JP2016101188A - Molded body for medical use - Google Patents
Molded body for medical use Download PDFInfo
- Publication number
- JP2016101188A JP2016101188A JP2014239496A JP2014239496A JP2016101188A JP 2016101188 A JP2016101188 A JP 2016101188A JP 2014239496 A JP2014239496 A JP 2014239496A JP 2014239496 A JP2014239496 A JP 2014239496A JP 2016101188 A JP2016101188 A JP 2016101188A
- Authority
- JP
- Japan
- Prior art keywords
- component
- tert
- acid
- butyl
- molding
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- -1 polyethylene terephthalate Polymers 0.000 claims abstract description 77
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- 229920000139 polyethylene terephthalate Polymers 0.000 claims abstract description 32
- 239000005020 polyethylene terephthalate Substances 0.000 claims abstract description 32
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000000465 moulding Methods 0.000 claims abstract description 25
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims abstract description 18
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims abstract description 17
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- 238000000034 method Methods 0.000 claims description 22
- 239000008280 blood Substances 0.000 claims description 20
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- 238000001746 injection moulding Methods 0.000 claims description 9
- 238000001125 extrusion Methods 0.000 claims description 4
- 238000000071 blow moulding Methods 0.000 claims description 2
- 229920001577 copolymer Polymers 0.000 claims 1
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- 125000001142 dicarboxylic acid group Chemical group 0.000 abstract 1
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- 125000004437 phosphorous atom Chemical group 0.000 description 4
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- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 2
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- HXIQYSLFEXIOAV-UHFFFAOYSA-N 2-tert-butyl-4-(5-tert-butyl-4-hydroxy-2-methylphenyl)sulfanyl-5-methylphenol Chemical compound CC1=CC(O)=C(C(C)(C)C)C=C1SC1=CC(C(C)(C)C)=C(O)C=C1C HXIQYSLFEXIOAV-UHFFFAOYSA-N 0.000 description 2
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 2
- AIBRSVLEQRWAEG-UHFFFAOYSA-N 3,9-bis(2,4-ditert-butylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP1OCC2(COP(OC=3C(=CC(=CC=3)C(C)(C)C)C(C)(C)C)OC2)CO1 AIBRSVLEQRWAEG-UHFFFAOYSA-N 0.000 description 2
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- ZJIPHXXDPROMEF-UHFFFAOYSA-N dihydroxyphosphanyl dihydrogen phosphite Chemical compound OP(O)OP(O)O ZJIPHXXDPROMEF-UHFFFAOYSA-N 0.000 description 2
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Images
Abstract
Description
本発明は、イソフタル酸をジカルボン酸成分の一部として共重合した共重合ポリエチレンテレフタレートを成形して得られた成形体であって、−30℃未満の低温下で使用および/または保管利用したときの割れが抑制された医療用成形体に関する。 The present invention is a molded article obtained by molding a copolymerized polyethylene terephthalate obtained by copolymerizing isophthalic acid as a part of a dicarboxylic acid component, and is used and / or stored at a low temperature of less than -30 ° C. The present invention relates to a molded product for medical use in which cracking of the material is suppressed.
近年、医療用分野において使用される医療用容器や医療用機器では落下時に割れにくいことからガラスから樹脂への素材切り替えが進んでいる。特に真空採血管やプレフィルドシリンジといった医療用容器は、輸送中や取り扱い操作中に破損し易いため、ポリエチレン、塩化ビニル、ポリエチレンテレフタレートなどの樹脂製容器が好まれて使われている。その中でもガスバリア性、視認性に優れ、燃焼時に塩素ガス発生の無いポリエチレンテレフタレートが特に好まれて使用される。
ところで、真空採血管で採血された血液は、鮮度を保つため冷凍保管される。従来冷凍保管する際の保管温度は−10〜−20℃であったが、近年冷凍保管技術の進歩によって−30℃未満の低温で保管されるようになってきた。それに伴い、−30℃未満の低温下ではポリエチレンテレフタレートの脆化と血液の凍結膨張による応力によって真空採血管が割れてしまい、血液が飛散するという問題点が発生している。
In recent years, in medical containers and medical devices used in the medical field, the material switching from glass to resin has been progressing because it is difficult to break when dropped. In particular, medical containers such as vacuum blood collection tubes and prefilled syringes are easily damaged during transportation and handling operations, and therefore, resin containers such as polyethylene, vinyl chloride, and polyethylene terephthalate are preferred. Among them, polyethylene terephthalate which is excellent in gas barrier properties and visibility and does not generate chlorine gas during combustion is particularly preferred and used.
By the way, the blood collected by the vacuum blood collection tube is stored frozen to maintain freshness. Conventionally, the storage temperature at the time of freezing storage is −10 to −20 ° C. However, in recent years, it has been stored at a low temperature below −30 ° C. due to the advancement of the freezing storage technology. Along with this, at a low temperature of less than −30 ° C., the vacuum blood collection tube is broken due to the embrittlement of polyethylene terephthalate and the stress caused by the freezing and expansion of blood, and the blood is scattered.
特許文献1には、酸成分としてイソフタル酸を5〜15モル%共重合した共重合ポリエチレンテレフタレートを真空採血管に用いる技術が示されており、特許文献2には、ポリエチレンテレフタレートとイソフタル酸共重合ポリエチレンテレフタレートの混合物を真空採血管に使用する技術が示されている。しかしながら、何れもイソフタル酸を共重合する目的はガスバリア性を向上する目的であり、−30℃未満での低温保管時の割れの問題については何ら示唆されてはいない。そのため、−30℃未満においても割れの発生が抑制された真空採血管の開発が望まれている。
本発明は、−30℃未満の低温下で使用および/または保管利用したときの割れの発生が抑制された医療用成形体を提供することを目的とする。 An object of the present invention is to provide a medical molded article in which occurrence of cracks when used and / or stored at a low temperature of less than -30 ° C is suppressed.
本発明者らは、上記目的を達成せんとして鋭意研究を重ねた結果、イソフタル酸を特定範囲で共重合した共重合ポリエチレンテレフタレートを成形して得られた成形体が、−30℃未満で使用および/または保管利用したときの割れが抑制されることを発見し、上記問題を解決できるに至った。 As a result of intensive research aimed at achieving the above-mentioned object, the present inventors have used a molded product obtained by molding a copolymerized polyethylene terephthalate obtained by copolymerizing isophthalic acid in a specific range at less than -30 ° C. It was discovered that cracking when used for storage was suppressed, and the above problem could be solved.
すなわち、グリコール成分(A成分)およびジカルボン酸成分(B成分)からなる共重合ポリエチレンテレフタレートであって、該グリコール成分がエチレングリコール(A−1成分)であり、かつ該ジカルボン酸成分がテレフタル酸(B−1成分)94〜99モル%およびイソフタル酸(B−2成分)1〜6モル%からなるジカルボン酸である共重合ポリエチレンテレフタレートを成形して得られる−30℃未満で使用および/または保管利用される医療用成形体が提供される。なお、医療用成形体としては、上記真空採血管以外にシャーレ、遠沈管、フラスコ、コンテナ、医療用チューブ、輸液バッグ等が挙げられる。本発明は、前記医療用成形体を−30℃未満で使用および/または保管する方法を包含する。 That is, a copolymerized polyethylene terephthalate comprising a glycol component (A component) and a dicarboxylic acid component (B component), wherein the glycol component is ethylene glycol (A-1 component), and the dicarboxylic acid component is terephthalic acid ( B-1 component) 94-99 mol% and isophthalic acid (B-2 component) 1-6 mol% dicarboxylic acid copolymerized polyethylene terephthalate obtained by molding and used and / or stored below -30 ° C A medical molded body to be used is provided. Examples of the medical molded body include petri dishes, centrifuge tubes, flasks, containers, medical tubes, infusion bags, and the like in addition to the vacuum blood collection tube. The present invention includes a method of using and / or storing the medical molded body at a temperature below -30 ° C.
本発明は、−30℃未満で使用および/または保管利用される医療用成形体において、成形体の割れを抑制することが出来る。また、イソフタル酸を共重合しているため、ガスバリア性にも優れ、減圧度の保持に対しても有効である。 The present invention can suppress cracking of a molded article for medical use that is used and / or stored at temperatures below -30 ° C. In addition, since isophthalic acid is copolymerized, it has excellent gas barrier properties and is effective for maintaining the degree of vacuum.
以下、本発明の医療用成形体に使用する共重合ポリエチレンテレフタレートの調製方法、成形加工方法について順次説明する。 Hereinafter, a method for preparing a copolymerized polyethylene terephthalate used in the medical molded article of the present invention and a molding method will be sequentially described.
本発明に使用する共重合ポリエチレンテレフタレートは、グリコール成分(A成分)としてエチレングリコール(A−1成分)、ジカルボン酸成分としてテレフタル酸(B−1成分)94〜99モル%およびイソフタル酸(B−2成分)1〜6モル%からなるジカルボン酸を使用する共重合ポリエチレンテレフタレートである。
ジカルボン酸中のテレフタル酸(B−1成分)とイソフタル酸(B−2成分)の共重合割合は、好ましくはB−1成分94〜98モル%、B−2成分2〜6モル%、さらに好ましくはB−1成分95〜98モル%、B−2成分2〜5モル%、最も好ましくは、B−1成分95〜97モル%、B−2成分3〜5モル%である。B−2成分の比率が1〜6モル%の範囲外であると、−30℃未満で保管、使用した場合に、割れが抑制されない。
The copolymerized polyethylene terephthalate used in the present invention comprises ethylene glycol (A-1 component) as a glycol component (A component), 94 to 99 mol% of terephthalic acid (B-1 component) as a dicarboxylic acid component, and isophthalic acid (B- It is a copolymerized polyethylene terephthalate using a dicarboxylic acid consisting of 2 to 6 mol%.
The copolymerization ratio of terephthalic acid (B-1 component) and isophthalic acid (B-2 component) in the dicarboxylic acid is preferably 94 to 98 mol% for the B-1 component, 2 to 6 mol% for the B-2 component, The B-1 component is preferably 95 to 98 mol%, the B-2 component is 2 to 5 mol%, and most preferably the B-1 component is 95 to 97 mol%, and the B-2 component is 3 to 5 mol%. When the ratio of the B-2 component is outside the range of 1 to 6 mol%, cracking is not suppressed when stored and used at less than -30 ° C.
共重合ポリエチレンテレフタレートの固有粘度(IV)は、0.5〜0.8dl/gであることが好ましい。固有粘度の範囲は、より好ましいは0.55〜0.75dl/g、さらに好ましくは0.55〜0.7dl/gである。固有粘度が0.8dl/gより大きいと、射出成形時の流動性の低下によりシリンダ温度を上げる必要があるため、成形サイクルが長くなる場合がある。一方固有粘度が0.5dl/gよりも小さいと靭性の低下を招き、−30℃未満の低温下での割れが発生し易くなる場合がある。なお、固有粘度は、樹脂0.6gをフェノール/テトラクロロエタン=3/2(重量比)混合溶媒50ml中に加熱溶融した後、室温に冷却し、得られた樹脂溶液の粘度を、オストワルド式粘度管を用いて35℃の温度条件で測定し、得られた溶液粘度のデータから求める。 The intrinsic viscosity (IV) of the copolymerized polyethylene terephthalate is preferably 0.5 to 0.8 dl / g. The range of the intrinsic viscosity is more preferably 0.55 to 0.75 dl / g, still more preferably 0.55 to 0.7 dl / g. If the intrinsic viscosity is greater than 0.8 dl / g, it is necessary to increase the cylinder temperature due to a decrease in fluidity during injection molding, which may result in a longer molding cycle. On the other hand, if the intrinsic viscosity is less than 0.5 dl / g, the toughness is lowered, and cracking at a low temperature of less than −30 ° C. is likely to occur. The intrinsic viscosity is 0.6 g of the resin heated and melted in 50 ml of a phenol / tetrachloroethane = 3/2 (weight ratio) mixed solvent, cooled to room temperature, and the viscosity of the obtained resin solution is the Ostwald viscosity. Measurement is performed at a temperature of 35 ° C. using a tube, and the obtained solution viscosity data is used.
本発明の共重合ポリエチレンテレフタレートは、エステル交換法あるいは直接エステル化法のいずれの方法でも製造することができる。エステル交換法にて製造する場合はエステル交換反応触媒を必要とする。
エステル交換反応触媒としては特に限定されず、一般にポリエチレンテレフタレートのエステル交換反応触媒として広く用いられるマンガン化合物、カルシウム化合物、マグネシウム化合物、チタン化合物、亜鉛化合物、ナトリウム化合物、カリウム化合物、セリウム化合物、リチウム化合物等が挙げられる。また、整色剤としても作用するエステル交換反応触媒として、コバルト化合物が含有されていてもよい。
The copolymerized polyethylene terephthalate of the present invention can be produced by either a transesterification method or a direct esterification method. In the case of producing by the transesterification method, a transesterification reaction catalyst is required.
The transesterification reaction catalyst is not particularly limited, and manganese compounds, calcium compounds, magnesium compounds, titanium compounds, zinc compounds, sodium compounds, potassium compounds, cerium compounds, lithium compounds, etc. that are generally widely used as transesterification catalysts for polyethylene terephthalate Is mentioned. Further, a cobalt compound may be contained as a transesterification reaction catalyst that also acts as a color adjusting agent.
本発明の共重合ポリエチレンテレフタレートを直接エステル化法にて製造する場合は、上記エステル交換法の場合のようにエステル交換反応触媒を使用しないため触媒を失活させる必要はないものの、安定剤としてリン化合物の残存量が全酸成分に対して5〜100ミリモル%となるよう添加することが好ましい。リン化合物の残存量が上記範囲にあれば、耐熱性および色相の点で好ましい。 When the copolymerized polyethylene terephthalate of the present invention is produced by a direct esterification method, it is not necessary to deactivate the catalyst because a transesterification reaction catalyst is not used as in the case of the above transesterification method. It is preferable to add such that the remaining amount of the compound is 5 to 100 mmol% with respect to the total acid component. If the residual amount of the phosphorus compound is in the above range, it is preferable in terms of heat resistance and hue.
重縮合触媒としてはチタン化合物、アンチモン化合物およびゲルマニウム化合物が好ましく用いられる。アンチモン化合物としては酸化アンチモン、酢酸アンチモン、アンチモン酸グリコレート等があげられるが中でも三酸化アンチモンが好ましく用いられる。アンチモン化合物が含有される場合、アンチモン化合物の含有量は三酸化アンチモンに換算して全酸成分に対して5〜40ミリモル%であることが好ましい。アンチモン化合物の含有量が5ミリモル%未満の場合重合活性が低く、重縮合時間が長くなり生産サイクルの低下等の経済面で好ましくないばかりでなく、副反応生成物の増加および色相の悪化等の品質面でも劣るため好ましくない。アンチモン化合物の含有量が40ミリモル%を超える場合、アンチモン化合物の析出に起因する黒色化等、色相面および分解反応の促進による副反応生成物が多くなるという点で好ましくない。 As the polycondensation catalyst, a titanium compound, an antimony compound and a germanium compound are preferably used. Examples of the antimony compound include antimony oxide, antimony acetate, and antimonic acid glycolate, among which antimony trioxide is preferably used. When the antimony compound is contained, the content of the antimony compound is preferably 5 to 40 mmol% based on the total acid component in terms of antimony trioxide. When the content of the antimony compound is less than 5 mmol%, the polymerization activity is low, the polycondensation time becomes long, and it is not preferable from an economic viewpoint such as a decrease in production cycle. Since it is inferior also in quality, it is not preferable. When the content of the antimony compound exceeds 40 mmol%, it is not preferable from the viewpoint that the amount of side reaction products due to acceleration of the hue surface and decomposition reaction such as blackening due to precipitation of the antimony compound increases.
ゲルマニウム化合物としては二酸化ゲルマニウムが好ましく用いられる。ゲルマニウム化合物が含有される場合、ゲルマニウム化合物の含有量は全酸成分に対して15〜50ミリモル%であることが好ましい。15ミリモル%未満の場合重合活性が低く、重縮合時間が長くなり生産サイクルの低下等の経済面で好ましくないばかりでなく、副反応生成物の増加および色相の悪化等の品質面でも劣るため好ましくない。ゲルマニウム化合物の含有量が50ミリモル%を超える場合、分解反応の促進による副反応生成物が多くなるという点で好ましくない。
チタン化合物としては、テトラアルキルチタネートが好ましく用いられる。チタン化合物が含有される場合、安定剤としてn−ブチルホスフェートが必要である。含まれるチタン原子に対するリン原子のモル比率(P/Ti)が1〜3となるようにする必要がある。P/Tiが1未満であると、相対的にリン原子濃度が少なくなるため、得られるポリマーの色相が、不十分になり黄味を帯びるようになり、かつその耐熱性が低下することもある。一方、P/Tiの値が3を超えると相対的にリン原子濃度が多くなるため重合性、すなわち重縮合反応速度が低下等の経済面で好ましくない。また、チタン化合物の含有量としては全酸成分に対して2〜40ミリモル%であることが好ましい。チタン化合物の含有量が2ミリモル%未満の場合重合活性が低く、重縮合時間が長くなり生産サイクルの低下等の経済面で好ましくない。チタン化合物の含有量が40ミリモル%を超える場合、得られるポリマーの色相が不十分になり、黄色味を帯びるようになり、その実用性が低下することがある。
As the germanium compound, germanium dioxide is preferably used. When a germanium compound is contained, the content of the germanium compound is preferably 15 to 50 mmol% with respect to the total acid component. If it is less than 15 mmol%, the polymerization activity is low, the polycondensation time becomes long, and it is not preferable in terms of economy such as a decrease in production cycle, etc., but it is also inferior in terms of quality such as increase of side reaction products and deterioration of hue, etc. Absent. When the content of the germanium compound exceeds 50 mmol%, it is not preferable in that the side reaction product increases due to the promotion of the decomposition reaction.
Tetraalkyl titanate is preferably used as the titanium compound. When a titanium compound is contained, n-butyl phosphate is required as a stabilizer. It is necessary that the molar ratio (P / Ti) of phosphorus atoms to titanium atoms contained is 1 to 3. When P / Ti is less than 1, the phosphorus atom concentration is relatively reduced, so that the hue of the resulting polymer becomes inadequate and yellowish, and its heat resistance may be lowered. . On the other hand, if the value of P / Ti exceeds 3, the phosphorus atom concentration is relatively increased, which is not preferable in terms of economics such as a decrease in polymerizability, that is, a polycondensation reaction rate. Moreover, it is preferable that it is 2-40 mmol% as content of a titanium compound with respect to all the acid components. When the content of the titanium compound is less than 2 mmol%, the polymerization activity is low, the polycondensation time becomes long, and this is not preferable in terms of economy such as a reduction in production cycle. When the content of the titanium compound exceeds 40 mmol%, the resulting polymer has an insufficient hue and becomes yellowish, which may reduce its practicality.
共重合ポリエチレンテレフタレートを所望の固有粘度に調整するために、さらに固相重合をかけることが出来る。固相重合における反応温度は、230℃以下とすることが好ましい。固相重合反応温度が230℃を超えて実施される場合、得られるポリマーの結晶化度が高くなり、成形品の外観を損ない、核剤として作用するため成形品の白化等をもたらすため好ましくない。
なお、本発明のポリエチレンテレフタレートは、本発明の趣旨に反しない範囲で、酸化防止剤、離型剤等の各添加剤を含むことが出来る。
In order to adjust the copolymerized polyethylene terephthalate to a desired intrinsic viscosity, solid phase polymerization can be further applied. The reaction temperature in the solid phase polymerization is preferably 230 ° C. or lower. When the solid-state polymerization reaction temperature is carried out exceeding 230 ° C., the degree of crystallinity of the resulting polymer is increased, the appearance of the molded product is impaired, and it acts as a nucleating agent, resulting in whitening of the molded product. .
In addition, the polyethylene terephthalate of this invention can contain each additive, such as antioxidant and a mold release agent, in the range which is not contrary to the meaning of this invention.
<酸化防止剤>
本発明では酸化防止剤として、ヒンダードフェノール系化合物、ホスファイト系化合物、ホスホナイト系化合物、およびチオエーテル系化合物からなる群より選ばれる少なくとも1種の酸化防止剤を使用することができる。酸化防止剤を配合する事により、成形加工時の色相や流動性が安定するだけでなく、耐加水分解性の向上にも効果がある。
<Antioxidant>
In the present invention, as the antioxidant, at least one antioxidant selected from the group consisting of hindered phenol compounds, phosphite compounds, phosphonite compounds, and thioether compounds can be used. By blending an antioxidant, not only is the hue and fluidity at the time of molding stabilized, it is also effective in improving hydrolysis resistance.
ヒンダードフェノール系化合物としては、例えば、α−トコフェロール、ブチルヒドロキシトルエン、シナピルアルコール、ビタミンE、n−オクタデシル−β−(4’−ヒドロキシ−3’,5’−ジ−tert−ブチルフェル)プロピオネート、2−tert−ブチル−6−(3’−tert−ブチル−5’−メチル−2’−ヒドロキシベンジル)−4−メチルフェニルアクリレート、2,6−ジ−tert−ブチル−4−(N,N−ジメチルアミノメチル)フェノール、3,5−ジ−tert−ブチル−4−ヒドロキシベンジルホスホネートジエチルエステル、2,2’−メチレンビス(4−メチル−6−tert−ブチルフェノール)、2,2’−メチレンビス(4−エチル−6−tert−ブチルフェノール)、4,4’−メチレンビス(2,6−ジ−tert−ブチルフェノール)、2,2’−メチレンビス(4−メチル−6−シクロヘキシルフェノール)、2,2’−ジメチレン−ビス(6−α−メチル−ベンジル−p−クレゾール)2,2’−エチリデン−ビス(4,6−ジ−tert−ブチルフェノール)、2,2’−ブチリデン−ビス(4−メチル−6−tert−ブチルフェノール)、4,4’−ブチリデンビス(3−メチル−6−tert−ブチルフェノール)、トリエチレングリコール−N−ビス−3−(3−tert−ブチル−4−ヒドロキシ−5−メチルフェニル)プロピオネート、1,6−へキサンジオールビス[3−(3,5−ジ−tert−ブチル−4−ヒドロキシフェニル)プロピオネート]、ビス[2−tert−ブチル−4−メチル6−(3−tert−ブチル−5−メチル−2−ヒドロキシベンジル)フェニル]テレフタレート、3,9−ビス{2−[3−(3−tert−ブチル−4−ヒドロキシ−5−メチルフェニル)プロピオニルオキシ]−1,1,−ジメチルエチル}−2,4,8,10−テトラオキサスピロ[5,5]ウンデカン、4,4’−チオビス(6−tert−ブチル−m−クレゾール)、4,4’−チオビス(3−メチル−6−tert−ブチルフェノール)、2,2’−チオビス(4−メチル−6−tert−ブチルフェノール)、ビス(3,5−ジ−tert−ブチル−4−ヒドロキシベンジル)スルフィド、4,4’−ジ−チオビス(2,6−ジ−tert−ブチルフェノール)、4,4’−トリ−チオビス(2,6−ジ−tert−ブチルフェノール)、2,2−チオジエチレンビス−[3−(3,5−ジ−tert−ブチル−4−ヒドロキシフェニル)プロピオネート]、2,4−ビス(n−オクチルチオ)−6−(4−ヒドロキシ−3’,5’−ジ−tert−ブチルアニリノ)−1,3,5−トリアジン、N,N’−ヘキサメチレンビス−(3,5−ジ−tert−ブチル−4−ヒドロキシヒドロシンナミド)、N,N’−ビス[3−(3,5−ジ−tert−ブチル−4−ヒドロキシフェニル)プロピオニル]ヒドラジン、1,1,3−トリス(2−メチル−4−ヒドロキシ−5−tert−ブチルフェニル)ブタン、1,3,5−トリメチル−2,4,6−トリス(3,5−ジ−tert−ブチル−4−ヒドロキシベンジル)ベンゼン、トリス(3,5−ジ−tert−ブチル−4−ヒドロキシフェニル)イソシアヌレート、トリス(3,5−ジ−tert−ブチル−4−ヒドロキシベンジル)イソシアヌレート、1,3,5−トリス(4−tert−ブチル−3−ヒドロキシ−2,6−ジメチルベンジル)イソシアヌレート、1,3,5−トリス2[3(3,5−ジ−tert−ブチル−4−ヒドロキシフェニル)プロピオニルオキシ]エチルイソシアヌレート、およびテトラキス[メチレン−3−(3’,5’−ジ−tert−ブチル−4−ヒドロキシフェニル)プロピオネート]メタンなどが例示される。上記化合物の中でも、本発明においてはテトラキス[メチレン−3−(3−tert−ブチル−4−ヒドロキシ−5−メチルフェニル)プロピオネート]メタン、オクタデシル−3−(3,5−ジ−tert−ブチル−4−ヒドロキシフェニル)プロピオネート、および3,9−ビス[2−{3−(3−tert−ブチル−4−ヒドロキシ−5−メチルフェニル)プロピオニルオキシ}−1,1−ジメチルエチル]−2,4,8,10−テトラオキサスピロ[5,5]ウンデカンが好ましく利用される。特にオクタデシル−3−(3,5−ジ−tert−ブチル−4−ヒドロキシフェニル)プロピオネートが好ましい。これらはいずれも入手容易である。上記ヒンダードフェノール系化合物は、単独でまたは2種以上を組み合わせて使用することができる。 Examples of the hindered phenol compound include α-tocopherol, butylhydroxytoluene, sinapyl alcohol, vitamin E, n-octadecyl-β- (4′-hydroxy-3 ′, 5′-di-tert-butylfel) propionate. 2-tert-butyl-6- (3′-tert-butyl-5′-methyl-2′-hydroxybenzyl) -4-methylphenyl acrylate, 2,6-di-tert-butyl-4- (N, N-dimethylaminomethyl) phenol, 3,5-di-tert-butyl-4-hydroxybenzylphosphonate diethyl ester, 2,2′-methylenebis (4-methyl-6-tert-butylphenol), 2,2′-methylenebis (4-ethyl-6-tert-butylphenol), 4,4′-methylenebi (2,6-di-tert-butylphenol), 2,2′-methylenebis (4-methyl-6-cyclohexylphenol), 2,2′-dimethylene-bis (6-α-methyl-benzyl-p-cresol) ) 2,2′-ethylidene-bis (4,6-di-tert-butylphenol), 2,2′-butylidene-bis (4-methyl-6-tert-butylphenol), 4,4′-butylidenebis (3- Methyl-6-tert-butylphenol), triethylene glycol-N-bis-3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate, 1,6-hexanediol bis [3- (3 , 5-di-tert-butyl-4-hydroxyphenyl) propionate], bis [2-tert-butyl-4-methyl 6- ( -Tert-butyl-5-methyl-2-hydroxybenzyl) phenyl] terephthalate, 3,9-bis {2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1 , 1, -dimethylethyl} -2,4,8,10-tetraoxaspiro [5,5] undecane, 4,4′-thiobis (6-tert-butyl-m-cresol), 4,4′-thiobis (3-methyl-6-tert-butylphenol), 2,2′-thiobis (4-methyl-6-tert-butylphenol), bis (3,5-di-tert-butyl-4-hydroxybenzyl) sulfide, 4 , 4′-di-thiobis (2,6-di-tert-butylphenol), 4,4′-tri-thiobis (2,6-di-tert-butylphenol) ), 2,2-thiodiethylenebis- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 2,4-bis (n-octylthio) -6- (4-hydroxy -3 ′, 5′-di-tert-butylanilino) -1,3,5-triazine, N, N′-hexamethylenebis- (3,5-di-tert-butyl-4-hydroxyhydrocinnamide), N, N′-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyl] hydrazine, 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butyl Phenyl) butane, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, tris (3,5-di-tert-butyl) 4-hydroxyphenyl) isocyanurate, tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris (4-tert-butyl-3-hydroxy-2,6- Dimethylbenzyl) isocyanurate, 1,3,5-tris 2 [3 (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] ethyl isocyanurate, and tetrakis [methylene-3- (3 ′, 5′-di-tert-butyl-4-hydroxyphenyl) propionate] methane and the like. Among the above compounds, tetrakis [methylene-3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate] methane, octadecyl-3- (3,5-di-tert-butyl-) is used in the present invention. 4-hydroxyphenyl) propionate and 3,9-bis [2- {3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy} -1,1-dimethylethyl] -2,4 , 8,10-Tetraoxaspiro [5,5] undecane is preferably used. Particularly preferred is octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate. All of these are readily available. The said hindered phenol type compound can be used individually or in combination of 2 or more types.
ホスファイト系化合物としては、トリフェニルホスファイト、トリス(ノニルフェニル)ホスファイト、トリデシルホスファイト、トリオクチルホスファイト、トリオクタデシルホスファイト、ジデシルモノフェニルホスファイト、ジオクチルモノフェニルホスファイト、ジイソプロピルモノフェニルホスファイト、モノブチルジフェニルホスファイト、モノデシルジフェニルホスファイト、モノオクチルジフェニルホスファイト、トリス(ジエチルフェニル)ホスファイト、トリス(ジ−iso−プロピルフェニル)ホスファイト、トリス(ジ−n−ブチルフェニル)ホスファイト、トリス(2,4−ジ−tert−ブチルフェニル)ホスファイト、トリス(2,6−ジ−tert−ブチルフェニル)ホスファイト、ジステアリルペンタエリスリトールジホスファイト、ビス(2,4−ジ−tert−ブチルフェニル)ペンタエリスリトールジホスファイト、ビス(2,6−ジ−tert−ブチル−4−メチルフェニル)ペンタエリスリトールジホスファイト、ビス(2,6−ジ−tert−ブチル−4−エチルフェニル)ペンタエリスリトールジホスファイト、ビス{2,4−ビス(1−メチル−1−フェニルエチル)フェニル}ペンタエリスリトールジホスファイト、フェニルビスフェノールAペンタエリスリトールジホスファイト、ビス(ノニルフェニル)ペンタエリスリトールジホスファイト、およびジシクロヘキシルペンタエリスリトールジホスファイト等が挙げられる。さらに他のホスファイト系化合物としては二価フェノール類と反応し環状構造を有するものも使用できる。例えば、2,2’−メチレンビス(4,6−ジ−tert−ブチルフェニル)(2,4−ジ−tert−ブチルフェニル)ホスファイト、2,2’−メチレンビス(4,6−ジ−tert−ブチルフェニル)(2−tert−ブチル−4−メチルフェニル)ホスファイト、および2,2−メチレンビス(4,6−ジ−tert−ブチルフェニル)オクチルホスファイト等が挙げられる。好適なホスファイト系化合物は、ジステアリルペンタエリスリトールジホスファイト、ビス(2,4−ジ−tert−ブチルフェニル)ペンタエリスリトールジホスファイト、ビス(2,6−ジ−tert−ブチル−4−メチルフェニル)ペンタエリスリトールジホスファイト、およびビス{2,4−ビス(1−メチル−1−フェニルエチル)フェニル}ペンタエリスリトールジホスファイトである。 Phosphite compounds include triphenyl phosphite, tris (nonylphenyl) phosphite, tridecyl phosphite, trioctyl phosphite, trioctadecyl phosphite, didecyl monophenyl phosphite, dioctyl monophenyl phosphite, diisopropyl mono Phenyl phosphite, monobutyl diphenyl phosphite, monodecyl diphenyl phosphite, monooctyl diphenyl phosphite, tris (diethylphenyl) phosphite, tris (di-iso-propylphenyl) phosphite, tris (di-n-butylphenyl) ) Phosphite, tris (2,4-di-tert-butylphenyl) phosphite, tris (2,6-di-tert-butylphenyl) phosphite, distearyl pentae Thritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, bis ( 2,6-di-tert-butyl-4-ethylphenyl) pentaerythritol diphosphite, bis {2,4-bis (1-methyl-1-phenylethyl) phenyl} pentaerythritol diphosphite, phenylbisphenol A penta Examples include erythritol diphosphite, bis (nonylphenyl) pentaerythritol diphosphite, and dicyclohexylpentaerythritol diphosphite. Furthermore, as other phosphite compounds, those that react with dihydric phenols and have a cyclic structure can be used. For example, 2,2′-methylenebis (4,6-di-tert-butylphenyl) (2,4-di-tert-butylphenyl) phosphite, 2,2′-methylenebis (4,6-di-tert- Butylphenyl) (2-tert-butyl-4-methylphenyl) phosphite, 2,2-methylenebis (4,6-di-tert-butylphenyl) octyl phosphite, and the like. Suitable phosphite compounds are distearyl pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-methyl). Phenyl) pentaerythritol diphosphite, and bis {2,4-bis (1-methyl-1-phenylethyl) phenyl} pentaerythritol diphosphite.
また、例えば2,4,8,10−テトラ−t−ブチル−6−[3−(3−メチル−4−ヒドロキシ−5−t−ブチルフェニル)プロポキシ]ジベンゾ[d,f][1,3,2]ジオキサホスフェピン〔「スミライザーGP」(住友化学株式会社製)として市販されている。〕、2,10−ジメチル−4,8−ジ−t−ブチル−6−[3−(3,5−ジ−t−ブチル−4−ヒドロキシフェニル)プロポキシ]−12H−ジベンゾ[d,g][1,3,2]ジオキサホスホシン、2,4,8,10−テトラ−t−ブチル−6−[3−(3、5−ジ−t−ブチル−4−ヒドロキシフェニル)プロポキシ]ジベンゾ[d,f][1,3,2]ジオキサホスフェピン、2,4,8,10−テトラ−t−ペンチル−6−[3−(3,5−ジ−t−ブチル−4−ヒドロキシフェニル)プロポキシ]−12−メチル−12H−ジベンゾ[d,g][1,3,2]ジオキサホスホシン、2,10−ジメチル−4,8−ジ−t−ブチル−6−[3−(3,5−ジ−t−ブチル−4−ヒドロキシフェニル)プロピオニルオキシ]−12H−ジベンゾ[d,g][1,3,2]ジオキサホスホシン、2,4,8,10−テトラ−t−ペンチル−6−[3−(3,5−ジ−t−ブチル−4−ヒドロキシフェニル)プロピオニルオキシ]−12−メチル−12H−ジベンゾ[d,g][1,3,2]ジオキサホスホシン、2,4,8,10−テトラ−t−ブチル−6−[3−(3,5−ジ−t−ブチル−4−ヒドロキシフェニル)プロピオニルオキシ]−ジベンゾ[d,f][1,3,2]ジオキサホスフェピン、2,10−ジメチル−4,8−ジ−t−ブチル−6−(3,5−ジ−t−ブチル−4−ヒドロキシベンゾイルオキシ)−12H−ジベンゾ[d,g][1,3,2]ジオキサホスホシン、2,4,8,10−テトラ−t−ブチル−6−(3,5−ジ−t−ブチル−4−ヒドロキシベンゾイルオキシ)−12−メチル−12H−ジベンゾ[d,g][1,3,2]ジオキサホスホシン、2,10−ジメチル−4,8−ジ−t−ブチル−6−[3−(3−メチル−4−ヒドロキシ−5−t−ブチルフェニル)プロポキシ]−12H−ジベンゾ[d,g][1,3,2]ジオキサホスホシン、2,4,8,10−テトラ−t−ブチル−6−[3−(3,5−ジ−t−ブチル−4−ヒドロキシフェニル)プロポキシ]−12H−ジベンゾ[d,g][1,3,2]ジオキサホスホシン、2,10−ジエチル−4,8−ジ−t−ブチル−6−[3−(3,5−ジ−t−ブチル−4−ヒドロキシフェニル)プロポキシ]−12H−ジベンゾ[d,g][1,3,2]ジオキサホスホシン、2,4,8,10−テトラ−t−ブチル−6−[2,2−ジメチル−3−(3−t−ブチル−4−ヒドロキシ−5−メチルフェニル)プロポキシ]−ジベンゾ[d,f][1,3,2]ジオキサホスフェピンなどを挙げることができる。これらはいずれも入手容易である。上記ホスファイト系化合物は、単独でまたは2種以上を組み合わせて使用することができる。 Also, for example, 2,4,8,10-tetra-t-butyl-6- [3- (3-methyl-4-hydroxy-5-t-butylphenyl) propoxy] dibenzo [d, f] [1,3 , 2] dioxaphosphine [commercially available as “Sumilyzer GP” (manufactured by Sumitomo Chemical Co., Ltd.). 2,10-dimethyl-4,8-di-t-butyl-6- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propoxy] -12H-dibenzo [d, g] [1,3,2] dioxaphosphocin, 2,4,8,10-tetra-t-butyl-6- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propoxy] dibenzo [D, f] [1,3,2] dioxaphosphine, 2,4,8,10-tetra-t-pentyl-6- [3- (3,5-di-t-butyl-4- Hydroxyphenyl) propoxy] -12-methyl-12H-dibenzo [d, g] [1,3,2] dioxaphosphocin, 2,10-dimethyl-4,8-di-t-butyl-6- [3 -(3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] -12H Dibenzo [d, g] [1,3,2] dioxaphosphocine, 2,4,8,10-tetra-t-pentyl-6- [3- (3,5-di-t-butyl-4- Hydroxyphenyl) propionyloxy] -12-methyl-12H-dibenzo [d, g] [1,3,2] dioxaphosphocin, 2,4,8,10-tetra-t-butyl-6- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy] -dibenzo [d, f] [1,3,2] dioxaphosphine, 2,10-dimethyl-4,8-di -T-butyl-6- (3,5-di-t-butyl-4-hydroxybenzoyloxy) -12H-dibenzo [d, g] [1,3,2] dioxaphosphocin, 2,4,8 , 10-Tetra-t-butyl-6- (3,5-di-t-butyl-4- Roxybenzoyloxy) -12-methyl-12H-dibenzo [d, g] [1,3,2] dioxaphosphocin, 2,10-dimethyl-4,8-di-t-butyl-6- [3- (3-Methyl-4-hydroxy-5-t-butylphenyl) propoxy] -12H-dibenzo [d, g] [1,3,2] dioxaphosphocine, 2,4,8,10-tetra-t -Butyl-6- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propoxy] -12H-dibenzo [d, g] [1,3,2] dioxaphosphocine, 2,10 -Diethyl-4,8-di-t-butyl-6- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propoxy] -12H-dibenzo [d, g] [1,3 2] Dioxaphosphocin, 2,4,8,10-tetra-t-butyl Ru-6- [2,2-dimethyl-3- (3-t-butyl-4-hydroxy-5-methylphenyl) propoxy] -dibenzo [d, f] [1,3,2] dioxaphosphine And so on. All of these are readily available. The above phosphite compounds can be used alone or in combination of two or more.
ホスホナイト系化合物としては、テトラキス(2,4−ジ−tert−ブチルフェニル)−4,4’−ビフェニレンジホスホナイト、テトラキス(2,4−ジ−tert−ブチルフェニル)−4,3’−ビフェニレンジホスホナイト、テトラキス(2,4−ジ−tert−ブチルフェニル)−3,3’−ビフェニレンジホスホナイト、テトラキス(2,6−ジ−tert−ブチルフェニル)−4,4’−ビフェニレンジホスホナイト、テトラキス(2,6−ジ−tert−ブチルフェニル)−4,3’−ビフェニレンジホスホナイト、テトラキス(2,6−ジ−tert−ブチルフェニル)−3,3’−ビフェニレンジホスホナイト、ビス(2,4−ジ−tert−ブチルフェニル)−4−フェニル−フェニルホスホナイト、ビス(2,4−ジ−tert−ブチルフェニル)−3−フェニル−フェニルホスホナイト、ビス(2,6−ジ−n−ブチルフェニル)−3−フェニル−フェニルホスホナイト、ビス(2,6−ジ−tert−ブチルフェニル)−4−フェニル−フェニルホスホナイト、ビス(2,6−ジ−tert−ブチルフェニル)−3−フェニル−フェニルホスホナイト等が挙げられる。テトラキス(ジ−tert−ブチルフェニル)−ビフェニレンジホスホナイト、ビス(ジ−tert−ブチルフェニル)−フェニル−フェニルホスホナイトが好ましく、テトラキス(2,4−ジ−tert−ブチルフェニル)−ビフェニレンジホスホナイト、ビス(2,4−ジ−tert−ブチルフェニル)−フェニル−フェニルホスホナイトがより好ましい。かかるホスホナイト系化合物は上記アルキル基が2以上置換したアリール基を有するホスファイト系化合物との併用可能であり好ましい。ホスホナイト系化合物としてはテトラキス(2,4−ジ−tert−ブチルフェニル)−ビフェニレンジホスホナイトが好ましく、該ホスホナイトを主成分とする安定剤は、Sandostab P−EPQ(商標、Clariant社製)およびIrgafos P−EPQ(商標、CIBA SPECIALTY CHEMICALS社製)として市販されておりいずれも利用できる。上記ホスホナイト系化合物は、単独でまたは2種以上を組み合わせて使用することができる。 Examples of the phosphonite compound include tetrakis (2,4-di-tert-butylphenyl) -4,4′-biphenylenediphosphonite, tetrakis (2,4-di-tert-butylphenyl) -4,3′-biphenyl. Range phosphonite, tetrakis (2,4-di-tert-butylphenyl) -3,3'-biphenylene diphosphonite, tetrakis (2,6-di-tert-butylphenyl) -4,4'-biphenylene diphospho Knight, tetrakis (2,6-di-tert-butylphenyl) -4,3′-biphenylene diphosphonite, tetrakis (2,6-di-tert-butylphenyl) -3,3′-biphenylene diphosphonite, Bis (2,4-di-tert-butylphenyl) -4-phenyl-phenylphosphonite, bis (2,4- -Tert-butylphenyl) -3-phenyl-phenylphosphonite, bis (2,6-di-n-butylphenyl) -3-phenyl-phenylphosphonite, bis (2,6-di-tert-butylphenyl) Examples include -4-phenyl-phenyl phosphonite, bis (2,6-di-tert-butylphenyl) -3-phenyl-phenyl phosphonite. Tetrakis (di-tert-butylphenyl) -biphenylenediphosphonite, bis (di-tert-butylphenyl) -phenyl-phenylphosphonite are preferred, and tetrakis (2,4-di-tert-butylphenyl) -biphenylenediphosphonite Knight and bis (2,4-di-tert-butylphenyl) -phenyl-phenylphosphonite are more preferred. Such a phosphonite compound is preferable because it can be used in combination with a phosphite compound having an aryl group in which two or more alkyl groups are substituted. The phosphonite compound is preferably tetrakis (2,4-di-tert-butylphenyl) -biphenylenediphosphonite, and stabilizers based on the phosphonite are Sandostab P-EPQ (trademark, manufactured by Clariant) and Irgafos. P-EPQ (trademark, manufactured by CIBA SPECIALTY CHEMICALS) is commercially available and any of them can be used. The said phosphonite type compound can be used individually or in combination of 2 or more types.
チオエーテル系化合物の具体例として、ジラウリルチオジプロピオネート、ジトリデシルチオジプロピオネート、ジミリスチルチオジプロピオネート、ジステアリルチオジプロピオネート、ペンタエリスリトール−テトラキス(3−ラウリルチオプロピオネート)、ペンタエリスリトール−テトラキス(3−ドデシルチオプロピオネート)、ペンタエリスリトール−テトラキス(3−オクタデシルチオプロピオネート)、ペンタエリスリトールテトラキス(3−ミリスチルチオプロピオネート)、ペンタエリスリトール−テトラキス(3−ステアリルチオプロピオネート)等が挙げられる。上記チオエーテル系化合物は、単独でまたは2種以上を組み合わせて使用することができる。 Specific examples of thioether compounds include dilauryl thiodipropionate, ditridecyl thiodipropionate, dimyristyl thiodipropionate, distearyl thiodipropionate, pentaerythritol-tetrakis (3-lauryl thiopropionate), Pentaerythritol-tetrakis (3-dodecylthiopropionate), pentaerythritol-tetrakis (3-octadecylthiopropionate), pentaerythritol tetrakis (3-myristylthiopropionate), pentaerythritol-tetrakis (3-stearylthio) Propionate) and the like. The said thioether type compound can be used individually or in combination of 2 or more types.
酸化防止剤の含有量は、共重合ポリエチレンテレフタレート100重量部に対し、0.01〜2重量部が好ましく、より好ましくは0.03〜1重量部、さらに好ましくは0.05〜0.5重量部である。酸化防止剤の含有量が0.01重量部より少ない場合は酸化防止効果が不足し、成形加工時の色相や流動性が不安定になるだけでなく、耐加水分解性も悪化する場合がある。また、かかる含有量が2重量部よりも多い場合、酸化防止剤由来の反応成分などがかえって耐加水分解性を悪化させてしまう場合がある。
また、前記ヒンダードフェノール系化合物とホスファイト系化合物、ホスホナイト系化合物、チオエーテル系化合物のいずれか1種類以上を組み合わせて使用することが好ましい。ヒンダードフェノール系化合物とホスファイト系化合物、ホスホナイト系化合物、チオエーテル系化合物のいずれか1種類以上を組み合わせて使用することで、安定剤としての相乗効果が発揮され、より成形加工時の色相、流動性の安定化、耐加水分解性の向上に効果がある。
The content of the antioxidant is preferably 0.01 to 2 parts by weight, more preferably 0.03 to 1 part by weight, and still more preferably 0.05 to 0.5 parts by weight with respect to 100 parts by weight of the copolymerized polyethylene terephthalate. Part. When the content of the antioxidant is less than 0.01 parts by weight, the antioxidant effect is insufficient, and not only the hue and fluidity at the time of molding become unstable, but also the hydrolysis resistance may deteriorate. . In addition, when the content is more than 2 parts by weight, the reaction component derived from the antioxidant may be deteriorated and the hydrolysis resistance may be deteriorated.
Further, it is preferable to use a combination of one or more of the hindered phenol compounds and phosphite compounds, phosphonite compounds, and thioether compounds. By using a combination of one or more of hindered phenol compounds and phosphite compounds, phosphonite compounds, and thioether compounds, a synergistic effect as a stabilizer is exhibited, and hue and flow during molding are further improved. It is effective in stabilizing the properties and improving the hydrolysis resistance.
<離型剤>
本発明では離型剤を使用することができる。離型剤として具体的には、脂肪酸、脂肪酸金属塩、オキシ脂肪酸、パラフィン、低分子量のポリオレフィン、脂肪酸アミド、アルキレンビス脂肪酸アミド、脂肪族ケトン、脂肪酸部分鹸化エステル、脂肪酸低級アルコールエステル、脂肪酸多価アルコールエステル、脂肪酸ポリグリコールエステル、変性シリコーン等を挙げることができる。これらを配合することで機械特性、成形性、耐熱性に優れた成形品を得ることができる。
<Release agent>
In the present invention, a release agent can be used. Specific examples of release agents include fatty acids, fatty acid metal salts, oxy fatty acids, paraffins, low molecular weight polyolefins, fatty acid amides, alkylene bis fatty acid amides, aliphatic ketones, fatty acid partial saponified esters, fatty acid lower alcohol esters, fatty acid polyvalents. Examples include alcohol esters, fatty acid polyglycol esters, and modified silicones. By blending these, a molded product excellent in mechanical properties, moldability, and heat resistance can be obtained.
脂肪酸としては炭素数6〜40のものが好ましく、具体的には、オレイン酸、ステアリン酸、ラウリン酸、ヒドロキシステアリン酸、ベヘン酸、アラキドン酸、リノール酸、リノレン酸、リシノール酸、パルミチン酸、モンタン酸およびこれらの混合物等が挙げられる。脂肪酸金属塩としては炭素数6〜40の脂肪酸のアルカリ(土類)金属塩が好ましく、具体的にはステアリン酸カルシウム、モンタン酸ナトリウム、モンタン酸カルシウム等が挙げられる。
オキシ脂肪酸としては1,2−オキシステリン酸等が挙げられる。パラフィンとしては炭素数18以上のものが好ましく、流動パラフィン、天然パラフィン、マイクロクリスタリンワックス、ペトロラクタム等が挙げられる。
Fatty acids having 6 to 40 carbon atoms are preferred. Specifically, oleic acid, stearic acid, lauric acid, hydroxystearic acid, behenic acid, arachidonic acid, linoleic acid, linolenic acid, ricinoleic acid, palmitic acid, montan Examples thereof include acids and mixtures thereof. The fatty acid metal salt is preferably an alkali (earth) metal salt of a fatty acid having 6 to 40 carbon atoms, and specific examples include calcium stearate, sodium montanate, and calcium montanate.
Examples of the oxy fatty acid include 1,2-oxysteric acid. Paraffin having 18 or more carbon atoms is preferable, and examples thereof include liquid paraffin, natural paraffin, microcrystalline wax, petrolactam and the like.
低分子量のポリオレフィンとしては例えば分子量5000以下のものが好ましく、具体的にはポリエチレンワックス、マレイン酸変性ポリエチレンワックス、酸化タイプポリエチレンワックス、塩素化ポリエチレンワックス、ポリプロピレンワックス等が挙げられる。脂肪酸アミドとしては炭素数6以上のものが好ましく、具体的にはオレイン酸アミド、エルカ酸アミド、ベヘン酸アミド等が挙げられる。
アルキレンビス脂肪酸アミドとしては炭素数6以上のものが好ましく、具体的にはメチレンビスステアリン酸アミド、エチレンビスステアリン酸アミド、N,N−ビス(2−ヒドロキシエチル)ステアリン酸アミド等が挙げられる。脂肪族ケトンとしては炭素数6以上のものが好ましく、高級脂肪族ケトン等が挙げられる。
As the low molecular weight polyolefin, for example, those having a molecular weight of 5000 or less are preferable, and specific examples include polyethylene wax, maleic acid-modified polyethylene wax, oxidized type polyethylene wax, chlorinated polyethylene wax, and polypropylene wax. Fatty acid amides having 6 or more carbon atoms are preferred, and specific examples include oleic acid amide, erucic acid amide, and behenic acid amide.
The alkylene bis fatty acid amide is preferably one having 6 or more carbon atoms, and specifically includes methylene bis stearic acid amide, ethylene bis stearic acid amide, N, N-bis (2-hydroxyethyl) stearic acid amide and the like. As the aliphatic ketone, those having 6 or more carbon atoms are preferable, and examples thereof include higher aliphatic ketones.
脂肪酸部分鹸化エステルとしてはモンタン酸部分鹸化エステル等が挙げられる。脂肪酸低級アルコールエステルとしてはステアリン酸エステル、オレイン酸エステル、リノール酸エステル、リノレン酸エステル、アジピン酸エステル、ベヘン酸エステル、アラキドン酸エステル、モンタン酸エステル、イソステアリン酸エステル等が挙げられる。
脂肪酸多価アルコールエステルとしては、グリセロールトリステアレート、グリセロールジステアレート、グリセロールモノステアレート、ペンタエリスルトールテトラステアレート、ペンタエリスルトールトリステアレート、ペンタエリスルトールジミリステート、ペンタエリスルトールモノステアレート、ペンタエリスルトールアジペートステアレート、ソルビタンモノベヘネート等が挙げられる。脂肪酸ポリグリコールエステルとしてはポリエチレングリコール脂肪酸エステル、ポリトリメチレングリコール脂肪酸エステル、ポリプロピレングリコール脂肪酸エステル等が挙げられる。
Examples of the fatty acid partial saponified ester include a montanic acid partial saponified ester. Examples of the fatty acid lower alcohol ester include stearic acid ester, oleic acid ester, linoleic acid ester, linolenic acid ester, adipic acid ester, behenic acid ester, arachidonic acid ester, montanic acid ester, isostearic acid ester and the like.
Examples of fatty acid polyhydric alcohol esters include glycerol tristearate, glycerol distearate, glycerol monostearate, pentaerythritol tetrastearate, pentaerythritol tristearate, pentaerythritol dimyristate, pentaerythritol Examples include tall monostearate, pentaerythritol adipate stearate, sorbitan monobehenate and the like. Examples of fatty acid polyglycol esters include polyethylene glycol fatty acid esters, polytrimethylene glycol fatty acid esters, and polypropylene glycol fatty acid esters.
変性シリコーンとしてはポリエーテル変性シリコーン、高級脂肪酸アルコキシ変性シリコーン、高級脂肪酸含有シリコーン、高級脂肪酸エステル変性シリコーン、メタクリル変性シリコーン、フッ素変性シリコーン等が挙げられる。
そのうち脂肪酸、脂肪酸金属塩、オキシ脂肪酸、脂肪酸エステル、脂肪酸部分鹸化エステル、パラフィン、低分子量ポリオレフィン、脂肪酸アミド、アルキレンビス脂肪酸アミドが好ましく、脂肪酸部分鹸化エステル、アルキレンビス脂肪酸アミドがより好ましい。なかでもモンタン酸エステル、モンタン酸部分鹸化エステル、ポリエチレンワックス、酸化ポリエチレンワックス、ソルビタン脂肪酸エステル、エルカ酸アミド、エチレンビスステアリン酸アミドが好ましく、特にモンタン酸部分鹸化エステル、エチレンビスステアリン酸アミドが好ましい。
離型剤は、1種類で用いても良いし2種以上を組み合わせて用いても良い。離型剤の含有量は、共重合ポリエチレンテレフタレート100重量部に対し、好ましくは0.01〜3重量部、より好ましくは0.03〜2重量部である。
Examples of the modified silicone include polyether-modified silicone, higher fatty acid alkoxy-modified silicone, higher fatty acid-containing silicone, higher fatty acid ester-modified silicone, methacryl-modified silicone, and fluorine-modified silicone.
Of these, fatty acid, fatty acid metal salt, oxy fatty acid, fatty acid ester, fatty acid partial saponified ester, paraffin, low molecular weight polyolefin, fatty acid amide, and alkylene bis fatty acid amide are preferable, and fatty acid partial saponified ester and alkylene bis fatty acid amide are more preferable. Of these, montanic acid ester, montanic acid partially saponified ester, polyethylene wax, oxidized polyethylene wax, sorbitan fatty acid ester, erucic acid amide, and ethylene bisstearic acid amide are preferable, and montanic acid partially saponified ester and ethylene bisstearic acid amide are particularly preferable.
A mold release agent may be used by 1 type and may be used in combination of 2 or more type. The content of the release agent is preferably 0.01 to 3 parts by weight, more preferably 0.03 to 2 parts by weight, with respect to 100 parts by weight of the copolymerized polyethylene terephthalate.
<成形体の製造について>
本発明の共重合ポリエチレンテレフタレートは、通常ペレットとして得られ、これを原料として射出成形、押出成形など、各種成形方法によって成形体を製造することができる。
射出成形においては、通常のコールドランナー方式の成形法だけでなく、ホットランナー方式の成形法も可能である。かかる射出成形においては、通常の成形方法だけでなく、適宜目的に応じて、射出圧縮成形、射出プレス成形、ガスアシスト射出成形、発泡成形(超臨界流体の注入によるものを含む)、インサート成形、インモールドコーティング成形、断熱金型成形、急速加熱冷却金型成形、二色成形、サンドイッチ成形、および超高速射出成形などの射出成形法を用いて成形品を得ることができる。これら各種成形法の利点は既に広く知られるところである。
押出成形においては、各種異形押出成形品、シート、フィルムなどの製品を得ることができる。またシート、フィルムの成形にはインフレーション法や、カレンダー法、キャスティング法なども使用可能である。さらに特定の延伸操作をかけることにより熱収縮チューブとして成形することも可能である。
<Manufacture of molded body>
The copolymerized polyethylene terephthalate of the present invention is usually obtained as a pellet, and a molded product can be produced by using various molding methods such as injection molding and extrusion molding using this as a raw material.
In the injection molding, not only a normal cold runner molding method but also a hot runner molding method is possible. In such injection molding, not only a normal molding method but also an injection compression molding, an injection press molding, a gas assist injection molding, a foam molding (including those by injection of a supercritical fluid), an insert molding, depending on the purpose as appropriate. A molded product can be obtained using an injection molding method such as in-mold coating molding, heat insulating mold molding, rapid heating / cooling mold molding, two-color molding, sandwich molding, and ultrahigh-speed injection molding. The advantages of these various molding methods are already widely known.
In extrusion molding, products such as various profile extrusion molded articles, sheets, and films can be obtained. For forming sheets and films, an inflation method, a calendar method, a casting method, or the like can also be used. It is also possible to form a heat-shrinkable tube by applying a specific stretching operation.
本発明の共重合ポリエチレンテレフタレートを回転成形やブロー成形などに供することにより、中空成形品を得ることも可能である。
本発明の共重合ポリエチレンテレフタレートを成形体に加工する場合、例えば射出成形であれば、130〜160℃の熱風乾燥機で5時間以上予備乾燥した後、シリンダ温度260〜300℃で溶融し、金型温度20〜60℃の金型に射出して成形することが好ましい。
By using the copolymerized polyethylene terephthalate of the present invention for rotational molding or blow molding, it is possible to obtain a hollow molded product.
When the copolymerized polyethylene terephthalate of the present invention is processed into a molded body, for example, in the case of injection molding, it is preliminarily dried for 5 hours or more in a hot air dryer at 130 to 160 ° C., and then melted at a cylinder temperature of 260 to 300 ° C. It is preferable to mold by injection into a mold having a mold temperature of 20 to 60 ° C.
予備乾燥温度が130℃未満では乾燥が不十分となり、ペレット中に残存した水分によって樹脂分解を起こし、固有粘度が安定しない場合があり、予備乾燥温度が160℃より高いとペレットが黄変し、成形体の外観が損なわれる場合がある。シリンダ温度が260℃未満では流動性低下や未溶融樹脂が発生し、外観や物性が損なわれる場合があり、シリンダ温度が300℃を超えると樹脂分解によって成形体の固有粘度が安定しなくなる場合がある。金型温度が20℃未満では流動性の低下を招くため好ましくなく、金型温度が60℃を超えると樹脂の固化時間が長くなり、成形サイクルが長くなるため好ましくない。 If the predrying temperature is less than 130 ° C, the drying becomes insufficient, the resin may be decomposed by moisture remaining in the pellets, and the intrinsic viscosity may not be stable. If the predrying temperature is higher than 160 ° C, the pellets turn yellow. The appearance of the molded body may be impaired. If the cylinder temperature is less than 260 ° C, fluidity may be lowered or unmelted resin may be generated, and the appearance and physical properties may be impaired. If the cylinder temperature exceeds 300 ° C, the intrinsic viscosity of the molded product may not be stable due to resin decomposition. is there. If the mold temperature is less than 20 ° C., the fluidity is lowered, which is not preferable. If the mold temperature exceeds 60 ° C., the solidification time of the resin becomes long and the molding cycle becomes long.
以下、実施例により本発明を詳述する。ただし、本発明はこれらに限定されるものではない。 Hereinafter, the present invention will be described in detail by way of examples. However, the present invention is not limited to these.
1.共重合ポリエチレンテレフタレートの製造方法
下記の製造例に示す方法により、共重合ポリエチレンテレフタレートの製造を行った。また製造例中における固有粘度の値は下記方法によって求めた。
(1)固有粘度(IV)の測定方法
樹脂0.6gをo-クロロフェノール50ml中で100℃、1時間加熱溶解した後、室温に冷却し、得られた樹脂溶液の粘度を、オストワルド式粘度管を用いて35℃の温度条件で測定し、得られた溶液粘度のデータから当該樹脂の固有粘度(IV)を求めた。
(2)ポリエチレンテレフタレートの製造
1. Production method of copolymerized polyethylene terephthalate Copolymerized polyethylene terephthalate was produced by the method shown in the production examples below. Moreover, the value of the intrinsic viscosity in a manufacture example was calculated | required by the following method.
(1) Intrinsic Viscosity (IV) Measurement Method 0.6 g of resin was dissolved in 50 ml of o-chlorophenol at 100 ° C. for 1 hour by heating and then cooled to room temperature. The viscosity of the resulting resin solution was determined to be Ostwald viscosity. Measurement was performed using a tube under a temperature condition of 35 ° C., and the intrinsic viscosity (IV) of the resin was determined from the obtained solution viscosity data.
(2) Production of polyethylene terephthalate
[製造例1:共重合ポリエチレンテレタフレート PET−1]
表1記載のポリマー組成となる様に数量を調合した高純度テレフタル酸,イソフタル酸およびエチレングリコールからなる混合スラリーを一定速度でエステル化反応器に供給し、撹拌しながら270℃で0.3MPaへ窒素加圧して、発生する水とエチレングリコールを系外に留去しながらエステル化反応を実施した。得られたオリゴマーの半分に同重量の前記混合スラリーを供給し、撹拌しながら270℃の常圧下で、発生する水とエチレングリコールを系外に留去しながらエステル化反応を実施した。同様の操作を5回繰り返し行い、品質の安定したポリエステルオリゴマーを作成した。
次いでこのポリエステルオリゴマーを重縮合反応容器に移送し、撹拌しながら重縮合触媒として二酸化ゲルマニウム触媒を全ジカルボン酸成分に対して25ミリモル%となるように投入した。そして、安定剤として正リン酸を全ジカルボン酸成分に対してリン原子が12.2ミリモル%となるように投入した。引続き系内の反応温度を270℃から285℃、又、反応圧力を常圧から60Paにそれぞれ段階的に上昇および減圧し、反応で発生する水、エチレングリコールを系外に除去しながら重縮合反応を行った。重縮合反応の進行度合いは撹拌翼の負荷として確認し、所望の重合度に達した時点で反応を終了した。その後、系内の反応物を吐出部からストランド状に連続的に押出し、冷却しカッティングして、約3mmの粒状ペレットを得た。得られた組成、物性を表1に示した。
[Production Example 1: Copolyethylene terephthalate PET-1]
A mixed slurry composed of high-purity terephthalic acid, isophthalic acid and ethylene glycol, prepared in quantities so as to have the polymer composition shown in Table 1, is fed to the esterification reactor at a constant rate and increased to 0.3 MPa at 270 ° C. with stirring. The esterification reaction was carried out while applying nitrogen pressure and distilling off the generated water and ethylene glycol out of the system. The mixed slurry of the same weight was supplied to half of the obtained oligomer, and the esterification reaction was carried out while distilling off the generated water and ethylene glycol under normal pressure at 270 ° C. while stirring. The same operation was repeated 5 times to produce a polyester oligomer with stable quality.
Next, this polyester oligomer was transferred to a polycondensation reaction vessel, and while stirring, a germanium dioxide catalyst as a polycondensation catalyst was added so as to be 25 mmol% with respect to the total dicarboxylic acid component. Then, orthophosphoric acid was added as a stabilizer so that the phosphorus atom was 12.2 mmol% with respect to the total dicarboxylic acid component. Subsequently, the reaction temperature in the system is increased from 270 ° C. to 285 ° C., and the reaction pressure is gradually increased and reduced from normal pressure to 60 Pa, respectively. Went. The degree of progress of the polycondensation reaction was confirmed as a load on the stirring blade, and the reaction was terminated when the desired degree of polymerization was reached. Thereafter, the reaction product in the system was continuously extruded in a strand form from the discharge part, cooled and cut to obtain about 3 mm granular pellets. The obtained composition and physical properties are shown in Table 1.
[製造例2〜9:共重合ポリエチレンテレタフレート PET−2〜9]
表1記載のポリマー組成となる様に、高純度テレフタル酸,イソフタル酸の数量を変更した以外は、製造例1と同様の方法で行った。その結果を表1に示した。
[Production Examples 2 to 9: Copolymerized polyethylene terephthalate PET-2 to 9]
The procedure was the same as in Production Example 1 except that the quantities of high-purity terephthalic acid and isophthalic acid were changed so that the polymer composition shown in Table 1 was obtained. The results are shown in Table 1.
2.真空採血管での低温保管テスト
製造例1〜9で得られた粒状ペレットを用いて表2に示すシリンダ温度、成形サイクルにて有底管2を成形した。次に、35kPaまで減圧した密閉ボックス内で、栓体3を有底管2の開口部に挿入し密封した。これにガンマ線を10kGy照射し、真空採血管1を得た。
金属針の片方を水槽に接続し、他方を真空採血管1の栓体3に刺通させ、8.5mLの水を真空採血管1内に満たした。次に、ラックを用いて水を満たした真空採血管1を垂直に立て、ラックに載せたままフリーザーに3時間保管した後、室温に取り出し、破損により水漏れしたものをカウントした。なお、フリーザー内の温度は、−20℃、−30℃、−40℃、−80℃の各設定とし、試験は各水準10本ずつ行った。その結果を表2に示した。
2. Low temperature storage test in vacuum blood collection tube Using the granular pellets obtained in Production Examples 1 to 9, the bottomed
One of the metal needles was connected to the water tank, the other was pierced through the
<実施例1〜7>
ジカルボン酸中のテレフタル酸(B−1成分)およびイソフタル酸(B−2成分)の含有比率が請求項1の規定範囲内である実施例1〜7は、−30℃未満での保管においても真空採血管の破損が抑制され、医療用成形体として優れた特性を持っていた。
<Examples 1-7>
Examples 1 to 7, in which the content ratio of terephthalic acid (component B-1) and isophthalic acid (component B-2) in the dicarboxylic acid are within the specified range of
<比較例1>
ジカルボン中のイソフタル酸(B−2成分)の含有比率が請求項1の規定範囲の上限を超えるPET−8を用いた場合、−30℃未満での保管において破損が多発した。
<Comparative Example 1>
When PET-8 in which the content ratio of isophthalic acid (component B-2) in the dicarboxylic acid exceeds the upper limit of the prescribed range of
<比較例2>
ジカルボン酸中のテレフタル酸(B−1成分)の含有比率が100モル%であるPET−9を用いた場合、−30℃未満での保管において破損が多発した。
<Comparative Example 2>
When PET-9 in which the content ratio of terephthalic acid (component B-1) in dicarboxylic acid was 100 mol%, breakage occurred frequently during storage at less than -30 ° C.
1.真空採血管
2.有底管
3.栓体
1. 1. Vacuum
Claims (4)
The medical molded body according to any one of claims 1 to 3, which is molded by a molding method selected from the group consisting of injection molding, extrusion molding, thermoforming, and blow molding.
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WO2008078808A1 (en) * | 2006-12-27 | 2008-07-03 | Medibic | Vacuum blood collection tube |
JP2011229758A (en) * | 2010-04-28 | 2011-11-17 | Kaneka Corp | Vacuum blood collection tube |
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WO2008078808A1 (en) * | 2006-12-27 | 2008-07-03 | Medibic | Vacuum blood collection tube |
JP2011229758A (en) * | 2010-04-28 | 2011-11-17 | Kaneka Corp | Vacuum blood collection tube |
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