JPH02276856A - Polyethylene terephthalate blend for blow molding - Google Patents
Polyethylene terephthalate blend for blow moldingInfo
- Publication number
- JPH02276856A JPH02276856A JP2834690A JP2834690A JPH02276856A JP H02276856 A JPH02276856 A JP H02276856A JP 2834690 A JP2834690 A JP 2834690A JP 2834690 A JP2834690 A JP 2834690A JP H02276856 A JPH02276856 A JP H02276856A
- Authority
- JP
- Japan
- Prior art keywords
- polyethylene terephthalate
- blow molding
- blend
- molding
- transparency
- 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 title claims abstract description 48
- 229920000139 polyethylene terephthalate Polymers 0.000 title claims abstract description 48
- 239000005020 polyethylene terephthalate Substances 0.000 title claims abstract description 48
- 238000000071 blow moulding Methods 0.000 title claims abstract description 12
- 239000000203 mixture Substances 0.000 title claims abstract description 10
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 claims abstract description 54
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 10
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 abstract description 8
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 abstract description 7
- 238000000465 moulding Methods 0.000 abstract description 7
- 239000007790 solid phase Substances 0.000 abstract description 7
- 238000001746 injection moulding Methods 0.000 abstract description 6
- 238000002156 mixing Methods 0.000 abstract description 5
- 229920002959 polymer blend Polymers 0.000 abstract description 5
- 238000002844 melting Methods 0.000 abstract description 4
- 230000008018 melting Effects 0.000 abstract description 4
- 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 abstract description 3
- 239000000975 dye Substances 0.000 abstract description 2
- 239000011261 inert gas Substances 0.000 abstract description 2
- 239000000314 lubricant Substances 0.000 abstract description 2
- 239000000049 pigment Substances 0.000 abstract description 2
- 230000000379 polymerizing effect Effects 0.000 abstract 1
- 229920000642 polymer Polymers 0.000 description 11
- 238000002347 injection Methods 0.000 description 9
- 239000007924 injection Substances 0.000 description 9
- 235000013305 food Nutrition 0.000 description 7
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 229920008651 Crystalline Polyethylene terephthalate Polymers 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 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
- 238000001125 extrusion Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 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
- 229920000728 polyester Polymers 0.000 description 2
- 239000004800 polyvinyl chloride Substances 0.000 description 2
- 229920000915 polyvinyl chloride Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- QYQADNCHXSEGJT-UHFFFAOYSA-N cyclohexane-1,1-dicarboxylate;hydron Chemical compound OC(=O)C1(C(O)=O)CCCCC1 QYQADNCHXSEGJT-UHFFFAOYSA-N 0.000 description 1
- YZFOGXKZTWZVFN-UHFFFAOYSA-N cyclopentane-1,1-dicarboxylic acid Chemical compound OC(=O)C1(C(O)=O)CCCC1 YZFOGXKZTWZVFN-UHFFFAOYSA-N 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- BTVWZWFKMIUSGS-UHFFFAOYSA-N dimethylethyleneglycol Natural products CC(C)(O)CO BTVWZWFKMIUSGS-UHFFFAOYSA-N 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000010137 moulding (plastic) Methods 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 238000007666 vacuum forming Methods 0.000 description 1
Abstract
Description
【発明の詳細な説明】
本発明は中空成形用ポリエチレンテレフタレート配合物
に関する。詳しくは透明性、寸法安定性に優れかつアセ
トアルデヒド含有量の少ない中空成形用ポリエチレンテ
レフタレート配合物に関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to polyethylene terephthalate formulations for blow molding. Specifically, the present invention relates to a polyethylene terephthalate compound for blow molding which has excellent transparency and dimensional stability and has a low acetaldehyde content.
ポリエステル、特にポリエチレンテレフタレートは侵れ
た物理的性質、化学的性質を有しているので、線維、フ
ィルム、プラスチック成形分野などで広く用いられてい
る。Polyester, especially polyethylene terephthalate, has excellent physical and chemical properties and is therefore widely used in the fields of fiber, film, and plastic molding.
従来プラスチック中空成形品向は樹脂としては主として
ポリ塩化ビニルが用いられてきた妙ζ近年、該ポリマの
衛生問題によシ、食品向は中空成形容器の分野でその使
用が制限を受けるようになってきた。一方、ポリエチレ
ンテレフタレートは、前述の通ム優れ念諸特注を有して
いるにもかかわらず、中空成形分野、特に食品容器分野
への進出が十分でなかった。この原因は、主に、ポリマ
の溶融時の粘度が；氏いことおよび結晶化が速く製品が
白化しやすいこと並びに製品中にアセトアルデヒドが残
存することにあった。これらの間層のうち前二者て対し
ては成形技術の観点から各種の改良がなされ一応ポリ塩
化ビニルの代替としての機能をもつようになったが、依
然としてポリエチレンテレフタレートには、アセトアル
デヒドを含有するため、充填物の味や臭が変化してしま
うという欠点がある。Conventionally, polyvinyl chloride has been mainly used as the resin for plastic blow-molded products, but in recent years, due to sanitary issues with this polymer, its use in the field of blow-molded food containers has been restricted. It's here. On the other hand, polyethylene terephthalate has not made sufficient inroads into the blow molding field, especially the food container field, despite having many special orders. The main causes of this are that the viscosity of the polymer is low when melted, that the product crystallizes quickly and that the product tends to whiten, and that acetaldehyde remains in the product. Of these interlayers, various improvements have been made to the former two from the viewpoint of molding technology, and they have come to function as a substitute for polyvinyl chloride, but polyethylene terephthalate still contains acetaldehyde. This has the disadvantage that the taste and odor of the filling may change.
ポリエチレンテレフタレート製食品容器中のアルデヒド
含有量は１５ｐｐｍ以下、好ましくは１０ｐｐｍ以下で
あることカー食品の味、臭を変化させないための必要条
件である。The aldehyde content in polyethylene terephthalate food containers must be 15 ppm or less, preferably 10 ppm or less, which is a necessary condition for not changing the taste and odor of car food.
ポリエチレンテレフタレート中のアセトアルデヒドを減
少せしめる方法として、具体的には、減圧、あるいは不
活性気流下に１９０℃以上、融点以下の＠度で数時間乃
至数十時間処理するいわゆる固相重合法が知られている
。しかしながら、固相重合処理は、ポリエチレンテレフ
タレートチップ表面に強固な結晶が生成するためか、固
相重合したチップを用いて得られる中空成形品は透明性
が十分で々いという欠点き有する。この透明性は成形時
のポリマ温度を通常よシ高めることにより、解決できる
が、溶融ポリマ温度を高めることは該ポリマの熱分解を
促進するためポリエチレンテレフタレート中のアセトア
ルデヒド含量の増加をもたらすという大きな欠点を伴な
う。As a method for reducing acetaldehyde in polyethylene terephthalate, specifically, a so-called solid phase polymerization method is known in which the polyethylene terephthalate is treated at 190° C. or higher and below the melting point for several hours to several tens of hours under reduced pressure or an inert gas flow. ing. However, the solid phase polymerization process has the disadvantage that the hollow molded product obtained using the solid phase polymerized chip does not have sufficient transparency, probably because strong crystals are formed on the surface of the polyethylene terephthalate chip. This transparency can usually be overcome by increasing the polymer temperature during molding, but a major drawback is that increasing the molten polymer temperature promotes thermal decomposition of the polymer, leading to an increase in the acetaldehyde content in the polyethylene terephthalate. accompanied by.
一方、ポリエチレンテレフタレート中空成形品の透明性
を向上せしめる方法として、ポリエチレンテレフタレー
トに対して第３成分を共重合する方法か一般的に知られ
ている。この場合、ポリマが難結晶性となるため当然な
がら、透明性は向上するものの、ポリマの融点が低下し
てぐる。その結果、高温下ではチップ同志が融着しゃす
くな９、低アセトアルデヒド化のための高温処理力ζ極
めて困難となる。On the other hand, as a method for improving the transparency of polyethylene terephthalate blow molded products, a method is generally known in which a third component is copolymerized with polyethylene terephthalate. In this case, since the polymer becomes difficult to crystallize, the transparency naturally improves, but the melting point of the polymer decreases. As a result, the chips are less likely to fuse to each other at high temperatures9, making high-temperature processing power ζ extremely difficult for reducing acetaldehyde.
かかる実状に鑑み、本発明者らは食品容器等に適したポ
リエチレンテレフタレート中空成形品の透明性、耐衝撃
性、寸法安定性、低アセトアルデヒド化を同時に達成丁
べく鋭意検討した結果、本発明に到達したものである。In view of these circumstances, the present inventors have conducted intensive studies to simultaneously achieve transparency, impact resistance, dimensional stability, and low acetaldehyde in polyethylene terephthalate hollow molded products suitable for food containers, etc., and have arrived at the present invention. This is what I did.
すなわち本発明は、結晶化度が４０％以上、７０％未満
で、アセトアルデヒド含有量が５ｐｐｍ未満であるポリ
エチレンテレフタレートおよび共重合成分を３〜２０モ
ルチ共重合せしめた変成ポリエチレンテレフタレートか
らなりかつ該共重合成分が全重合体混合物中０．５〜５
％ルＳｔ占める中空成形用ポリエチレンテレフタレート
配合物を提供するものである。That is, the present invention consists of a modified polyethylene terephthalate having a crystallinity of 40% or more and less than 70% and an acetaldehyde content of less than 5 ppm, and a modified polyethylene terephthalate obtained by copolymerizing 3 to 20 moles of a copolymer component; 0.5 to 5 components in the total polymer mixture
% St. A polyethylene terephthalate composition for blow molding is provided.
本発明で用いられる結晶化度が４０％以上、７０％未満
で、アセトアルデヒド含有量が５ｐｐｍ以下であるポリ
エチレンテレフタレートは、溶融重合で得たポリエチレ
ンテレフタレートを減圧下または不活性ガス気流下にお
いて、通常１９０１−以上融点より約１０℃低い温度範
囲で少なくとも２時間固相重合せしめることによって得
ることができる。The polyethylene terephthalate used in the present invention has a crystallinity of 40% or more and less than 70% and an acetaldehyde content of 5 ppm or less. Polyethylene terephthalate obtained by melt polymerization is usually 1901 It can be obtained by solid state polymerization for at least 2 hours at a temperature range of about 10°C lower than the melting point.
ここでいうポリエチレンテレフタレートの結晶化度は密
度より求めたものである。密度の測定は密度勾配管法に
より求めたものであシ、軽液としてｎ−へブタン、重液
として四塩化炭素全連続的に混合し用いた。密度より結
晶化度を求めるには下式を用いる。The crystallinity of polyethylene terephthalate here is determined from the density. The density was determined by the density gradient tube method, and n-hebutane was used as a light liquid, and carbon tetrachloride was used as a heavy liquid, all of which were mixed continuously. The following formula is used to determine the degree of crystallinity from the density.
ただムρは試料の密度、Ｉ’Ｇは非晶部の密度 １．３
３５（ｆ／Ｊ）Ｐ６は結晶部の密度 １．４５５ （ｔ
／ａｄ）またポリエチレンテレフタレート中のアセトア
ルデヒド含量は、たとえば液体窒素中でポリエチレンテ
レフタレートを微粉末に粉砕して、この粉末を島津裏作
所製４０Ｍ型ガスクロマトグラフ中に入れ１６５℃に加
熱し、標準に対する生成ピークを比べて遊離したアセト
アルデヒド量全求めることにより測定される。However, ρ is the density of the sample, and I'G is the density of the amorphous part. 1.3
35 (f/J) P6 is the density of the crystal part 1.455 (t
/ad) The acetaldehyde content in polyethylene terephthalate can be determined by, for example, grinding polyethylene terephthalate into a fine powder in liquid nitrogen, placing this powder in a 40M gas chromatograph manufactured by Shimadzu Ura Seisakusho, and heating it to 165°C. It is measured by comparing the peaks and determining the total amount of acetaldehyde released.
ポリエチレンテレフタレート成形品中のアルデヒド量は
工５ｐ７ｍ以下、好ましくはＬＯｐｐｔｎ以下にするこ
とが食品の味、奥を変化させないための必要条件である
。It is a necessary condition to keep the amount of aldehyde in the polyethylene terephthalate molded product below 5p7m, preferably below LOpptn, in order not to change the taste and depth of the food.
かくして得られた結晶化ポリエチレンテレフタレートの
みを用いて得た中空成形品は、前述の如くの理由で、成
形品の透明性と低アセトアルデヒド化とを両立させるこ
とは事実上著しく困難である。かかる問題に対し、本発
明者らは一上記した特性を有する結晶化ポリエチレンテ
レフタレート【、共重合成分全３〜２０モルチ共重合せ
しめた変成ポリエチレンテレフタレート？共重合成分が
全重合体混合物中０．５〜５モル％を占めるように配合
することによって、驚くべきことに得られる中空成形品
の透明性と低アルデヒド化とを両立させることができる
ことを見出したのである。For the reasons described above, it is actually extremely difficult to achieve both transparency and low acetaldehyde in the hollow molded product obtained using only the crystallized polyethylene terephthalate thus obtained. In order to solve this problem, the present inventors have developed a crystallized polyethylene terephthalate having the above-mentioned properties. We have surprisingly found that by blending the copolymer component so that it occupies 0.5 to 5 mol% of the total polymer mixture, it is possible to achieve both transparency and low aldehyde content in the resulting blow molded product. It was.
変性ポリエチレンテレフタレートにおける共重合成分は
ポリエチレンテレフタレートを溶融重合で得る際にこれ
に共重合させうるものであれば本質的にはいづれでもよ
く、例えばイソフタル酸、フタル酸、２，６−す７タレ
ンジカルボン酸等の芳香族ジカルボン酸、アジピン酸、
セパシン酸、シクロヘキサンジカルボン酸、シクロペン
タンジカルボン酸の如きの脂肪族、脂環族ジカルボン酸
、ジオール成分としてはプロピレンクリコール、２・２
−ジメチル−１・３プロパンジオール、ｌ・３−７’ロ
パンジオール、１・３−７−タンジオール、１・４−ブ
タンジオール、１・５−ベンタンジオール、１・６−ヘ
キサンジオール、１・２−シクロヘキサンジメタツール
、１°３−シクロヘキサンジメタツール、ｌ・４−シク
ロヘキサンジメタツール、２．２−ビス（４−β−ヒド
ロキシフェニル）プロパン、ジエチレングリコール、ト
リエチレングリコール等が挙げられる。The copolymerization component in modified polyethylene terephthalate may essentially be any component that can be copolymerized with polyethylene terephthalate when it is obtained by melt polymerization, such as isophthalic acid, phthalic acid, and 2,6-7thalene dicarboxylic acid. Aromatic dicarboxylic acids such as acids, adipic acid,
Aliphatic and alicyclic dicarboxylic acids such as sepacic acid, cyclohexanedicarboxylic acid, and cyclopentanedicarboxylic acid; diol components include propylene glycol, 2.2
-dimethyl-1,3-propanediol, 1,3-7'ropanediol, 1,3-7-tanediol, 1,4-butanediol, 1,5-bentanediol, 1,6-hexanediol, 1,2- Examples include cyclohexane dimetatool, 1°3-cyclohexane dimetatool, 1.4-cyclohexane dimetatool, 2,2-bis(4-β-hydroxyphenyl)propane, diethylene glycol, triethylene glycol, and the like.
該共重合成分の共重合割合は３〜２０モルチである。共
重合成分量が３８−％以下の場合は、成形品の透明性と
低アルデヒド化の両者をバランスよく満足させることが
できない。また２０モル％を越えると溶融成形前のポリ
マ乾燥が十分性なえず、結果として成形品中のアルデヒ
ド含量が高まジ好ましくない。The copolymerization ratio of the copolymer components is 3 to 20 molar. When the copolymerization content is less than 38%, it is not possible to satisfy both the transparency and low aldehyde content of the molded article in a well-balanced manner. Moreover, if it exceeds 20 mol %, the polymer cannot be dried sufficiently before melt molding, and as a result, the aldehyde content in the molded product increases, which is undesirable.
かかる変性ポリエチレンテレフタレートは通常固相重合
に供する前の状態で結晶化ポリエチレンテレフタレート
と配合される。配合割合は、共重合成分が全重合体混合
物中０．５〜５モル％を占めるような割合であることが
必要である。該配合物中の共重合成分が０．５モルチ未
満のときは成形品の透明性が悪化し、５モルＳｔ越える
と寸法安定性に劣る欠点が生じる。Such modified polyethylene terephthalate is usually blended with crystallized polyethylene terephthalate before being subjected to solid phase polymerization. The blending ratio needs to be such that the copolymerization component occupies 0.5 to 5 mol% of the total polymer mixture. If the copolymerization component in the blend is less than 0.5 mol St, the transparency of the molded article will deteriorate, and if it exceeds 5 mol St, there will be a drawback of poor dimensional stability.
また本発明に用いられるポリエチレンテレフタレートの
極限粘度は特に限定されないが好ましくは結晶化ポリエ
チレンテレフタレート成分が０．６５〜１．３であり、
該共重合成分が０．５５〜１．２である。かくして得ら
れたポリエチレンテレフタレート配合物は中空成形に供
される。Further, the intrinsic viscosity of the polyethylene terephthalate used in the present invention is not particularly limited, but preferably the crystallized polyethylene terephthalate component is 0.65 to 1.3,
The copolymerization component is 0.55 to 1.2. The polyethylene terephthalate blend thus obtained is subjected to blow molding.
成形品の製造方法は、押出成形あるいは射出成形、ある
いは射出／押出併用成形法が適用される力ζ真空成形、
プロー成形、−軸または二軸延伸成形と組合せて用いる
ことができる。このうち特に成形機内のポリマ滞留時間
の短い、すなわちポリマの結晶核が完全に融解しきれな
ぺ換言すれば得られる成形品の透明性が懸念されるよう
な、射出成形に供した場合に、良好な透明性と低アセト
アルデヒド化が達成されるので特に好ましい。The manufacturing method of the molded product is extrusion molding, injection molding, or vacuum forming using injection/extrusion combination molding.
It can be used in combination with blow molding, -axial or biaxial stretching molding. Among these, when subjected to injection molding, the residence time of the polymer in the molding machine is particularly short, that is, the crystal nuclei of the polymer are not completely melted, and in other words, there is a concern about the transparency of the resulting molded product. This is particularly preferred since good transparency and low acetaldehyde are achieved.
また該両配合成分のいずれかまたは両者に、必要に応じ
て従来公知の顔料、染料、静電防止剤、耐候剤、滑剤等
を添加することは全く自由である。Further, it is completely free to add conventionally known pigments, dyes, antistatic agents, weathering agents, lubricants, etc. to either or both of the two components as necessary.
かくして得られたポリエチレンテレフタレート成形品は
透明性、低アルデヒド性に優れ、特に食品、化粧品、雑
貨等の充てん・包装材料として極めて優れているもので
ある。The polyethylene terephthalate molded product thus obtained has excellent transparency and low aldehyde properties, and is particularly excellent as a filling/packaging material for foods, cosmetics, miscellaneous goods, etc.
以下実施例を挙げて本発明を具体的に説明するが本発明
はこれらの例のみに限定されるものではない。実施例中
の特注値は次の方法により測定した。The present invention will be specifically explained below with reference to Examples, but the present invention is not limited to these Examples. Custom values in Examples were measured by the following method.
ヘイズ：ＡＳＴＭ−Ｄ−１００３−５９Ｔに準じ、厚み
４閣の射出角板について測定した。Haze: Measured on an exit square plate with a thickness of 4 mm in accordance with ASTM-D-1003-59T.
極限粘度二〇−クロロフェノール溶媒を用い２５℃で測
定した。Intrinsic viscosity was measured at 25°C using 20-chlorophenol solvent.
実施例 １゜
テレフタル酸ジメチルとエチレングリコールのエステル
交換反応に引きつづ〈重縮合反応によって極限粘度０．
５４、平均長さ３■×長径３ｍＸ短径２■の円柱状チッ
プを得る。Example 1゜The transesterification reaction of dimethyl terephthalate and ethylene glycol was followed by a polycondensation reaction to achieve an intrinsic viscosity of 0.
54. Obtain a cylindrical chip with an average length of 3 mm x major axis of 3 m x short axis of 2 mm.
該ポリエステルチップを１５０℃、３時間熱風乾燥した
後、加熱窒素気流下で２２０℃、１５時間連続的に固相
重合を行ない９０重量部を採取した。After drying the polyester chips with hot air at 150° C. for 3 hours, solid phase polymerization was performed continuously at 220° C. for 15 hours under a heated nitrogen stream, and 90 parts by weight were collected.
得られた結晶性ポリエチレンテレフタレートはアセトア
ルデヒド含量１ ｐｐｍ 、結晶化度６３％、極限粘度
０．９０を有してい念。一方、インフタル酸成分をｌＯ
モルチ共重合した極限粘度０．６２ｉ有するポリエチレ
ン（テレ／イソ）フタレート共重合チップラ１３０℃、
１時間の予備乾燥後１５０℃、２時間本乾燥し１０重量
部を採取した。次いで両者を混合した後シリンダー温度
２７５℃の射出成形機を用い内容積２７ＣＣ，重量２６
１の円筒状有底パリソンを得、１０５℃の雰囲気下で二
軸延伸を行ない内容積４０房の２軸延伸ボトルを得た。The obtained crystalline polyethylene terephthalate had an acetaldehyde content of 1 ppm, a degree of crystallinity of 63%, and an intrinsic viscosity of 0.90. On the other hand, the inphthalic acid component was
Molch copolymerized polyethylene (tele/iso)phthalate copolymer with an intrinsic viscosity of 0.62i at 130°C,
After preliminary drying for 1 hour, main drying was performed at 150° C. for 2 hours, and 10 parts by weight was collected. Then, after mixing both, using an injection molding machine with a cylinder temperature of 275°C, the inner volume was 27CC and the weight was 26mm.
A cylindrical bottomed parison of No. 1 was obtained and biaxially stretched in an atmosphere at 105° C. to obtain a biaxially stretched bottle with an internal volume of 40 cells.
得られたボトルポリマー中のアセトアルデヒド含有量は
７．６ｐｐｍでかつ透明性に優れていた。（同一条件で
射出した４ｍ厚みの射出板ヘイズは５．６％であった）
。The resulting bottle polymer had an acetaldehyde content of 7.6 ppm and excellent transparency. (The haze of a 4m thick injection plate injected under the same conditions was 5.6%)
.
一方、結晶性ポリエチレンテレフタレートのみで射出成
形したものはアセトアルデヒド含有量７．０ｐｐｍであ
ったが、射出板ヘイズは１２％と透明性に劣っていた。On the other hand, the one injection-molded only with crystalline polyethylene terephthalate had an acetaldehyde content of 7.0 ppm, but the injection plate haze was 12%, which was poor in transparency.
実施例 ２゜
減圧下２１７℃で固相重合した結晶化度５７チ、アセト
アルデヒド含ｉ １．４ｐｙｎ、極限粘度０．７２ｉ有
する結晶化ポリ二ｆＬ／ンテレフタレート９０重二を部
とあらかじめ１６０℃、３時間乾燥したジエチレングリ
コール成分を７モルチ共重合した極限粘ｉ０．６２ｉ有
する共重合ポリエチレンテレフタレートチップ１０重量
部を混合し、シリンダ温度２８０℃の射出成形機を用い
４■厚の射出板を得た。Example 2 One part of crystallized poly(2fL/nterephthalate) having a crystallinity of 57 degrees, an acetaldehyde content of 1.4 pyn, and an intrinsic viscosity of 0.72 degrees polymerized in a solid state at 217 degrees Celsius under reduced pressure was preliminarily heated at 160 degrees Celsius and 10 parts by weight of copolymerized polyethylene terephthalate chips having an intrinsic viscosity i of 0.62i obtained by copolymerizing 7 mol of diethylene glycol component dried for 3 hours were mixed, and an injection molding machine with a cylinder temperature of 280° C. was used to obtain an injection plate with a thickness of 4 cm.
該射出板のヘイズは５．９％でアセトアルデヒド含有量
９．２ｐｐｍであり透明性、低アセトアルデヒド性共に
優れていた。The haze of the injection plate was 5.9%, the acetaldehyde content was 9.2 ppm, and both transparency and low acetaldehyde properties were excellent.
手続補正書
平成２年３月１２日
特許庁長官 吉 １）文 毅 殿
１、事件の表示
平成２年特許願第２８３４６号
２、発明の名称
中空成形用ポリエチレンテレフタレート配合物３、補正
をする者
事件との関係 特許出願人
名称 三井石油化学工業株式会社
４、代理人
５、補正により増加する発明の数
な し
６、補正の対象
明細書の特許請求の範囲および発明の詳細な説明／
７補正の内容
（１）特許請求の範囲を別紙のとおり補正する。Procedural amendment March 12, 1990 Commissioner of the Japan Patent Office Yoshi 1) Takeshi Moon 1, Description of the case 1990 Patent Application No. 28346 2, Name of the invention Polyethylene terephthalate compound for blow molding 3, Person making the amendment Relationship to the case Name of patent applicant Mitsui Petrochemical Industries, Ltd. 4, Agent 5, Number of inventions not increased by amendment 6, Claims of the specification to be amended and detailed description of the invention / 7 Amendment Contents (1) The scope of claims is amended as shown in the attached sheet.
（２）明細Ｓ（以下同じ）５頁１行の「共重合成分」を
「２゜６−ナフタレンジカルボン酸成分」と補正する。(2) "Copolymerization component" on page 5, line 1 of Specification S (the same applies hereinafter) is corrected to "2°6-naphthalene dicarboxylic acid component".
（３）７頁１１行〜８頁７行の「させうる 〜 挙げら
れる。」を「させうるものであり本発明では２，６−ナ
フタレンジカルボン酸成分が用いられる。」と補正する
。(3) From page 7, line 11 to page 8, line 7, "can be made to be mentioned" is corrected to "can be made to be made, and in the present invention, a 2,6-naphthalene dicarboxylic acid component is used."
（４）１１頁１行の「実施例１」を「参考例１」と補正
する。(4) Correct “Example 1” in line 1 on page 11 to “Reference Example 1.”
（５１１２頁８行の「実施例２」を「参考例２」と補正
する。(“Example 2” on page 5112, line 8 is corrected to “Reference Example 2.”
（６）１３頁２行の後に次の文を挿入する。(6) Insert the following sentence after the second line on page 13.
「実施例１
減圧下２１７℃で固相重合した結晶化度５７％、アセト
アルデヒド含量１．４ｐｐｍ、極限粘度０．７２を有す
る結晶性ポリエチレンテレフタレート９０重量部と、あ
らかじめ１６０℃、３時間乾燥した２、６−ナフタレン
ジカルボン酸成分を１０モル％共重合した極限粘度０．
８５を有する共重合ポリエチレンテレフタレートチップ
１０重量部を混合し、シリンダー温度２８０℃の射出成
形機を用い４ｍｍ厚の射出板を得た。該射出板のヘイズ
値は５．８％で、アセトアルデヒド含有量７．３ｐｐｍ
であり、透明性、低アセトアルデヒド性共に優れていた
。一方結晶性ポリエチレンテレフタレートのみで射出成
形したものはアセトアルデヒド含有ｆ！に７．０ｐｐｍ
であったが、射出板ヘイズは１２％と透明性は劣った。Example 1 90 parts by weight of crystalline polyethylene terephthalate having a crystallinity of 57%, an acetaldehyde content of 1.4 ppm, and an intrinsic viscosity of 0.72 were solid-phase polymerized at 217° C. under reduced pressure, and 2. , 6-naphthalene dicarboxylic acid component copolymerized with 10 mol %, intrinsic viscosity 0.
10 parts by weight of copolymerized polyethylene terephthalate chips having No. 85 were mixed, and an injection plate having a thickness of 4 mm was obtained using an injection molding machine with a cylinder temperature of 280°C. The haze value of the injection plate is 5.8%, and the acetaldehyde content is 7.3 ppm.
It was excellent in both transparency and low acetaldehyde properties. On the other hand, products injection molded only from crystalline polyethylene terephthalate contain acetaldehyde. 7.0ppm to
However, the haze of the injection plate was 12%, and the transparency was poor.
」特許請求の範囲
結晶化度が４０％以上、７０％未満で、アセトアルデヒ
ド含有量が５ ｐｐｍ未満であるポリエチレンテレフタ
レートおよび２，６−ナフタレンジカルボン酸成分を３
〜２０モル％共重合せしめた変性ポリエチレンテレフタ
レートからなり、かっ該共重合成分が全重合体混合物中
０５〜５モル％を占めろことを特徴とする。中空成形用
ポリエチレンテレフタレート配合物。``Claims: Polyethylene terephthalate and 2,6-naphthalenedicarboxylic acid components having a crystallinity of 40% or more and less than 70% and an acetaldehyde content of less than 5 ppm.
It consists of modified polyethylene terephthalate copolymerized with ~20 mol%, and is characterized in that the copolymerized component accounts for 0.5~5 mol% of the total polymer mixture. Polyethylene terephthalate compound for blow molding.
Claims (1)
ド含有量が５ｐｐｍ未満であるポリエチレンテレフタレ
ートおよびジカルボン酸を３〜２０モル％共重合せしめ
た変成ポリエチレンテレフタレートからなり、かつ該共
重合成分が全重合体混合物中０．５〜５モル％を占める
ことを特徴とする中空成形用ポリエチレンテレフタレー
ト配合物。It is made of modified polyethylene terephthalate obtained by copolymerizing 3 to 20 mol% of polyethylene terephthalate and dicarboxylic acid with a crystallinity of 40% or more and less than 70% and an acetaldehyde content of less than 5 ppm, and the copolymerization component is A polyethylene terephthalate blend for blow molding, characterized in that it accounts for 0.5 to 5 mol% in the combined mixture.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2834690A JPH02276856A (en) | 1990-02-09 | 1990-02-09 | Polyethylene terephthalate blend for blow molding |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2834690A JPH02276856A (en) | 1990-02-09 | 1990-02-09 | Polyethylene terephthalate blend for blow molding |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP14245981A Division JPH0231111B2 (en) | 1981-09-11 | 1981-09-11 | CHUKUSEIKEIYOHORIECHIRENTEREFUTAREETOHAIGOBUTSU |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02276856A true JPH02276856A (en) | 1990-11-13 |
| JPH0327584B2 JPH0327584B2 (en) | 1991-04-16 |
Family
ID=12246043
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2834690A Granted JPH02276856A (en) | 1990-02-09 | 1990-02-09 | Polyethylene terephthalate blend for blow molding |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02276856A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6727294B2 (en) * | 1998-07-28 | 2004-04-27 | Mitsubishi Engineering-Plastics Corporation | Thermoplastic resin composition containing a naphthalene dicarboxylic acid moiety and an aliphatic diol moiety |
| JP2006150957A (en) * | 2004-11-05 | 2006-06-15 | Toyobo Co Ltd | Manufacturing method for polyester preform and manufacturing method for polyester stretch-molded object |
| JP2010163513A (en) * | 2009-01-14 | 2010-07-29 | Teijin Dupont Films Japan Ltd | Biaxially drawn polyester film for optical use |
-
1990
- 1990-02-09 JP JP2834690A patent/JPH02276856A/en active Granted
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6727294B2 (en) * | 1998-07-28 | 2004-04-27 | Mitsubishi Engineering-Plastics Corporation | Thermoplastic resin composition containing a naphthalene dicarboxylic acid moiety and an aliphatic diol moiety |
| JP2006150957A (en) * | 2004-11-05 | 2006-06-15 | Toyobo Co Ltd | Manufacturing method for polyester preform and manufacturing method for polyester stretch-molded object |
| JP2010163513A (en) * | 2009-01-14 | 2010-07-29 | Teijin Dupont Films Japan Ltd | Biaxially drawn polyester film for optical use |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0327584B2 (en) | 1991-04-16 |
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