JP2008238449A - Method for manufacturing white polyester resin composition - Google Patents
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- JP2008238449A JP2008238449A JP2007078780A JP2007078780A JP2008238449A JP 2008238449 A JP2008238449 A JP 2008238449A JP 2007078780 A JP2007078780 A JP 2007078780A JP 2007078780 A JP2007078780 A JP 2007078780A JP 2008238449 A JP2008238449 A JP 2008238449A
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- 229920001225 polyester resin Polymers 0.000 title claims abstract description 86
- 239000004645 polyester resin Substances 0.000 title claims abstract description 86
- 239000000203 mixture Substances 0.000 title claims abstract description 68
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 25
- 238000000034 method Methods 0.000 title claims abstract description 17
- 238000004898 kneading Methods 0.000 claims abstract description 79
- 230000002087 whitening effect Effects 0.000 claims abstract description 34
- 239000000463 material Substances 0.000 claims abstract description 31
- 229920005989 resin Polymers 0.000 claims abstract description 31
- 239000011347 resin Substances 0.000 claims abstract description 31
- 239000010954 inorganic particle Substances 0.000 claims description 21
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 230000006866 deterioration Effects 0.000 abstract description 27
- 239000012463 white pigment Substances 0.000 abstract description 3
- 230000015556 catabolic process Effects 0.000 abstract description 2
- 238000006731 degradation reaction Methods 0.000 abstract description 2
- 229920000728 polyester Polymers 0.000 description 26
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 18
- 239000002245 particle Substances 0.000 description 15
- 230000006835 compression Effects 0.000 description 13
- 238000007906 compression Methods 0.000 description 13
- 229920006267 polyester film Polymers 0.000 description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 10
- 239000008188 pellet Substances 0.000 description 7
- 229920001577 copolymer Polymers 0.000 description 6
- 229920000306 polymethylpentene Polymers 0.000 description 6
- 239000011116 polymethylpentene Substances 0.000 description 6
- KKEYFWRCBNTPAC-UHFFFAOYSA-N terephthalic acid group Chemical group C(C1=CC=C(C(=O)O)C=C1)(=O)O KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 6
- 239000004973 liquid crystal related substance Substances 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- -1 alkylene glycols Chemical class 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 230000020169 heat generation Effects 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- 230000001771 impaired effect Effects 0.000 description 3
- 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 3
- 239000000049 pigment Substances 0.000 description 3
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-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
- 239000004743 Polypropylene Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-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
- 230000015572 biosynthetic process Effects 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 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
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920005672 polyolefin resin Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 2
- 239000011342 resin composition Substances 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004734 Polyphenylene sulfide Substances 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-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
- 239000000654 additive Substances 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000000306 component Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- VNGOYPQMJFJDLV-UHFFFAOYSA-N dimethyl benzene-1,3-dicarboxylate Chemical compound COC(=O)C1=CC=CC(C(=O)OC)=C1 VNGOYPQMJFJDLV-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium oxide Inorganic materials O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 238000007373 indentation Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- PVADDRMAFCOOPC-UHFFFAOYSA-N oxogermanium Chemical compound [Ge]=O PVADDRMAFCOOPC-UHFFFAOYSA-N 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920006350 polyacrylonitrile resin Polymers 0.000 description 1
- 229920001083 polybutene Polymers 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 229920005990 polystyrene resin Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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- Processes Of Treating Macromolecular Substances (AREA)
- Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
Abstract
Description
本発明は、白色化材が混練分散された白色ポリエステル樹脂組成物の製造方法に関するものである。さらに詳しくは、白色化材が高度に混練分散され、混練時の熱劣化や色相の悪化が抑制された、特に液晶ディスプレイ用反射板基材等に使用される白色ポリエステルフィルムに好適な白色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 white polyester resin composition in which a whitening material is kneaded and dispersed. More specifically, a white polyester resin that is highly suitable for white polyester films, particularly used for reflector substrates for liquid crystal displays, in which whitening materials are highly kneaded and dispersed, and thermal deterioration and hue deterioration during kneading are suppressed. The present invention relates to a method for producing a composition.
ポリエステルに硫酸バリウムや酸化チタンなどの白色顔料、または、非相溶樹脂を含有させて白色ポリエステルフィルムとすることが特開２００４−５０４７９号公報（特許文献１）や特開２００５−１２５７００号公報（特許文献２）で提案されている。これらに提案される白色ポリエステルフィルムは、液晶ディスプレイ用反射板基材として好適に使用されると開示されているが、そのためには白色顔料や非相溶樹脂がポリエステル中で高度に分散含有されている必要がある。一般的に、これら白色顔料や非相溶樹脂をポリエステル中に分散含有させる手段として、あらかじめ白色顔料を分散精製処理したスラリーとして、ポリエステル合成中に添加する方法や、二軸押出機を用いポリエステル中に白色顔料や非相溶樹脂を添加混練させる方法が提案されているが、前者の方法では添加時にヒートショックなどで再凝集が起こったり、後者の方法では混練時の剪断発熱でポリエステルの劣化が起こり色相を悪化させるなどの問題が潜在されており、満足のいく品質を有する白色ポリエステルフィルムを得るのは困難であった。 Japanese Patent Application Laid-Open No. 2004-50479 (Patent Document 1) and Japanese Patent Application Laid-Open No. 2005-125700 (white patent film) include white pigments such as barium sulfate and titanium oxide, or incompatible resins. This is proposed in Patent Document 2). The white polyester films proposed for these are disclosed as being suitably used as a reflector substrate for liquid crystal displays, but for that purpose, white pigments and incompatible resins are highly dispersed and contained in the polyester. Need to be. Generally, as a means of dispersing and containing these white pigments and incompatible resins in the polyester, as a slurry obtained by dispersing and purifying the white pigment in advance, a method of adding during polyester synthesis, or using a twin-screw extruder in the polyester A method of adding and kneading a white pigment or an incompatible resin is proposed, but in the former method, re-aggregation occurs due to heat shock at the time of addition, or in the latter method, degradation of the polyester is caused by shearing heat generation during kneading. Problems such as occurrence and deterioration of hue have been latent, and it has been difficult to obtain a white polyester film having satisfactory quality.
本発明の目的は、上述の従来技術が有する問題を解消し、白色化材が高度に混練分散含有されながらも、混練時の熱劣化や色相の悪化等が抑制された白色ポリエステル樹脂組成物の製造方法を提供することにある。 The object of the present invention is to solve the above-mentioned problems of the prior art and to provide a white polyester resin composition in which the whitening material is highly kneaded and dispersed and the thermal deterioration and hue deterioration during kneading are suppressed. It is to provide a manufacturing method.
本発明者らは、上記従来技術の有する問題を解決しようと鋭意研究した結果、二軸混練部と単軸混練部とをこの順で有するタンデム型混練押出機を用いると、極めて短時間に混練を高度に行うことができ、その結果上記課題を解決できることを見出し、本発明に到達した。 As a result of intensive research aimed at solving the problems of the above-mentioned conventional techniques, the present inventors kneaded in a very short time using a tandem kneading extruder having a biaxial kneading section and a single-shaft kneading section in this order. As a result, the inventors have found that the above-described problems can be solved, and have reached the present invention.
かくして本発明によれば、白色化材５〜７０重量％とポリエステル樹脂３０〜９５重量％とを溶融混練するポリエステル樹脂組成物の製造方法であって、
溶融混練を二軸混練部と単軸混練部とをこの順で有するタンデム型混練押出機で行なう白色ポリエステル樹脂組成物の製造方法が提供される。
Thus, according to the present invention, there is provided a method for producing a polyester resin composition comprising melt-kneading 5 to 70% by weight of a whitening material and 30 to 95% by weight of a polyester resin,
There is provided a method for producing a white polyester resin composition in which melt kneading is carried out by a tandem kneading extruder having a biaxial kneading part and a uniaxial kneading part in this order.
また、本発明の好ましい態様として、二軸混練部の軸の回転速度が５００〜１０００ｒｐｍで、単軸混練部の軸の回転速度が８０〜１５０ｒｐｍであること、二軸混練部のシリンダー長（Ｌ）とシリンダー径（Ｄ）の比（Ｌ／Ｄ）が５〜１０であること、二軸混練部のシリンダー長（Ｌ）が３００〜１０００ｍｍであること、、白色化材が白色無機粒子で、その添加量が、ポリエステル樹脂組成物の重量を基準として、３０〜７０重量％の範囲であること、白色化剤がポリエステルと非相溶な樹脂で、添加量が、樹脂組成物の重量を基準として、５〜４０重量％の範囲であることの少なくともいずれか一つを具備する白色ポリエステル樹脂組成物の製造方法も提供される。 As a preferred embodiment of the present invention, the rotational speed of the shaft of the biaxial kneading section is 500 to 1000 rpm, the rotational speed of the shaft of the uniaxial kneading section is 80 to 150 rpm, and the cylinder length (L ) And the cylinder diameter (D) ratio (L / D) is 5 to 10, the cylinder length (L) of the biaxial kneading part is 300 to 1000 mm, the whitening material is white inorganic particles, The addition amount is in the range of 30 to 70% by weight based on the weight of the polyester resin composition, the whitening agent is a resin incompatible with the polyester, and the addition amount is based on the weight of the resin composition. A method for producing a white polyester resin composition having at least one of 5 to 40% by weight is also provided.
本発明によれば、白色化材を５〜７０重量％という高濃度に添加された白色ポリエステル樹脂組成物を製造する方法として、特定のタンデム型混練押出機による混練分散という方法を採用したことにより、ポリエステル樹脂中に高度に分散させることができ、かつ、混練時の剪断発熱によるポリエステル樹脂の熱劣化や色相の悪化が抑制できることから、液晶ディスプレイ用反射板基材等に使用される白色ポリエステルフィルムとして好適な白色ポリエステル樹脂組成物を得ることができる。 According to the present invention, as a method for producing a white polyester resin composition in which a whitening material is added at a high concentration of 5 to 70% by weight, a method of kneading and dispersing by a specific tandem kneading extruder is adopted. White polyester film used for reflector substrates for liquid crystal displays, etc. because it can be highly dispersed in the polyester resin and can suppress deterioration of the heat and hue of the polyester resin due to shear heat generation during kneading A suitable white polyester resin composition can be obtained.
以下、本発明を詳細に説明する。
［ポリエステル樹脂］
本発明におけるポリエステルは、単独重合体でも共重合体であってもよい。共重合体の場合、共重合成分の割合は、本発明の効果を損なわない範囲であれば特に制限されないが、繰り返し単位を基準として、４０モル％以下、さらに２０モル％以下であることが好ましい。
Hereinafter, the present invention will be described in detail.
[Polyester resin]
The polyester in the present invention may be a homopolymer or a copolymer. In the case of a copolymer, the proportion of the copolymer component is not particularly limited as long as it does not impair the effects of the present invention, but is preferably 40 mol% or less, more preferably 20 mol% or less, based on the repeating unit. .
本発明におけるポリエステルは、全ジカルボン酸成分の６０モル％以上、さらに６５モル％以上、特に８５モル％以上がテレフタル酸または２，６−ナフタレンジカルボン酸、全グリコール成分の７０モル％以上、さらに８０モル％以上、特に８５モル％以上がエチレングリコールからなるものが好ましい。なお、このようなポリエステルは、それ自体公知の方法により製造できる。 In the polyester of the present invention, the total dicarboxylic acid component is 60 mol% or more, further 65 mol% or more, particularly 85 mol% or more is terephthalic acid or 2,6-naphthalenedicarboxylic acid, 70 mol% or more of all glycol components, and further 80 It is preferred that the mol% or more, particularly 85 mol% or more is composed of ethylene glycol. Such a polyester can be produced by a method known per se.
ポリエステルが共重合体の場合、共重合成分は、それ自体公知のものを採用でき、例えば、ジカルボン酸成分としてはコハク酸、アジピン酸、セバシン酸、フタル酸、イソフタル酸、テレフタル酸（主たる酸成分がテレフタル酸でない場合）、２，６−ナフタレンジカルボン酸（主たる酸成分が２，６−ナフタレンジカルボン酸でない場合）、５−ナトリウムジカルボン酸を、またグリコール成分としては、トリメチレングリコール、ジエチレングリコール、プロピレングリコール、１，４−ブタンジオールなどのアルキレングリコール、１，４−シクロヘキサンジメタノールなどを挙げることができる。なお、これらの共重合成分は１種のみでなく２種以上を併用してもよい。 In the case where the polyester is a copolymer, the copolymer component may be a known one. For example, as the dicarboxylic acid component, succinic acid, adipic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid (main acid component) Is not terephthalic acid), 2,6-naphthalenedicarboxylic acid (when the main acid component is not 2,6-naphthalenedicarboxylic acid), 5-sodium dicarboxylic acid, and glycol components include trimethylene glycol, diethylene glycol, propylene Examples include glycols, alkylene glycols such as 1,4-butanediol, and 1,4-cyclohexanedimethanol. In addition, these copolymerization components may use not only 1 type but 2 or more types together.
本発明におけるポリエステルの固有粘度は、オルトクロロフェノール溶媒下で３５℃で測定した固有粘度で、０．４ｄｌ／ｇ〜０．８ｄｌ／ｇ、さらに０．５ｄｌ／ｇ〜０．７ｄｌ／ｇであことが好ましい。固有粘度が下限未満の場合は、本発明により製造された白色ポリエステル樹脂組成物を、各製品に使用する際に要求される機械強度などの特性が不足することがある。他方、固有粘度が上限を超える場合は、溶融重合工程およびフィルム製膜工程などにおける溶融混練時の生産性が損なわれることがある。
また、本発明におけるポリエステルには、公知の各種添加剤、例えば、酸化防止剤、帯電防止剤、紫外線吸収剤が添加されていても良い。
The intrinsic viscosity of the polyester in the present invention is an intrinsic viscosity measured at 35 ° C. in an orthochlorophenol solvent, and is 0.4 dl / g to 0.8 dl / g, and further 0.5 dl / g to 0.7 dl / g. It is preferable. When the intrinsic viscosity is less than the lower limit, characteristics such as mechanical strength required when the white polyester resin composition produced according to the present invention is used for each product may be insufficient. On the other hand, when the intrinsic viscosity exceeds the upper limit, productivity at the time of melt kneading in the melt polymerization step and the film forming step may be impaired.
In addition, various known additives such as an antioxidant, an antistatic agent, and an ultraviolet absorber may be added to the polyester in the present invention.
［白色化材］
本発明における白色化材は、本発明の目的を損なわなければ特に限定されるものではないが、白色性を効率良く達成し得るとの観点から、白色無機粒子またはポリエステルと非相溶な樹脂であることが好ましい。
白色無機粒子としては、硫酸バリウム、酸化チタン、炭酸カルシウム、二酸化ケイ素などが好ましく挙げられ、これらの中でも硫酸バリウムが特に好ましい。これらは単独であっても良いし、２種以上の白色無機粒子を併用して使用しても構わない。
[Whitening material]
The whitening material in the present invention is not particularly limited as long as the object of the present invention is not impaired, but from the viewpoint that whiteness can be achieved efficiently, it is a resin incompatible with white inorganic particles or polyester. Preferably there is.
Preferred examples of the white inorganic particles include barium sulfate, titanium oxide, calcium carbonate, and silicon dioxide. Among these, barium sulfate is particularly preferable. These may be used alone or in combination of two or more kinds of white inorganic particles.
本発明における白色無機粒子は、かさ密度が０．５〜０．８５ｇ／ｍｌの範囲にあることが好ましい。かさ密度が下限未満では、ポリエステルに添加する際の粒子の搬送性が悪いため、安定した定量供給が難しく一定濃度の組成物を得ることが困難となったり、フィルムなどに製膜した際に品質のばらつきが大きくなる。白色無機粒子の好ましいかさ密度は、０．５５〜０．８５ｇ／ｍｌ、特に０．６〜０．８ｇ／ｍｌの範囲である。このようなかさ密度は、例えば粉砕処理などによって高くすることができ、他方フィルターによる濾過処理で微細粒子を取り除くことで低くすることができる。 The white inorganic particles in the present invention preferably have a bulk density in the range of 0.5 to 0.85 g / ml. If the bulk density is less than the lower limit, the transportability of the particles when added to the polyester is poor, so it is difficult to obtain a constant concentration, it is difficult to obtain a composition with a constant concentration, and the quality when filmed on a film, etc. The variation of the is increased. The preferred bulk density of the white inorganic particles is in the range of 0.55 to 0.85 g / ml, particularly 0.6 to 0.8 g / ml. Such a bulk density can be increased by, for example, a pulverization process, and can be decreased by removing fine particles by a filtration process using a filter.
また、本発明における白色無機粒子は、圧縮時流動エネルギーが１００００ｍＪ以下である必要がある。圧縮時流動エネルギーとは、粒子に一定の荷重をかけ圧縮処理をした後の粒子の流動性を表す指標であり、例えば、ホッパーなどへの貯蔵時の粒子の固まりやすさや、力を加えた時のばらけやすさなどを示すものである。圧縮時流動エネルギーが１００００ｍＪ以上であると、その粒子は非常に固まりやすく、力を加えてもばらけにくいものであるため、ポリエステル中へ添加する際、安定して定量供給することが困難であるとともに、混練操作の際、凝集が壊れにくく分散性が不良となる。白色無機粒子の好ましい圧縮時流動エネルギーは、９５００ｍＪ以下、特に９０００ｍＪ以下の範囲である。このような圧縮時流動エネルギーは、フィルターによる濾過処理で微細粒子を取り除くことなどで低くすることができる。 Further, the white inorganic particles in the present invention need to have a flow energy during compression of 10,000 mJ or less. The flow energy during compression is an index that represents the fluidity of particles after applying a certain load to the particles and compressing them.For example, when particles are easily stored in a hopper or when force is applied. It shows the ease of dissemination. If the flow energy during compression is 10000 mJ or more, the particles are very likely to harden and are difficult to disperse even when force is applied, and therefore it is difficult to stably and quantitatively supply them when added to polyester. At the same time, the agglomeration is difficult to break during the kneading operation, resulting in poor dispersibility. A preferable compression flow energy of the white inorganic particles is 9500 mJ or less, particularly 9000 mJ or less. Such compression flow energy can be lowered by removing fine particles by filtration using a filter.
また、本発明におけるポリエステル樹脂に非相溶な樹脂とは、ポリエステル以外の熱可塑性樹脂であって、かつポリエステルに対して非相溶性を示す熱可塑性樹脂であり、ポリエステル中では粒子状に分散し、延伸によりフィルム中に空洞を形成せしめる効果が大きい樹脂が好ましい。より具体的に述べれば、非相溶樹脂とは、ポリエステルと上記非相溶樹脂とを溶融した系を、公知の方法、好ましくは、示差走査熱量計（ＤＳＣ）、動的粘弾性測定等で測定した場合に、ポリエステルに相当するガラス転移温度（以降、Ｔｇと省略する）以外に該非相溶樹脂に相当するＴｇが観察される樹脂である。 In addition, the resin incompatible with the polyester resin in the present invention is a thermoplastic resin other than polyester and is incompatible with the polyester, and is dispersed in the form of particles in the polyester. A resin having a large effect of forming cavities in the film by stretching is preferred. More specifically, the incompatible resin refers to a system in which polyester and the incompatible resin are melted by a known method, preferably a differential scanning calorimeter (DSC), dynamic viscoelasticity measurement or the like. When measured, it is a resin in which Tg corresponding to the incompatible resin is observed in addition to the glass transition temperature corresponding to polyester (hereinafter abbreviated as Tg).
このような非相溶樹脂の融点は、ポリエステル樹脂の融点と同等もしくはやや低温であって、かつ製膜時にフィルムを熱固定して結晶化させる際の温度（熱処理温度）よりも高温であることが特に好ましい。かかる点から該非相溶樹脂の中でも、ポリエチレン、ポリプロピレン、ポリブテン、ポリメチルペンテンのようなポリオレフィン樹脂、ポリスチレン樹脂、ポリアクリレート樹脂、ポリカーボネート樹脂、ポリアクリロニトリル樹脂、ポリフェニレンスルフィド樹脂およびフッ素系樹脂などが好ましく用いられる。これらの非相溶樹脂は、単独重合体であっても共重合体であってもよく、さらには２種以上の非相溶樹脂を併用してもよい。これらの中でも、臨界表面張力の小さなポリプロピレンやポリメチルペンテンのようなポリオレフィン樹脂が好ましく、さらにはポリメチルペンテンが最も好ましい。該ポリメチルペンテンは相対的にポリエステルとの表面張力差が大きく、かつ融点が高いため、添加量当たりの空洞形成の効果が大きいという特徴があり、非相溶樹脂として特に好ましいものである。 The melting point of such an incompatible resin is equal to or slightly lower than the melting point of the polyester resin, and is higher than the temperature (heat treatment temperature) at which the film is thermally fixed and crystallized during film formation. Is particularly preferred. From this point, among the incompatible resins, polyolefin resins such as polyethylene, polypropylene, polybutene, and polymethylpentene, polystyrene resins, polyacrylate resins, polycarbonate resins, polyacrylonitrile resins, polyphenylene sulfide resins, and fluorine resins are preferably used. It is done. These incompatible resins may be homopolymers or copolymers, and two or more incompatible resins may be used in combination. Among these, polyolefin resins such as polypropylene and polymethylpentene having a small critical surface tension are preferable, and polymethylpentene is most preferable. Since the polymethylpentene has a relatively large difference in surface tension from polyester and a high melting point, it has a feature that the effect of forming cavities per added amount is large, and is particularly preferable as an incompatible resin.
本発明における白色化材は、白色ポリエステル樹脂組成物の重量を基準として、ポリエステル樹脂中に５〜７０重量％添加させる必要がある。白色化材が白色無機粒子である場合、その添加量は３０〜７０重量％であることが好ましく、更に３５〜７０重量％、特に４０〜７０重量％であることが好ましい。白色無機粒子の添加量が下限未満では、白色ポリエステルフィルムとしたときの白度や反射特性などが不十分となりやすい。一方、白色無機粒子の添加量が上限を超えると、白色無機粒子の分散性が不充分となったり、フィルム等に成形する際、製膜性が低下しやすい。また、白色化材がポリエステルと非相溶な樹脂である場合、その添加量は５〜４０重量％であることが好ましく、更に５〜３０重量％、特に５〜２５重量％であることが好ましい。非相溶樹脂の添加量が下限未満では、白色ポリエステルフィルムとした時の白度や反射特性などが不十分となりやすい。一方、非相溶樹脂の添加量が上限を超えると、白色ポリエステルフィルムとした際、フィルム自体の強度等機械特性が低くなりすぎる恐れがある。 The whitening material in the present invention needs to be added in an amount of 5 to 70% by weight in the polyester resin based on the weight of the white polyester resin composition. When the whitening material is white inorganic particles, the addition amount is preferably 30 to 70% by weight, more preferably 35 to 70% by weight, and particularly preferably 40 to 70% by weight. If the amount of white inorganic particles added is less than the lower limit, the whiteness and reflection characteristics of the white polyester film tend to be insufficient. On the other hand, when the addition amount of the white inorganic particles exceeds the upper limit, the dispersibility of the white inorganic particles becomes insufficient, or the film forming property tends to be lowered when forming into a film or the like. Further, when the whitening material is a resin incompatible with polyester, the addition amount is preferably 5 to 40% by weight, more preferably 5 to 30% by weight, and particularly preferably 5 to 25% by weight. . When the addition amount of the incompatible resin is less than the lower limit, the whiteness and reflection characteristics of the white polyester film tend to be insufficient. On the other hand, when the addition amount of the incompatible resin exceeds the upper limit, when a white polyester film is used, mechanical properties such as strength of the film itself may be too low.
[タンデム型二軸混練押出機]
本発明におけるタンデム型混練押出機は、第１段目混練機として二軸混練部を、第２段目混練機として単軸混練部とをこの順で連結した構造を持つものである。第１段目混練機は二軸混練部であり、高い混練分散性を得られることから、軸、すなわちスクリューまたはローターの回転速度が５００〜１０００ｒｐｍの高速回転ができる構造としたものであることが好ましい。軸の回転速度が下限未満では、白色ポリエステル樹脂組成物を製造する際、白色化材の分散性が不十分となりやすい。一方、軸の回転速度が１０００ｒｐｍを超えると、混練の際の剪断発熱が大きくなりすぎるため、ポリエステル樹脂が熱劣化を起こして機械特性が悪化したり、色相が悪化したりする恐れがある。好ましい回転速度は、４５０〜８００ｒｐｍ、さらに５００〜７００ｒｐｍの範囲である。
[Tandem type twin screw extruder]
The tandem kneading extruder in the present invention has a structure in which a biaxial kneading unit is connected as a first stage kneading machine and a single axis kneading unit is connected in this order as a second stage kneading machine. The first stage kneader is a biaxial kneading section, and can obtain a high kneading dispersibility, so that the shaft, that is, the screw or rotor can be rotated at a high speed of 500 to 1000 rpm. preferable. If the rotational speed of the shaft is less than the lower limit, the dispersibility of the whitening material tends to be insufficient when producing a white polyester resin composition. On the other hand, if the rotational speed of the shaft exceeds 1000 rpm, the shear heat generation during kneading becomes excessively large, so that there is a possibility that the polyester resin undergoes thermal deterioration and mechanical properties are deteriorated or hue is deteriorated. A preferable rotational speed is in the range of 450 to 800 rpm, and further 500 to 700 rpm.
本発明において、二軸混練部のシリンダー長（Ｌ）とシリンダー径（Ｄ）の比（Ｌ／Ｄ）は５〜１０の範囲であることが好ましい。Ｌ／Ｄが５未満であると混練長が短すぎるため混練度が不足し、白色化材の分散性が不十分となりやすい。一方、Ｌ／Ｄが１０を超えると、混練長が長すぎて高温状態での滞留時間が大きくなるため、ポリエステル樹脂が熱劣化を起こして機械特性が悪化したり、色相が悪化したりする恐れがある。好ましいＬ／Ｄは６〜８の範囲である。また、二軸混練部のシリンダー長（Ｌ）は３００〜１０００ｍｍの範囲であることが好ましい。Ｌが３００ｍｍ未満であると混練長が短すぎるため混練度が不足し、白色化材の分散性が不十分となりやすい。一方、Ｌが１０００ｍｍを超えると、混練長が長すぎて高温状態での滞留時間が大きくなるため、ポリエステル樹脂が熱劣化を起こして機械特性が悪化したり、色相が悪化したりする恐れがある。好ましい（Ｌ）は３５０〜７００ｍｍ、さらに４００〜５００ｍｍの範囲である。 In this invention, it is preferable that ratio (L / D) of the cylinder length (L) of a biaxial kneading part and a cylinder diameter (D) is the range of 5-10. When L / D is less than 5, the kneading length is too short, so the degree of kneading is insufficient and the dispersibility of the whitening material tends to be insufficient. On the other hand, if the L / D exceeds 10, the kneading length is too long and the residence time at a high temperature is increased, so that the polyester resin may be thermally deteriorated to deteriorate the mechanical properties or the hue. There is. The preferred L / D is in the range of 6-8. Moreover, it is preferable that the cylinder length (L) of a biaxial kneading part is the range of 300-1000 mm. If L is less than 300 mm, the kneading length is too short, so the degree of kneading is insufficient, and the dispersibility of the whitening material tends to be insufficient. On the other hand, if L exceeds 1000 mm, the kneading length is too long and the residence time in a high temperature state becomes long, so that there is a possibility that the polyester resin is thermally deteriorated and mechanical properties are deteriorated or hue is deteriorated. . Preferable (L) is 350 to 700 mm, more preferably 400 to 500 mm.
更に、第１段目混練機の樹脂出口部には、シリンダー内の樹脂充満率を調整できることから、絞り機構を備えていることが好ましい。シリンダー内の樹脂充満率を調整することにより、滞留時間の調整が可能となる。 Furthermore, since the resin filling rate in the cylinder can be adjusted at the resin outlet of the first stage kneader, it is preferable to have a throttle mechanism. The residence time can be adjusted by adjusting the resin filling rate in the cylinder.
本発明におけるタンデム型混練押出機の第２段目混練機は、白色ポリエステル樹脂組成物の熱劣化や色相悪化を抑制するために単軸混練機である。すなわち、第１段目の混練機で強力に短時間で混練を行い、第２段目混練機では熱劣化などを抑えつつ均一に押し出すようにそれぞれの混練部の役割を分担したのが本発明の特徴の一つである。単軸混練部がないと、樹脂の混練により押出される量が不均一化し、例えばチップなどにする場合、その形状にバラツキが生じ、それをフィルムなどに製膜しようとすると、かみこみ不良などによって得られる製品の品位が損なわれたりする。そのような観点から、単軸混練部の軸、すなわちスクリューまたはローターの回転速度は８０〜１５０ｒｐｍであることが好ましい。単軸混練部の軸の回転速度がこの範囲であると、剪断発熱を低く抑えることができ、白色ポリエステル樹脂組成物の熱劣化や色相悪化を抑制でき、しかも吐出も安定化しやすいことから好ましい。 The second-stage kneader of the tandem kneading extruder in the present invention is a single-screw kneader in order to suppress thermal deterioration and hue deterioration of the white polyester resin composition. That is, the present invention divides the role of each kneading section so that kneading is performed strongly in a short time in the first stage kneader, and the second stage kneader is extruded uniformly while suppressing thermal deterioration. Is one of the features. If there is no uniaxial kneading part, the amount extruded by resin kneading becomes non-uniform, for example, when making chips etc., the shape will vary, and when trying to form it on a film etc., there is a bad bite, etc. The quality of the product obtained by this may be impaired. From such a viewpoint, the rotation speed of the shaft of the single-shaft kneading part, that is, the screw or the rotor is preferably 80 to 150 rpm. When the rotational speed of the shaft of the uniaxial kneading part is within this range, it is preferable because shear heat generation can be suppressed low, thermal deterioration and hue deterioration of the white polyester resin composition can be suppressed, and discharge can be easily stabilized.
本発明におけるタンデム型混練押出機を使用した混練分散の利点は、二軸混練部において短時間で強混練することにより、熱劣化や色相悪化を抑制しつつ高い混練分散性が得られるため、単軸混練部では混練による熱劣化や色相悪化を抑制しつつ定量的に押し出すことができ、その結果熱劣化や色相悪化が少なく、均一な白色ポリエステル樹脂組成物が得られることにある。 The advantage of kneading and dispersing using the tandem kneading extruder in the present invention is that, by kneading strongly in a short time in a biaxial kneading section, high kneading and dispersibility can be obtained while suppressing thermal deterioration and hue deterioration. In the shaft kneading part, it is possible to quantitatively extrude while suppressing heat deterioration and hue deterioration due to kneading, and as a result, there is little heat deterioration and hue deterioration and a uniform white polyester resin composition can be obtained.
[白色ポリエステル樹脂組成物の製造]
本発明における白色ポリエステル樹脂組成物の製造方法について以下に説明する。
ポリエステル樹脂中に白色化材を混練分散させる混練装置としては、上述したタンデム型混練押出機を使用する。タンデム型二軸混練押出機へのポリエステル樹脂および白色化材の供給方法は、例えばスクリュー式または振動式などの定量供給フィーダーを使用して、第１段目混練機にそれぞれ定量供給するのが好ましい。
[Production of white polyester resin composition]
The manufacturing method of the white polyester resin composition in this invention is demonstrated below.
As the kneading apparatus for kneading and dispersing the whitening material in the polyester resin, the above-described tandem kneading extruder is used. As a method for supplying the polyester resin and the whitening material to the tandem-type twin-screw kneader / extruder, it is preferable to quantitatively supply the polyester resin and the whitening material to the first-stage kneader, for example, using a screw-type or vibration-type quantitative feeder. .
二軸混練部に供給されたポリエステル樹脂および白色化材は、軸の回転速度が４００〜１０００ｒｐｍといった高速回転下で溶融混練分散されながら短時間で第１段目混練機を通過させるのが好ましい。この際、第１段目混練機のシリンダー温度はポリエステル樹脂が溶融可能な温度であれば特に限定されないが、熱劣化や色相悪化の抑制の観点から２００℃〜３００℃の範囲であることが好ましい。 The polyester resin and whitening material supplied to the biaxial kneading section are preferably passed through the first stage kneader in a short time while being melt-kneaded and dispersed under a high-speed rotation such as a shaft rotation speed of 400 to 1000 rpm. At this time, the cylinder temperature of the first stage kneader is not particularly limited as long as the polyester resin can be melted, but it is preferably in the range of 200 ° C. to 300 ° C. from the viewpoint of suppressing thermal deterioration and hue deterioration. .
第１段目混練機を通過した白色ポリエステル樹脂組成物は、溶融状態のまま第２段目混練機である単軸混練部に供給される。単軸混練部では、軸の回転速度が８０〜１５０ｒｐｍといった低速回転下で均一混練されながら第２段目混練機を通過させるのが好ましい。この際、第２段目混練機のシリンダー温度は、第１段目混練機と同様にポリエステル樹脂が溶融可能な温度であれば特に限定されないが、熱劣化や色相悪化の抑制の観点から２８０℃以下でかつポリマーを溶融可能な範囲の温度とすることが好ましい。第２段目混練機を通過した溶融状態の白色ポリエステル樹脂組成物は、異物などを除去する目的で、フィルターなどでろ過処理をしても良い。
このようにして得られた白色ポリエステル樹脂組成物は、例えばカッティングされたペレット状など、所望の形態の組成物として、従来公知の方法で得ることができる。
The white polyester resin composition that has passed through the first stage kneader is supplied to a single-screw kneading section that is a second stage kneader in a molten state. In the single-shaft kneading section, it is preferable to pass the second-stage kneader while being uniformly kneaded under a low-speed rotation such as a shaft rotation speed of 80 to 150 rpm. At this time, the cylinder temperature of the second stage kneader is not particularly limited as long as the polyester resin can be melted similarly to the first stage kneader, but it is 280 ° C. from the viewpoint of suppressing thermal deterioration and hue deterioration. It is preferable that the temperature be within the range that allows the polymer to be melted. The molten white polyester resin composition that has passed through the second stage kneader may be filtered with a filter or the like for the purpose of removing foreign substances.
The white polyester resin composition thus obtained can be obtained by a conventionally known method as a composition in a desired form such as a cut pellet.
本発明の白色ポリエステル樹脂組成物は、熱劣化や色相悪化が少なくでき、好ましくはＬ＊値が７８〜９０、ｂ＊値が３〜１２、ａ＊値が−２〜２の範囲にあることが好ましい。白色ポリエステル樹脂組成物の色相がこのような範囲にあることで、白色ポリエステルフィルムとしたとき、白度や反射特性に優れ、特に液晶ディスプレイ用反射板基材に好適に用いることができる。 The white polyester resin composition of the present invention can reduce thermal deterioration and hue deterioration, and preferably has an L * value of 78 to 90, a b * value of 3 to 12, and an a * value of -2 to 2. Is preferred. When the hue of the white polyester resin composition is in such a range, when it is a white polyester film, it is excellent in whiteness and reflection characteristics, and can be suitably used particularly for a reflector substrate for liquid crystal displays.
以下、実施例により本発明をさらに説明する。なお、得られた白色ポリエステル樹脂組成物の特性は下記の方法で測定、評価した。 Hereinafter, the present invention will be further described by examples. In addition, the characteristic of the obtained white polyester resin composition was measured and evaluated by the following method.
（１）極限粘度（ＩＶ、ｄｌ／ｇ）
ポリエステルをオルトクロロフェノール中に、加熱溶解した後、一旦冷却させ、不溶分を取り除いた後、その溶液をオストワルド式粘度管を用いて３５℃の温度条件で測定した溶液粘度から算出した。
(1) Intrinsic viscosity (IV, dl / g)
The polyester was dissolved in orthochlorophenol by heating and then cooled, and the insoluble matter was removed. Then, the solution was calculated from the solution viscosity measured at 35 ° C. using an Ostwald viscosity tube.
（２）白色ポリエステル樹脂組成物の色相（Ｌ＊値、ａ＊値、ｂ＊値）
得られた白色ポリエステル樹脂組成物を２８５℃、真空下で１０分間溶融し、これをアルミニウム板上で厚さ３．０ｍｍのプレートに成形後ただちに氷水中で急冷し、該プレートを１４０℃、１時間乾燥結晶化処理を行った。その後、色差計調整用の白色標準プレート上に置き、プレート表面のハンターＬ＊、ａ＊、及びｂ＊を、ミノルタ社製ハンター型色差計（ＣＲ−２００型）を用いて、ＪＩＳ Ｚ−８７２９に準じて測定した。Ｌ＊は明度を示し、その数値が大きいほど明度が高いことを示し、ａ＊はその値が大きいほど赤着色の度合いが大きいことを示し、ｂ＊はその値が大きいほど黄着色の度合いが大きいことを示す。
(2) Hue of the white polyester resin composition (L * value, a * value, b * value)
The obtained white polyester resin composition was melted at 285 ° C. under vacuum for 10 minutes, molded into a plate having a thickness of 3.0 mm on an aluminum plate, and immediately cooled in ice water. A time dry crystallization treatment was performed. Thereafter, the plate is placed on a white standard plate for color difference adjustment, and the hunters L * , a * , and b * on the plate surface are JIS Z-8729 using a Minolta Hunter color difference meter (CR-200 type). It measured according to. L * indicates lightness, and the larger the value, the higher the lightness, a * indicates that the greater the value, the greater the degree of red coloring, and b * the greater the value, the greater the degree of yellow coloring. Indicates big.
（３）白色化材の分散性評価
（ア）白色化材が白色無機粒子の場合
得られた白色ポリエステル樹脂組成物をぺレットの状態で、吐出部に２０００メッシュの金網フィルターを取り付けた(株)東洋精機製作所製小型二軸押し出し機（ラボプラストミル:二軸スクリュウフルフライト２Ｄ２５Ｓ型）に３００℃にて２Ｋｇ／Ｈｒの流速で供給し、フィルター圧力の変化を測定した。そして、下記式より濾過圧上昇度（△Ｐ値）を算出した。
△Ｐ＝Ｐ６０−Ｐ１５
（ここでＰ１５はテスト開始１５分後のフィルター圧力（ＭＰａ）を、Ｐ６０はテスト開始６０分後のフィルター圧力（ＭＰａ）をそれぞれ示す。）
白色化剤の分散性が悪いものほどフィルターで目詰まりを起こし濾過圧上昇度（ΔＰ）は高くなるため、ΔＰが高いものほど分散性不良、ΔＰが低いものほど分散性良好と判断した。
(3) Dispersibility evaluation of whitening material (a) When whitening material is white inorganic particles The obtained white polyester resin composition is in a pellet state, and a 2000-mesh wire mesh filter is attached to the discharge part (stock) ) A small twin screw extruder manufactured by Toyo Seiki Seisakusho (laboplast mill: twin screw screw full flight type 2D25S) was supplied at 300 ° C. at a flow rate of 2 kg / hr, and the change in filter pressure was measured. And the filtration pressure rise degree ((DELTA) P value) was computed from the following formula.
ΔP = P 60 −P 15
(Here, P 15 indicates the filter pressure (MPa) 15 minutes after the start of the test, and P 60 indicates the filter pressure (MPa) 60 minutes after the start of the test.)
As the whitening agent has a lower dispersibility, the filter is clogged and the filtration pressure increase (ΔP) becomes higher. Therefore, the higher the ΔP, the better the dispersibility, and the lower the ΔP, the better the dispersibility.
（イ）白色化材がポリエステルと非相溶な樹脂の場合
得られた白色ポリエステル樹脂組成物を、ミクロトームにより、厚さ０．１μｍに裁断し、トプコン製透過型電子顕微鏡ＬＥＭ−２０００によって、倍率１００００倍で観察し、ポリエステル樹脂中に分散している非相溶樹脂のそれぞれの面積を５０個求め、それらの平均の面積円相当径を、直径として分散径を算出した。分散径が小さいほど、分散性に優れることを意味する。
(I) When the whitening material is a resin incompatible with polyester The obtained white polyester resin composition was cut into a thickness of 0.1 μm by a microtome, and magnification was measured with a Topcon transmission electron microscope LEM-2000. Observed at a magnification of 10,000 times, 50 areas of each of the incompatible resins dispersed in the polyester resin were determined, and the dispersion diameter was calculated using the average area equivalent circle diameter as the diameter. It means that the smaller the dispersion diameter, the better the dispersibility.
（４）白色ポリエステル樹脂組成物の反射率
（ア）白色ポリエステルフィルムの製造
得られた白色ポリエステル樹脂組成物をペレット状にカッティングし、このペレットを２８０℃に加熱された押出機に供給してダイスよりシート状に押し出した後、表面温度２５℃の冷却ドラム上で冷却固化して未延伸フィルムを得る。得られた未延伸フィルムを回転金属ロールで搬送しながら赤外線ヒーター加熱により１００℃の延伸温度で縦方向に２．９倍延伸する。次いで、フィルムの両端をクリップで保持しながらテンターに導き熱風加熱により１２０℃の延伸温度で横方向に３．６倍延伸する。更にテンター内で２１０℃の温度で熱固定して厚さ１００μｍの白色ポリエステルフィルムを得た。
(4) Reflectance of white polyester resin composition (a) Production of white polyester film The obtained white polyester resin composition is cut into pellets, and the pellets are fed to an extruder heated to 280 ° C to form a die. After extruding into a sheet more, it is cooled and solidified on a cooling drum having a surface temperature of 25 ° C. to obtain an unstretched film. The resulting unstretched film is stretched 2.9 times in the longitudinal direction at a stretching temperature of 100 ° C. by heating with an infrared heater while being conveyed by a rotating metal roll. Next, while holding both ends of the film with clips, the film is guided to a tenter and stretched 3.6 times in the transverse direction at a stretching temperature of 120 ° C. by heating with hot air. Furthermore, it was heat-set at a temperature of 210 ° C. in a tenter to obtain a white polyester film having a thickness of 100 μm.
（イ）反射率の測定
分光光度計（島津製作所製ＵＶ−３１０１ＰＣ）に積分球を取り付け、ＢａＳＯ４白板を１００％とした時の反射率を、得られた白色ポリエステルフィルムについて波長４００〜７００ｎｍの範囲にわたって測定する。得られたチャートより２ｎｍ間隔で反射率を読み取った。上記の範囲内で平均値を求めた上、次の基準で判定した。
○：全測定領域において反射率９０％以上
△：測定領域において平均反射率９０％以上で一部分９０％未満がある。
×：全測定領域において反射率が９０％未満
(A) Measurement of reflectance An integrating sphere was attached to a spectrophotometer (Shimadzu Corporation UV-3101PC), and the reflectance when the BaSO 4 white plate was taken as 100% was measured with respect to the obtained white polyester film at a wavelength of 400 to 700 nm. Measure over range. The reflectance was read from the obtained chart at intervals of 2 nm. The average value was determined within the above range, and then judged according to the following criteria.
◯: Reflectance 90% or more in all measurement regions Δ: Average reflectance 90% or more and less than 90% in the measurement region.
X: Reflectance is less than 90% in the entire measurement region
（５）白色無機粒子のかさ密度
白色無機粒子のかさ密度は一定容量容器に白色無機粒子を満たし、その時の白色無機粒子の重量を秤量し、単位容量当たりの重量を計算して求めた。
(5) Bulk density of white inorganic particles The bulk density of the white inorganic particles was obtained by filling the white inorganic particles in a certain volume container, weighing the white inorganic particles at that time, and calculating the weight per unit volume.
（６）白色無機粒子の圧縮時流動エネルギー
シスメックス社製粉体流動性分析装置パウダーレオメーターＦＴ４を使用し、以下の方法で測定した。
１６０ｍｌの測定容器に白色無機粒子を添加し、圧縮用ピストンで４０Ｎの圧縮力で圧縮させながら、容器が一杯になるまで添加圧縮を繰り返した。次いで、粒子が満たされた容器中に、ブレード（回転翼）を回転させながら押し込んでいき、その際、ブレードが回転することで得られる回転トルクと垂直荷重を同時に測定した。この測定値から得られるエネルギー値を、押し込み深さ毎にプロットしてエネルギー勾配曲線を得た。このエネルギー勾配曲線を積分して得られた面積を圧縮時流動エネルギーとした。
(6) Flow energy during compression of white inorganic particles A powder rheometer FT4 manufactured by Sysmex Corporation was used and measured by the following method.
White inorganic particles were added to a 160 ml measuring container, and the compression was repeated until the container was full while being compressed with a compression force of 40 N with a compression piston. Next, the blade (rotary blade) was pushed into the container filled with particles while rotating, and at that time, the rotational torque and vertical load obtained by rotating the blade were measured simultaneously. The energy value obtained from this measured value was plotted for each indentation depth to obtain an energy gradient curve. The area obtained by integrating this energy gradient curve was defined as the flow energy during compression.
［実施例１］
（１）ポリエステル樹脂Ａの製造
テレフタル酸ジメチル８９部およびイソフタル酸ジメチル１１部とエチレングリコール７０部の混合物に、テトラ−ｎ−ブチルチタネート（Ｔｉ元素として０．００２５部）を加圧反応が可能なＳＵＳ製容器に仕込み、０．０７ＭＰａの加圧を行い１４０℃から２４０℃に昇温しながらエステル交換反応させた後常圧に戻し、リン酸トリメチル０．００８７部を添加し、エステル交換反応を終了させた。
その後重合触媒として酸化ゲルマニウム０．０２１部を加え、混合物を重合容器に移し、常法にて高真空のもと重縮合反応を行い、最終内温が２９０℃まで昇温し反応を終了させ、極限粘度０．７１ｄｌ／ｇ、融点が２２６℃のポリエステル樹脂Ａを得た。
[Example 1]
(1) Production of Polyester Resin A Tetra-n-butyl titanate (0.0025 part as Ti element) can be pressure-reacted to a mixture of 89 parts of dimethyl terephthalate and 11 parts of dimethyl isophthalate and 70 parts of ethylene glycol. Charge into a SUS container, pressurize to 0.07 MPa, let it transesterify while raising the temperature from 140 ° C. to 240 ° C., then return to normal pressure, add 0.0087 parts of trimethyl phosphate, Ended.
Thereafter, 0.021 part of germanium oxide is added as a polymerization catalyst, the mixture is transferred to a polymerization vessel, a polycondensation reaction is performed under high vacuum in a conventional manner, the final internal temperature is raised to 290 ° C., and the reaction is terminated. A polyester resin A having an intrinsic viscosity of 0.71 dl / g and a melting point of 226 ° C. was obtained.
（２）白色ポリエステル樹脂組成物の製造
白色化材としてかさ密度が０．７４ｇ／ｍｌ、圧縮時流動エネルギーが８９１１ｍＪの硫酸バリウム粒子（平均粒径：１．２μｍ）とポリエステル樹脂として上述のポリエステル樹脂Ａとを、神戸製鋼所製タンデム型二軸混錬押し出し機ＮＥＸ−Ｔ６０型機にそれぞれ定量性を持つスクリューフィーダーより連続定量供給し、第１段目二軸混練機（Ｌ＝４１５ｍｍ、Ｌ／Ｄ＝７）でローター回転速度６００ｒｐｍ、シリンダー温度２４０℃の条件にて混錬処理した。続いて溶融状態の白色ポリエステル樹脂組成物を第２段目単軸混練押出機に供給し、スクリュー回転速度１１５ｒｐｍ、シリンダー温度２４０℃の条件にてストランド状に押し出し、これをカッティングして、硫酸バリウム粒子濃度６０％の白色ポリエステル樹脂組成物からなるペレットを得た。このときの生産能力（速度）は１２０Ｋｇ／Ｈｒとした。得られた白色ポリエステル樹脂組成物の特性を表１に示す。
(2) Production of White Polyester Resin Composition Barium sulfate particles (average particle size: 1.2 μm) having a bulk density of 0.74 g / ml and a flow energy during compression of 8911 mJ as a whitening material and the above-described polyester resin as a polyester resin A is continuously and quantitatively supplied from a screw feeder having quantitativeness to the tandem type twin screw kneading extruder NEX-T60 type manufactured by Kobe Steel, and the first stage twin screw kneader (L = 415 mm, L / L). D = 7) kneading was performed under conditions of a rotor rotational speed of 600 rpm and a cylinder temperature of 240 ° C. Subsequently, the molten white polyester resin composition was supplied to the second stage single-screw kneading extruder, extruded into a strand shape under the conditions of a screw rotation speed of 115 rpm and a cylinder temperature of 240 ° C., and this was cut into barium sulfate. A pellet made of a white polyester resin composition having a particle concentration of 60% was obtained. The production capacity (speed) at this time was 120 kg / hr. The characteristics of the obtained white polyester resin composition are shown in Table 1.
［実施例２］
白色化材をポリメチルペンテンに変更し、かつ得られる樹脂組成物の重量を基準として、ポリメチルペンテンの割合が１２重量％となるように添加する以外は、実施例１と同様な操作をして白色ポリエステル樹脂組成物を得た。得られた白色ポリエステル樹脂組成物の特性を表１に示す。
[Example 2]
The whitening material was changed to polymethylpentene, and the same operation as in Example 1 was performed except that the polymethylpentene ratio was 12% by weight based on the weight of the resin composition obtained. Thus, a white polyester resin composition was obtained. The characteristics of the obtained white polyester resin composition are shown in Table 1.
［比較例１］
実施例１と同様の白色化材およびポリエステル樹脂を、タンデム型ではない二軸混練押出機：神戸製鋼所製ＫＴＸ−４６型機（Ｌ＝２６８０ｍｍ、Ｌ／Ｄ＝５８）にそれぞれ定量性を持つスクリューフィーダーにより連続定量供給し、スクリュー回転速度４００ｒｐｍ、シリンダー温度２４０℃の条件にて混練処理後、ストランド状に押し出し、これをカッティングして、硫酸バリウム粒子濃度６０％の白色ポリエステル樹脂組成物からなるペレットを得た。このときの生産能力（速度）は５０ｋｇ／ｈｒとした。得られた白色ポリエステル樹脂組成物の特性を表１に示す。
[Comparative Example 1]
A whitening material and a polyester resin similar to those in Example 1 are quantitative in a twin-screw kneading extruder that is not a tandem type: KTX-46 type machine (L = 2680 mm, L / D = 58) manufactured by Kobe Steel. It is continuously fed by a screw feeder, kneaded under conditions of a screw rotation speed of 400 rpm and a cylinder temperature of 240 ° C., then extruded into a strand shape, and cut to form a white polyester resin composition having a barium sulfate particle concentration of 60%. Pellets were obtained. The production capacity (speed) at this time was 50 kg / hr. The characteristics of the obtained white polyester resin composition are shown in Table 1.
［比較例２および３］
白色ポリエステル樹脂組成物中の硫酸バリウム粒子の濃度を、表１に示す濃度に変更する以外は、実施例１と同様の操作で白色ポリエステル樹脂組成物を得た。得られた白色ポリエステル樹脂組成物の特性を表１に示す。
[Comparative Examples 2 and 3]
A white polyester resin composition was obtained in the same manner as in Example 1, except that the concentration of barium sulfate particles in the white polyester resin composition was changed to the concentration shown in Table 1. The characteristics of the obtained white polyester resin composition are shown in Table 1.
［実施例３］
白色無機粒子のかさ密度、圧縮時流動エネルギー、濃度を表１の通りとする以外は、実施例１と同様な操作をして白色ポリエステル組成物を得た。得られた白色ポリエステル組成物の特性を表１に示す。
[Example 3]
A white polyester composition was obtained in the same manner as in Example 1 except that the bulk density, flow energy during compression, and concentration of the white inorganic particles were as shown in Table 1. Table 1 shows the characteristics of the obtained white polyester composition.
［比較例４］
白色化材としてかさ密度が０．９３ｇ／ｍｌ、圧縮時流動エネルギーが１３１６０ｍＪの硫酸バリウム粒子（平均粒径：１．４μｍ）と上述のポリエステル樹脂Ａを、タンデム型ではない二軸混練押出機：神戸製鋼所製ＫＴＸ−４６型機（Ｌ＝２６８０ｍｍ、Ｌ／Ｄ＝５８）にそれぞれ定量性を持つスクリューフィーダーにより連続定量供給し、スクリュー回転速度４００ｒｐｍ、シリンダー温度２４０℃の条件にて混練処理後、ストランド状に押し出し、これをカッティングして、硫酸バリウム粒子濃度６０％の白色ポリエステル樹脂組成物からなるペレットを得た。このときの生産能力（速度）は５０ｋｇ／ｈｒとした。得られた白色ポリエステル樹脂組成物の特性を表１に示す。
[Comparative Example 4]
As a whitening material, a barium sulfate particle (average particle size: 1.4 μm) having a bulk density of 0.93 g / ml and a flow energy during compression of 13160 mJ and the above-described polyester resin A are not tandem type twin-screw kneading extruders: Continuously supplied to Kobe Steel KTX-46 type machine (L = 2680mm, L / D = 58) with a quantitative screw feeder, after kneading process under conditions of screw rotation speed 400rpm and cylinder temperature 240 ° C These were extruded into strands and cut to obtain pellets made of a white polyester resin composition having a barium sulfate particle concentration of 60%. The production capacity (speed) at this time was 50 kg / hr. The characteristics of the obtained white polyester resin composition are shown in Table 1.
［実施例４］
二軸混練部の軸の回転数を９５０ｒｐｍ、単軸混練部の軸の回転数を１４０ｒｐｍとなるように変更した以外は、実施例１と同様な操作をして白色ポリエステル樹脂組成物を得た。得られた白色ポリエステル樹脂組成物の特性を表１に示す。
[Example 4]
A white polyester resin composition was obtained by performing the same operation as in Example 1 except that the rotation speed of the shaft of the biaxial kneading part was changed to 950 rpm and the rotation speed of the shaft of the single screw kneading part was changed to 140 rpm. . The characteristics of the obtained white polyester resin composition are shown in Table 1.
［実施例５］
二軸混練部の軸の回転数を５５０ｒｐｍ、単軸混練部の軸の回転数を９０ｒｐｍとなるように変更した以外は、実施例１と同様な操作をして白色ポリエステル樹脂組成物を得た。得られた白色ポリエステル樹脂組成物の特性を表１に示す。
[Example 5]
A white polyester resin composition was obtained in the same manner as in Example 1, except that the rotation speed of the shaft of the biaxial kneading section was changed to 550 rpm and the rotation speed of the shaft of the single-shaft kneading section was changed to 90 rpm. . The characteristics of the obtained white polyester resin composition are shown in Table 1.
本発明の白色ポリエステル樹脂組成物の製造方法は、白色化材を高度に混練分散することができ、かつ、混練時の熱劣化や色相の悪化も抑制することが可能なことから、特に液晶ディスプレイ用反射板基材等に使用される白色ポリエステルフィルムに好適な白色ポリエステル樹脂組成物を提供することができる。 The method for producing the white polyester resin composition of the present invention is capable of highly kneading and dispersing the whitening material, and can also suppress thermal deterioration and hue deterioration during kneading, so that the liquid crystal display is particularly effective. It is possible to provide a white polyester resin composition suitable for a white polyester film used for a reflector substrate for use.
Claims (6)
溶融混練を二軸混練部と単軸混練部とをこの順で有するタンデム型混練押出機で行なうことを特徴とする白色ポリエステル樹脂組成物の製造方法。 A method for producing a polyester resin composition comprising melt-kneading 5 to 70% by weight of a whitening material and 30 to 95% by weight of a polyester resin,
A method for producing a white polyester resin composition, wherein melt kneading is carried out by a tandem kneading extruder having a biaxial kneading part and a uniaxial kneading part in this order.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012172043A (en) * | 2011-02-21 | 2012-09-10 | Teijin Ltd | White polyester composition and method for producing the same |
| JP7421612B1 (en) | 2022-08-10 | 2024-01-24 | 株式会社シーティーイー | Twin-screw continuous kneading extrusion device |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012172043A (en) * | 2011-02-21 | 2012-09-10 | Teijin Ltd | White polyester composition and method for producing the same |
| JP7421612B1 (en) | 2022-08-10 | 2024-01-24 | 株式会社シーティーイー | Twin-screw continuous kneading extrusion device |
| WO2024034420A1 (en) * | 2022-08-10 | 2024-02-15 | 株式会社シーティーイー | Biaxial continuous kneading extrusion device |
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