JPH0420774B2 - - Google Patents
Info
- Publication number
- JPH0420774B2 JPH0420774B2 JP3582189A JP3582189A JPH0420774B2 JP H0420774 B2 JPH0420774 B2 JP H0420774B2 JP 3582189 A JP3582189 A JP 3582189A JP 3582189 A JP3582189 A JP 3582189A JP H0420774 B2 JPH0420774 B2 JP H0420774B2
- Authority
- JP
- Japan
- Prior art keywords
- polyester
- mol
- present
- polyethylene terephthalate
- hydroxyethoxy
- 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.)
- Expired - Lifetime
Links
- 229920000728 polyester Polymers 0.000 claims description 32
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 25
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 25
- -1 Polyethylene terephthalate Polymers 0.000 claims description 23
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 22
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 12
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 7
- IAXFZZHBFXRZMT-UHFFFAOYSA-N 2-[3-(2-hydroxyethoxy)phenoxy]ethanol Chemical compound OCCOC1=CC=CC(OCCO)=C1 IAXFZZHBFXRZMT-UHFFFAOYSA-N 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 5
- WTPYFJNYAMXZJG-UHFFFAOYSA-N 2-[4-(2-hydroxyethoxy)phenoxy]ethanol Chemical compound OCCOC1=CC=C(OCCO)C=C1 WTPYFJNYAMXZJG-UHFFFAOYSA-N 0.000 claims description 3
- 230000035699 permeability Effects 0.000 description 13
- 238000000034 method Methods 0.000 description 11
- KKEYFWRCBNTPAC-UHFFFAOYSA-N terephthalic acid group Chemical group C(C1=CC=C(C(=O)O)C=C1)(=O)O KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 8
- 229920001577 copolymer Polymers 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 description 3
- 229920001634 Copolyester Polymers 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 239000004677 Nylon Substances 0.000 description 2
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 238000000071 blow moulding Methods 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 238000010030 laminating Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229920001778 nylon Polymers 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000005033 polyvinylidene chloride Substances 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-N 0.000 description 1
- QCDWFXQBSFUVSP-UHFFFAOYSA-N 2-phenoxyethanol Chemical compound OCCOC1=CC=CC=C1 QCDWFXQBSFUVSP-UHFFFAOYSA-N 0.000 description 1
- 229910005793 GeO 2 Inorganic materials 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- ORLQHILJRHBSAY-UHFFFAOYSA-N [1-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1(CO)CCCCC1 ORLQHILJRHBSAY-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003856 thermoforming Methods 0.000 description 1
- 229920006230 thermoplastic polyester resin Polymers 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D1/00—Containers having bodies formed in one piece, e.g. by casting metallic material, by moulding plastics, by blowing vitreous material, by throwing ceramic material, by moulding pulped fibrous material, by deep-drawing operations performed on sheet material
- B65D1/02—Bottles or similar containers with necks or like restricted apertures, designed for pouring contents
- B65D1/0207—Bottles or similar containers with necks or like restricted apertures, designed for pouring contents characterised by material, e.g. composition, physical features
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、耐ガス透過性、耐熱性、耐衝撃性、
透明性等に優れたポリエステル容器に関し、更に
詳しくはポリエステル二軸延伸容器に関する。
〔従来の技術〕
ポリエチレンテレフタレート樹脂（以下PET
と呼ぶ場合がある）の二軸延伸成形品は、機械的
強度、剛性、耐熱性、耐薬品性、耐油性、透明性
等の優れた性質を活かしてフイルム、シート及び
容器等の包装材料として広く用いられている。し
かしながら、PETを主体とした二軸延伸吹込成
形された容器にも欠点がないわけではなく、例え
ば充分な熱固定ができないこと、耐ガス透過性が
充分でないこと等の欠点を有している。中でも耐
ガス透過性の不充分さは、PET本来の材質に起
因するものであり、成形加工により解決すること
が困難であつた。
PET容器の耐ガス透過性を改良する方法とし
ては、PETに比べて耐ガス透過性に優れる樹脂、
例えばポリ塩化ビニリデン、エチレン・酢酸ビニ
ル共重合体鹸化物、ポリアミド等と積層する方法
が考えられるが、かかる樹脂はいずれにしても
PETとの接着性に劣るので、たとえPETで挟ん
だ三層構造としても、延伸成形あるいは使用時に
一部が剥離し耐ガス透過性が低下する虞れがあつ
た。
又、一方では、PETに代えてポリエチレンイ
ソフタレート又はその共重合体を用いること（特
開昭59−64624号公報）、あるいはポリエチレンイ
ソフタレートとポリエチレンテレフタレート等と
をブレンドする方法（特開昭59−64658号公報）
等が提案されている。しかしながら、いずれにし
てもポリエチレンイソフタレートを用いる方法は
高融点のオリゴマーを含んでいるために、成形品
に好ましからざる異物として混入する。同じく
PETの耐ガス透過性を改良する方法として、イ
ソフタル酸を用いるとともに、ジヒドロキシ化合
物としてエチレングリコールとともに１，３ビス
（２−ヒドロキシエトキシ）ベンゼンを共重合し
たコポリエステル（特開昭58−167617号公報）が
提案されている。
しかしながら、かかるコポリエステルも単独で
の成形品は、強度が低く耐熱性も不良であり実用
に耐えない。
〔発明が解決しようとする課題〕
かかる状況に鑑み、本発明者は、耐ガス透過性
に優れ且つ耐熱性、耐衝撃性、透明性等をも有す
る二軸延伸ポリエステル容器を得るべく種々検討
した結果、ポリエチレンテレフタレートと、特定
量のイソフタル酸及び１，３ビス（２−ヒドロキ
シエトキシ）ベンゼンあるいは１，４ビス（２−
ヒドロキシエトキシ）ベンゼンを共重合した共重
合ポリエステルとを混合した組成物を二軸延伸成
形することにより、上記目的が達成できることが
分かり本発明を完成するに至つた。
〔課題を解決するための手段〕
すなわち本発明は、
(1)(a)ポリエチレンテレフタレート(A)５ないし95
重量％と、(b)ジカルボン酸成分の20ないし100モ
ル％がイソフタル酸からなり、ジヒドロキシ化合
物成分の５ないし90モル％が、１，３ビス（２−
ヒドロキシエトキシ）ベンゼンあるいは１，４ビ
ス（ヒドロキシエトキシ）ベンゼン及び10ないし
95モル％がエチレングリコールからなる共重合ポ
リエステル(B)５ないし95重量％とからなるポリエ
ステル組成物を二軸延伸成形してなることを特徴
とするポリエステル容器である。
本発明におけるポリエチレンテレフタレート(A)
とは、通常ジカルボン酸成分の80モル％を越え
る、好ましくは90モル％以上がテレフタル酸であ
り、グリコール成分の80モル％以上、好ましくは
90モル％以上がエチレングリコールである結晶性
の熱可塑性ポリエステル樹脂である。尚、残余の
他のジカルボン酸としては、具体的には例えばイ
ソフタル酸、ジフエニルエーテルル−４，４−ジ
カルボン酸、ナフタリン−１，４−または２，６
−ジカルボン酸等の芳香族ジカルボン酸、シユウ
酸、コハク酸、アジピン酸、セバシン酸、ウンデ
カジカルボン酸等の脂肪族ジカルボン酸、ヘキサ
ヒドロテレフタル酸等の脂環族ジカルボン酸等が
挙げられ、他のグリコール成分としては、プロピ
レングリコール、１，４−ブタンジオール、ネオ
ペンチルグリコール等の脂肪族グリコール、シク
ロヘキサンジメタノール等の脂環族グリコール、
ビスフエノールＡ等の芳香族ジヒドロキシ化合物
等が挙げられる。
本発明におけるポリエチレンテレフタレート(A)
の分子量は、容器を製造し得るものであれば特に
限定されないが、通常オルトクロロフエノール25
℃における極限粘度〔η〕（以下と呼ぶ）が0.6
dl／ｇ以上、好ましくは0.8ないし0.85dl／ｇの
範囲のものである。
本発明における共重合ポリエステル(B)とは、ジ
カルボン酸成分の20ないし100モル％、好ましく
は50ないし100モル％がイソフタル酸からなり、
ジヒドロキシ化合物成分の５ないし90モル％、好
ましくは10ないし85モル％が１，３ビス（２−ヒ
ドロキシエトキシ）ベンゼンあるいは１，４ビス
（２−ヒドロキシエトキシ）ベンゼン及び10ない
し95モル％、好ましくは15ないし90モル％がエチ
レングリコールからなる共重合ポリエステルであ
る。ジカルボン酸成分の100モル％未満がイソフ
タル酸である場合、他のジカルボン酸成分として
はテレフタル酸が使用できる。この場合のテレフ
タル酸の量は80モル％以下、好ましくは50モル％
以下である。イソフタル酸が20モル％未満のもの
を用いても耐ガス透過性が改良されず、１，３ビ
ス（２−ヒドロキシエトキシ）ベンゼンあるいは
１，４ビス（ヒドロキシエトキシ）ベンゼンが５
モル％未満のものを用いてもオリゴマーの発生を
抑制できない。一方90モル％を越えるものは、重
縮合の速度が低下して望ましくない。
前記共重合ポリエステル(B)の分子量は、容器を
製造し得るものであれば特に限定はされないが、
通常オルトクロロフエノール溶媒におけるが
0.6dl／ｇ以上、好ましくは0.8ないし0.85dl／ｇ
の範囲のものである。
本発明におけるポリエステル組成物は、前記ポ
リエチレンテレフタレート(A)５ないし95重量％、
好ましくは50ないし90重量％、及び共重合ポリエ
ステル(B)５ないし95重量％、好ましくは10ないし
50重量％から構成される。共重合ポリエステル(B)
の量が５重量％未満では、耐ガス透過性が改良さ
れず、一方95重量％を越えるものは耐熱性、耐衝
撃性等が低下する。
本発明で用いるポリエステル組成物を得るに
は、前記ポリエチレンテレフタレート(A)及び共重
合ポリエステル(B)を、前記範囲で種々公知の方法
例えばヘンシエルミキサー、Ｖ−ブレンダー、リ
ボンブレンダー、タンブラーブレンダー等で混合
する方法、更には、混合後一軸押出機、二軸押出
機、ニーダー、バンバリーミキサー等で溶融混練
し造粒あるいは粉砕する方法を採用することがで
きる。
本発明で用いるポリエステル組成物には、耐熱
安定剤、耐候安定剤、帯電防止剤、滑剤、離型
剤、核剤、顔料分散剤、顔料あるいは染料等の通
常ポリエステルに添加使用される各種配合剤を本
発明の目的を損なわない範囲で添加しておいても
よい。
本発明のポリエステル容器は、上記ポリエステ
ル組成物を二軸延伸成形してなるポリエステル二
軸延伸容器である。
本発明のポリエステル容器は、縦方向に1.5な
いし3.5倍、好ましくは２ないし３倍、横方向に
２ないし５倍、好ましくは３ないし4.5倍に延伸
したものが好ましい。
本発明のポリエステル容器は、前記ポリエステ
ル組成物を用いて従来のPETの二軸延伸吹込成
形方法に準じて製造することが出来る。すなわち
通常の射出成形機により成形された有底パリソ
ン、あるいは押出成形機により成形されたパリソ
ンの一端を有底化して得られた有底パリソンを、
ポリエステル組成物の延伸温度である80ないし
120℃、好ましくは90ないし1100℃で、吹込成形
金型内で軸方向に移動するロツドと加圧気体の吹
込により縦方向に1.5ないし3.5倍、好ましくは２
ないし３倍、及び横方向に２ないし５倍、好まし
くは３ないし4.5倍に延伸する方法が例示できる。
また射出成形による成形方法としては、コール
ド・パリソンによる２ステージ方式あるいはホツ
ト・パリソンによる１ステージ方式のいずれでも
よい。
このほか二軸延伸フイルム、押出成形シートを
使用し、真空圧空成形等の熱成形により容器を製
造することもできる。
尚、本発明のポリエステル容器は、更に容器の
剛性を改良するために、ポリエチレンテレフタレ
ート(A)を内層及び外層に積層しておいてもよい。
本発明のポリエステル容器の種類としては、ボ
トル、トレーその他任意の形状の容器があげられ
る。
〔発明の効果〕
本発明のポリエステル容器は、従来のポリエチ
レンイソフタレートあるいはポリエチレンイソフ
タレート組成物からなる容器に比べて、成形時に
オリゴマーの混入が少なく、耐ガス透過性、耐熱
性、耐衝撃性、透明性等にも優れている。
更に本発明のポリエステル容器は、従来のポリ
エチレンテレフタレートあるいはポリエチレンテ
レフタレート組成物からなる容器に比べ、耐ガス
透過性に優れ、又ポリエチレンテレフタレートに
ポリ塩化ビニリデン等の耐ガス透過性に優れた素
材を積層した容器の様に、運搬時等に被膜が破れ
て耐ガス透過性が低下することもなく、更に特殊
ナイロンやエチレン・酢酸ビニル共重合体鹸化物
の様に高湿度下での耐ガス透過性の低下も少な
い。
更に特殊ナイロンやエチレン・酢酸ビニル共重
合体鹸化物の様にPETに混入した場合に、透明
性が低下することもないのでリサイクル性に優れ
ている。
〔実施例〕
次に実施例を挙げて本発明を更に詳しく説明す
るが、本発明はその要旨を越えない限り、これら
の例に何ら制約されるものではない。
実施例１〜５、比較例１
GeO2触媒を用いてテレフタル酸：イソフタル
酸／エチレングリコール：１，３ビス（２−ヒド
ロキシエトキシ）ベンゼン＝10：90／85：15のポ
リエステルコポリマーを製造し、オルトクロロフ
エノール溶媒下でのが0.85dl／ｇのポリマーを
得た（以下、COPET−１と称す）。このポリマ
ーを用いて三井ペツト樹脂(株)のポリエチレンテレ
フタレートJI35とのドライブレンドによりポリエ
ステル組成物とし、延伸温度100℃で、縦方向2.5
倍、横方向４倍の二軸延伸吹込成形によるボトル
成形を行い、胴部厚さ250μの１のボトルを得
た。このボトルの切片を用い、その炭酸ガス透過
性をPERMATRAN−型測定器を用いて調べ
た結果は表の通りである。
【表】[Detailed description of the invention] [Industrial application field] The present invention provides gas permeation resistance, heat resistance, impact resistance,
The present invention relates to polyester containers with excellent transparency, and more particularly to biaxially stretched polyester containers. [Conventional technology] Polyethylene terephthalate resin (hereinafter referred to as PET)
Biaxially oriented molded products (sometimes referred to as ) can be used as packaging materials for films, sheets, containers, etc. by taking advantage of their excellent properties such as mechanical strength, rigidity, heat resistance, chemical resistance, oil resistance, and transparency. Widely used. However, biaxially stretched blow-molded containers mainly made of PET are not without drawbacks, such as inability to achieve sufficient heat fixation and insufficient gas permeability. Among these, the insufficient gas permeability resistance is due to the original material of PET, and it has been difficult to solve it by molding. One way to improve the gas permeability of PET containers is to use resins that have better gas permeability than PET.
For example, a method of laminating with polyvinylidene chloride, saponified ethylene/vinyl acetate copolymer, polyamide, etc. can be considered, but in any case, such resins
Because it has poor adhesion to PET, even if it has a three-layer structure sandwiched between PET, there is a risk that part of it will peel off during stretch molding or use, resulting in a decrease in gas permeability. On the other hand, there is a method of using polyethylene isophthalate or its copolymer instead of PET (Japanese Unexamined Patent Publication No. 59-64624), or a method of blending polyethylene isophthalate and polyethylene terephthalate, etc. Publication No. 64658)
etc. have been proposed. However, in any case, the method using polyethylene isophthalate contains oligomers with a high melting point, so they are mixed into the molded product as undesirable foreign substances. Similarly
As a method for improving the gas permeability of PET, isophthalic acid is used, and a copolyester obtained by copolymerizing 1,3-bis(2-hydroxyethoxy)benzene with ethylene glycol as a dihydroxy compound (Japanese Patent Application Laid-Open No. 167617/1982) ) has been proposed. However, molded products made of such copolyester alone have low strength and poor heat resistance, and cannot be put to practical use. [Problems to be Solved by the Invention] In view of this situation, the present inventor conducted various studies in order to obtain a biaxially oriented polyester container that has excellent gas permeability and also has heat resistance, impact resistance, transparency, etc. As a result, polyethylene terephthalate and specific amounts of isophthalic acid and 1,3 bis(2-hydroxyethoxy)benzene or 1,4 bis(2-
It was found that the above object could be achieved by biaxially stretching a composition mixed with a copolymerized polyester obtained by copolymerizing (hydroxyethoxy)benzene, and the present invention was completed. [Means for solving the problem] That is, the present invention provides (1) (a) polyethylene terephthalate (A) 5 to 95
(b) 20 to 100 mol % of the dicarboxylic acid component consists of isophthalic acid, and 5 to 90 mol % of the dihydroxy compound component consists of 1,3 bis(2-
hydroxyethoxy)benzene or 1,4bis(hydroxyethoxy)benzene and 10 to
This is a polyester container characterized by being formed by biaxially stretching a polyester composition comprising 5 to 95% by weight of a copolymerized polyester (B) comprising 95% by mole of ethylene glycol. Polyethylene terephthalate (A) in the present invention
Usually, more than 80 mol%, preferably 90 mol% or more of the dicarboxylic acid component is terephthalic acid, and 80 mol% or more of the glycol component, preferably
A crystalline thermoplastic polyester resin containing 90 mol% or more of ethylene glycol. The remaining dicarboxylic acids include, for example, isophthalic acid, diphenyl ether-4,4-dicarboxylic acid, naphthalene-1,4- or 2,6-dicarboxylic acid.
- Aromatic dicarboxylic acids such as dicarboxylic acid, aliphatic dicarboxylic acids such as oxalic acid, succinic acid, adipic acid, sebacic acid, undecadicarboxylic acid, alicyclic dicarboxylic acids such as hexahydroterephthalic acid, and others. The glycol components include aliphatic glycols such as propylene glycol, 1,4-butanediol, and neopentyl glycol, alicyclic glycols such as cyclohexanedimethanol,
Aromatic dihydroxy compounds such as bisphenol A and the like can be mentioned. Polyethylene terephthalate (A) in the present invention
The molecular weight is not particularly limited as long as the container can be manufactured, but usually orthochlorophenol 25
The intrinsic viscosity [η] (hereinafter referred to as) at °C is 0.6
dl/g or more, preferably in the range of 0.8 to 0.85 dl/g. The copolymerized polyester (B) in the present invention is composed of 20 to 100 mol% of the dicarboxylic acid component, preferably 50 to 100 mol% of isophthalic acid,
5 to 90 mol%, preferably 10 to 85 mol% of the dihydroxy compound component is 1,3 bis(2-hydroxyethoxy)benzene or 1,4 bis(2-hydroxyethoxy)benzene and 10 to 95 mol%, preferably It is a copolyester containing 15 to 90 mol% of ethylene glycol. If less than 100 mole percent of the dicarboxylic acid component is isophthalic acid, terephthalic acid can be used as the other dicarboxylic acid component. The amount of terephthalic acid in this case is not more than 80 mol%, preferably 50 mol%
It is as follows. Even if less than 20 mol% of isophthalic acid is used, the gas permeation resistance is not improved.
Even if less than mol% is used, the generation of oligomers cannot be suppressed. On the other hand, if it exceeds 90 mol%, the rate of polycondensation decreases, which is undesirable. The molecular weight of the copolymerized polyester (B) is not particularly limited as long as it can manufacture containers, but
Usually in orthochlorophenol solvent
0.6dl/g or more, preferably 0.8 to 0.85dl/g
It is within the range of . The polyester composition in the present invention comprises 5 to 95% by weight of the polyethylene terephthalate (A),
Preferably 50 to 90% by weight, and copolymerized polyester (B) 5 to 95% by weight, preferably 10 to 90% by weight.
Consists of 50% by weight. Copolymerized polyester (B)
If the amount is less than 5% by weight, gas permeability resistance will not be improved, while if it exceeds 95% by weight, heat resistance, impact resistance, etc. will decrease. To obtain the polyester composition used in the present invention, the polyethylene terephthalate (A) and the copolymerized polyester (B) are mixed using various known methods within the range described above, such as a Henschel mixer, a V-blender, a ribbon blender, a tumbler blender, etc. A method of mixing, and further a method of melt-kneading and granulating or pulverizing with a single-screw extruder, twin-screw extruder, kneader, Banbury mixer, etc. after mixing can be adopted. The polyester composition used in the present invention includes various additives that are usually added to polyester, such as heat stabilizers, weather stabilizers, antistatic agents, lubricants, mold release agents, nucleating agents, pigment dispersants, pigments, and dyes. may be added within a range that does not impair the purpose of the present invention. The polyester container of the present invention is a biaxially stretched polyester container formed by biaxially stretching the above polyester composition. The polyester container of the present invention is preferably stretched 1.5 to 3.5 times, preferably 2 to 3 times, in the machine direction, and 2 to 5 times, preferably 3 to 4.5 times, in the transverse direction. The polyester container of the present invention can be manufactured using the polyester composition according to a conventional PET biaxial stretch blow molding method. That is, a parison with a bottom formed by a normal injection molding machine, or a parison with a bottom obtained by converting one end of a parison formed by an extrusion molding machine to a bottom,
80 to 80, which is the stretching temperature of the polyester composition.
At 120°C, preferably 90 to 1100°C, the rod is moved longitudinally in the blow mold by a factor of 1.5 to 3.5, preferably 2
Examples include a method of stretching the film by 3 to 3 times, and 2 to 5 times in the transverse direction, preferably 3 to 4.5 times.
The injection molding method may be either a two-stage method using a cold parison or a one-stage method using a hot parison. In addition, the container can also be manufactured by thermoforming such as vacuum-pressure forming using a biaxially stretched film or an extrusion molded sheet. In addition, in order to further improve the rigidity of the polyester container of the present invention, polyethylene terephthalate (A) may be laminated on the inner layer and the outer layer. Examples of the polyester container of the present invention include bottles, trays, and other arbitrary shaped containers. [Effects of the Invention] Compared to conventional containers made of polyethylene isophthalate or polyethylene isophthalate compositions, the polyester container of the present invention contains less oligomer during molding, and has excellent gas permeability, heat resistance, impact resistance, It also has excellent transparency. Furthermore, the polyester container of the present invention has excellent gas permeability resistance compared to conventional containers made of polyethylene terephthalate or polyethylene terephthalate compositions, and is made by laminating polyethylene terephthalate with a material having excellent gas permeation resistance such as polyvinylidene chloride. Unlike containers, the coating will not be torn during transportation and gas permeability will not deteriorate, and in addition, special nylon and saponified ethylene/vinyl acetate copolymers will not have gas permeability under high humidity. There is little decline. Furthermore, unlike special nylon or saponified ethylene/vinyl acetate copolymer, it does not reduce transparency when mixed into PET, making it highly recyclable. [Examples] Next, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these Examples as long as the gist thereof is not exceeded. Examples 1 to 5, Comparative Example 1 A polyester copolymer of terephthalic acid: isophthalic acid/ethylene glycol: 1,3 bis(2-hydroxyethoxy)benzene = 10:90/85:15 was produced using a GeO 2 catalyst, A polymer having a molecular weight of 0.85 dl/g in orthochlorophenol solvent was obtained (hereinafter referred to as COPET-1). Using this polymer, a polyester composition was made by dry blending with polyethylene terephthalate JI35 from Mitsui Pettsu Resin Co., Ltd., and the stretching temperature was 100°C, and the length was 2.5% in the machine direction.
Bottle molding was carried out by biaxial stretch blow molding with double and 4 times in the transverse direction to obtain a bottle with a body thickness of 250 μm. Using a section of this bottle, its carbon dioxide permeability was examined using a PERMATRAN-type measuring device, and the results are shown in the table. 【table】
Claims (1)
重量％と、(b)ジカルボン酸成分の20ないし100モ
ル％がイソフタル酸からなり、ジヒドロキシ化合
物成分の５ないし90モル％が、１，３ビス（２−
ヒドロキシエトキシ）ベンゼンあるいは１，４ビ
ス（ヒドロキシエトキシ）ベンゼン及び10ないし
95モル％がエチレングリコールからなる共重合ポ
リエステル(B)５ないし95重量％とからなるポリエ
ステル組成物を二軸延伸成形してなることを特徴
とするポリエステル容器。1 (a) Polyethylene terephthalate (A) 5 to 95
(b) 20 to 100 mol % of the dicarboxylic acid component consists of isophthalic acid, and 5 to 90 mol % of the dihydroxy compound component consists of 1,3 bis(2-
hydroxyethoxy)benzene or 1,4bis(hydroxyethoxy)benzene and 10 to
A polyester container characterized in that it is formed by biaxially stretching a polyester composition comprising 5 to 95% by weight of a copolymerized polyester (B) comprising 95% by mole of ethylene glycol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1035821A JPH0263716A (en) | 1989-02-15 | 1989-02-15 | Polyester vessel |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1035821A JPH0263716A (en) | 1989-02-15 | 1989-02-15 | Polyester vessel |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP19266884A Division JPS6172051A (en) | 1984-09-17 | 1984-09-17 | Polyester composition and container made thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0263716A JPH0263716A (en) | 1990-03-05 |
| JPH0420774B2 true JPH0420774B2 (en) | 1992-04-06 |
Family
ID=12452616
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1035821A Granted JPH0263716A (en) | 1989-02-15 | 1989-02-15 | Polyester vessel |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0263716A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ID23606A (en) * | 1998-02-25 | 2000-05-04 | Mitsui Chemicals Inc | NEW POLYESTER PELETS AND THE SAME PROCESS OF MAKING PELETS |
| FR2871665B1 (en) * | 2004-06-18 | 2007-02-09 | Montjabon Diane De | BOX IMPROVED IN PARTICULAR FOR MAKE-UP PRODUCT |
-
1989
- 1989-02-15 JP JP1035821A patent/JPH0263716A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0263716A (en) | 1990-03-05 |
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| EXPY | Cancellation because of completion of term |