JPS6351122A - Manufacture of multilayer stretch blow molded vessel - Google Patents
Manufacture of multilayer stretch blow molded vesselInfo
- Publication number
- JPS6351122A JPS6351122A JP19653986A JP19653986A JPS6351122A JP S6351122 A JPS6351122 A JP S6351122A JP 19653986 A JP19653986 A JP 19653986A JP 19653986 A JP19653986 A JP 19653986A JP S6351122 A JPS6351122 A JP S6351122A
- Authority
- JP
- Japan
- Prior art keywords
- evoh
- pes
- modified
- modified evoh
- multilayer
- 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
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- 229920000728 polyester Polymers 0.000 claims abstract description 47
- 238000000071 blow moulding Methods 0.000 claims abstract description 12
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical group C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000005977 Ethylene Substances 0.000 claims abstract description 11
- 238000007127 saponification reaction Methods 0.000 claims abstract description 8
- 229920006395 saturated elastomer Polymers 0.000 claims abstract description 6
- 239000005038 ethylene vinyl acetate Substances 0.000 claims abstract description 4
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims abstract 3
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical group O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 claims description 11
- 238000001746 injection moulding Methods 0.000 claims description 8
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 5
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims description 3
- 239000000155 melt Substances 0.000 claims description 2
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical class C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 claims 1
- UFRKOOWSQGXVKV-UHFFFAOYSA-N ethene;ethenol Chemical class C=C.OC=C UFRKOOWSQGXVKV-UHFFFAOYSA-N 0.000 abstract description 80
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 abstract description 23
- 239000004715 ethylene vinyl alcohol Substances 0.000 abstract description 22
- 230000004888 barrier function Effects 0.000 abstract description 15
- 238000000034 method Methods 0.000 abstract description 8
- 229920001169 thermoplastic Polymers 0.000 abstract description 3
- 239000004416 thermosoftening plastic Substances 0.000 abstract description 3
- LLLVZDVNHNWSDS-UHFFFAOYSA-N 4-methylidene-3,5-dioxabicyclo[5.2.2]undeca-1(9),7,10-triene-2,6-dione Chemical compound C1(C2=CC=C(C(=O)OC(=C)O1)C=C2)=O LLLVZDVNHNWSDS-UHFFFAOYSA-N 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract description 2
- 230000002349 favourable effect Effects 0.000 abstract 1
- 229920003208 poly(ethylene sulfide) Polymers 0.000 abstract 1
- 229920006393 polyether sulfone Polymers 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 25
- 229920000139 polyethylene terephthalate Polymers 0.000 description 24
- 239000005020 polyethylene terephthalate Substances 0.000 description 24
- 238000002347 injection Methods 0.000 description 18
- 239000007924 injection Substances 0.000 description 18
- 239000007789 gas Substances 0.000 description 14
- 239000004840 adhesive resin Substances 0.000 description 10
- 229920006223 adhesive resin Polymers 0.000 description 10
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 238000000465 moulding Methods 0.000 description 9
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 8
- 229920001577 copolymer Polymers 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- -1 polyethylene terephthalate Polymers 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 6
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 4
- 239000001569 carbon dioxide Substances 0.000 description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 description 4
- 230000032798 delamination Effects 0.000 description 4
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000001361 adipic acid Substances 0.000 description 3
- 235000011037 adipic acid Nutrition 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 2
- MMINFSMURORWKH-UHFFFAOYSA-N 3,6-dioxabicyclo[6.2.2]dodeca-1(10),8,11-triene-2,7-dione Chemical group O=C1OCCOC(=O)C2=CC=C1C=C2 MMINFSMURORWKH-UHFFFAOYSA-N 0.000 description 2
- 229920002126 Acrylic acid copolymer Polymers 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 125000005907 alkyl ester group Chemical group 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000012792 core layer Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 235000015243 ice cream Nutrition 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- 230000002087 whitening effect Effects 0.000 description 2
- VBGPWCBAFNCNJZ-UHFFFAOYSA-N 1-ethenylpyrrolidin-3-one Chemical compound C=CN1CCC(=O)C1 VBGPWCBAFNCNJZ-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- KZSNJWFQEVHDMF-BYPYZUCNSA-N L-valine Chemical compound CC(C)[C@H](N)C(O)=O KZSNJWFQEVHDMF-BYPYZUCNSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 241001122767 Theaceae Species 0.000 description 1
- KZSNJWFQEVHDMF-UHFFFAOYSA-N Valine Natural products CC(C)C(N)C(O)=O KZSNJWFQEVHDMF-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 235000013405 beer Nutrition 0.000 description 1
- 235000013361 beverage Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 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 1
- KVNRLNFWIYMESJ-UHFFFAOYSA-N butyronitrile Chemical compound CCCC#N KVNRLNFWIYMESJ-UHFFFAOYSA-N 0.000 description 1
- 235000014171 carbonated beverage Nutrition 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 235000015203 fruit juice Nutrition 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 229920000554 ionomer Polymers 0.000 description 1
- 235000008960 ketchup Nutrition 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 235000010746 mayonnaise Nutrition 0.000 description 1
- 239000008268 mayonnaise Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 239000007870 radical polymerization initiator Substances 0.000 description 1
- 239000002453 shampoo Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 239000004474 valine Substances 0.000 description 1
Landscapes
- Laminated Bodies (AREA)
- Blow-Moulding Or Thermoforming Of Plastics Or The Like (AREA)
Abstract
Description
【発明の詳細な説明】
Ａ６ 産業上の利用分野
本発明は、ガス遮断性に優れ、かつ外観良好で、強度に
優れた多層延伸中空成形容器を安定に製造する方法に関
する。DETAILED DESCRIPTION OF THE INVENTION A6 Field of Industrial Application The present invention relates to a method for stably producing a multilayer stretch blow-molded container that has excellent gas barrier properties, good appearance, and excellent strength.
Ｂ、従来の技術
従来、ポリエチレンテレフタレー）（ＰＦ：ＪＴ）の延
伸中空成形容器は主として、食品の包装用容器として市
販されているが、酸素や炭酸ガス等のガス遮断性に劣り
、さらにガス遮断性に優れた改良ＰＥＴ容器が望まれて
いる。B. Conventional technology Conventionally, stretch blow-molded containers made of polyethylene terephthalate (PF: JT) are mainly commercially available as food packaging containers, but they have poor gas barrier properties such as oxygen and carbon dioxide gas, and An improved PET container with excellent barrier properties is desired.
そこで、かかるＰＥＴとガス遮断性に優れた樹脂を複合
する技術が種々紹介されており、例えば特開昭５３−１
０８１６２号公報によれば、ｌ） Ｅ Ｔとエチレン−
酢酸ビニル共重合体ケン化物（ＥＶＯＨ）を複合し、延
伸中空成形（延伸ブロー成形）する技術が開示されてい
る。Therefore, various technologies have been introduced to combine such PET with resins having excellent gas barrier properties, such as JP-A-53-1
According to Publication No. 08162, l) ET and ethylene-
A technique has been disclosed in which a saponified vinyl acetate copolymer (EVOH) is composited and stretch blow molded.
しかしながら、従来公知のかかるＥＶＯＨとＰＥＴを複
合して、多層パリソン（予備成形中空体）合成形し、次
いで延伸中空成形を試みると、多層パリソンが白化し、
次の延伸中空成形が不能であったり、あるいは多層パリ
ソンが見掛上、一応成形できた場合でも、延伸中空成形
が困難であり、ＥＶＯＨ層に厚み斑を生じたり、筋が入
ったり、ウロコ状の縞模様を生じたり、極端な場合には
、かかるＥＶＯＨ層に亀裂やピンホールを生ずるなどの
問題点がある。かかる問題点は、かかる多層パリソンを
成形直後、強力に急冷固化することにより改善される傾
向にあるが、充分ではなく、商品価値のちるものは得難
い。However, when conventionally known EVOH and PET are composited into a multilayer parison (preformed hollow body) and then stretch blow molding is attempted, the multilayer parison turns white.
The next stretch blow-molding may not be possible, or even if the multilayer parison can be formed, the stretch blow-molding may be difficult, and the EVOH layer may have uneven thickness, streaks, or scales. There are problems such as striped patterns and, in extreme cases, cracks and pinholes in the EVOH layer. These problems tend to be improved by rapidly solidifying such multilayer parisons immediately after molding, but this is not sufficient and it is difficult to obtain products with low commercial value.
また、かかるＥＶＯＨとＰＥＴよりなる多層パリソンの
成形条件及び延伸中空成形条件■共に極めて狭い範囲に
限定され、工業上、安定して製造することは困難である
。In addition, both the molding conditions and the stretch blow molding conditions (1) for such a multilayer parison made of EVOH and PET are limited to extremely narrow ranges, making it difficult to manufacture stably from an industrial perspective.
更に、前記ＥＶＯＨとＰＥＴを復合し、延伸中１ 生成
形を試みると、主として、ＥＶＯＨの肉厚部分、例えば
容器の首部（ネジ部分）付近、あるいは底部が白化し、
そもそもＰＥＴの延伸中空成形容器が、本来、特徴とし
ている透明性を損い、容器外観の悪い商品価値のないも
のしか得られない０またＰＥＴの延伸中空成形容器は、
本来、強度に優れた容器であるが、前記ＥＶＯＨとＰＥ
Ｔを複合して、延伸中空成形した容器は、ＥＶＯＨ層と
ＰＥ７層の間で、層間剥離し易く、また内容物充填後の
落下強度や衝撃強度も大幅に低下するこ゛とが分った。Furthermore, when the EVOH and PET are combined and a plastic shape is attempted during stretching, the thick portions of the EVOH, such as the vicinity of the neck (threaded portion) or the bottom of the container, become white.
In the first place, PET stretch blow-molded containers lose their original characteristic of transparency, resulting in containers with poor appearance and no commercial value.In addition, PET stretch blow-molded containers are
Originally, it is a container with excellent strength, but the EVOH and PE
It was found that in a stretch-blow-molded container made of composite T, delamination is likely to occur between the EVOH layer and the PE7 layer, and the drop strength and impact strength after filling are also significantly reduced.
すカわちＰＥＴ単層の延伸中空成形容器は、極めて優れ
た落下強度や衝撃強度を有するにもかかわらず、かかる
ＰＥＴとＥＶＯＨを複合した場合には、大幅に強度が低
下するという重大な問題点がある。Although stretch blow-molded containers made of a single layer of PET have extremely excellent drop strength and impact strength, there is a serious problem in that when such PET and EVOH are combined, the strength decreases significantly. There is a point.
さらにまたＥＶＯＨと他の合成樹脂とを共射出して、パ
リソンを得、これをブロー成形することも特公昭５８−
８９７１号公報などにより知られているが、ＥＶＯＨを
用いたのでは、容器のネジ部や底部など肉厚部分におけ
る白化や、延伸性が不十分なため、厚み斑、亀裂、ピン
ホールなどの欠点が生じ易く、酉市価値のあるものを安
定して製造することは困難である。Furthermore, it is also possible to co-inject EVOH and other synthetic resins to obtain a parison, and then blow molding this.
It is known from Publication No. 8971, etc., but when EVOH is used, there are disadvantages such as whitening in thick parts such as the threads and bottom of the container, and uneven thickness, cracks, and pinholes due to insufficient stretchability. It is difficult to stably produce products of market value.
本発明は前記課題について検討した結果、到達したもの
であり、透明性、強度および外観の良好な多層延伸中空
容器を得んとするものである。The present invention was achieved as a result of studies on the above-mentioned problems, and aims to provide a multilayer stretched hollow container with good transparency, strength, and appearance.
Ｄ１問題点を解決するための手段
本発明は、飽和ポリエステルと、ピロリドン環を含む単
位の含量０．１〜１０モル％、エチレン単位の含７２０
〜６０モルチおよび酢酸ビニル成分のケン化度が９５モ
ルチ以上である変性ＥＶＯＨ（変性ＥＶＯＨ）を共射出
してパリソンを得、これを延伸ブロー成形することを特
徴とする多層延伸中空容器の製造方法である。Means for Solving Problem D1 The present invention uses a saturated polyester, a content of pyrrolidone ring-containing units from 0.1 to 10 mol%, and an ethylene unit content of 720%.
A method for manufacturing a multilayer stretched hollow container, characterized by co-injecting modified EVOH (modified EVOH) having a saponification degree of ~60 molar and a vinyl acetate component of 95 molar or higher to obtain a parison, and stretching and blow molding the parison. It is.
Ｅ０発明のよシ詳細な説明
本発明における熱可塑性飽和ポリエステル（ＰＥＳ）と
しては芳香族ジカルボン酸またはそのアルキルエステル
とグリコールを主成分とする縮合重合体が用いられるが
、特に本発明の目的を達成するには、エチレン−テレフ
タレートを主体とするＰＥＳが好ましい。そして加工性
、強度を大幅に損わない範囲で共重合成分として、イソ
フタル酸、ナフタレンジカルボン酸、アジピン酸、七ノ
（シン酸、または、これらのアルキルエステル誘導体な
どのジカルボン酸成分やプロピレングリコール、１．４
−ブタンジオール、シクロヘキサンジメタツール、ネオ
ペンチルグリコール、ビスフェノールＡ１ジエチレング
リコールなトＣ）グリコール成分を共重合せしめた共重
合体を用いることも可能である。Detailed Description of the E0 Invention The thermoplastic saturated polyester (PES) used in the present invention is a condensation polymer containing an aromatic dicarboxylic acid or its alkyl ester and glycol as main components. Therefore, PES mainly composed of ethylene terephthalate is preferable. Dicarboxylic acid components such as isophthalic acid, naphthalene dicarboxylic acid, adipic acid, heptano(cynic acid) or alkyl ester derivatives thereof, propylene glycol, 1.4
It is also possible to use copolymers obtained by copolymerizing glycol components such as -butanediol, cyclohexane dimetatool, neopentyl glycol, and bisphenol A1 diethylene glycol.
好マシくは、エチレン−テレフタレート単位を８０モル
チ以上含有するポリエチレンテレフタレート系熱可塑性
ポリエステルであり、最も好適な例としては、ボリエテ
レンテレフタレー）（ＰＥＴ）、１．４−シクロヘキサ
ンジメタツールまたはジエチレングリコールを全グリコ
ール成分１００モル’％ｌ、０．５〜２０モル条共重合
せしめたＰＥＳあるいはイソフタル酸やアジピン酸を全
ジカルボン酸成分１００モルチ当υ、１〜２０モル条共
重合せしめたＰＥＳなどが挙げられる。Preferably, it is a polyethylene terephthalate thermoplastic polyester containing 80 moles or more of ethylene terephthalate units, and the most preferable examples are polyethylene terephthalate (PET), 1,4-cyclohexane dimetatool, or PES in which diethylene glycol is copolymerized with 100 mol% of the total glycol component in a 0.5 to 20 mol strip, or PES in which isophthalic acid or adipic acid is copolymerized in a 1 to 20 mol strip with 100 mol % of the total dicarboxylic acid component, etc. can be mentioned.
ここで、耐熱性、耐クリープ性、強度及び、入手の容易
性、経済性等の観点からは、かかる変性のないＰＥＳす
なわちＰＥＴが有利であるが、本発明にかかる変性ＥＶ
ＯＨと組み合せて、共射出成形により多層延伸中空成形
容器を製造する場合には、共射出成形性、及び延伸中空
成形性の点で、１．４−シクロヘキサンジメタツールや
ジエチレングリコールで変性したＰＥＳあるいはイソフ
タル酸やアジピン酸で変性したＰＥＳが好ましい。かか
るＰＥＳにおいては、エチレン−テレフタレート単位が
８０モル係未満の場合には、加工性に劣り、強度も低下
するのみならず、耐熱性、耐クリープ性にも劣るので、
好ましくない。Here, from the viewpoint of heat resistance, creep resistance, strength, easy availability, economical efficiency, etc., PES without such modification, that is, PET, is advantageous, but the modified EV according to the present invention
When producing a multilayer stretch blow-molded container by co-injection molding in combination with OH, PES modified with 1,4-cyclohexane dimetatool or diethylene glycol or PES modified with isophthalic acid or adipic acid is preferred. In such PES, if the ethylene terephthalate unit is less than 80 molar, processability is poor, strength is reduced, and heat resistance and creep resistance are also poor.
Undesirable.
また本発明で用いられるＰＥ５（ＰＥＴを含む）として
はフェノールｓｏｙ量チとテトラクロルエタン５０重量
％の混合溶剤に溶解し、温度３０℃において測定した固
有粘度〔η〕（単位ｄｌｌｔ）が０．５〜１．５のもの
、好ましくは０．６〜１のものである。〔η〕が０．５
未満のＰＥＳは、落下強度、耐＠撃性に劣シ、また〔η
〕が１．５を越えるＰＥＳは、特殊な重合装置、重合条
件を必要とするため、生産性、経済性に劣るのみならず
、射出成形時、成形機内に滞留しやすくゲルやアイシュ
・アイを生じるので好ましくない。更に、〔η〕が０．
５未溝のＰＥＳ、あるいは〔η〕が１．５を越えるＰＥ
Ｓは、本発明にかかる変性ＥＶＯＨと複合した場合の共
射出成形性に劣るのみならず共射出成形性にも劣り、し
かも外観の良好なものが得難い。PE5 (including PET) used in the present invention is dissolved in a mixed solvent of phenol soy and 50% by weight of tetrachloroethane, and has an intrinsic viscosity [η] (unit: dllt) of 0. 5 to 1.5, preferably 0.6 to 1. [η] is 0.5
PES of less than [η
] of more than 1.5 requires special polymerization equipment and polymerization conditions, which not only lowers productivity and economy, but also tends to accumulate in the molding machine during injection molding, causing gel and ice-eye formation. This is not desirable because it occurs. Furthermore, [η] is 0.
5 PES with no groove or PE with [η] exceeding 1.5
S not only has poor co-injection moldability when combined with the modified EVOH according to the present invention, but also poor co-injection moldability, and it is difficult to obtain a product with a good appearance.
次に本発明において変性ＥＶＯＨとしては、ピロリドン
環を含む単位を０．１〜１０モル％、好ましくは０．５
〜５モルチ含有することが重要である。Next, in the present invention, the modified EVOH contains 0.1 to 10 mol%, preferably 0.5 mol% of units containing a pyrrolidone ring.
It is important to contain ~5 molti.
本発明においては変性ＥＶＯＨに未変性ＥＶＯＨを混合
して使用することもできる。かかる変性ＥＶＯＨと未変
性ＥＶＯＨの混合物を用いる場合にも、混合物中のピロ
リドン環を含む単位の含有率は、０．１〜１０モル％、
好ましくは０．５〜５モルチにする必要がある。In the present invention, unmodified EVOH may be mixed with modified EVOH. Even when using a mixture of such modified EVOH and unmodified EVOH, the content of units containing a pyrrolidone ring in the mixture is 0.1 to 10 mol%,
Preferably it is necessary to make it 0.5 to 5 molty.
変性ＥＶＯＨ単品使用及び変性ＥＶＯＨと未変性ＥＶＯ
Ｈの混合物使用のいずれの場合も、かかるピロリドン環
を含む単位が０．１モルφ未満の場合には、従来公知の
ＥＶＯＨとの性能の差が顕著ではなく、本発明の効果が
奏せられず、また１０モモルφ越えると耐水・耐湿性に
劣り、高湿時のガス遮断性が損われ、熱安定性にも劣シ
加熱時着色しヤすくなシ、溶融時ゲルやアイシュ・アイ
を生じやすい等の欠点が顕著となる。Use of modified EVOH alone, modified EVOH and unmodified EVO
In any case where a mixture of H is used, when the number of units containing such a pyrrolidone ring is less than 0.1 mole φ, the difference in performance from conventionally known EVOH is not significant, and the effects of the present invention are not achieved. Moreover, if the diameter exceeds 10 mmoles, the water resistance and humidity resistance will be poor, the gas barrier property at high humidity will be impaired, the thermal stability will be poor, and it will be easily discolored when heated, and will cause gel or ice cream when melted. Disadvantages such as easy handling become noticeable.
また本発明で用いられる変性ＥＶＯＨ及びかかる変性Ｅ
ＶＯＨに混合される未変性ＥＶＯＨのエチレン単位の含
有率は、２０〜６０モルチの泥圧が好ましく、−層好適
には、２５〜５５モルチである。エチレン単位の含有率
が２０モモルφ満の場合には融点と分解点が接近し、熱
安定性、溶融成形性に劣シ、また耐水・耐湿性が低下し
、高湿時のガス遮断性に劣る。またエチレン単位の含有
率が、６０モモルφ越えると溶融成形性、耐水・耐湿性
は改善されるものの低湿時のガス遮断性に劣り、また耐
熱性も損われ、好ましくない。Also, modified EVOH used in the present invention and such modified E
The content of ethylene units in unmodified EVOH to be mixed with VOH is preferably 20 to 60 molar, preferably 25 to 55 molar. If the content of ethylene units is less than 20 mmol φ, the melting point and decomposition point will be close to each other, resulting in poor thermal stability and melt moldability, as well as decreased water resistance and moisture resistance, resulting in poor gas barrier properties at high humidity. Inferior. Furthermore, if the content of ethylene units exceeds 60 mmol φ, melt moldability and water/moisture resistance are improved, but gas barrier properties at low humidity are poor, and heat resistance is also impaired, which is not preferable.
本発明で用いられる変性ＥＶＯＨ及びかかる変性ＥＶＯ
Ｈに混合される未変性ｇｖｏｕのケン化度は、９５モモ
ルφ上が良く、好ましくは９８モモルφ上、−層好まし
くは９９モモルφ上が良い。Modified EVOH used in the present invention and such modified EVO
The degree of saponification of the unmodified gvou mixed with H is preferably 95 mmol φ or higher, preferably 98 mmol φ or higher, and preferably 99 mmol φ or higher.
かかるケン化度が９５モル饅未満では、熱安定性に劣り
、情態成形時に着色し、ゲルやアイシュ・アイを生じヤ
すく、耐水・耐湿性に劣り、また、高湿時はもとより、
低湿時のガス遮断性も低下するＯ
前記の通り、本発明でいう変性ＥＶＯＨには、変性ＥＶ
ＯＨと未変性ＥＶＯＨの混合物も含むものであるが、か
かる混合物を用いる場合には、ピロリドン環を相対的に
高濃度で含むＥＶＯＨを一旦製造し、これを未変性ＥＶ
ＯＨと適宜、混合し、かかる混合物中のどロリドン環を
含む単位が、混合物全体で０．１〜１０モル％、好まし
くは０．５〜５モルチにすれば良く、この方法は経済性
に優れ、しかも要求される性能及び用途に応じて、種々
の変性ＥＶＯＨを任意に、しかも容易に得られる点で好
ましい。If the degree of saponification is less than 95 moles, the thermal stability will be poor, the product will be colored during temperature molding, it will easily form gel or ice cream, it will have poor water resistance and humidity resistance, and it will not only be used under high humidity conditions.
The gas barrier property at low humidity also decreases.As mentioned above, the modified EVOH in the present invention includes modified EVOH
It also includes a mixture of OH and unmodified EVOH, but when using such a mixture, EVOH containing a relatively high concentration of pyrrolidone rings is first produced, and then this is mixed with unmodified EVOH.
It is sufficient to mix it with OH as appropriate so that the unit containing the dorolidone ring in the mixture is 0.1 to 10 mol%, preferably 0.5 to 5 mol% of the entire mixture, and this method is highly economical. Moreover, it is preferable in that various modified EVOHs can be obtained arbitrarily and easily depending on the required performance and use.
尚、変性ＥＶＯＨと未変性ＥＶＯＨの混合物を使用する
場合には、必ずしも両者のエチレン含有率及びケン化度
は同一である必要はなく、前記したエチレン含有率及び
ケン化度を有する変性ＥＶＯＨと未変性ＥＶＯＨであれ
ば、エチレン含有率あるいはケン化度が異なったＥＶＯ
Ｈを混合して用いるのも良い。その場合には、成型条件
幅が拡大するという好ましい効果を奏する。In addition, when using a mixture of modified EVOH and unmodified EVOH, the ethylene content and saponification degree of both do not necessarily have to be the same. For modified EVOH, EVO with different ethylene content or degree of saponification
It is also good to use a mixture of H. In that case, a desirable effect is produced in that the range of molding conditions is expanded.
本発明の効果は、本発明にかかる変性ＥＶＯＨとＰＥＳ
を多層状に射出成形して、多層延伸中空成形容器を製造
する場合に、特に顕著に認められるものである。The effect of the present invention is that the modified EVOH and PES according to the present invention
This is particularly noticeable when a multilayer stretch blow-molded container is manufactured by injection molding into a multilayered form.
かかる変性Ｅ Ｖ ＯＨとＰＥＳを多層状に射出成形し
て多層パリソンを成形する場合には、変性ＥＶＯＨのメ
ルトフローレートの限定が特に重要である。When molding a multilayer parison by injection molding such modified EVOH and PES in a multilayered manner, it is particularly important to limit the melt flow rate of the modified EVOH.
ｆｆｘわち、変性ＥＶＯＨ（７）ＪＩＳ Ｋ６７６０に
よる温度２１０℃、荷］１２１６０！！の条件下で測定
したメルト７０ Ｖ−ト（ＭＦＲ）は、０．５〜３０ｇ
／１０分、特に、１．０〜２０９／１０分であることが
好まＬいｏ ＭＦＲが０．５ｇ／１０分未満Ｓるいは３
０９７１０分を越えると、多層射出成形したパリソンの
変性ＥＶＯＨの軸方向への厚み分布が不均一となる。す
なわち、ＭＦＲが０．５，９７１０分未満の場合には、
パリソンキャビティ内のゲートに近い位置の変性ＥＶＯ
Ｈの厚みが極端に厚くなり、ゲートから離れた位置の変
性ＥＶＯＨの厚みが極端に薄くなる傾向があシ、また３
０ ｇ７１０分を越える場合には、逆にパリソンキャビ
ティ内のゲートに近い位置の変性ＥＶＯＨの厚みが極端
に薄くなり、ゲートから離れた位置の変性ＥＶＯＨの厚
みが極端に厚ぐなる傾向がある。すなわち、ＭＦＨの小
さすき°る変性ＥＶＯＨを用いた場合には、かかる変性
ＥＶＯＨがバリンンキャビテイ内のゲート近くに集まシ
やすく、逆にＭＦＨの大きすき゛る変性ＥＶＯＨを用い
た場合には、変性Ｅ Ｖ ＯＨがゲートから離れた位置
に集まシやすくなるという問題点を生じ、いずれの場合
も、多層射出パリソン中の変性ＥＶＯＨの軸方向の厚み
斑は大きくなり、このような多層射出パリソンを延伸中
空成形しても、厚みが均一でかつ外観良好な多層延伸中
空成形容器は到底得られない。ffx, modified EVOH (7) JIS K6760 temperature 210°C, load] 12160! ! Melt 70 V-t (MFR) measured under the conditions of 0.5 to 30 g
/10 minutes, especially preferably from 1.0 to 209/10 minutes.Lo MFR is less than 0.5 g/10 minutesS or 3
If the time exceeds 0.9710 minutes, the thickness distribution of the modified EVOH in the multilayer injection molded parison in the axial direction becomes non-uniform. That is, if the MFR is less than 0.5,9710 minutes,
Modified EVO located close to the gate in the parison cavity
There is a tendency that the thickness of H becomes extremely thick and the thickness of modified EVOH at a position away from the gate becomes extremely thin.
If it exceeds 0 g710 minutes, on the contrary, the thickness of the modified EVOH at a position close to the gate in the parison cavity tends to become extremely thin, and the thickness of the modified EVOH at a position away from the gate tends to become extremely thick. That is, when a modified EVOH with a small MFH is used, the modified EVOH tends to collect near the gate in the valine cavity, and conversely, when a modified EVOH with a large MFH is used, the modified EVOH tends to collect near the gate in the barrier cavity. A problem arises in that EVOH tends to collect at a position away from the gate, and in either case, the thickness unevenness in the axial direction of the modified EVOH in the multilayer injection parison increases, making it difficult to use such a multilayer injection parison. Even with stretch blow molding, it is impossible to obtain a multilayer stretch blow molded container with uniform thickness and good appearance.
ピロリドン環を含む単位、エチレン単位および酢酸ビニ
ル単位、また必要に応じて、他の単量体からなる多元共
重合体は従来公知のラジカル重合開始剤を用いて共重合
して得られ、更にそのケン化物は、かかる共重合体を苛
性アルカリでケン化して工業的に製造される。A multicomponent copolymer consisting of a unit containing a pyrrolidone ring, an ethylene unit, a vinyl acetate unit, and, if necessary, other monomers, is obtained by copolymerization using a conventionally known radical polymerization initiator. Saponified products are industrially produced by saponifying such copolymers with caustic alkali.
かかるピロリドン環を含む単量体としてはＮ−ビニル−
２−ピロリドン、Ｎ−ビニル−３−ピロリドンあるいは
それらの誘導体が挙げられるが、入手が容易でメジ、経
済性からみてＮ−ビニル−２−ピロリドンが好ましい。The monomer containing such a pyrrolidone ring is N-vinyl-
Examples include 2-pyrrolidone, N-vinyl-3-pyrrolidone, and derivatives thereof, and N-vinyl-2-pyrrolidone is preferred from the viewpoint of easy availability and economy.
本発明は、前記の如く、変性ＥＶＯＨとＰＥＳを多層状
に共射出成形したのち延伸中空成形する技術を含むもの
であるが、その場合の層構成は一般に、
ＰＥＳ／変性ＥＶＯＨ／ＰＥＳ、あるいはＰＥＳ／ｉ性
ＥＶＯＨ／ＰＥＳ／１ｉＥＶＯＨ／ＰＥＳの如く、変性
ＥＶＯＨをＰＥＳで挾持するのが、多層射出パリソンの
成形の容易性及びガス遮断材である変性ＥＶＯＨの保護
の点で好ましい。As described above, the present invention includes a technique in which modified EVOH and PES are co-injected into a multilayered structure and then stretch-hollow molded. It is preferable to sandwich the modified EVOH with PES, such as EVOH/PES/1iEVOH/PES, from the viewpoint of ease of molding the multilayer injection parison and protection of the modified EVOH as a gas barrier material.
かかる多層共射出成形法の代表例を述べると、まずＰＥ
Ｓを、多層ホットランナ−ノズルよｐ金型ゲートを通し
て、パリソンキャビティーに一部射出し、かかるＰＥＳ
の射出を続はながら、同時に、変性Ｅ Ｖ ＯＨを前記
多ノーホットランナーノズルよシ前記金型ゲートを通し
てパリンン中ヤビテイに同心円状に射出して、かかる変
性ＥＶＯＨを前記ＰＥＳの中間に層状に位置せしめる。To describe a typical example of such multilayer co-injection molding method, first, PE
A portion of S is injected into the parison cavity through a multilayer hot runner nozzle and a p mold gate, and the PES
While continuing the injection of the PES, at the same time, the modified EVOH is injected concentrically through the multi-no-hot runner nozzle and through the mold gate, and the modified EVOH is positioned in a layer in the middle of the PES. urge
但しはじめにＰＥＳの１部を射出した後、変性ＥＶＯＨ
の射出を開始するに際し、ＥＶＯＨの金型内への流入を
円滑にするためＰＥＳの射出を０．１〜０．３秒間、好
ましくは０．１〜０．２秒間中断するよってする。中断
時間が０．１秒未満ではＥＶＯＨが金型内に入シに＜＜
、Ｏ，ａ秒を越えるとＥＶＯＨ層の１部がＰＥＳ層で挾
持されずに最外層及び、または最内層にはみ出したり容
器の首部または肩部に偏って挿入されるので好ましくな
い。次いで変性ＥＶＯＨの射出を停止したのち、同時ま
たはやや遅れてＰＥＳの射出を停止し、パリソンキャビ
ティー内に樹脂を満たすことにまυ変性ＥＶＯＨをＰＥ
Ｓで完全に包み込むことができ、結局ＰＥＳの表層と変
性ＥＶＯＨの内核層（中間Ｎ）を有する多層パリソンを
成形することができる。However, after first injecting a portion of PES, the modified EVOH
When starting injection of PES, the injection of PES is interrupted for 0.1 to 0.3 seconds, preferably 0.1 to 0.2 seconds, in order to allow EVOH to smoothly flow into the mold. If the interruption time is less than 0.1 seconds, EVOH will not enter the mold.
, O, a seconds, it is not preferable because a part of the EVOH layer is not held between the PES layers and protrudes into the outermost layer and/or the innermost layer, or is inserted unevenly into the neck or shoulder of the container. Next, after stopping the injection of modified EVOH, the injection of PES is stopped at the same time or a little later, and the modified EVOH is injected into PE to fill the parison cavity with resin.
It is possible to completely envelop it with S and eventually form a multilayer parison having a surface layer of PES and an inner core layer (middle N) of modified EVOH.
この方法によれば、意外にも、変性ＥＶＯＨ層とＰＥＳ
層の間に、両者を接着する接着性樹脂層を設けなくても
、実用に耐える耐層間剥離性を付与することができる。According to this method, surprisingly, the modified EVOH layer and PES
Practical delamination resistance can be imparted without providing an adhesive resin layer between the layers to bond them together.
この特性は、本発明が特定するす性Ｅ Ｖ ＯＨとＰＥ
Ｓを組み合せた場合Ｋ。This property is the characteristic of the sonic EV OH and PE specified by the present invention.
K when combining S.
特に顕著であることから、かかる特性は、本発明の有用
な作用効果の一つであるっ
もちろん本発明では、変性ＥＶＯＨ層とＰＥＳ層の間に
接着性樹脂層を設けても良く、その場合には、例えばＰ
ＥＳ／接着性樹脂／変性ＥＶＯＨ／接着性樹脂／ＰＥＳ
の如く多層状に射出成形すれば良いが、かかる接着性樹
脂は、一般に高価であシ、シかもパリソン成形機が複雑
となシ、操作も煩雑になるなどの不都合がある一方、充
分な層間接着力が得られるので、絞り出し式ボトルのよ
うに繰り返し外力を受ける容器等には好ましい。かかる
接着性樹脂としては、特開昭５９−１１５３２７号公報
あるいは特開昭５９−１３６２５４号公報等に記載の変
性ポリエステルあるいは、特開昭５４−５３１７９号公
報に記載の不飽和カルボン酸で変性したポリオレフィン
などが挙げられる。ここで不飽和カルボン酸としては、
（メタ）アクリル酸、マレイン酸及びその無水物等が代
表例として挙げられ、またポリオレフィンとしては、ポ
リエチレン、エチレン−酢酸ビニル共重合体、エチレン
−（メタ）アクリル酸共重合体、エチレン−（メタ）ア
クリル酸アルキルエステル共重合体、アイオノマー、ポ
リプロピレン、エチレン−プロピレン共重合体等が挙げ
られる。Since this property is particularly remarkable, this characteristic is one of the useful effects of the present invention. Of course, in the present invention, an adhesive resin layer may be provided between the modified EVOH layer and the PES layer, and in that case, For example, P
ES/adhesive resin/modified EVOH/adhesive resin/PES
However, such adhesive resins are generally expensive, require complicated parison molding machines, and are complicated to operate. Because adhesive strength can be obtained, it is preferable for containers that are repeatedly subjected to external forces, such as squeeze-type bottles. Such adhesive resins include modified polyesters described in JP-A-59-115327 or JP-A-59-136254, or modified with unsaturated carboxylic acids described in JP-A-54-53179. Examples include polyolefin. Here, the unsaturated carboxylic acid is
Representative examples include (meth)acrylic acid, maleic acid, and its anhydride, and examples of polyolefins include polyethylene, ethylene-vinyl acetate copolymer, ethylene-(meth)acrylic acid copolymer, and ethylene-(meth)acrylic acid copolymer. ) Acrylic acid alkyl ester copolymers, ionomers, polypropylene, ethylene-propylene copolymers, and the like.
次にこのようにして得た多層射出パリノンを延伸ブロー
成形する方法について述べる。パリノンはコールドパリ
ンンまたはホットパリソンとして延伸ブロー成形に供さ
れるが、延伸ブロー成形時の温度はＸ要で、その延伸温
度は、７５℃以上、１５０℃以下の温度範囲から選択す
る必要がある。Next, a method for stretch blow molding the multilayer injection parinone thus obtained will be described. Parinon is subjected to stretch blow molding as cold parison or hot parison, but the temperature during stretch blow molding must be X, and the stretching temperature must be selected from a temperature range of 75°C or higher and 150°C or lower. .
この温度の範囲外では、延伸不能であったシ見掛上、延
伸は可能であっても、本発明による効果は低下する。Outside this temperature range, the effect of the present invention decreases even though stretching is apparently possible.
また延伸倍率は、軸方向及び周方向にそれぞれ１．５倍
以上７倍以下の範囲、好ましくは２．０倍以上５倍以下
の範囲が良い。また延伸は同時延伸でもよいし、逐次延
伸でもよい。かかる延伸倍率が１．５倍未満では、落下
強度、衝撃強度、ガス遮断性及び透明性等が不十分なも
のとなシ、また７倍を越えると変性Ｅ Ｖ Ｏｌ−Ｉに
厚み斑を生じ、また亀裂を生じるなどして好ましくない
。Further, the stretching ratio is preferably in the range of 1.5 times or more and 7 times or less, preferably 2.0 times or more and 5 times or less in the axial direction and the circumferential direction, respectively. Further, the stretching may be simultaneous stretching or sequential stretching. If the stretching ratio is less than 1.5 times, drop strength, impact strength, gas barrier properties, transparency, etc. will be insufficient, and if it exceeds 7 times, thickness unevenness will occur in the modified E V Ol-I. , and may also cause cracks, which is undesirable.
本発明において、変性ＥＶＯＨの厚み（変性ＥＶ ＯＩ
−ｆが２層以上の多層に分れている場合は、その合計の
厚み）は多層延伸中空成型容器の胴部中央周状側壁にお
いて、２〜１００μ、好ましくは５〜５０μが良い。変
性Ｂ Ｖ ＯＨの厚みが２μ未満の場合、ガス遮断性に
おいて不満足であるし、１ｏ。In the present invention, the thickness of modified EVOH (modified EV OI
When -f is divided into two or more multilayers, the total thickness thereof is preferably from 2 to 100μ, preferably from 5 to 50μ, on the central peripheral side wall of the body of the multilayer stretched hollow-molded container. If the thickness of the modified B V OH is less than 2μ, the gas barrier properties are unsatisfactory and the thickness is 1o.
μを越えると延伸性に劣る。ＰＥＳの厚み（ＰＥＳが２
層以上の多層に分れている場合は、その合計の厚み）は
１００〜５００μであり、好ましくは２００〜３５０μ
である。またＰＥＳ／変性ＥＶＯＨ／ＰＥＳの構成をと
る場合は外層のＰＥ５５０〜１５０μ、内層のＰＥ８５
０〜１５０μであることが好ましく、外ＡのＰＥＳの厚
さは内層のＰＥＳの厚さより小さい方が好ましい。If it exceeds μ, the stretchability is poor. Thickness of PES (PES is 2
If it is divided into multiple layers, the total thickness is 100 to 500μ, preferably 200 to 350μ.
It is. In addition, when using a PES/modified EVOH/PES configuration, the outer layer has PE550-150μ and the inner layer has PE85.
The thickness is preferably 0 to 150μ, and the thickness of the outer PES is preferably smaller than the thickness of the inner layer PES.
また本発明は、必髪に応じて接着性樹脂を用いるもので
あるが、一つの接着性樹脂の厚みは、容器の胴部中央周
状側壁において、２〜１００μが好ましい。接着性樹脂
層の厚みが２μ以下では、接着効果が少なく、また１０
０μを越えると、経済性、耐クリープ性に劣る。Further, in the present invention, an adhesive resin is used depending on the necessity, and the thickness of one adhesive resin is preferably 2 to 100 μm on the circumferential side wall at the center of the body of the container. If the thickness of the adhesive resin layer is less than 2μ, the adhesive effect will be small, and if the thickness is less than 10μ
If it exceeds 0μ, the economy and creep resistance will be poor.
而して、多層延伸中空成形容器の総厚は、胴部中央周状
側壁において、１００μ〜３ｕで用いるのが好ましく、
この範囲内で、用途に応じて使い分ければ良いが、通常
２００μ〜ＩＵ程度で用いるのが、容器の実用強度と経
済性のバランスで一層望ましい。容器総厚が１００μ以
下では、落下強度、衝撃強度等の強度に劣シ、３ｕを越
えると、中空延伸性に劣シ、また目付量増大によるコス
ト高となシ、経済性に劣る。Therefore, the total thickness of the multilayer stretched blow-molded container is preferably 100 μ to 3 μ at the center circumferential side wall of the body.
Within this range, it may be used depending on the purpose, but it is usually more desirable to use about 200μ to IU in terms of the balance between practical strength of the container and economical efficiency. If the total thickness of the container is less than 100μ, the strength such as drop strength and impact strength will be poor, and if it exceeds 3u, the hollow stretchability will be poor, and the cost will increase due to the increased basis weight, resulting in poor economic efficiency.
本発明にかかるＰＥＳ、変性ＥＶＯＨ及び接着性樹脂に
は、顔料、染料等の着色剤、帯電防止剤、紫外線吸収剤
、熱安定剤などの添加剤を加えることも良い。Additives such as colorants such as pigments and dyes, antistatic agents, ultraviolet absorbers, and heat stabilizers may also be added to the PES, modified EVOH, and adhesive resin according to the present invention.
本発明にかかる多層延伸中空成形容器は、酸素や、炭酸
ガス等のガス遮断性に優れ、また保香性、透明性、外観
、強度に優れているので、炭酸飲料、果汁、乳酸飲料、
茶、コーヒー、ビール等の飲料用容器として、またケチ
ャツプ、マヨネーズ、大川前、ドレッシング等の食品用
容器として、更に洗剤、シャンプー、化粧品、農薬、医
薬品等の容器として有用である。The multilayer stretch blow-molded container according to the present invention has excellent barrier properties against gases such as oxygen and carbon dioxide, and also has excellent aroma retention, transparency, appearance, and strength, so it can be used for carbonated drinks, fruit juices, lactic acid drinks, etc.
They are useful as containers for beverages such as tea, coffee, and beer, as containers for foods such as ketchup, mayonnaise, Okawamae, and dressings, and as containers for detergents, shampoos, cosmetics, agricultural chemicals, and pharmaceuticals.
以下、実施例を挙げて説明する。Examples will be described below.
Ｆ、実施例
実施例Ｉ
Ｎ−ビニル−２−ピロリドン含有率２モル％、エチレン
含有率３０モル％、酢酸ビニル含有率６８モルチよりな
る共重合体をメタノール中、α、α′−アゾビスインブ
チロニトリルを触媒として重合した。次いで該共重合体
をメタノール中、水酸化ナトリウムを触媒としてケン化
し、酢酸ビニル成分のケン化度が９９．５％のケン化物
（変性ＥＶＯＨ，Ａ”）を得た。該変性Ｅ Ｖ ＯＨ・
Ａのメル）７ｏ−レート（２１０℃、荷Ｍ２１６０ｇ）
は、３．１Ｆ／１０分、融点は１６４℃であった。F. Examples Example I A copolymer consisting of 2 mol % N-vinyl-2-pyrrolidone, 30 mol % ethylene, and 68 mol vinyl acetate was mixed with α,α'-azobisin in methanol. Polymerization was carried out using butyronitrile as a catalyst. Next, the copolymer was saponified in methanol using sodium hydroxide as a catalyst to obtain a saponified product (modified EVOH, A'') with a saponification degree of vinyl acetate component of 99.5%.
Mel of A) 7o-rate (210℃, load M2160g)
The temperature was 3.1F/10 minutes, and the melting point was 164°C.
℃のポリエチレンテレフタレー）（ＰＥＴ、Ａ）を選び
、まずかかるＰＥＴ−Ａをバレル温度２８５℃の１次射
出成形機に仕込み、次いで、該変性ＥＶＯＨ，Ａをバレ
ル温度２４５℃の２次射出成形機に仕込んだ。℃ polyethylene terephthalate) (PET, A) is selected, first, such PET-A is charged into a primary injection molding machine with a barrel temperature of 285℃, and then the modified EVOH,A is subjected to secondary injection molding with a barrel temperature of 245℃. Loaded it into the machine.
次いで、２８０℃に設定した多層ホットランナ−ノズル
より金型ゲートを通して、まずＰＥＴ−Ａを温度２０℃
のパリソンキャビティーに一部射出し、射出開始後ｉ、
２秒後、０．１秒間ＰＥＴ、Ａの射出を中断した。一
方変性ＥＶＯＨ−Ａは射出開始後１．２秒後、前記多層
ホットランナ−ノズルより前記金型ゲートを通じて、前
記パリソンキャビティーに同心円状に射出した。ＰＥＴ
、Ａは０．１秒間の射出中断後は再度変性Ｅ Ｖ ＯＨ
・Ａとともに射出を続けた。この時、射出するｆ’ＥＴ
−Ａの樹脂量を同時に射出する変性ＥＶＯＨ−Ａの樹脂
量よう多くすることによシ、変性ＥＶＯＨ−Ａは、表皮
としてパリソンキャビティーの表面に出ることはなく、
ＰＥＴ、Ａが変性ＥＶＯＨ−Ａを包みつつ、パリソンキ
ャビティーを進行した。Next, PET-A was first heated to a temperature of 20°C through a mold gate through a multilayer hot runner nozzle set at 280°C.
Partially injected into the parison cavity of , after injection started i,
After 2 seconds, the injection of PET and A was interrupted for 0.1 seconds. On the other hand, modified EVOH-A was concentrically injected into the parison cavity from the multilayer hot runner nozzle through the mold gate 1.2 seconds after the start of injection. PET
, A is denatured EV OH again after 0.1 second injection interruption.
・Continued ejection with A. At this time, the ejected f'ET
-By increasing the amount of resin A to the amount of modified EVOH-A injected at the same time, the modified EVOH-A does not come out as a skin on the surface of the parison cavity.
PET, A, was advanced through the parison cavity while enveloping the modified EVOH-A.
次いで変性ＥＶＯＨの射出を停止したのち、やや遅れて
ＰＥＴ、Ａの射出を停止し、パリンンキャビティー内に
樹脂を完全に満たすことによシ、変性ＥＶＯＨ−ＡをＰ
ＥＴ、Ａで完全に包み込むことができた。Next, after stopping the injection of modified EVOH, the injection of PET and A is stopped with a slight delay, and by completely filling the resin in the resin cavity, the modified EVOH-A is injected into PET.
I was able to completely wrap it up with ET and A.
かくして、ＰＢＴ、Ａの表層（内外層）と変性ＥＶＯＨ
−Ａの内核層（中間層）を有する多層パリソンを成形す
ることができた。Thus, the surface layer (inner and outer layer) of PBT, A and the modified EVOH
A multilayer parison having an inner core layer (middle layer) of -A could be molded.
得られた多層パリソンを温調ポットに移し、多層パリソ
ンを１１０℃に温調し、次いで該温調された多層パリソ
ンをブロー金型に移し、延伸ロッドにより軸方向に２倍
延伸し、同時如約１０１ｙ／−の加圧空気によｐ周状方
向に３倍延伸して、金型形状に添わせ、冷却後、取シ出
し容ｔ ｉ、 ｓ −ｅ ｓ 目付６０ｇの容器を製造
した。The obtained multilayer parison was transferred to a temperature-controlled pot, the temperature of the multilayer parison was controlled to 110°C, the temperature-controlled multilayer parison was then transferred to a blow mold, and it was stretched twice in the axial direction using a stretching rod. It was stretched 3 times in the p-circumferential direction using pressurized air at a pressure of about 101 y/- to conform to the mold shape, and after cooling, a container with a take-out capacity ti, s-es and a basis weight of 60 g was manufactured.
イひられた多層延伸中空容器の胴部周状側壁の総厚は３
８０μ、層構成は内層ＰＥＴ、Ａ２４０μ／中間層変性
ＥＶＯＨ−Ａ ２０ ｔ、ｔ／外Ｉ→ＰＥＴ、Ａ□２０
μであった。The total thickness of the circumferential side wall of the body of the flattened multilayer stretched hollow container is 3
80μ, layer configuration: inner layer PET, A240μ/intermediate layer modified EVOH-A 20t,t/outer I→PET, A□20
It was μ.
製造条件及び評価結果を表−１及び表−２に示す０衣−
１に記載の条件にて、ｉ、５Ａ容器をＢ ４した。Manufacturing conditions and evaluation results are shown in Table 1 and Table 2.
The 5A container was heated to B4 under the conditions described in 1.
評価結果を表−２に示す。The evaluation results are shown in Table-2.
評価方法
容器内に炭酸水を充填して密栓し、該容器を留閉した箱
に収納、６５ＳＲＨＫ調湿した窒素ガスで箱内をパージ
し、容器壁を通して透過した炭酸ガスをＭｏｄｅｒｎ
Ｃｏｎｔｒｏｌｓ社製Ｐｅｒｍａｔｒａｎ Ｃ−ｆｉ炭
酸ガス透過性測定装置にて検出する。Evaluation method Fill a container with carbonated water, seal it tightly, store the container in a closed box, purge the inside of the box with 65SRHK humidity-controlled nitrogen gas, and remove the carbon dioxide that permeated through the container wall using the Modern
Detection is performed using a Permatran C-fi carbon dioxide gas permeability measuring device manufactured by Controls.
■ 容器外観 製造した容器外観を肉眼にて判定する。■ Container appearance Visually judge the appearance of the manufactured container.
■厚み斑
容器を切開し、ＥＶＯＨ）−及びＰＥＳ層の厚みを測定
する。② Thickness Variations Cut the container open and measure the thickness of the EVOH)- and PES layers.
容器に水を十分充填し、１ｍの高芒よシ、鵡ンク
瓢リート面に、容器底部を下にして垂直に落下し、容器
の耐層間剥離性及び変形性を肉眼にて見る。A container is sufficiently filled with water, and the container is dropped vertically onto a 1 m high awning surface with the bottom of the container facing down, and the delamination resistance and deformability of the container are observed with the naked eye.
Ｇ０発明の効果
本発明の効果は、
■ ガス遮断性の向上、
■ 多層延伸中空成型性の改善（厚み斑、筋、ウロコ状
の縞模様、亀裂やピンホール等のないこと）、
■ 容器の肉厚部分例えば首部（ネジ部分）及び底部の
白化防止、透明性の改善、
■ 耐層間剥離性の改善、
■ 落下強度、衝撃強度等の強度の改善、および
■ 成型条件幅の拡大（工業的に安定して生産できるこ
と）、
である。G0 Effects of the Invention The effects of the present invention are: ■ Improvement in gas barrier properties, ■ Improvement in multilayer stretch hollow moldability (no thickness unevenness, streaks, scale-like striped patterns, cracks, pinholes, etc.), ■ Improvement of containers. Preventing whitening of thick parts such as the neck (screw part) and bottom, improving transparency, ■ Improving delamination resistance, ■ Improving strength such as drop strength and impact strength, and ■ Expanding the range of molding conditions (industrial ), and stable production is possible.
Claims (3)
含量０．１〜１０モル％、エチレン単位の含量２０〜６
０モル％および酢酸ビニル成分のケン化度が９５モル％
以上である変性エチレン−酢酸ビニル共重合体ケン化物
を共射出成形してパリソンを得、これを延伸ブロー成形
することを特徴とする多層延伸中空成形容器の製造方法
。(1) Saturated polyester, content of units containing pyrrolidone rings: 0.1 to 10 mol%, content of ethylene units: 20 to 6
0 mol% and saponification degree of vinyl acetate component is 95 mol%
A method for producing a multilayer stretch blow-molded container, which comprises co-injection molding the saponified modified ethylene-vinyl acetate copolymer described above to obtain a parison, and stretch-blow molding the parison.
リドンである特許請求の範囲第１項記載の多層延伸中空
成形容器の製造方法。(2) The method for producing a multilayer stretch blow-molded container according to claim 1, wherein the unit containing a pyrrolidone ring is N-vinyl-2-pyrrolidone.
〕（単位ｄｌ／ｇ）が０．５〜１．５であり、ピロリド
ン環を含むエチレン−酢酸ビニル共重合体ケン化物の温
度２１０℃、荷重２１６０ｇにおけるメルトフローレー
ト（単位ｇ／１０分）が０．５〜３０である特許請求の
範囲第１項記載の多層延伸中空成形容器の製造方法。(3) Intrinsic viscosity of saturated polyester at 30°C [η
] (unit: dl/g) is 0.5 to 1.5, and the melt flow rate (unit: g/10 min) of the saponified ethylene-vinyl acetate copolymer containing a pyrrolidone ring at a temperature of 210°C and a load of 2160 g is 0.5 to 30. The method for producing a multilayer stretch blow-molded container according to claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19653986A JPS6351122A (en) | 1986-08-21 | 1986-08-21 | Manufacture of multilayer stretch blow molded vessel |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19653986A JPS6351122A (en) | 1986-08-21 | 1986-08-21 | Manufacture of multilayer stretch blow molded vessel |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6351122A true JPS6351122A (en) | 1988-03-04 |
| JPH0588172B2 JPH0588172B2 (en) | 1993-12-21 |
Family
ID=16359419
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP19653986A Granted JPS6351122A (en) | 1986-08-21 | 1986-08-21 | Manufacture of multilayer stretch blow molded vessel |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6351122A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0736375A1 (en) * | 1991-03-20 | 1996-10-09 | Kuraray Co., Ltd. | A method for producing a multi-layer construction film |
-
1986
- 1986-08-21 JP JP19653986A patent/JPS6351122A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0736375A1 (en) * | 1991-03-20 | 1996-10-09 | Kuraray Co., Ltd. | A method for producing a multi-layer construction film |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0588172B2 (en) | 1993-12-21 |
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