JP3597943B2 - Polyester resin composition and hollow molded article comprising the same - Google Patents
Polyester resin composition and hollow molded article comprising the same Download PDFInfo
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- JP3597943B2 JP3597943B2 JP12322196A JP12322196A JP3597943B2 JP 3597943 B2 JP3597943 B2 JP 3597943B2 JP 12322196 A JP12322196 A JP 12322196A JP 12322196 A JP12322196 A JP 12322196A JP 3597943 B2 JP3597943 B2 JP 3597943B2
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- resin composition
- polyester resin
- molded article
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Description
【0001】
【発明の属する技術分野】
本発明は熱可塑ポリエステル樹脂組成物及びその組成物を用いた中空成形体に関し、さらに詳しくは、透明性及び成形性等に優れたポリエステル樹脂組成物及びその中空成形体に関する。
【0002】
【従来の技術】
従来より調味料、油、ジュース、炭酸飲料、ビール、日本酒、化粧品、洗剤等の容器用の素材としてガラスが広く使用されていた。しかし、ガラスは製造コストが高いので通常使用後の容器を回収し、循環再生する方法が採用されている。また、ガラス容器は破損し易く、取り扱いが不便であるなどの欠点があった。
【0003】
ガラス容器のこれらの欠点を解消しようとしてガラス容器からプラスチック容器への転換が急速に進んでいる。これらのプラスチック素材のうちでポリエチレンテレフタレートは機械的強度、耐熱性、透明性およびガスバリアー性に優れているので、ジュース、清涼飲料水、炭酸飲料、調味料、洗剤、化粧品等の容器の素材として採用されている。
【0004】
しかしながら、用途によっては紫外線遮断能が十分でないため外部からの紫外線の照射により内容物の食品が変質して味が落ちたり、化粧品が退色して商品価値を低めるという問題点がある。また、耐熱性が十分でないために完全な殺菌、高温充填ができない等の問題点がある。
【0005】
最近、ポリエチレンテレフタレートにポリエチレンナフタレンジカルボキシレートを配合すれば、かような問題を改善できることが知られてきた。
【0006】
しかしながら、このポリエチレンテレフタレートとポリエチレンナフタレンジカルボキシレートとは相溶性に劣り、単に両者をブレンドしただけでは得られるブレンド物は白化し、不透明になるという問題点があることも知られている。
【0007】
また、十分に相溶化させ透明性の良好なポリマーとすると、溶融成形後のブロー成形でドローダウンしてしまい賦形することが難しい。
【0008】
【発明が解決しようとする課題】
このような問題点を解決するために、本発明者らは鋭意検討したところ、主たる繰り返し単位がエチレンテレフタレートである熱可塑ポリエステルと主たる繰り返し単位がエチレンナフタレンジカルボキシレートである熱可塑ポリエステルとの溶融混合体ポリエステルについて、この融点、固有粘度及び溶融混合体ポリエステルに占めるエチレンナフタレンジカルボキシレート単位の割合が式(1)、(2)で表わされる透明性及び成形性の優れたポリエステル樹脂組成物及びその中空成形体が得られることを見出し、本発明を完成するに至った。
【0009】
本発明の課題は、中空成形体を製造するに際し、成形体として透明性及び成形性の優れたポリエステル樹脂組成物を得ることにある。
【0010】
【課題を解決するための手段】
本発明者は、かかる問題点に着目し、主たる繰り返し単位がエチレンテレフタレートである熱可塑ポリエステルと主たる繰り返し単位がエチレンナフタレンジカルボキシレートである熱可塑性ポリエステルとの溶融混合体ポリエステルについて、その融点、固有粘度及び溶融混合体ポリエステルに占めるエチレンナフタレンジカルボキシレート単位の割合(A)が次の式(1)及び式(2)で表わされる(A)が5〜45重量%の範囲において透明性及び成形性の優れたポリエステル樹脂組成物である。
【0011】
【数2】
更に、本発明のポリエステル樹脂組成物は中空成形体に成形したとき、成形性が良好であって、中空成形体は透明性が維持され、しかもエチレンナフタレンジカルボキシレート成分の作用によって、中空成形体は紫外線遮蔽性を有する利点がある。
【0012】
本発明を説明する。
【0013】
本発明の混合体ポリエステルを溶融ブレンドして準備するにあたっては、通常のゴムまたはプラスチックスを溶融ブレンドするのに用いられる装置、例えば、熱ロール、バンバリーミキサー、押出機などを利用することが出来るが、通常は一軸または二軸の押出機が用いられる。ブレンド温度は配合系が熱分解しはじめる温度以下の条件が設定されるものであって、その温度は260〜300℃、好ましくは270〜290℃の温度にて行われる。
【0014】
本発明の溶融混合体ポリエステルは相溶化が進むと透明となり、その相溶化度合は融点で表わされる[式(2)]。
【0015】
また、この混合体に占めるエチレンナフタレンジカルボキシレート単位の割合及び相溶化度合いでの溶融混合体の成形性は固有粘度(IV)で表わされる[式(1)]。
【0016】
溶融混合体ポリエステルの融点、固有粘度及び溶融混合体ポリエステルに占めるエチレンナフタレンジカルボキシレート単位の割合を式(1)及び式(2)の範囲で調整することにより透明性及び成形性の優れたポリエステル樹脂組成物が得られる。
【0017】
この混合体ポリエステルに含まれるエチレンナフタレンジカルボキシレート単位の重量比率(A)は5重量%〜45重量%である。
【0018】
エチレンナフタレンジカルボキシレート単位が5重量%未満及び45重量%を超える場合は透明性、成形性のバランスを式(1)及び式(2)で規定することが困難である。
【0019】
【数3】
式(1):
0.46×(A)/100−0.01×融点+3.05≦固有粘度≦0.46×(A)/100−0.01×融点+3.35
式(2):
−121.43×(A)/100+248.57≦融点≦−33.33×(A)/100+250.0
本発明におけるエチレンテレフタレートを主たる繰り返し単位とする熱可塑性ポリエステルはエチレンテレフタレートのホモポリマーを主たる対象とするが、テレフタル酸成分を例えばイソフタル酸、ナフタレンジカルボン酸、ジフェニルジカルボン酸、ジフェノキシエタンジカルボン酸、ジフェニルエーテルジカルボン酸、ジフェニルスルホンジカルボン酸等のような他の芳香族ジカルボン酸、ヘキサヒドロテレフタル酸、ヘキサヒドロイソフタル酸等の如き脂環族ジカルボン酸、アジピン酸、セバチン酸、アゼライン酸等のような脂肪族ジカルボン酸、p―β―ヒドロキシエトキシ安息香酸、ε―オキシカプロン酸等のようなオキシ酸等の他の二官能性カルボン酸の1種以上を共重合化したものでもよい。
【0020】
更に、エチレングリコールの一部を、例えばトリメチレングリコール、テトラメチレングリコール、ヘキサメチレングリコール、デカメチレングリコール、ネオペンチルグリコール、ジエチレングリコール、1,1―シクロヘキサンジメタノール、1,4―シクロヘキサンジメタノール、2,2―ビス(4′―β―ヒドロキシフェニル)プロパンカ、ビス(4′―β―ヒドロキシエトキシフェニル)スルホン酸等の他の多官能化合物の1種以上で置換して5wt%以下の範囲で共重合せしめたコポリマーであってもよい。
【0021】
主たる繰り返し単位がエチレンナフタレンジカルボキシレートである熱可塑性ポリエステルは、ポリエチレン―2,6―ナフタレンジカルボキシレートのホモポリマーを主たる対象とするか、2,6―ナフタレンジカルボン酸成分の一部を2,7―、1,5―、1,7―その他のナフタレンジカルボン酸の異性体或はテレフタル酸或は前述の多官能性カルボン酸の1種以上で、及び又はエチレングリコール成分の1部を前述の多官能性グリコールの1種以上で各20wt%以下の範囲において共重合せしめたコポリマーであってもよい。
【0022】
本発明に係るポリエステル樹脂組成物は、そのまま、或はシート状、板状、管状、中空状、容器等の形状で用いることができる。
【0023】
本発明に係る中空成形体は一般の成形法、例えば射出ブロー成形、配向ブロー、押出ブロー法等が適用される。配向ブロー法の適当な例としては、ポリマーを適当な形状の中空円筒有底状の非晶性プリフォームとする(例えば、長さ15cm、内径1cm、外径1.4cm)。
【0024】
そして、ポリマーのガラス転移点(Tg)以上にプリフォームを余熱し、その容器の表面積を約1.5〜1.6倍程度まで延伸せしめる。なお、容器の熱処理は適宜に行うことができる。
【0025】
かくして、通常の方法によって製造され本発明の中空成形体は透明性、外観に優れているので種々の用途に利用することができ、例えば、調味料、油、酒類、化粧品、洗剤、清涼飲料容器、炭酸飲料、ジュースの容器として使用することができる。
【0026】
【実施例】
以下、実施例により本発明を補説する。なお主な物性値の測定条件は次の通りである。
【0027】
(1)固有粘度(IV):
テトラクロロエタン:フェノール=4:6の混合溶媒を用いて35℃で測定したもの。
【0028】
(2)融点(Tm):
示差熱量計(TA Instrument 製、DSC2100を使用)により5℃/min.の昇温速度で測定。
【0029】
(3)ヘーズ:
日本電色工業社製濁度計にて測定。
【0030】
[実施例1〜3]
IV1.0のポリエチレンテレフタレート(PET)及びIV0.71のポリエチレンナフタレンジカルボキシレート(PEN)チップを各々160℃で5時間熱風乾燥した後Automatick社製二軸押出機を用いてシリンダー温度285〜305℃、スクリュー回転数120〜250rpmにて溶融ブレンドした。溶融ブレンドは上記の二軸押出機の吐出口から吐出したものを冷却水によって急冷し、カッターにて直径、長さともにほぼ約3mmにカットしたペレット(チップ)とした。得られたチップのIV、Tmは表1の通りであった。
【0031】
このチップを160℃で5時間熱風乾燥した後、名機製作所製M―100DM射出成形機を用い、シリンダー設定275℃とし、10℃の冷却水で冷却してある金型内に射出成形してプリフォームを得た。このプリフォームは円筒状胴部の外径が22〜24mm、肉厚3.5mm、全長150mmの一端が有底化された形状のものであり、実質的に非晶質の無色透明な成形体であった。
【0032】
この有底プリフォームを100〜130℃でボトル状金型内で軸方向に延伸し、かつ10〜20kg/cm2の窒素ガスにより横方向に膨脹せしめ、胴部外径82mm、全高280mm、内容積1450〜1550mlのボトルを成形した。
【0033】
得られたボトルの外観、胴部延伸倍率、口部・肩部、胴部、底部の重量分布及び胴部を用いて測定したヘーズを表1に示す。
【0034】
【表1】
【0035】
[実施例4]
IV1.1のPET及びIV0.80のPENチップを各々160℃で5時間熱風乾燥した後Automatick社製二軸押出機を用いてシリンダー温度295℃、スクリュー回転数180rpmにて溶融ブレンドした。溶融ブレンドは上記の二軸押出機の吐出口から吐出したものを冷却水によって急冷し、カッターにて直径、長さ共にほぼ約3mmにカットしたチップとした。得られたチップのIV、Tmは表1の通りであった。
【0036】
そのチップを160℃で5時間熱風乾燥した後、実施例1〜3と同様に名機製作所製M―100DM射出成形機を用い、シリンダー設定275℃とし、10℃の冷却水で冷却してある金型内に射出成形してプリフォームを得た。このプリフォームは円筒状胴部の外径が22〜24mm、肉厚3.5mm、全長150mmの一端が有底化された形状のものであり実質的に非晶質の無色透明な成形体であった。
【0037】
この有底プリフォームを130〜140℃でボトル状金型内で軸方向に延伸し、かつ10〜20kg/cm2の窒素ガスにより横方向に膨脹せしめ、胴部外径82mm、全高300mm、内容積1450〜1550mlのボトルを成形した。
【0038】
得られたボトルの外観、胴部延伸倍率、口部・肩部、胴部、底部の重量分布及び胴部を用いて測定したヘーズを表1に示す。
【0039】
[比較例1]
IV0.70のPET及びIV0.56のPENチップを用い、実施例1〜3と同様に評価した。
【0040】
[比較例2]
IV1.1のPET及びIV0.70のPENチップを用い、実施例1〜3と同様に評価した。
【0041】
[比較例3]
IV0.83のPET及びIV0.71のPENチップを用い、実施例1〜3と同様に評価した。
【0042】
【発明の効果】
本発明により透明性及び成形性の優れたポリエステル樹脂組成物及びそれからなる中空成形体を得ることが可能となった。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a thermoplastic polyester resin composition and a hollow molded article using the composition, and more particularly, to a polyester resin composition having excellent transparency and moldability and a hollow molded article thereof.
[0002]
[Prior art]
Conventionally, glass has been widely used as a material for containers such as seasonings, oils, juices, carbonated drinks, beer, sake, cosmetics, and detergents. However, since the production cost of glass is high, a method of recovering the container after normal use and recycling it is adopted. Further, the glass container has drawbacks such as easy breakage and inconvenient handling.
[0003]
The conversion from glass containers to plastic containers is rapidly progressing in an attempt to overcome these disadvantages of glass containers. Among these plastic materials, polyethylene terephthalate has excellent mechanical strength, heat resistance, transparency and gas barrier properties, so it is used as a material for containers for juices, soft drinks, carbonated drinks, seasonings, detergents, cosmetics, etc. Has been adopted.
[0004]
However, depending on the application, the ultraviolet ray blocking ability is not sufficient, so that the irradiation of ultraviolet rays from the outside deteriorates the content of the food and deteriorates the taste, or the cosmetics are discolored to lower the commercial value. Further, there is a problem that complete sterilization and high-temperature filling cannot be performed due to insufficient heat resistance.
[0005]
Recently, it has been known that such a problem can be solved by blending polyethylene naphthalene dicarboxylate with polyethylene terephthalate.
[0006]
However, it is also known that polyethylene terephthalate and polyethylene naphthalenedicarboxylate are inferior in compatibility, and there is a problem in that a blend obtained by simply blending both becomes white and opaque.
[0007]
Further, if the polymer is sufficiently compatibilized to obtain a polymer having good transparency, it is difficult to form the polymer because it is drawn down by blow molding after melt molding.
[0008]
[Problems to be solved by the invention]
In order to solve such problems, the present inventors have conducted intensive studies, and found that the melting of a thermoplastic polyester whose main repeating unit is ethylene terephthalate and a thermoplastic polyester whose main repeating unit is ethylene naphthalene dicarboxylate are performed. For the mixed polyester, the melting point, the intrinsic viscosity and the ratio of the ethylene naphthalenedicarboxylate unit in the molten mixed polyester are represented by the formulas (1) and (2). The present inventors have found that such a hollow molded article can be obtained, and have completed the present invention.
[0009]
Object of the present invention, when manufacturing the hollow molded body is to obtain an excellent polyester resin composition of transparency and moldability as shaped bodies.
[0010]
[Means for Solving the Problems]
The present inventors have focused on such a problem, and have a melting point and specific properties of a melt-mixed polyester of a thermoplastic polyester whose main repeating unit is ethylene terephthalate and a thermoplastic polyester whose main repeating unit is ethylene naphthalene dicarboxylate. When the viscosity and the ratio (A) of ethylene naphthalenedicarboxylate units in the polyester of the melt mixture are represented by the following formulas (1) and (2), (A) is in the range of 5 to 45% by weight, and transparency and molding are performed. It is a polyester resin composition having excellent properties.
[0011]
(Equation 2)
Further, when the polyester resin composition of the present invention is molded into a hollow molded article, the moldability is good, the hollow molded article is kept transparent, and the hollow molded article is formed by the action of the ethylene naphthalenedicarboxylate component. Has the advantage of having an ultraviolet shielding property.
[0012]
The present invention will be described.
[0013]
In preparing the mixed polyester of the present invention by melt-blending, it is possible to use a device used for melt-blending ordinary rubber or plastics, such as a hot roll, a Banbury mixer, and an extruder. Usually, a single or twin screw extruder is used. The blending temperature is set at a temperature not higher than the temperature at which the blending system starts to thermally decompose, and the temperature is set at 260 to 300 ° C, preferably 270 to 290 ° C.
[0014]
The molten polyester of the present invention becomes transparent as the compatibilization proceeds, and the degree of the compatibilization is represented by the melting point [Formula (2)].
[0015]
Further, the moldability of the molten mixture in terms of the ratio of ethylene naphthalenedicarboxylate units in the mixture and the degree of compatibilization is represented by the intrinsic viscosity (IV) [Formula (1)].
[0016]
Polyester excellent in transparency and moldability by adjusting the melting point, intrinsic viscosity of the melt-mixed polyester and the proportion of ethylene naphthalenedicarboxylate units in the melt-mixed polyester within the ranges of formulas (1) and (2). A resin composition is obtained.
[0017]
The weight ratio (A) of the ethylene naphthalenedicarboxylate units contained in the mixed polyester is 5% by weight to 45% by weight.
[0018]
When the amount of the ethylene naphthalenedicarboxylate unit is less than 5% by weight or more than 45% by weight, it is difficult to define the balance between transparency and moldability by the formulas (1) and (2).
[0019]
(Equation 3)
Equation (1):
0.46 × (A) /100-0.01×melting point + 3.05 ≦ intrinsic viscosity ≦ 0.46 × (A) /100-0.01×melting point + 3.35
Equation (2):
−121.43 × (A) /100+248.57≦melting point ≦ −33.33 × (A) /100+250.0
The thermoplastic polyester having ethylene terephthalate as a main repeating unit in the present invention is mainly intended for a homopolymer of ethylene terephthalate. Other aromatic dicarboxylic acids such as dicarboxylic acid, diphenylsulfone dicarboxylic acid, etc .; alicyclic dicarboxylic acids such as hexahydroterephthalic acid, hexahydroisophthalic acid, etc .; aliphatics such as adipic acid, sebacic acid, azelaic acid, etc. One obtained by copolymerizing one or more other difunctional carboxylic acids such as oxyacids such as dicarboxylic acid, p-β-hydroxyethoxybenzoic acid, and ε-oxycaproic acid may be used.
[0020]
Further, a part of ethylene glycol may be used, for example, trimethylene glycol, tetramethylene glycol, hexamethylene glycol, decamethylene glycol, neopentyl glycol, diethylene glycol, 1,1-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, Substituted with at least one other polyfunctional compound such as 2-bis (4'-β-hydroxyphenyl) propaneca, bis (4'-β-hydroxyethoxyphenyl) sulfonic acid and copolymerized in a range of 5 wt% or less. It may be a stiffened copolymer.
[0021]
The thermoplastic polyester whose main repeating unit is ethylene naphthalenedicarboxylate is mainly intended for a homopolymer of polyethylene-2,6-naphthalenedicarboxylate, or a portion of 2,6-naphthalenedicarboxylic acid component is 2,2. 7-, 1,5-, 1,7-other isomers of naphthalenedicarboxylic acid or terephthalic acid or one or more of the above-mentioned polyfunctional carboxylic acids and / or one part of the ethylene glycol component It may be a copolymer obtained by copolymerizing one or more polyfunctional glycols in a range of 20 wt% or less.
[0022]
The polyester resin composition according to the present invention can be used as it is, or in the form of a sheet, plate, tube, hollow, container, or the like.
[0023]
For the hollow molded article according to the present invention, a general molding method, for example, injection blow molding, orientation blow, extrusion blow method or the like is applied. As a suitable example of the orientation blow method, the polymer is an amorphous preform having a hollow cylindrical bottom having a suitable shape (for example, a length of 15 cm, an inner diameter of 1 cm, and an outer diameter of 1.4 cm).
[0024]
Then, the preform is preheated to a temperature equal to or higher than the glass transition point (Tg) of the polymer, and the surface area of the container is stretched to about 1.5 to 1.6 times. In addition, the heat treatment of the container can be appropriately performed.
[0025]
Thus, the hollow molded article of the present invention produced by a usual method is excellent in transparency and appearance and can be used for various uses. For example, seasonings, oils, alcoholic beverages, cosmetics, detergents, soft drink containers Can be used as a container for carbonated drinks, juices.
[0026]
【Example】
Hereinafter, the present invention will be supplemented by examples. The main measurement conditions of the physical properties are as follows.
[0027]
(1) Intrinsic viscosity (IV):
Measured at 35 ° C. using a mixed solvent of tetrachloroethane: phenol = 4: 6.
[0028]
(2) Melting point (Tm):
5 ° C./min. Measured at a heating rate of
[0029]
(3) Haze:
Measured by Nippon Denshoku Industries turbidity meter.
[0030]
[Examples 1 to 3]
Polyethylene terephthalate (PET) IV IV and polyethylene naphthalene dicarboxylate (PEN) IV 0.71 chips were each dried with hot air at 160 ° C. for 5 hours, and then cylinder temperature was 285-305 ° C. using a twin screw extruder manufactured by Automatick. The melt blending was performed at a screw rotation speed of 120 to 250 rpm. The melt-blended product was discharged from the discharge port of the twin-screw extruder, rapidly cooled with cooling water, and cut into a pellet (chip) having a diameter and a length of about 3 mm with a cutter. Table 1 shows IV and Tm of the obtained chip.
[0031]
This chip was dried with hot air at 160 ° C. for 5 hours, and then injection-molded into a mold cooled with 10 ° C. cooling water using a M-100DM injection molding machine manufactured by Meiki Seisakusho at a cylinder setting of 275 ° C. I got a preform. This preform has a cylindrical body having an outer diameter of 22 to 24 mm, a thickness of 3.5 mm, a total length of 150 mm, and one end having a bottom, and is a substantially amorphous colorless and transparent molded body. Met.
[0032]
The bottomed preform was stretched axially within the bottle-shaped mold at 100 to 130 ° C., and allowed to expand in the lateral direction by the nitrogen gas in the 10-20 kg / cm 2, the body portion outer diameter 8 2 mm, Height 280 mm, A bottle having an internal volume of 1450 to 1550 ml was molded.
[0033]
Table 1 shows the appearance of the resulting bottle, the body stretching ratio, the weight distribution of the mouth / shoulder, the body, and the bottom, and the haze measured using the body.
[0034]
[Table 1]
[0035]
[Example 4]
The PET of IV1.1 and the PEN chip of IV0.80 were each dried with hot air at 160 ° C. for 5 hours, and then melt-blended using a twin screw extruder manufactured by Automatic at a cylinder temperature of 295 ° C. and a screw rotation speed of 180 rpm. The melt-blended product was rapidly cooled with cooling water from the discharge port of the twin-screw extruder, and cut into chips of approximately 3 mm in both diameter and length with a cutter. Table 1 shows IV and Tm of the obtained chip.
[0036]
After the chips were dried with hot air at 160 ° C. for 5 hours, the cylinders were set at 275 ° C. and cooled with 10 ° C. cooling water using an M-100DM injection molding machine manufactured by Meiki Seisakusho in the same manner as in Examples 1 to 3. A preform was obtained by injection molding in a mold. This preform has a cylindrical body having an outer diameter of 22 to 24 mm, a wall thickness of 3.5 mm, and a total length of 150 mm, and has a bottom with one end, and is a substantially amorphous colorless and transparent molded body. there were.
[0037]
The bottomed preform was stretched axially within the bottle-shaped mold at 130 to 140 ° C., and allowed to expand in the lateral direction by the nitrogen gas in the 10-20 kg / cm 2, the body portion outer diameter 8 2 mm, total height 300 mm, A bottle having an internal volume of 1450 to 1550 ml was molded.
[0038]
Table 1 shows the appearance of the resulting bottle, the body stretching ratio, the weight distribution of the mouth / shoulder, the body, and the bottom, and the haze measured using the body.
[0039]
[Comparative Example 1]
Evaluation was performed in the same manner as in Examples 1 to 3, using PET having an IV of 0.70 and a PEN chip having an IV of 0.56.
[0040]
[Comparative Example 2]
Evaluation was performed in the same manner as in Examples 1 to 3, using a PET of IV1.1 and a PEN chip of IV0.70.
[0041]
[Comparative Example 3]
Evaluation was performed in the same manner as in Examples 1 to 3, using PET having an IV of 0.83 and a PEN chip having an IV of 0.71.
[0042]
【The invention's effect】
ADVANTAGE OF THE INVENTION By this invention, it became possible to obtain the polyester resin composition excellent in transparency and moldability, and the hollow molded body which consists of it.
Claims (2)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
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JP12322196A JP3597943B2 (en) | 1996-05-17 | 1996-05-17 | Polyester resin composition and hollow molded article comprising the same |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
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JP12322196A JP3597943B2 (en) | 1996-05-17 | 1996-05-17 | Polyester resin composition and hollow molded article comprising the same |
Publications (2)
Publication Number | Publication Date |
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JPH09302205A JPH09302205A (en) | 1997-11-25 |
JP3597943B2 true JP3597943B2 (en) | 2004-12-08 |
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JP12322196A Expired - Lifetime JP3597943B2 (en) | 1996-05-17 | 1996-05-17 | Polyester resin composition and hollow molded article comprising the same |
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Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
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AU7937898A (en) * | 1997-07-04 | 1999-01-25 | Mitsubishi Plastics Inc. | Polyester resin composition and bottle produced from the resin composition |
DE19946323A1 (en) | 1999-09-28 | 2001-03-29 | Bayer Ag | Polymer blends containing modified polyester |
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1996
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