無機粒子を該二軸押出機に供給する供給口より侵入する空気等を除去するため、該二軸押出機のシリンダー中間部にベント孔を設けたベント式二軸押出機であることが好ましい。又、該二軸押出機のスクリューの回転方向は同方向、異方向が挙げられるが、無機粒子の高分散化の観点から同方向が好ましい。 In the melt-kneading of the polyester resin and the inorganic particles by the twin-screw extruder, the volatile matter, moisture, and air and the like entering from the supply port for supplying the polyester resin and the inorganic particles to the twin-screw extruder are removed. It is preferable that the twin-screw extruder has a vent hole provided in the middle of the cylinder of the twin-screw extruder. Further, the rotation direction of the screw of the twin-screw extruder may be the same direction or a different direction, but the same direction is preferable from the viewpoint of high dispersion of inorganic particles.
該無機粒子の粒子形状は球状であることが好ましく、その球形比は０．９以上１．０以下が好ましく、０．９３以上１．０以下がより好ましい。球形比が前記範囲であると、形状が均一であることより、二軸押出機で溶融混練する際に適度なせん断力が加わることとなり、製造されたポリエステル樹脂組成物中の無機粒子が高分散する可能性がある。尚、無機粒子の球形比は該無機粒子の電子顕微鏡写真よりその長径、短径を測定し、その比より求めることができる。
該無機粒子の平均粒子径は０．１μｍ以上１．０μｍ以下が好ましく、０．３μｍ以上０．５μｍ以下がより好ましい。平均粒子径が前記範囲であると適度な粒子径であることより、二軸押出機で溶融混練する際に適度なせん断力が加わることとなり、製造されたポリエステル樹脂組成物中の無機粒子が高分散化する可能性がある。尚、無機粒子の平均粒子径はレーザー回折／散乱式粒度分布測定装置により求めることができる。
The particle shape of the inorganic particles is preferably spherical, and the spherical ratio thereof is preferably 0.9 or more and 1.0 or less, and more preferably 0.93 or more and 1.0 or less. When the spherical ratio is in the above range, since the shape is uniform, an appropriate shearing force is applied when melt-kneading with a twin-screw extruder, and the inorganic particles in the produced polyester resin composition are highly dispersed. there's a possibility that. The spherical ratio of the inorganic particles can be obtained by measuring the major axis and the minor axis from the electron micrograph of the inorganic particles and calculating the ratio.
The average particle size of the inorganic particles is preferably 0.1 μm or more and 1.0 μm or less, and more preferably 0.3 μm or more and 0.5 μm or less. When the average particle size is in the above range, the particle size is appropriate, so that an appropriate shearing force is applied when melt-kneading with a twin-screw extruder, and the inorganic particles in the produced polyester resin composition are high. May be decentralized. The average particle size of the inorganic particles can be determined by a laser diffraction / scattering type particle size distribution measuring device.
前記ポリエステル樹脂の固有粘度と、前記ポリエステル樹脂組成物の固有粘度との差は０．０５ｄＬ／ｇ以上０．２０ｄＬ／ｇ以下が好ましく、０．０６ｄＬ／ｇ以上０．１９ｄＬ／ｇ以下がより好ましく、０．０７ｄＬ／ｇ以上０．１８ｄＬ／ｇ以下がさらに好ましい。前記範囲内であることにより無機粒子の分散性が良好である可能性がある。この理由は定かではないが、ポリエステル樹脂の固有粘度が高い値から低い値に次第に変化するため、ポリエステル樹脂と無機粒子との馴染みやせん断力が無機粒子の高分散化に好適な領域を経ることができるためと考えられる。 The difference between the intrinsic viscosity of the polyester resin and the intrinsic viscosity of the polyester resin composition is preferably 0.05 dL / g or more and 0.20 dL / g or less, and more preferably 0.06 dL / g or more and 0.19 dL / g or less. , 0.07 dL / g or more and 0.18 dL / g or less is more preferable. Within the above range, the dispersibility of the inorganic particles may be good. The reason for this is not clear, but since the intrinsic viscosity of the polyester resin gradually changes from a high value to a low value, the familiarity and shearing force between the polyester resin and the inorganic particles pass through a region suitable for high dispersion of the inorganic particles. It is thought that this is possible.
以下、実施例により本発明を更に詳細に説明するが、本発明はその要旨を超えない限り以下の実施例に限定されるものではない。本発明における球状シリカ粒子、ポリエステル樹脂、ポリエステル樹脂組成物は以下の測定方法によって測定、評価を行った。 Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the following Examples as long as the gist of the present invention is not exceeded. The spherical silica particles, the polyester resin, and the polyester resin composition in the present invention were measured and evaluated by the following measuring methods.
＜ポリエステル樹脂、ポリエステル樹脂組成物の固有粘度の測定＞
試料約０．２５ｇを、フェノール／１，１，２，２−テトラクロロエタン（質量比１／１）の混合溶媒約２５ｍＬに、濃度が１．００ｇ／ｄＬとなるように溶解させた後、３０℃まで冷却し、３０℃において全自動溶液粘度計（センテック社製、「ＤＴ５５３」）にて、試料溶液及び溶媒のみの落下秒数を測定し、以下の式により、固有粘度（ＩＶ）を算出した。
ＩＶ＝（（１＋４ＫＨηｓｐ）０．５−１）／（２ＫＨＣ）
ここで、 ηｓｐ=η／η０−１ であり、ηは試料溶液の落下秒数、η０は溶媒のみ
の落下秒数、Ｃは試料溶液濃度（ｇ／ｄＬ）、ＫＨはハギンズの定数である。ＫＨは０．
３３を採用した。なお試料の溶解条件は、１１０℃で３０分間である。
<Measurement of intrinsic viscosity of polyester resin and polyester resin composition>
About 0.25 g of the sample is dissolved in about 25 mL of a mixed solvent of phenol / 1,1,2,2-tetrachloroethane (mass ratio 1/1) so as to have a concentration of 1.00 g / dL, and then 30. Cool to ℃, measure the number of seconds that only the sample solution and solvent fall with a fully automatic solution viscometer (“DT553” manufactured by Centec) at 30 ℃, and calculate the intrinsic viscosity (IV) by the following formula. bottom.
IV = ((1 + 4KHη sp ) 0.5 -1) / (2KHC)
Here, η sp = η / η 0-1 , η is the number of seconds for the sample solution to fall, η 0 is the number of seconds for the solvent to fall, C is the concentration of the sample solution (g / dL), and KH is the Huggins constant. Is. KH is 0.
33 was adopted. The dissolution condition of the sample is 110 ° C. for 30 minutes.
＜無機粒子の平均粒子径＞
試料１ｇにメタノール１ｇを入れ、５分間超音波分散させた後、更に水８ｇを入れ、再度５分間超音波分散させた調製液をレーザ回折/散乱式粒度分布測定装置（堀場製作所社
製、「ＬＡ−９２０」）を用いて平均粒子径を測定した。この場合の平均粒子径とは体積分率で５０％に達するときの粒子径である。
<Average particle size of inorganic particles>
1 g of methanol was added to 1 g of the sample, ultrasonically dispersed for 5 minutes, then 8 g of water was further added, and the prepared solution was ultrasonically dispersed again for 5 minutes. The average particle size was measured using LA-920 "). The average particle size in this case is the particle size when the volume fraction reaches 50%.
＜無機粒子の球形比＞
無機粒子の電子顕微鏡写真から任意の粒子１０個を選定し、長径と短径を測定し、以下式から各粒子の球形比を算出した。
各粒子の球形比＝粒子の短径／粒子の長径
その後、以下式から各粒子の球形比の平均を算出し、球形比とした。
球形比＝各粒子の球形比の合計／１０
<Spherical ratio of inorganic particles>
Ten arbitrary particles were selected from the electron micrographs of the inorganic particles, the major axis and the minor axis were measured, and the spherical ratio of each particle was calculated from the following formula.
Spherical ratio of each particle = minor axis of particle / major axis of particle Then, the average of the spherical ratio of each particle was calculated from the following formula and used as the spherical ratio.
Spherical ratio = total spherical ratio of each particle / 10
＜ポリエステル樹脂組成物中の無機粒子の平均粒子径＞
３．２ｇのポリエステル樹脂組成物に１６０ｍｌのフェノール−テトラクロロエタン混合溶媒（２／３）を加えた後、１３０℃で加熱しながら３０分攪拌してポリエステル樹脂組成物を溶解させスラリー液とした。該スラリー液を室温まで冷却した後、粒度分布計（日機装社製 マイクロトラックＨＲＡ）を用いて平均粒子径を測定した。この場合の平均粒子径とは体積分率で５０％に達するときの粒子径である。
<Average particle size of inorganic particles in polyester resin composition>
After adding 160 ml of a phenol-tetrachloroethane mixture solvent (2/3) to 3.2 g of the polyester resin composition, the mixture was stirred for 30 minutes while heating at 130 ° C. to dissolve the polyester resin composition to prepare a slurry liquid. After cooling the slurry liquid to room temperature, the average particle size was measured using a particle size distribution meter (Microtrac HRA manufactured by Nikkiso Co., Ltd.). The average particle size in this case is the particle size when the volume fraction reaches 50%.
＜粒子分散性の評価＞
前記ポリエステル樹脂組成物中の無機粒子の平均粒子径の測定結果で得られた粒度積算分布から粒子径１０μｍ以上の粒子の割合（体積基準、％）を算出した。該割合が小さいほど粒子分散性が良好である。該割合が５．０％以下の場合に◎（優秀）、５．１％以上１０．０％以下の場合に○（良好）、１０．１％以上１５．０以下の場合に△（可）、１５．１％以上の場合に×（不可）と判定した。
<Evaluation of particle dispersibility>
The proportion (volume basis,%) of particles having a particle size of 10 μm or more was calculated from the particle size integrated distribution obtained from the measurement results of the average particle size of the inorganic particles in the polyester resin composition. The smaller the ratio, the better the particle dispersibility. When the ratio is 5.0% or less, ◎ (excellent), when 5.1% or more and 10.0% or less, ○ (good), when 10.1% or more and 15.0 or less, Δ (possible) , When it was 15.1% or more, it was judged as × (impossible).
＜球状シリカ粒子の製造＞
撹拌機、滴下装置および温度計を備えた容量２００Ｌの反応器に、メチルアルコール６７．５４ｋｇと、２８重量％アンモニア水（水および触媒）２６．３３ｋｇとを仕込み、撹拌しながら液温を３３±０．５℃に調節した。一方、滴下装置に、テトラメトキシシラン１３．４５ｋｇをメチルアルコール５．５９ｋｇに溶解させた溶液を仕込んだ。反応器中の液温を３３±０．５℃に保持しながら、滴下装置から前記溶液を１時間かけて滴下し、滴下終了後、さらに１時間、液温を前記温度に保持しながら撹拌することにより、テトラメトキシシランの加水分解および縮合を行い、球状シリカ粒子前駆体を含有する分散液を得た。前記分散液を、瞬間真空蒸発装置により気流乾燥させることにより、焼成処理なしの球状シリカ粒子を得た。瞬間真空蒸発装置としては、クラックス・システム８Ｂ型（ホソカワミクロン株式会社製）を使用した。得られた焼成処理なしのシリカ粒子をルツボに入れ、電気炉を用いて１０５０℃で１時間焼成した後、冷却して、次いで粉砕機を用いて粉砕することにより、焼成処理ありの球状シリカ粒子を得た。
<Manufacturing of spherical silica particles>
67.54 kg of methyl alcohol and 26.33 kg of 28 wt% aqueous ammonia (water and catalyst) were charged into a 200 L reactor equipped with a stirrer, dropping device and thermometer, and the liquid temperature was adjusted to 33 ± while stirring. The temperature was adjusted to 0.5 ° C. On the other hand, a solution prepared by dissolving 13.45 kg of tetramethoxysilane in 5.59 kg of methyl alcohol was charged into the dropping device. While maintaining the liquid temperature in the reactor at 33 ± 0.5 ° C., the solution is added dropwise from the dropping device over 1 hour, and after the completion of the dropping, the solution is stirred for another 1 hour while maintaining the liquid temperature at the temperature. As a result, tetramethoxysilane was hydrolyzed and condensed to obtain a dispersion liquid containing a spherical silica particle precursor. The dispersion was air-dried with an instantaneous vacuum evaporator to obtain spherical silica particles without calcination. As the instantaneous vacuum evaporator, a cracks system 8B type (manufactured by Hosokawa Micron Co., Ltd.) was used. The obtained silica particles without firing treatment are placed in a rut, fired at 1050 ° C. for 1 hour using an electric furnace, cooled, and then crushed using a crusher to obtain spherical silica particles with firing treatment. Got
（実施例１）
平均粒子径０．５μｍ（焼成処理あり）の球状シリカ粒子が表１の割合となるようにポリエステル樹脂（三菱化学社製 ＧＭ７０１Ｓ 固有粘度０．８５ｄＬ／ｇ）と混合させた後、ベント式混練機である二軸押出機（ＡＵＴＯＭＡＴＩＫ社製 ＺＣＭ スクリュー同方向回転 バレル内径Ｄ：７１ｍｍ）へ投入し、ベント口真空度を０．０９８ｍＨｇに設定し、シリンダー温度２８０℃、スクリュー回転数１５０ｒｐｍ、吐出量９５ｋｇ／ｈにて溶融混練し、ペレット化した。結果を表１に示す。
(Example 1)
Spherical silica particles with an average particle size of 0.5 μm (with firing treatment) are mixed with polyester resin (GM701S intrinsic viscosity 0.85 dL / g manufactured by Mitsubishi Chemical Corporation) so as to have the ratio shown in Table 1, and then a vent type kneader. It is put into a twin-screw extruder (ZCM screw co-rotating barrel inner diameter D: 71 mm manufactured by AUTOMATIK), the degree of vacuum at the vent port is set to 0.098 mHg, the cylinder temperature is 280 ° C, the screw rotation speed is 150 rpm, and the discharge amount is 95 kg. It was melt-kneaded at / h and pelletized. The results are shown in Table 1.
（実施例２）
吐出量を１１０ｋｇ／ｈに変更したこと以外は実施例１と同様に行った。結果を表１に示す。
(Example 2)
The same procedure as in Example 1 was carried out except that the discharge amount was changed to 110 kg / h. The results are shown in Table 1.
（比較例１）
スクリュー回転数を１８０ｒｐｍ、吐出量を１１０ｋｇ／ｈに変更したこと以外は実施例１と同様に行った。結果を表１に示す。
(Comparative Example 1)
The same procedure as in Example 1 was carried out except that the screw rotation speed was changed to 180 rpm and the discharge amount was changed to 110 kg / h. The results are shown in Table 1.
（比較例２）
スクリュー回転数を１８０ｒｐｍ、吐出量を９５ｋｇ／ｈに変更したこと以外は実施例１と同様に行った。結果を表１に示す。
(Comparative Example 2)
The procedure was the same as in Example 1 except that the screw rotation speed was changed to 180 rpm and the discharge amount was changed to 95 kg / h. The results are shown in Table 1.
（比較例３）
スクリュー回転数を１８０ｒｐｍ、吐出量を１４０ｋｇ／ｈに変更したこと以外は実施例１と同様に行った。結果を表１に示す。
(Comparative Example 3)
The same procedure as in Example 1 was carried out except that the screw rotation speed was changed to 180 rpm and the discharge amount was changed to 140 kg / h. The results are shown in Table 1.
（比較例４）
平均粒子径０．３μｍ（焼成処理あり）の球状シリカ粒子を用いて、粒子添加量を３．０重量部、スクリュー回転数を１８０ｒｐｍ、吐出量を１１０ｋｇ／ｈに変更したこと以外は実施例１と同様に行った。結果を表１に示す。
(Comparative Example 4)
Example 1 except that spherical silica particles having an average particle diameter of 0.3 μm (with firing treatment) were used, the amount of particles added was changed to 3.0 parts by weight, the screw rotation speed was changed to 180 rpm, and the discharge amount was changed to 110 kg / h. I went in the same way. The results are shown in Table 1.
本発明の製造方法により製造されたポリエステル樹脂組成物は実施例より明らかなように、無機粒子の分散性に優れていることより、フィルム表面の平坦性、フィルムの摩擦係数の低減及び摩耗特性の向上した成形品を得ることができ、多層セラミックキャパシタの離型フィルムなどへ適用可能である。 As is clear from the examples, the polyester resin composition produced by the production method of the present invention has excellent dispersibility of inorganic particles, so that the flatness of the film surface, the reduction of the friction coefficient of the film, and the wear characteristics are exhibited. An improved molded product can be obtained, and it can be applied to a release film of a multilayer ceramic capacitor and the like.
Claims (3)
該無機粒子がシリカ粒子であり、
該無機粒子の平均粒子径が０．１μｍ以上１．０μｍ以下であり、
該ポリエステル樹脂の固有粘度が０．７０ｄＬ／ｇ以上であり、
該無機粒子について、下記の無機粒子の流動表面角の測定法で規定の温度２５℃、規定の湿度５０％として測定した流動表面角と、該無機粒子について、下記の無機粒子の流動表面角の測定法で規定の温度２５℃、規定の湿度８０％として測定した流動表面角との差が３°以下であり、
該二軸押出機の運転条件が下記式（１）、（２）及び（３）を満たすポリエステル樹脂組成物の製造方法。
（無機粒子の流動表面角の測定法）
恒温恒湿室にて５時間、規定の温度及び規定の湿度に調整した無機粒子３００ｇを円筒回転法流動表面角測定器ＦＳＡ−１００（筒井理化学器械株式会社製）の円筒型試料容器に入れ、該円筒型試料容器を毎分１０回転で回転させ、定常状態となったのちに、円筒型試料容器に内在する無機粒子の最低点と最高点とを直線で結び、該直線と水平線との為す角度を流動表面角とする。
０．６２≦Ｑ／Ｎ≦０．７５ （１）
８０≦Ｑ≦２００ （２）
４０≦Ｄ≦１３０ （３）
（式中、Ｑは二軸押出機の吐出量（ｋｇ／ｈ）であり、Ｎは二軸押出機のスクリュー回転数（ｒｐｍ）であり、Ｄは二軸押出機のバレル径（ｍｍ）である。） A method for producing a polyester resin composition by melt-kneading a polyester resin and 0.5 parts by weight or more and 2.5 parts by weight or less of inorganic particles with respect to 100 parts by weight of the polyester resin by a twin-screw extruder. ,
The inorganic particles are silica particles,
The average particle size of the inorganic particles is 0.1 μm or more and 1.0 μm or less.
The intrinsic viscosity of the polyester resin is 0.70 dL / g or more.
The flow surface angle of the inorganic particles measured at a specified temperature of 25 ° C. and a specified humidity of 50% by the following method for measuring the flow surface angle of the inorganic particles, and the flow surface angle of the following inorganic particles for the inorganic particles. The difference from the flow surface angle measured at the specified temperature of 25 ° C and the specified humidity of 80% by the measurement method is 3 ° or less.
A method for producing a polyester resin composition, wherein the operating conditions of the twin-screw extruder satisfy the following formulas (1), (2) and (3).
(Measurement method of flow surface angle of inorganic particles)
300 g of inorganic particles adjusted to the specified temperature and specified humidity in a constant temperature and humidity chamber were placed in a cylindrical sample container of the cylindrical rotation method flow surface angle measuring device FSA-100 (manufactured by Tsutsui Rikagaku Kikai Co., Ltd.) for 5 hours. The cylindrical sample container is rotated at 10 rpm, and after a steady state is established, the lowest point and the highest point of the inorganic particles contained in the cylindrical sample container are connected by a straight line, and the straight line and the horizontal line are formed. Let the angle be the flow surface angle.
0.62 ≤ Q / N ≤ 0.75 (1)
80 ≦ Q ≦ 200 (2)
40 ≦ D ≦ 130 (3)
(In the formula, Q is the discharge amount (kg / h) of the twin-screw extruder, N is the screw rotation speed (rpm) of the twin-screw extruder, and D is the barrel diameter (mm) of the twin-screw extruder. be.)
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