JPH032009A - Rotary molded container and preparation thereof - Google Patents
Rotary molded container and preparation thereofInfo
- Publication number
- JPH032009A JPH032009A JP1140198A JP14019889A JPH032009A JP H032009 A JPH032009 A JP H032009A JP 1140198 A JP1140198 A JP 1140198A JP 14019889 A JP14019889 A JP 14019889A JP H032009 A JPH032009 A JP H032009A
- Authority
- JP
- Japan
- Prior art keywords
- layer
- evoh
- polyolefin
- inner layer
- container
- 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
- 238000002360 preparation method Methods 0.000 title description 2
- UFRKOOWSQGXVKV-UHFFFAOYSA-N ethene;ethenol Chemical compound C=C.OC=C UFRKOOWSQGXVKV-UHFFFAOYSA-N 0.000 claims abstract description 114
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 claims abstract description 113
- 239000004715 ethylene vinyl alcohol Substances 0.000 claims abstract description 113
- 229920000098 polyolefin Polymers 0.000 claims abstract description 62
- 238000004519 manufacturing process Methods 0.000 claims abstract description 18
- 229920006223 adhesive resin Polymers 0.000 claims description 49
- 239000004840 adhesive resin Substances 0.000 claims description 49
- 238000000465 moulding Methods 0.000 claims description 42
- 239000000843 powder Substances 0.000 claims description 39
- 238000009499 grossing Methods 0.000 claims description 35
- 238000001816 cooling Methods 0.000 claims description 25
- 239000000203 mixture Substances 0.000 claims description 13
- -1 polyethylene Polymers 0.000 claims description 13
- 239000004698 Polyethylene Substances 0.000 claims description 11
- 229920000573 polyethylene Polymers 0.000 claims description 10
- 150000001735 carboxylic acids Chemical class 0.000 claims description 4
- 239000005038 ethylene vinyl acetate Substances 0.000 claims description 4
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims description 4
- 229920005672 polyolefin resin Polymers 0.000 claims description 3
- 238000000034 method Methods 0.000 abstract description 18
- 230000004888 barrier function Effects 0.000 abstract description 17
- 239000000126 substance Substances 0.000 abstract description 15
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 abstract description 10
- 239000005977 Ethylene Substances 0.000 abstract description 10
- 229920001577 copolymer Polymers 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 481
- 238000010438 heat treatment Methods 0.000 description 28
- 239000000155 melt Substances 0.000 description 18
- 239000007789 gas Substances 0.000 description 14
- 229920005989 resin Polymers 0.000 description 11
- 239000011347 resin Substances 0.000 description 11
- 238000005245 sintering Methods 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 238000002844 melting Methods 0.000 description 10
- 230000008018 melting Effects 0.000 description 10
- 239000002245 particle Substances 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- 238000007127 saponification reaction Methods 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 8
- 238000000071 blow moulding Methods 0.000 description 8
- 230000008859 change Effects 0.000 description 7
- 230000001070 adhesive effect Effects 0.000 description 6
- 230000032798 delamination Effects 0.000 description 6
- 210000004709 eyebrow Anatomy 0.000 description 6
- 229920001179 medium density polyethylene Polymers 0.000 description 6
- 239000004701 medium-density polyethylene Substances 0.000 description 6
- 238000001175 rotational moulding Methods 0.000 description 6
- 239000000853 adhesive Substances 0.000 description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- 239000004677 Nylon Substances 0.000 description 4
- 239000004952 Polyamide Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 229920001778 nylon Polymers 0.000 description 4
- 229920002647 polyamide Polymers 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000011229 interlayer Substances 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- RWPFLARVZWFRBO-DAIXLEOSSA-N (2R,3R)-2-(2,4-difluorophenyl)-1-(1,2,4-triazol-1-yl)butane-2,3-diol methanesulfonic acid Chemical compound CS(O)(=O)=O.C[C@@H](O)[C@](O)(Cn1cncn1)c1ccc(F)cc1F RWPFLARVZWFRBO-DAIXLEOSSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- OIPMQULDKWSNGX-UHFFFAOYSA-N bis[[ethoxy(oxo)phosphaniumyl]oxy]alumanyloxy-ethoxy-oxophosphanium Chemical compound [Al+3].CCO[P+]([O-])=O.CCO[P+]([O-])=O.CCO[P+]([O-])=O OIPMQULDKWSNGX-UHFFFAOYSA-N 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000005187 foaming Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000003317 industrial substance Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 238000009751 slip forming Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-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
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 239000004230 Fast Yellow AB Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 229920001903 high density polyethylene Polymers 0.000 description 1
- 239000004700 high-density polyethylene Substances 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 210000003127 knee Anatomy 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 229920001684 low density polyethylene Polymers 0.000 description 1
- 239000004702 low-density polyethylene Substances 0.000 description 1
- 239000002932 luster Substances 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
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 239000008267 milk Substances 0.000 description 1
- 210000004080 milk Anatomy 0.000 description 1
- 235000013336 milk Nutrition 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920001083 polybutene Polymers 0.000 description 1
- 229920013716 polyethylene resin Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000003507 refrigerant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic 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
- UKRDPEFKFJNXQM-UHFFFAOYSA-N vinylsilane Chemical class [SiH3]C=C UKRDPEFKFJNXQM-UHFFFAOYSA-N 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Landscapes
- Laminated Bodies (AREA)
- Moulding By Coating Moulds (AREA)
Abstract
Description
【発明の詳細な説明】
〈産業上の利用分野〉
本発明は、耐油性、耐薬品性、ガスバリヤ−性に優れた
容器に関する。さらに詳しくは、外層がポリオレフィン
、内層がエチレン−酢酸ビニル共重合体けん化物（ＥＶ
ＯＨ）からなる回転成形容器およびその製造法に関する
。DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a container with excellent oil resistance, chemical resistance, and gas barrier properties. More specifically, the outer layer is polyolefin, and the inner layer is saponified ethylene-vinyl acetate copolymer (EV
OH) and a method for producing the same.
〈従来の技術〉
ポリオレフィン製の大型容器は灯油缶、ドラム缶、水槽
、各種工業薬品缶、自動車用ガソリンタンク等積々の分
野において使用されているが・、その大きな欠点として
各種溶剤およびガスの透過性の大きいことが知られてい
る。その改良方法として各種溶剤およびガスの透過防止
効果に優れたＥＶＯＨを積層することが有効で、積層化
の方法についても種々の提案がなされており、なかでも
共押出ブロー成形に関して多くの提案がなされている。<Prior art> Large containers made of polyolefin are used in many fields such as kerosene cans, drums, water tanks, various industrial chemical cans, and gasoline tanks for automobiles. However, their major drawback is that they do not allow the permeation of various solvents and gases. It is known to have great sex. An effective way to improve this is to layer EVOH, which has excellent permeation prevention effects for various solvents and gases, and various proposals have been made regarding the lamination method, among which many proposals have been made regarding coextrusion blow molding. ing.
この共押出多層ブロー成形は、ポリオレフィンとＥ Ｖ
ＯＨ′ａ層化を始めとして、積層容器の量産には極め
て有効な製法ではあるが、高額の金型を使用するなど設
備投資額が高く、六層生産に適しているが、少量生産に
はコスト的に不利である。This coextrusion multilayer blow molding is a method for forming polyolefins and E V
Although it is an extremely effective manufacturing method for mass production of laminated containers, including OH'a layering, it requires a high capital investment due to the use of expensive molds, and is suitable for six-layer production, but it is not suitable for small-scale production. It is disadvantageous in terms of cost.
特に２５０リツトルを越える大型容器についてはほとん
ど利用されていない。また数十％発生するパリの回収再
使用に高度の技術を要するなどの問題点がある。プラス
チック製大型容器の製法としてはブロー成形のほかに、
回転成形が知られており、この方法は金型も安価で、パ
リの発生もほとんどなく、ｔｏ（ＩＱリットルを越える
大型容器にも利用されているが、複層化についてはあま
り検討されておらず特にポリオレフィンとＥＶＯＨの復
層化は全く検討されていなかった。In particular, large containers exceeding 250 liters are hardly used. There are also problems such as the need for advanced technology to collect and reuse the several tens of percent of Paris that is generated. In addition to blow molding, there are other manufacturing methods for large plastic containers.
Rotational molding is known, and this method has inexpensive molds, almost no flaking, and is used for large containers exceeding IQ liters, but multi-layering has not been studied much. In particular, no consideration has been given to layering polyolefin and EVOH.
たとえば「成形加工便覧」第５５６頁には外層がポリエ
チレン、内層がナイロンからなる回転成形容器について
記載され、また特開昭４８−４３４６３号には回転多層
容器について記載されているが、ポリオレフィンとＥＶ
ＯＨの積１化については記載されていない。For example, page 556 of the "Molding Handbook" describes a rotary molded container whose outer layer is made of polyethylene and whose inner layer is made of nylon, and JP-A No. 48-43463 describes a rotary multilayer container.
There is no description of the product 1 of OH.
〈発明が解決しようとする課題〉
本発明者はブロー成形に代えて、回転成形法で、ポリオ
レフィンとＥＶＯ）（の積層構成容器の作成を検討した
。共押出ブロー成形においては全層が同時に成形される
ので、層数は生産速度にそれ程影譬しないが、回転成形
では外層から逐次に一層ずつ成形されて行くので層数が
生産速度に大きく影響する。そこで本発明者らは外層に
ポリオレフィンを用い、内層にＥＶＯＨを用いて、強変
保持のため全層厚みを２ｍｍ以上として検討を始め几。<Problems to be Solved by the Invention> The present inventor investigated the creation of a laminated container consisting of polyolefin and EVO (polyolefin and EVO) using rotational molding instead of blow molding.In coextrusion blow molding, all layers are molded at the same time. Therefore, the number of layers does not have much influence on the production speed, but in rotary molding, the number of layers has a large effect on the production speed because the molding is performed one layer at a time starting from the outer layer.Therefore, the present inventors added polyolefin to the outer layer. We started considering using EVOH for the inner layer and making the total layer thickness 2 mm or more to maintain strong deformation.
また外層ポリオレフィンには必要に応じて接着性樹脂を
混合するか、または内層と外層との中間層に接着性樹脂
層を設けて外層と内層の接着性〜を向上させた。Further, an adhesive resin was mixed with the outer polyolefin layer as necessary, or an adhesive resin layer was provided as an intermediate layer between the inner layer and the outer layer to improve the adhesion between the outer layer and the inner layer.
検討の結巣、ポリオレフィンの外層の上に、または接着
性樹脂の中間層の上にＥＶＯＨの内層を積層する際に二
つの問題点があることが分かった。As a result of the study, two problems were found in laminating an inner layer of EVOH over an outer layer of polyolefin or over an intermediate layer of adhesive resin.
一つはＥＶＯ）（層を薄く成形しようとすると、ＥＶＯ
Ｈ層が不連続になったり、ピンホ゛−ルが生じるなど、
耐薬品性、ガスバリヤ−性を満足する連続したＥＶＯＨ
層の作成が困難であった。共押出ブロー成形ではＥＶＯ
Ｈ層の連続的薄層成形は極めて簡単で、例えばポリエチ
レン／接着性樹脂／ＥＶＯＨの三層構成で全層厚み４■
のガソリンタンクにおけるＥＶＯＨ層の厚みは０．１−
ｆ）、１５ａ＋ｍが標準的で、この厚みで薬品遮断性、
ガスバリヤ−性も十分なことが知られている。一方回転
成形では全層厚み４ｍｍの容器では内層のＥＶＯ）（層
の厚みを２ｍｍを越えて成形しないと、欠点のない連続
層が得られなかった。このようにＥＶＯＨ層の比率が高
いと、容器の耐衝撃性が低下して、容器の形状が限定さ
れるし、コスト高、容器重量増になるなど、問題点を有
し、解決を必要とした。One is EVO) (If you try to mold a thin layer, EVO
The H layer becomes discontinuous, pin holes occur, etc.
Continuous EVOH that satisfies chemical resistance and gas barrier properties
It was difficult to create layers. EVO in coextrusion blow molding
Continuous thin layer molding of the H layer is extremely easy; for example, a three-layer structure of polyethylene/adhesive resin/EVOH can be formed with a total thickness of 4 cm.
The thickness of the EVOH layer in the gasoline tank is 0.1-
f), 15a+m is standard, and this thickness provides chemical barrier properties.
It is also known to have sufficient gas barrier properties. On the other hand, in rotational molding, in a container with a total layer thickness of 4 mm, a continuous layer without defects could not be obtained unless the layer thickness exceeded 2 mm. The impact resistance of the container is reduced, the shape of the container is limited, the cost is high, the weight of the container is increased, and other problems arise, which require a solution.
もう一つの問題点は、平滑なポリオレフィン層または平
滑な接着性樹脂層の上にＥＶＯＨ層を形成したのでは層
間接着力が得られないことであった。通常共押出ブロー
成形ではエバールと接着性ポリオレフィン層との界面は
極めて平滑で、凹凸０．０１０ｍ１１１以下であるにも
かかわらず十分な層間接着力が得られている。一方回転
成形においても通常の方法でポリオレフィン層の成形に
続けてＥＶＯＨの成形にはいると平滑な界面が得られる
が、共押出ブロー成形時とは異なり不十分な接着力しか
得られず、改善が必要であった。Another problem was that interlayer adhesive strength could not be obtained when the EVOH layer was formed on a smooth polyolefin layer or a smooth adhesive resin layer. Normally, in coextrusion blow molding, the interface between EVAL and the adhesive polyolefin layer is extremely smooth, and sufficient interlayer adhesive strength is obtained despite the unevenness being less than 0.010 m111. On the other hand, in rotational molding, a smooth interface can be obtained by molding a polyolefin layer followed by EVOH molding using the usual method, but unlike coextrusion blow molding, insufficient adhesion strength can be obtained and improvements can be made. was necessary.
く課題を解決するための手段〉
本発明者は、これらの問題点について鋭意検討した結果
、ＥｖＯＨのメルトインデックスとＥＶＯＨ層に隣接す
る層の樹脂のメルトインデックス（すなわち外層のポリ
オレフィンのメルトインデックスまたは中間層の接着性
樹脂のメルトインデックス）との関係に留意し、容器成
形時の冷却速度を速めることにより連続したＥＶＯＨ層
の厚みを全層厚みの１／２以下にしてもＥＶＯＨ層の゛
連続形成が可能であり、また内層とこれと隣接する層と
がつくる界面を平滑ではなく、ある程度の凹凸を付ける
ことにより外層と内層の接着性を発現できることを見出
だし、本発明を完成するに至った。Means for Solving the Problems> As a result of intensive studies on these problems, the present inventors determined that the melt index of EvOH and the melt index of the resin in the layer adjacent to the EVOH layer (i.e., the melt index of the polyolefin in the outer layer or the intermediate layer) By paying attention to the relationship with the melt index of the adhesive resin of the layer and increasing the cooling rate during container molding, it is possible to continuously form the EVOH layer even if the thickness of the continuous EVOH layer is reduced to 1/2 or less of the total layer thickness. Furthermore, the inventors have discovered that the adhesiveness between the outer layer and the inner layer can be developed by making the interface between the inner layer and the adjacent layer not smooth, but rather uneven, to a certain extent, leading to the completion of the present invention. .
すなわち本発明は、外層がポリオレフィン、内層がＥＶ
ＯＨ層の少なくとも二層からなり、かつ内層が連続層を
形成し、内層とこれと隣接する層の界面により形成され
る凹凸が０．１１以上である回転成形容器である。That is, in the present invention, the outer layer is made of polyolefin and the inner layer is made of EV.
The rotomolded container is composed of at least two OH layers, the inner layer forms a continuous layer, and the unevenness formed by the interface between the inner layer and the layer adjacent thereto is 0.11 or more.
本発明の容器の外層はポリオレフィンからなる。The outer layer of the container of the invention consists of polyolefin.
ポリオレフィンは耐衝撃性に優れ、水蒸気透過性も小さ
く、また安価であり、さらにまた成形温度を比較的低く
することができるので、本発明の容器の外層として好適
である。ポリオレフィンとしては高、中、低密度ポリエ
チレン、ポリプロピレン、ポリブテン、エチレン−酢酸
ビニル共重合体の単独、あるいは混合物などが適宜使用
できる。Polyolefin is suitable as the outer layer of the container of the present invention because it has excellent impact resistance, low water vapor permeability, is inexpensive, and can be molded at a relatively low temperature. As the polyolefin, high, medium, and low density polyethylene, polypropylene, polybutene, and ethylene-vinyl acetate copolymers may be used alone or in mixtures.
中でもポリエチレンが低温強度にすぐれていて好適であ
る。容器を静置使用する場合はポリオレフィン単独でも
実用接着性は十分で、剥離を起゛こさず使用できるケー
スも多いが、移動容器として使用するときは衝撃による
界面剥離を避ける目的でポリオレフィンに接着性樹脂を
混合することが好ましい。この際の接着性樹脂としては
ポリオレフィンとＥＶＯＨの両方に接着性を示すもので
あればよく、ポリエチレン系をはじめ、エチレン−酢酸
ビニル共重合体系、ポリプロピレン系、ポリスチレン系
、ポリアミド系、ポリエステル系など各種樹脂が使用で
きるが、中でも外層用ポリオレフィンと同種のポリオレ
フィンを不飽和カルボン酸またはその誘導体から選ばれ
た少なくとも一種のモノマーで変性した変性ポリオレフ
ィンが良好である。ポリオレフィンの変性に使用するモ
ノマーとしては、不飽和カルボン酸又はその誘導体が使
用可能で、具体的には、アクリル酸、メタアクリル酸、
マレイン酸、フタル酸、イタコン酸あるいはこれらの無
水物、エステルなどを挙げることができる。Among them, polyethylene is preferred because it has excellent low-temperature strength. When the container is used stationary, polyolefin alone has sufficient practical adhesion and can be used without peeling in many cases, but when used as a moving container, polyolefin with adhesive properties is required to avoid interfacial peeling due to impact. Preferably, the resins are mixed. The adhesive resin used in this case may be any resin that exhibits adhesion to both polyolefin and EVOH, including polyethylene, ethylene-vinyl acetate copolymer, polypropylene, polystyrene, polyamide, and polyester. Although resins can be used, modified polyolefins obtained by modifying the same type of polyolefin as the polyolefin for the outer layer with at least one monomer selected from unsaturated carboxylic acids or derivatives thereof are preferred. As monomers used for modifying polyolefins, unsaturated carboxylic acids or derivatives thereof can be used, and specifically, acrylic acid, methacrylic acid,
Examples include maleic acid, phthalic acid, itaconic acid, anhydrides and esters thereof.
ポリオレフィンと接着性樹脂の好適な混合比率は、ポリ
オレフィン１００重量部に対して接着性樹脂２〜２００
重量部である。２重量部未満では接着力の著しい向上が
認められない場合が多く、一方２００重量部以上では接
着力向上効果に対しコストの増加が著しく、経済的に不
利である。A suitable mixing ratio of polyolefin and adhesive resin is 2 to 200 parts by weight of adhesive resin to 100 parts by weight of polyolefin.
Parts by weight. If the amount is less than 2 parts by weight, no significant improvement in adhesive strength is often observed, while if it is 200 parts by weight or more, the cost increases significantly compared to the effect of improving adhesive strength, which is economically disadvantageous.
本発明において、外層のポリオレフィン層（ポリオレフ
インと接着性樹脂などとの混合物である場合はその混合
物層）のメルトインデックスは、Ｊ ｆ Ｓ Ｋ６７
６０？、ニーよる方法テ１ＪＩ１１定して、２〜２０ｇ
／１０ｍ１ｎ （１９０℃、２１６０ｇ荷重下）が好適
である。メルトインデックスが２ｇ７１０ａｉｎ以下で
は溶融流動性が悪く成形時間か長くなり、かつ製品の表
面か荒れる。一方メルトインデックス２０／ｌｏ＠ｉｎ
以上では溶融流動性が良すぎて容器の均一な厚み分析が
とりにくくなり厚み斑が激しくなり、容器の変形を生じ
る。In the present invention, the melt index of the outer polyolefin layer (if it is a mixture of polyolefin and adhesive resin, the mixture layer) is J f S K67.
60? , 2 to 20g depending on the knee method Te1JI11
/10m1n (190°C, under a load of 2160g) is suitable. If the melt index is less than 2g710ain, the melt fluidity will be poor, the molding time will be long, and the surface of the product will be rough. On the other hand, melt index 20/lo@in
Above this, the melt fluidity is too good, making it difficult to analyze the uniform thickness of the container, resulting in severe thickness unevenness and deformation of the container.
また本発明においては、ポリオレフィン層とＥＶＯ）（
層の中間層に接着性樹脂層を設けることも好ましい態様
のひとつである。中間層に使用する接着性樹脂としては
航記した接着性樹脂と同様のものを使用することができ
る。In addition, in the present invention, the polyolefin layer and EVO) (
It is also one of the preferred embodiments to provide an adhesive resin layer as an intermediate layer of the layers. As the adhesive resin used for the intermediate layer, the same adhesive resins as those mentioned above can be used.
また本発明の容器の内層はＥＶＯＨからなる。Further, the inner layer of the container of the present invention is made of EVOH.
ＥＶＯＨは耐薬品性、ガスバリヤ−性に優れているので
、本発明の容器の内層として好適である。Since EVOH has excellent chemical resistance and gas barrier properties, it is suitable as the inner layer of the container of the present invention.
ＥＶＯＨとしては、エチレン含有率２０〜６５モル％、
好ましくは２０〜６０モル％、さらに好適には２０〜５
５モル％、けん化度９５モル％以上のものが好適に用い
られる。エチレン含有率２０モル％以下では熱安定性が
悪く成形時に変色を生じやすい。一方６５モル％以上で
は耐薬品性、ガスバリヤ−性が低下する。けん化度は９
５モル％以上が好適で、９５％未満では耐薬品性、ガス
バリヤ−性が低下する。EVOH has an ethylene content of 20 to 65 mol%,
Preferably 20 to 60 mol%, more preferably 20 to 5
5 mol % and saponification degree of 95 mol % or more are preferably used. When the ethylene content is less than 20 mol%, thermal stability is poor and discoloration is likely to occur during molding. On the other hand, if it exceeds 65 mol %, chemical resistance and gas barrier properties will decrease. Saponification degree is 9
A content of 5 mol % or more is preferable, and if it is less than 95%, chemical resistance and gas barrier properties will deteriorate.
またＥＶＯＨにはプロピレン、イソブチン、α−オクテ
ンなどのα−オレフィン、不ｔｐｉ和カルボン酸または
その塩またはそのエステル、Ｎ−ビニルピロリドン、ビ
ニルシラン化合物（ビニルトリメトキシシラン、ビニル
トリエトキシシランなど）単位を少量（例えば５モル％
以下）共重合さけてもよい。さらに、本発明において、
内層のＥＶＯＨ眉（ＥＶＯＨと池の樹脂との混合物であ
る場合はその混合物／ｉ）のメルトインデックスは２〜
３［１ｇ／ ｌｏｍｉｎ （１９０℃、２１６０ｇ荷重
下）が好適である。EVOH also contains units of α-olefins such as propylene, isobutyne, and α-octene, untpied carboxylic acids or salts thereof, or esters thereof, N-vinylpyrrolidone, and vinylsilane compounds (vinyltrimethoxysilane, vinyltriethoxysilane, etc.). Small amount (e.g. 5 mol%
(below) copolymerization may be avoided. Furthermore, in the present invention,
The melt index of the inner layer of EVOH eyebrows (if it is a mixture of EVOH and pond resin, the mixture/i) is 2 ~
3 [1 g/lomin (190°C, under a load of 2160 g) is suitable.
メルトインデックスが２以下では溶融流動性が悪く、一
方メルトインデックスが３０以上では溶融流動性が良す
ぎて、いずれもＥＶＯＨ層の成形が阻害される。If the melt index is 2 or less, the melt fluidity is poor, while if the melt index is 30 or more, the melt fluidity is too good, and in either case, the molding of the EVOH layer is inhibited.
またＥＶＯＨにはガスバリヤ−性、耐薬品性を著しく損
なわれない範囲で、他の樹脂、たとえばポリアミド（メ
タキンリレンジアミン基含有ポリアミド、６−ナイロン
、６．６−ナイロン、６．１０−ナイロンなどの各種ポ
リアミド）、ポリエステル（ポリエチレンテレフグレー
トなどの熱可塑性ポリエステル）などを適当！１ｋ（た
とえばＥＶＯＨに対して０，５〜１００重量％）配合す
ることは自由である。EVOH may also contain other resins, such as polyamide (methachinelylenediamine group-containing polyamide, 6-nylon, 6.6-nylon, 6.10-nylon, etc.), as long as gas barrier properties and chemical resistance are not significantly impaired. Various polyamides), polyesters (thermoplastic polyesters such as polyethylene terephraglate), etc. are suitable! 1k (for example, 0.5 to 100% by weight based on EVOH) may be blended freely.
またさらに、本発明におけるＥＶＯＨ層は連続的に形成
されている必要がある。ＥＶＯＨ層が不連続では薬品遮
断性、ガスバリヤ−性が不良で本発明の目的を達成でき
ない。ポリオレフィンを外層としＥＶＯＨを内層とする
回転成形容器におけるＥＶＯＨＩ！の不連続の形態は二
種類あり、一つは、ポリオレフィン層を完全に被覆でき
ずに部分的にＥＶＯＨ層が欠落している場合、もう一つ
は一応被覆はなされているがＥＶＯＨ層にピンホールが
ある場合で、このピンホールはポリオレフィン層の空洞
につながっている。Furthermore, the EVOH layer in the present invention needs to be formed continuously. If the EVOH layer is discontinuous, the chemical barrier properties and gas barrier properties will be poor and the object of the present invention cannot be achieved. EVOHI in a rotomolded container with an outer layer of polyolefin and an inner layer of EVOH! There are two types of discontinuity: one is when the polyolefin layer cannot be completely covered and the EVOH layer is partially missing, and the other is when the EVOH layer is partially covered, but the EVOH layer is not fully covered. If there is a hole, this pinhole is connected to a cavity in the polyolefin layer.
ＥＶＯＨ層の部分的欠落は内層ＥＶＯＨと外層ポリオレ
フィンの相対的流動性が深く関係しており、ＥＶＯＨ層
の部分的欠落を防ぐに好適な、内層のＥＶＯＨ層のメル
トインデックス（ＩＩＩＩＥｖ）と外層のポリオレフィ
ン層のメルトインデックス１ｔｐｏ）との関係は
０．３≦Ｍｌｚｖ／Ｍｌｐ。Partial loss of the EVOH layer is closely related to the relative fluidity of the inner EVOH layer and the outer polyolefin layer, and the melt index (IIIEv) of the inner EVOH layer and the polyolefin outer layer are suitable for preventing partial loss of the EVOH layer. The relationship with the layer melt index (1tpo) is 0.3≦Mlzv/Mlp.
であり、さらに好適な範囲は
０．５≦Ｍ Ｉ Ｅｖ／ Ｍ ｌ ｐｏ≦３．０である
ことを見出だした。It has been found that a more suitable range is 0.5≦M I Ev/M l po≦3.0.
またポリオレフィンを外層、接着性樹脂を中間層、ＥＶ
ＯＨを内層とする回転成形容器においては、ＥＶＯＨ層
の部分的欠落は内層ＥＶＯＨと中間層接着性樹脂の相対
的流動性が深く関係しており、ＥＶＯＨ層の部分的欠落
を防ぐに好適な、内層のＥＶＯＨ層のメルトインデック
ス（Ｍ＋、ｖ）と中間層の接着性樹脂層のメルトインデ
ックス（１１１ＩＡＤ）との関係は
０．３≦Ｍ［！ｖ／ ＭＩＡＤ
であり、さらに好適な範囲は
０．５≦−１１ｔｖ／ＭＩＡｏ≦３．０であることを見
出だした。In addition, polyolefin is used as an outer layer, adhesive resin is used as an intermediate layer, and EV
In rotomolded containers having OH as an inner layer, partial loss of the EVOH layer is closely related to the relative fluidity of the inner layer EVOH and the intermediate layer adhesive resin, and therefore, suitable for preventing partial loss of the EVOH layer. The relationship between the melt index (M+, v) of the inner EVOH layer and the melt index (111IAD) of the intermediate adhesive resin layer is 0.3≦M[! v/MIAD, and a more suitable range is 0.5≦-11tv/MIAo≦3.0.
なお前記メルトインデックスは、１９０°Ｃ，２１６０
ｇ荷重下に測定した値である。Note that the melt index is 190°C, 2160
This is the value measured under g load.
一方もうひとつのＥＶＯＨ層の不連続の形態であるＥＶ
ＯＨＦｉのピンホールについては、回転成形する際の冷
却速度が深く関係していることが分かった。検討当初、
空気冷却方法で検討していたときはＥＶＯＨ層の厚みが
全層厚みの１／２を越えて厚い場合はそれ程問題なかっ
たが、［／２以下ではＥＶＯＨ層と隣接するポリオレフ
ィン層または接着性樹脂層の空洞とこれにつながるＥＶ
ＯＨ層のピンホールが多発して、ＥＶＯＨ層の連続的形
成が出来なかった。その後検討を続けた結果、急速冷却
することにより、ＥＶＯＨ層の厚みが全層厚みのｌ／２
以下でもＥＶＯＨ層のピンホール発生の防止が可能とな
る事を見出だし、さらに検討の結集、成形後の冷却にお
いて、容器を５０℃以下まで５分以内で冷却することが
好ましく、さらに好適には３分以内で冷却することであ
ることを見出だした。On the other hand, another discontinuous form of EVOH layer is EV
It has been found that pinholes in OHFi are closely related to the cooling rate during rotational molding. At the beginning of the study,
When we were considering the air cooling method, there was no problem if the EVOH layer was thicker than 1/2 of the total layer thickness, but if it was less than 1/2, the polyolefin layer or adhesive resin adjacent to the EVOH layer Layer cavity and EV connected to it
There were many pinholes in the OH layer, and the EVOH layer could not be continuously formed. As a result of further investigation, we found that by rapid cooling, the thickness of the EVOH layer could be reduced to 1/2 of the total layer thickness.
We have found that it is possible to prevent the occurrence of pinholes in the EVOH layer by using the following method, and based on our research, it is preferable to cool the container to 50°C or less within 5 minutes after molding. It has been found that cooling can be achieved within 3 minutes.
ここで本発明の回転成形による二層容器の製造法を、２
袖回転成形機を用いて説明すると次の通りである。まず
、外層厚みに応じたポリオレフィン粉末の所定量を金型
に導入し、２軸回転しながら加熱して外層を成形する。Here, the method for manufacturing a two-layer container by rotational molding of the present invention is described in 2.
The explanation using a sleeve rotary molding machine is as follows. First, a predetermined amount of polyolefin powder corresponding to the thickness of the outer layer is introduced into a mold, and heated while rotating on two axes to mold the outer layer.
このときの加熱温度は２５０〜３００℃が好適である。The heating temperature at this time is preferably 250 to 300°C.
外層成形は粉体流動、焼・結、溶融、最後に層形成（ス
ムージング）の堰に為される。外層の層形成（スムージ
ング）の初期〜完了前に回転を止め、手早く内層厚みに
応じたＥＶＯＨ粉末の所定量を同じ金型に導入し、内層
成形に移る。ここで焼結とは粉体が軟化し、粉体同士が
結合している状態を言い、溶融とは粉体が溶融し、溶融
した粉体同士が結合している状態を言う。またスムージ
ングとは成形表面を平滑することであり、スムージング
の初期とは溶融した粉体が粒子状の結合ではなくなり、
完全に溶融して一体化した時期を言い、スムージングの
完了とは成形表面が平滑となった時期をいう。ＥＶＯＨ
の導入時期は成形表面が平滑にならないうちに、すなわ
ちスムージングの初期〜完了前であることが重要である
。完了前とは、完了する前であればいっても良いが、完
了１分前より前であることが好ましい。とくにスムージ
ング中期が最良である。The outer layer is formed by powder flow, sintering/sintering, melting, and finally layer formation (smoothing). From the beginning to the end of the outer layer formation (smoothing), the rotation is stopped, a predetermined amount of EVOH powder corresponding to the inner layer thickness is quickly introduced into the same mold, and the inner layer molding is started. Here, sintering refers to a state in which powders are softened and bonded to each other, and melting refers to a state in which powders are melted and the molten powders are bonded to each other. Also, smoothing refers to smoothing the molding surface, and the initial stage of smoothing means that the molten powder is no longer a particulate bond.
This refers to the time when the materials are completely melted and integrated, and the completion of smoothing refers to the time when the molded surface becomes smooth. EVOH
It is important to introduce before the molding surface becomes smooth, that is, from the beginning to before the completion of smoothing. "Before completion" may be used as long as it is before completion, but it is preferably less than one minute before completion. Especially, the middle stage of smoothing is the best.
内層成形も外層と同様、粉体流動、焼結、溶融、最後に
層形成（スムージング）の順に為されるが、内層成形で
はスムージングを完了させる。外層および内層の成形時
間は、層厚みにもよるが、それぞれ数分〜数十分である
。内層成形が終了した時点で急速冷却に移る。Like the outer layer, inner layer molding is performed in the order of powder flow, sintering, melting, and finally layer formation (smoothing), but smoothing is completed in inner layer molding. The molding time for the outer layer and the inner layer is several minutes to several tens of minutes, depending on the layer thickness. Once the inner layer molding is completed, rapid cooling begins.
急速冷却法としては、水槽浸せき方法、水シヤワ一方式
、冷媒使用方式などを用いて、容器を５０℃以下まで５
分以内に冷却することが好ましく、さらに好適には３分
以内である。通常の空気冷却方式では冷却にｌθ分〜敗
十分を要し、ＥＶＯＨ層の連続形成が困難である。Rapid cooling methods include water tank immersion method, water shower method, and refrigerant method.
Preferably, the cooling time is within 3 minutes, more preferably within 3 minutes. In a normal air cooling method, it takes lθ minutes to ten minutes for cooling, and it is difficult to continuously form an EVOH layer.
次に三層容器の製造法を、二軸回転成形機を用いて説明
すると次の通りである。まず、外層厚みに応じたポリオ
レフィン粉末の所定量を金型に導入し、２軸回転しなが
ら加熱して外層を成形する。Next, the method for manufacturing the three-layer container will be explained using a two-axis rotary molding machine. First, a predetermined amount of polyolefin powder corresponding to the thickness of the outer layer is introduced into a mold, and heated while rotating on two axes to mold the outer layer.
このときの加熱温度は２５０〜３００ ’Ｃが好適であ
る。The heating temperature at this time is preferably 250 to 300'C.
外層成形は粉体流動、焼結、溶融、最後に層形成（スム
ージング）の順に為される。外層の層形成（スムージン
グ）の途中または完了後回転を止め、手早く中間層厚み
に応じた接着性樹脂粉末の所定量を金型に導入し、回転
、加熱を再開し中間層を成形する。中間層成形も粉体流
動、焼結、溶融、最後に層形成（スムージング）の順に
為される。The outer layer is formed in the following order: powder flow, sintering, melting, and finally layer formation (smoothing). During or after the formation of the outer layer (smoothing), the rotation is stopped, a predetermined amount of adhesive resin powder corresponding to the thickness of the intermediate layer is quickly introduced into the mold, and rotation and heating are resumed to mold the intermediate layer. Intermediate layer molding is also performed in the order of powder flow, sintering, melting, and finally layer formation (smoothing).
中間層の層形成（スムージング）の初期〜完了前のいず
れかの時期にＥ Ｖ ’ＯＨ粉末の所定量を同じ金型に
導入し、内層成形に移る。内層成形も外層と同様、粉体
流動、焼結、溶融、最後に層形成（スムージング）の順
に為されるが、内層成形ではスムージングを完了させる
。外層、中間層、および内層の成形時間は、層厚みにも
よるが、それぞれ数分〜数士分である。内層成形が終了
した時点で急速冷却に移る。急速冷却の条件は前記した
二層容器の際の条件と同じである。A predetermined amount of EV'OH powder is introduced into the same mold at some point from the beginning to the completion of layer formation (smoothing) of the intermediate layer, and the process moves to inner layer molding. Like the outer layer, inner layer molding is performed in the order of powder flow, sintering, melting, and finally layer formation (smoothing), but smoothing is completed in inner layer molding. The molding time for the outer layer, middle layer, and inner layer each ranges from several minutes to several minutes, depending on the layer thickness. Once the inner layer molding is completed, rapid cooling begins. The conditions for rapid cooling are the same as those for the two-layer container described above.
このような方法により、内層がピンホールのない連続層
を形成し、かつ内層とこれと隣接する層の界面により、
形成される凹凸が０．ｉｎ＋ｎ以上の回転成形容器を得
ることができる。With this method, the inner layer forms a continuous layer without pinholes, and the interface between the inner layer and the adjacent layer allows
The unevenness formed is 0. A rotomolded container of in+n or more can be obtained.
ピンホールおよび空洞の発生の機構については十分な解
明ができていないが、外層ポリオレフィンと内層ＥＶＯ
Ｈとの冷却過程における収縮挙動または外層ポリオレフ
ィン、中間層接着性引脂および内層’Ｅ’ Ｖ ＯＨの
冷却過程における収縮挙動の相違が関与していると推定
される。Although the mechanism of pinhole and cavity generation has not been fully elucidated, the outer layer polyolefin and the inner layer EVO
It is presumed that the difference in the shrinkage behavior between H and the outer layer polyolefin, the intermediate layer adhesive resin, and the inner layer 'E' V OH during the cooling process is involved.
本発明において、前記界面の凹凸の定義および測定法は
次の通りとする。すなわちコーナー リブ、その池の全
層厚みが急激に変化している部分は除外して、全層厚み
変化および湾曲のない部分または緩やかな部分で、容器
から外壁面にほぼ垂直に切断面を、少なくとも３ケ所よ
り無作為に採取し、ヨ゛つ素溶液の塗布によりＥＶＯＨ
を染色して内層とこれと隣接する層とが作る界面線を鮮
明にした後、無作為に採った幅５ＩＩＩＩ１１の界面線
について、界面線の中心から凸部の最高値（＝最大高さ
）ｈＩｌｌと凹部の最低値（最大深さ）１ｍを測定し、
これを加えたちのｈＩｌｌＩ１１を求め、３ケ所以上の
ｈＩｌｌ＋Ｉｍの平均値をちって凹凸と定義する（第２
図、第５図参照）。In the present invention, the definition and measurement method of the unevenness of the interface are as follows. In other words, excluding the corner rib and the part where the total thickness of the pond changes rapidly, cut the cut surface from the container almost perpendicular to the outer wall surface at the part where there is no change in the total thickness and no curvature or a gentle part. Samples were taken randomly from at least three locations, and EVOH was removed by applying an iodine solution.
After dyeing to clarify the interface line created by the inner layer and the adjacent layer, the highest value of the convex part (= maximum height) from the center of the interface line for the interface line with a width of 5III11 taken at random. Measure hIll and the lowest value (maximum depth) of the recess, 1 m,
By adding this, hIllI11 is calculated, and the average value of hIll+Im at three or more locations is defined as unevenness (second
(See Figure 5).
内層とこれと隣接する層とが作る界面の凹凸を０．１ｍ
ｍ以上に成形するには、前記したとおり、内層用のＥＶ
ＯＨ粉末の金型への添加のタイミングが重要である。こ
のようにＥＶＯＨの添加時期を適切に・選ぶことにより
界面の凹凸を通常［１，１ｍｍ以上、好適には０．２〜
０．８ｍｍとすることができる。もちろん界面が凹凸に
なることで、ＥＶＯＨ層も界面の凹凸とほぼ対応する厚
み斑を持つことになるが、ＥＶＯＨ層が連続的に形成さ
れている限り十分な耐薬品性、ガスバリヤ−性、容器強
度が得られる。凹凸が０，１１未満では内層とこれと隣
接する層の間の接着力が不十分で、注入口などの端面で
の剥離、壁部での外層と内層の剥離とその後のＥＶＯＨ
層の亀裂発生などのトラブル発生の原因となる。凹凸の
上限についてはとくに制限はないが、凹凸が６１を越え
るとＥＶＯＨ層の不連続を生じる恐れがある。The unevenness of the interface between the inner layer and the adjacent layer is 0.1 m.
m or more, as mentioned above, the inner layer EV
The timing of adding the OH powder to the mold is important. In this way, by appropriately selecting the timing of adding EVOH, the unevenness of the interface can be reduced to 1.1 mm or more, preferably 0.2 to 1 mm.
It can be set to 0.8 mm. Of course, as the interface becomes uneven, the EVOH layer will also have a thickness unevenness that roughly corresponds to the unevenness of the interface, but as long as the EVOH layer is formed continuously, sufficient chemical resistance, gas barrier properties, and Provides strength. If the unevenness is less than 0.11, the adhesion between the inner layer and the adjacent layer is insufficient, resulting in peeling at the end face of the injection port, peeling between the outer layer and inner layer at the wall, and subsequent EVOH.
This may cause problems such as cracks in the layer. There is no particular restriction on the upper limit of the unevenness, but if the unevenness exceeds 61, there is a risk that discontinuity will occur in the EVOH layer.
本発明においては、内層のＥＶＯＨ層とこれと隣接する
層との界面が所定の凹凸を形成しておればよく、ＥＶＯ
）（層と隣接していない層、たとえば中間層に接着性樹
脂層を設けた場合、該接着性樹脂層と外層のポリオレフ
ィン層との界面は第５図に示すように、とくに凹凸であ
る必要はなく平滑でもよい。これは接着性樹脂層とポリ
オレフィン層は冷却による収縮の程度が近似しているた
め層間剥離が生じないためである。ただし接着性樹脂層
とポリオレフィン層との界面に凹凸を形成することは不
都合なことではない。ここで内層のＥＶＯＨ層と隣接す
る層とは外層のポリオレフィン層または中間層の接着性
樹脂層である場合が多いが、その他の樹脂層であっても
よい。In the present invention, it is sufficient that the interface between the inner EVOH layer and the layer adjacent thereto forms a predetermined unevenness;
) (When an adhesive resin layer is provided in a layer that is not adjacent to the layer, for example, an intermediate layer, the interface between the adhesive resin layer and the outer polyolefin layer needs to be particularly uneven, as shown in Figure 5. This is because the adhesive resin layer and the polyolefin layer shrink to similar degrees upon cooling, so delamination will not occur.However, the interface between the adhesive resin layer and the polyolefin layer may be smooth. It is not inconvenient to form the EVOH layer.Here, the layer adjacent to the inner EVOH layer is often the outer polyolefin layer or the intermediate adhesive resin layer, but it may be another resin layer. .
本発明に用いるポリオレフィン、接着性樹脂、ＥＶＯＨ
はいずれも粉末状で使用される。本°発明に好適な粉末
の粒度は３０〜１００メツシユである。Polyolefin, adhesive resin, EVOH used in the present invention
Both are used in powder form. The particle size of the powder suitable for the present invention is between 30 and 100 mesh.
形状は球形に近いほど好適である。ポリオレフィンに接
着性樹脂を混合する場合は、通常はそれぞれの粉末を混
合してなされるが、ポリオレフィンと接着性樹脂を先に
溶融混合した後、粉末化したものでもよい。一般にＥＶ
ＯＨは吸水性を有し、含水率が０．３％以上になると成
形時に発泡を生じるが、本発明の容器においてはＥＶＯ
Ｈ層が連続層を形成しているかぎり、ＥＶＯＨ層の若干
の発泡は問題にならず、含水ＥＶＯＨ粉末が使用可能で
あるが、好適な含水率は０．０２〜１．０％である。The closer the shape is to a spherical shape, the better. When an adhesive resin is mixed with a polyolefin, it is usually done by mixing the respective powders, but it is also possible to first melt and mix the polyolefin and the adhesive resin and then pulverize the mixture. Generally EV
OH has water absorption properties, and foaming occurs during molding when the water content exceeds 0.3%, but in the container of the present invention, EVO
As long as the H layer forms a continuous layer, some foaming of the EVOH layer is not a problem and a hydrous EVOH powder can be used, but the preferred water content is 0.02-1.0%.
本発明の容器には、内容物の注入口、取りだし口、圧力
調節口などの目的で、必要に応じて、主として金属製の
開口部を一個以上、取り付けてもよい。開口部の取り付
けは容器成形後に機成加工などでも可能であるが、本発
明の容器においては容器成形と同時に、所謂インサート
成形することが好ましい。内層にＥＶＯＨを用いている
ので金属との接着が良好で、また、冷却時の容器の収縮
が少な（て、開口部付近の残留歪みが小さく、衝撃を受
けた際の亀裂発生が少ない特徴を有する。The container of the present invention may be provided with one or more openings mainly made of metal, as necessary, for the purpose of filling the contents, taking out the contents, adjusting the pressure, etc. The opening can be attached by mechanical processing after the container is formed, but in the container of the present invention, it is preferable to perform so-called insert molding at the same time as the container is formed. Since EVOH is used for the inner layer, it has good adhesion to metal, and the container shrinks less when cooled (therefore, there is less residual strain near the opening, and less cracking occurs when subjected to impact. have
本発明の容器の好適な全層厚みは２＋ｎｍ以上であり、
上限についてはとくに限定はないが２０ａｍ程度である
。またさらに好適な全層厚みは２．５〜１０ｍｍである
。The preferred total thickness of the container of the present invention is 2+ nm or more,
There is no particular limitation on the upper limit, but it is approximately 20 am. Furthermore, a more suitable total layer thickness is 2.5 to 10 mm.
また本発明の容器の好適なＥＶＯＨ層の厚みは０．５ｍ
ｍ〜全層厚みの１／２である。ＥＶＯＨ！の厚みが０．
５ｍｍ未満では溶融流動性の如何にかかわらず連続した
ＥＶＯＨ層の成形がむづかしくなるし、耐薬品性、ガス
バリヤ−性能を得られない。一方ＥＶＯＨ層の厚みが全
層厚みの１／２を越えると、容器の強度の点、さらには
ＥＶＯＨは高価であることから経済性の点で不利である
。Further, the preferred thickness of the EVOH layer of the container of the present invention is 0.5 m.
m to 1/2 of the total thickness. EVOH! The thickness is 0.
If it is less than 5 mm, it will be difficult to form a continuous EVOH layer regardless of the melt flowability, and chemical resistance and gas barrier performance will not be obtained. On the other hand, if the thickness of the EVOH layer exceeds 1/2 of the total layer thickness, it is disadvantageous in terms of the strength of the container and also in terms of economic efficiency since EVOH is expensive.
中間層に接着性樹脂層を設ける場合の、該接着性樹脂層
の厚みは０．５１〜２■である。接着樹脂層は必ずしも
連続層を形成している必要はないが、外層内面の全面に
分布していることが必要で、接着性樹脂層厚みが０．５
ｍｍ以下では接着性樹脂の全面分布ができずに部分的に
接着不良を生じるおそれがある。接着性樹脂層が２ｍｍ
以上では経済的に不利である。When an adhesive resin layer is provided in the intermediate layer, the thickness of the adhesive resin layer is 0.51 to 2 cm. The adhesive resin layer does not necessarily have to form a continuous layer, but it needs to be distributed over the entire surface of the inner surface of the outer layer, and the adhesive resin layer has a thickness of 0.5
If the thickness is less than mm, the adhesive resin may not be distributed over the entire surface, which may result in partial adhesion failure. Adhesive resin layer is 2mm
The above is economically disadvantageous.
なお本発明の容器のポリオレフィン層からなる外層は最
外層であることが多いが、外層の外側にさらに必要に応
じ他の層を設けてもよい。またＥＶＯＨ層からなる内層
は最内層（容器内の充填物と接触する側）であることか
好適である。Although the outer layer made of the polyolefin layer of the container of the present invention is often the outermost layer, other layers may be further provided outside the outer layer as necessary. Further, it is preferable that the inner layer made of the EVOH layer is the innermost layer (the side that comes into contact with the filling in the container).
また本発明の容器の各層には酸化防止剤、熱安定化剤、
架橋剤などを配合することは自由である。In addition, each layer of the container of the present invention contains antioxidants, heat stabilizers,
It is free to add crosslinking agents and the like.
〈実施例〉
実施例１
上部に蓋装着可能なネジ付きインサートメタル開口部を
有する直径３０ｃｍ、容量３０リツトルの円筒形容器製
造用の、樹脂投入口を宵する鋼製金型（肉厚１．５ｍｍ
）を装着した二軸回転成形機を用いて、まず外層用の中
密度ポリエチレン（三井石油化学工業株式会社製、ネオ
ゼツクス２５４０Ｒ１密度＝ ０．９２５、Ｍｔ＝４．
０、粒度３０メツシユ） １００重量部と無水マレイン
酸変性ポリエチレン系接着性樹脂（三井石油化学工業株
式会社製、アトマーＮＲ１０６、密度＝ ０．９３、Ｍ
Ｉ＝９．０、粒度３０メツンユ）１００重量部との混合
物（Ｍ Ｉ ＝ ６．５） １．２３ｋｇを投入し、直
火加熱方式で、２７０°Ｃで、回転加熱して外層を成形
した。外層の成形は、粉体流動、焼結、溶融、スムージ
ングの順に進むが、このスムージングの中期（加熱開始
１１分後）に回転を止め、手早く内層用のＥＶＯＨ扮末
（株式会社クラレ製、エバールＥ Ｐ −Ｅ １０５、
エチレン含有率４４モル％、鹸化度９９．５モル％、密
度＝ １．１４、ＭＩ＝５．５、粒度４０メツンユ）
０．７８ｋｇを投入して、回転加熱を再開した。この系
のＭＩＥＶ／ ＥＩＰＯ＝ ０．８５である。ＥＶＯＨ
層のスムージングが完了したところ（ＥＶＯＨ投人９公
人９分後加熱を止めて、直ちに冷水シャワ一方式で２分
間で４０℃まで急速冷却して、外層ポリエチレン平均厚
み３ｆｆｌＩＩ＋、内層ＥＶＯＨ平均厚み１．５ａ＋ｓ
、全層平均厚み４．５＋ｌ１ｍの回転成形容器を得た。<Examples> Example 1 A steel mold (with a wall thickness of 1.5 mm) equipped with a resin inlet for manufacturing a cylindrical container with a diameter of 30 cm and a capacity of 30 liters, which has a threaded insert metal opening on the top to which a lid can be attached. 5mm
) using a two-axis rotary molding machine equipped with an outer layer of medium density polyethylene (manufactured by Mitsui Petrochemical Industries, Ltd., NEOSEX 2540R1 density = 0.925, Mt = 4.
0, particle size 30 mesh) and 100 parts by weight of maleic anhydride-modified polyethylene adhesive resin (manufactured by Mitsui Petrochemical Industries, Ltd., Atmer NR106, density = 0.93, M
1.23 kg of a mixture (MI = 6.5) with 100 parts by weight (I = 9.0, particle size 30 Metsuyu) was added, and an outer layer was formed by rotating and heating at 270 ° C using a direct flame heating method. . The molding of the outer layer proceeds in the order of powder flow, sintering, melting, and smoothing, but in the middle of this smoothing (11 minutes after the start of heating), the rotation is stopped and the EVOH dressing powder (manufactured by Kuraray Co., Ltd., EVAL) for the inner layer is quickly applied. E P-E 105,
Ethylene content 44 mol%, saponification degree 99.5 mol%, density = 1.14, MI = 5.5, particle size 40 mol%)
0.78 kg was added and rotational heating was restarted. MIEV/EIPO of this system is 0.85. EVOH
When the smoothing of the layer was completed (EVOH cast 9 public figures 9 minutes later, the heating was stopped and immediately cooled rapidly to 40°C in 2 minutes with one cold water shower. The outer layer polyethylene average thickness was 3fflII+, and the inner layer EVOH average thickness was 1. .5a+s
A rotomolded container having an average thickness of 4.5+1 m in all layers was obtained.
得られた容器の内層表面は平滑でＥＶＯＨ特有の光沢を
有し、ピンホールもなく完全な連続層を形成しており、
また外層と内層は強固に接着しており手で剥離できなか
った。得られた容器を開口部を開放し−で２０℃、６５
％ＲＨに２ケ月放置してＥＶＯＨ層の吸湿による重量変
化が無くなったのを確認の後、クロロホルムを１５ｋｇ
充填して、開口部をネジ蓋で密封した後、更に同条件で
３ケ月放置したが、重量変化は無（、また内層の何等の
変化も無く、容器の耐溶剤性、溶剤遮断性がすぐれてい
ることが確認できた。また別に、得られた容器について
２７リツトルの水を充填し、開口部にネジ蓋をした後、
底部を下にして、２ｆｆＩの高さからコンクリート面に
落下させたが、眉間剥離はなく、また内層に亀裂なども
生じなかった。また、底面平坦部の断面３ケ所について
測定した平均値は、外層厚み２．６ａ＋ｓ、内層厚み１
、３ａｍ、全層厚み３．９ｍｍ。The inner layer surface of the resulting container is smooth and has the characteristic gloss of EVOH, and forms a completely continuous layer with no pinholes.
Furthermore, the outer layer and inner layer were strongly adhered to each other and could not be peeled off by hand. The resulting container was heated at 20°C and 65°C with the opening opened.
After leaving it at %RH for 2 months and confirming that the weight change due to moisture absorption in the EVOH layer has disappeared, add 15 kg of chloroform.
After filling the container and sealing the opening with a screw cap, the container was left under the same conditions for 3 months, but there was no change in weight (or any change in the inner layer), and the container had excellent solvent resistance and solvent barrier properties. Separately, after filling the obtained container with 27 liters of water and putting a screw cap on the opening,
The product was dropped onto a concrete surface from a height of 2ffI with its bottom facing down, but there was no peeling between the eyebrows or cracks in the inner layer. In addition, the average value measured at three cross-sectional locations on the flat bottom part is that the outer layer thickness is 2.6a+s, and the inner layer thickness is 1.
, 3am, total thickness 3.9mm.
外層と内層が作る界面の凹凸は０．２８℃１ｍであった
。The unevenness of the interface between the outer layer and the inner layer was 0.28°C and 1 m.
一方側面円筒部の円周と直角方向の断面３ケ所について
測定した平均値は、外層厚み３．２ｍｍ５内層厚み１．
６ｏ＋ｍ、全層厚み４．８■、外層と内層が作る界面の
凹凸（↓０，２７ｍ＋ａであった。On the other hand, the average values measured at three cross sections in the direction perpendicular to the circumference of the side cylindrical part were: outer layer thickness: 3.2 mm, inner layer thickness: 1.
6o+m, total layer thickness 4.8cm, unevenness of the interface created by the outer layer and inner layer (↓0.27m+a).
実施例２
外層用の中密度ポリエチレン１００重量部と無水マレイ
ン酸変性ポリエチレン系接着性樹脂１６０重量部との混
合物の没入量を１．６４ｋｇ、内層用のＥＶＯＨの投入
量を１．０４ｋｇとし、外層成形の加熱時間１４分間、
内層用ＥＶＯＨ投人後の加熱時間１１分、冷却時間３分
を要した以外は、実施例１と同装置、同条件で容器を作
成し、外層の平均厚み４．０ｍｍ、内層の平均厚み２．
０ｍｍ、全層の平均厚み６．０ｍｙｌの容器を得た。得
られた容器の内層表面は平滑でＥＶＯＨ特有の光沢を有
し、ピンホールもなく完全な連続層を形成しており、ま
た外層と内層は強固に接着しており、実施例１と同様に
落下テストを実施したが、層間剥離はなく、内層に亀裂
は生じなかった。底面平坦部の断面３ケ所について測定
した平均値は、外層厚み３ 、５ｍｍ、内層厚み１．７
ｍａ＋、全層厚み５．２Ｉ、外層と内層が作る界面の凹
凸は０．３０ｍｍであった。一方側面円筒部の円周と直
角方向の断面３ケ所について測定した平均値は、外層厚
み４．３ｍｍ、内層厚み２．１ｍｍ、全層厚み８．４ｍ
ａ、外層と内層が作る界面の凹凸は３．４部ｍであった
。Example 2 The amount of the mixture of 100 parts by weight of medium density polyethylene and 160 parts by weight of maleic anhydride modified polyethylene adhesive resin for the outer layer was 1.64 kg, the amount of EVOH for the inner layer was 1.04 kg, and the amount of EVOH for the inner layer was 1.04 kg. Heating time for molding: 14 minutes,
A container was made using the same equipment and under the same conditions as in Example 1, except that it took 11 minutes for heating and 3 minutes for cooling after pouring the EVOH for the inner layer, and the average thickness of the outer layer was 4.0 mm, and the average thickness of the inner layer was 2. ．．
A container having a thickness of 0 mm and an average thickness of all layers of 6.0 ml was obtained. The inner layer surface of the obtained container was smooth and had the gloss characteristic of EVOH, and there were no pinholes, forming a completely continuous layer. Also, the outer layer and inner layer were strongly adhered, and as in Example 1. A drop test was conducted, but there was no delamination or cracks in the inner layer. The average values measured at three cross-sectional locations on the flat part of the bottom are: outer layer thickness of 3 and 5 mm, and inner layer thickness of 1.7 mm.
ma+, the total layer thickness was 5.2I, and the unevenness of the interface between the outer layer and the inner layer was 0.30 mm. On the other hand, the average values measured at three cross sections in the direction perpendicular to the circumference of the side cylindrical part are: outer layer thickness 4.3 mm, inner layer thickness 2.1 mm, and total layer thickness 8.4 m.
a. The unevenness of the interface between the outer layer and the inner layer was 3.4 parts m.
比較例１
゛冷却を空気冷却方式を用いて冷却に２０分を°要した
以外は実施例１゛と同装置、同条件で容器を作成した。Comparative Example 1 A container was prepared using the same equipment and under the same conditions as Example 1, except that an air cooling method was used for cooling and cooling took 20 minutes.
得られた容器は、内層表面は平滑でＥＶＯＨ特有の光沢
を有していたが、ポリエチレン混合物層の空洞につなが
るＥＶＯＨＩ！Ｉのピンホールが側面円筒部に多発して
、ＥＶＯＨ層の連続的形成が出来ていなかった。なお外
層と内層は強固に接着しており手で剥離できなかった。In the resulting container, the inner layer surface was smooth and had the gloss characteristic of EVOH, but the EVOH! There were many pinholes in the cylindrical side surface, and the EVOH layer could not be continuously formed. Note that the outer layer and inner layer were strongly adhered to each other and could not be peeled off by hand.
底面平坦部の断面３ケ所で外層と内層が作る界面の凹凸
を測定したところ、平均０．３０ｍｍであった。゛また
ピンホールを避けて採取した側面円筒部の円周と直角方
向の断面３ケ所で外層と内層が作る界面の凹凸を測定し
たところ平均０．５１ｍｍであった。When the unevenness of the interface between the outer layer and the inner layer was measured at three locations on the cross section of the flat bottom portion, the average was 0.30 mm. ``Furthermore, the unevenness of the interface between the outer layer and the inner layer was measured at three locations in a cross section perpendicular to the circumference of the side cylindrical portion, which was sampled while avoiding pinholes, and found an average of 0.51 mm.
比較例２
外層用樹脂（混合物）の投入ｆｉ０．８２ｋｇ、外層成
形スムージング中期迄の加熱時間８分、内層用ＥｖＯＨ
の投入量１．０４ｋｇ、 Ｅ Ｖ ＯＨ投入後内層スム
ージング完了迄の加熱時間１１分、空気空冷方式を用い
て冷却に１８分を要した以外は実施例１と同装置、同条
件を用いて容器を作成し、外層の平均厚み２−０ｍｗ、
内層平均厚み２ 、０ ｍ ｌｌ１％全層厚み４ 、
Ｏｍｍの容器を得た。得られた容器は、内層表面は平滑
でＥＶＯＨ特有の光沢を有していたが、側面円筒部にピ
ンホールが散見され、完全な連続層を形成していなかっ
た。なお外層と内層は強固に接着しており手で剥離でき
なかった。また実施例１と同様に落下テストを実施した
が、層間剥離はなく、内層に亀裂は生じなかった。底面
平坦部の断面３ケ所で外層と内層が作る界面の凹凸を測
定したところ、平均０．２６０１１１１であった。また
ピンホールから離れた側面円筒部の円周と直角方向の断
面３ケ所で外層と内層が作る界面の凹凸をρ１定したと
ころ平均０．３２ｍｍであった。Comparative Example 2 Input fi0.82 kg of resin (mixture) for outer layer, heating time 8 minutes until middle stage of outer layer molding smoothing, EvOH for inner layer
A container was prepared using the same equipment and conditions as in Example 1, except that the input amount was 1.04 kg, the heating time was 11 minutes until the inner layer smoothing was completed after EV OH was added, and it took 18 minutes to cool down using the air cooling method. and the average thickness of the outer layer is 2-0 mw,
Inner layer average thickness 2, 0 ml 1% total layer thickness 4,
A container of Omm was obtained. The obtained container had a smooth inner layer surface and a gloss characteristic of EVOH, but pinholes were found here and there in the cylindrical side surface, and a completely continuous layer was not formed. Note that the outer layer and inner layer were strongly adhered to each other and could not be peeled off by hand. Further, a drop test was conducted in the same manner as in Example 1, but there was no delamination between the layers and no cracks were generated in the inner layer. When the unevenness of the interface between the outer layer and the inner layer was measured at three locations on the cross section of the flat bottom portion, the average was 0.2601111. Further, when the unevenness of the interface between the outer layer and the inner layer was determined as ρ1 at three locations in the cross section in the direction perpendicular to the circumference of the side cylindrical portion away from the pinhole, the average was 0.32 mm.
比較例３
ＥＶＯＨの添加時期を外層のスムージング終了後に変更
（外層加熱時間１３分）した以外は実施例１と同装置、
同条件で容器を作成した。得られた容器の内層表面は平
滑でＥＶＯＨ特有の光沢を有し、穴、ピンホール等のも
なく完全な連続層を形成していたが、外層と内層の層間
接着力は弱く、手で引っ張ると剥離可能で、実施例１と
同様の落下テストで簡単に剥離が生じ、ＥＶＯＨ層の１
部に亀裂が生じた。底面平坦部の断面３ケ所および側面
円筒部の円周と直角方向の断面３ケ所で外層と内層が作
る鉄面の凹凸を測定した平均したところどちらも、０．
０５ｍｍ以下であった。Comparative Example 3 Same device as Example 1 except that the timing of adding EVOH was changed after the smoothing of the outer layer was completed (outer layer heating time was 13 minutes).
A container was created under the same conditions. The inner layer surface of the obtained container was smooth and had the characteristic gloss of EVOH, and it formed a completely continuous layer with no holes or pinholes, but the interlayer adhesion between the outer layer and the inner layer was weak and it was difficult to pull it by hand. The EVOH layer was easily peeled off in the same drop test as in Example 1.
A crack appeared in the part. The unevenness of the iron surface created by the outer layer and inner layer was measured at three cross-sectional locations on the flat bottom portion and at three cross-sectional locations perpendicular to the circumference of the side cylindrical portion, and both were averaged to be 0.
It was 0.05 mm or less.
実施例３
内層にエチレン含有率４８モル％、鹸化度９９．５モル
％、ＭＩ＝１４、粒度４０メツンユのＥＶＯＨ（昧弐会
社りラレ製、エバールＥ Ｐ −Ｇ １１０）を用いた
以外は、実施例１と同条件で容器を作成した。Example 3 Except for using EVOH (Eval E P-G 110, manufactured by Rirare) with an ethylene content of 48 mol%, a saponification degree of 99.5 mol%, MI = 14, and a particle size of 40 mol% for the inner layer. A container was created under the same conditions as in Example 1.
この系のＭ１εｖ／ＭＩＰＯ＝ ２．２である。得られ
た容器の内層表面は平滑でＥＶＯＨ特有の光沢を有し、
穴、ピンホール等もなく完全な連続層を形成しており、
また外層と内層は強固に接着しており手で剥離できなか
った。また実施例１と同様に落下テストを実施したが、
眉間剥離はなく、内層に亀裂は生じなかった。底面平坦
部の断面３ケ所について測定した平均値は、外層厚み２
．６ｍ＠、内層厚み１、ＬＩＩＩｍ、全層厚み３．７ｍ
ｍ、外層と内層が作る界面の凹凸は０．３６＋ｎｍであ
った。一方側面円筒部の円周と直角方向の断面３ケ所に
ついて測定した平均値は、外層厚み３ 、２ ｍ ｍ
％内層厚み１．７ｍｍ、全層厚み４．９ｍ＋ｎ、外層と
内層が作る界面の凹凸は０．３２ｏ＋ｍであった。M1εv/MIPO of this system is 2.2. The inner layer surface of the obtained container is smooth and has the gloss characteristic of EVOH,
Forms a completely continuous layer with no holes or pinholes.
Furthermore, the outer layer and inner layer were strongly adhered to each other and could not be peeled off by hand. In addition, a drop test was conducted in the same manner as in Example 1, but
There was no peeling between the eyebrows, and no cracks occurred in the inner layer. The average value measured at three cross-sectional locations on the flat bottom part is the outer layer thickness 2
．． 6m@, inner layer thickness 1, LIIIm, total layer thickness 3.7m
m, and the unevenness of the interface between the outer layer and the inner layer was 0.36+nm. On the other hand, the average value measured at three cross sections in the direction perpendicular to the circumference of the side cylindrical part is that the outer layer thickness is 3.2 mm.
The inner layer thickness was 1.7 mm, the total layer thickness was 4.9 m+n, and the unevenness of the interface between the outer layer and the inner layer was 0.32 o+m.
実施例４
内層にエチレン含有率３２モル％、鹸化度９９５モル％
、ＭＩ＝４．０、芋立度４０メツツユのＥＶＯＨ（株式
会社クラレ製、エパールＥ Ｐ −Ｆ １０４）を用い
た以外は、実施例１と同条件で容器を作成した。この系
のｉＡ Ｉ ｔ ｖ／ Ｅ Ｉ ｐ ｏ ＝ ０ 、６
２である。得られた容器の内層表面は平滑でＥＶＯＨ特
有の光沢を有し、ピンホール等もなく完全な連続層を形
成しており、また外層と内層は強固に接着しており手で
剥離できなかった。また実施例１と同様に落下テストを
実施したが、層間剥離はなく、内層に亀裂は生じなかっ
た。底面平坦部の断面３ケ所についてポ１１定した平均
値は、外層厚み２．６ｍｍ、内層厚み１ 、３ｍｍ、全
層厚み３．９ｍｏ＋、外層と内層か作る界面の凹凸は０
．３５＋Ｉ＋＋であった。一方側面円筒部の円周と直角
方向の断面３ケ所について測定した平均値は、外層厚み
３．２ｍｍ、内層厚み１．６ｍ＠、全層厚み４．’８ｍ
ｍ５外層と内層が作る界面の凹凸は０．３６１１＋ｆｆ
ｌであった。Example 4 Ethylene content in inner layer: 32 mol%, saponification degree: 995 mol%
A container was produced under the same conditions as in Example 1, except that EVOH (manufactured by Kuraray Co., Ltd., Epal EP-F 104) with an MI of 4.0 and a hardness of 40 was used. iA I tv/ E I po = 0, 6 for this system
It is 2. The inner layer surface of the obtained container was smooth and had the characteristic gloss of EVOH, and there were no pinholes, forming a completely continuous layer, and the outer layer and inner layer were strongly adhered and could not be peeled off by hand. . Further, a drop test was conducted in the same manner as in Example 1, but there was no delamination between the layers and no cracks were generated in the inner layer. The average values determined for three cross sections of the flat bottom part are: outer layer thickness 2.6 mm, inner layer thickness 1 and 3 mm, total layer thickness 3.9 mo+, and the unevenness of the interface between the outer layer and the inner layer is 0.
．． It was 35+I++. On the other hand, the average values measured at three cross sections in the direction perpendicular to the circumference of the side cylindrical part are: outer layer thickness 3.2 mm, inner layer thickness 1.6 m@, and total layer thickness 4.2 mm. '8m
m5 The unevenness of the interface between the outer layer and the inner layer is 0.3611+ff
It was l.
比較例４
内層にエチレン含有率３２モル％、鹸化度９９．５モル
％、Ｍ Ｉ ＝ １．３、粒度メツシュのＥＶＯＨ（株
式会社クラレ製、エバールＥ Ｐ −Ｆ １０１）を用
いた以外は、実施例１と同条件で容器を作成した。この
系のＭＩＥｖ／ １１１ｐｏ＝ ０．２０である。得ら
れた容器は内層表面が凹凸でかつＥＶＯＨか連続層を形
成しておらず、耐薬品性、ガスバリヤ−性能が期待でき
ないものであった。Comparative Example 4 Except for using EVOH (manufactured by Kuraray Co., Ltd., EVAL E P-F 101) with an ethylene content of 32 mol%, a saponification degree of 99.5 mol%, M I = 1.3, and a mesh particle size for the inner layer. A container was created under the same conditions as in Example 1. MIEv/111po of this system is 0.20. The resulting container had an uneven inner layer surface and did not form a continuous EVOH layer, and could not be expected to have chemical resistance or gas barrier performance.
実施例５
外層用樹脂粉末を中密度ポリエチレン単独とした・以外
は、実施例１と同装置、同条件で容器を作成し、外層の
平均厚み３．０ｍｍ、内層の平均厚み１．５ｍｍ、全層
の平均厚み４．５ｍｍの容器を得た。この系の旧εｖ
／ Ｅ Ｉ ｐ ｏ ＝ １ 、４である。得られた容
器の内層表面は平滑でＥＶＯＨ特有の光沢を有し、ピン
ホールらなく完全な連続層を形成しており、また外層と
内層の接着は充分で、空容器を底部を下にして２ｍの高
さから落下テストを実施したが、層間剥離はなく、内層
に亀裂は生じなかった。また別に、得られた容器を開口
部を開放して２０℃、６５％ＲＨに２ケ月放置してＥＶ
ＯＨ層の吸湿によるＭｉｌｋ変化が無くなったのを確認
の後、クロロホルムを１５ｋｇ充填して、開口部をネジ
蓋で密封した後、更に同条件で３ケ月放置したが、重量
変化は無く、また内層の何等の変化も無く、層間の剥離
も生じていなかった。底面平坦部の断面３ケ所について
測定した平均値は、外層厚み２．６０１１１１、内層厚
み１．３ｍｍ、全層厚み３．９ｍｍ、外層と内層が作る
界面の凹凸は０．３３ｍｍであった。一方側面円筒部の
円周と直角方向の断面３ケ所について測定した平均値は
、外層厚み３．２ｒＲ＋ｎ、内層厚み１ 、６ｍｍ、全
層厚み４．８１１１１０．外層と内層が作る界面の凹凸
は０ 、３０ｍｍであった。Example 5 A container was made using the same equipment and under the same conditions as in Example 1, except that the resin powder for the outer layer was medium density polyethylene alone, and the average thickness of the outer layer was 3.0 mm, the average thickness of the inner layer was 1.5 mm, and the entire container was A container with an average layer thickness of 4.5 mm was obtained. The old εv of this system
/ E I p o = 1,4. The surface of the inner layer of the obtained container was smooth and had the gloss characteristic of EVOH, and it formed a completely continuous layer without pinholes, and the adhesion between the outer layer and inner layer was sufficient, and the empty container could be placed with the bottom facing down. A drop test was conducted from a height of 2 m, but there was no delamination or cracks in the inner layer. Separately, EV
After confirming that there was no change in milk due to moisture absorption in the OH layer, 15 kg of chloroform was filled, the opening was sealed with a screw cap, and the opening was left for another 3 months under the same conditions, but there was no change in weight and the inner layer There was no change in the composition, and no peeling occurred between the layers. The average value measured at three cross-sectional locations on the flat bottom part was that the outer layer thickness was 2.601111 mm, the inner layer thickness was 1.3 mm, the total layer thickness was 3.9 mm, and the unevenness of the interface between the outer layer and the inner layer was 0.33 mm. On the other hand, the average values measured for three cross sections perpendicular to the circumference of the side cylindrical part are: outer layer thickness 3.2rR+n, inner layer thickness 1 and 6mm, and total layer thickness 4.811110. The unevenness of the interface between the outer layer and the inner layer was 0.30 mm.
実施例６
上部に蓋装着可能なネジ付きインサートメタル開口部を
有する直径３０ｃｍ、容量３０リツトルの円筒形容器製
造用の、樹脂投入口を有する調製金型（肉厚１．５ｍｍ
）を装着した二軸回転成形機を用いて、まず外層用の中
密度ポリエチレン（三井石油化学工業株式会社製、ネオ
ゼックス２５４ＯＲ１密度＝ ０．９２５． Ｍ に４
．０、粒度３０メツンユ） ０．６２ｋｇ投入し、直火
加熱方式で、２７０ ’Ｃで、回転加熱して外層を成形
する。外層の成形は、粉体流動、焼結、溶融、スムージ
ングの順に進むが、このスムージングの中期（加熱開始
７分後）に回転を止め、手早く中間層用のポリエチレン
系接着性樹脂（三井石油化学工業株式会社製、アトマー
Ｎ Ｒ１０６、密度＝ ０．９３、Ｍ Ｉ ” ９．０
、粒度３０メツシユ） ０．６１ｋｇを投入し回転加熱
を再開する。中間層の成形も、粉体流動、焼結、溶融、
スムージングの順に進むが、このスムージングの中期（
加熱再開６分後）に回転を止め、ＥＶＯＨ粉体（株式会
社クラレ製、エバールＥ Ｐ −２１０５、エチレン含
有率４４モル％、鹸化度９９．５モル％、密度＝１１４
、Ｍ Ｉ ＝ ５．５、粒度４０メツシユ） ０．７８
ｋｇを投入して、回転加熱を再開する。この系のＭ Ｉ
ｔ Ｖ／ Ｍ Ｉ Ａｏ ＝ ０ 、６１である。内
層の成形も、粉体流動、焼結、溶融、スムージングの順
に進むが、ＥＶＯＨ層のスムージングが完了したとこ、
ろ（ＥＶＯＨ投入９分後）で加熱を止めて、直ちに冷水
シャワ一方式で２分間で４０ ’（まで急速冷却して、
外層＋中間層平均厚み３．０、内層平均厚み１．５Ｉ、
全層平均厚み４．５ｍｍの回転成形容器を得た。得られ
た容器の内層表面は平滑でＥＶＯＨ特有の光沢を有し、
ピンホールもなく完全な連続層を形成しており、また外
層と中間層、および中間層と内層は強固に接着しており
手で剥離できなかった。また、得られた容器について２
７リツトルの水を充填し、開口部にネジ蓋をした後、底
部を下にして、２ｍの高さからコンクリート面に落下さ
せたが、層間剥離はなく、また内層に亀裂などら生じな
かった。また、底面平坦部の断面３ケ所について測定し
た平均値は、外層＋中間層厚み２．６１１１１１％内層
厚み１．３ｍ１ｍ、全層厚み３．９ｍｆｆ１、中間層と
内層が作る界面の凹凸は０．３２ｍｍであった。一方側
面円筒部の円周と直角方向の断面３ケ所について測定し
た平均値は、外層＋中間層厚み３．２■、内層厚み１
、６ｍｍ、全層厚み４ 、８ｍｍ５外層と内層が作る界
面の凹凸は０．３３ｍｍであった。Example 6 A preparation mold (wall thickness 1.5 mm) with a resin inlet for manufacturing a cylindrical container with a diameter of 30 cm and a capacity of 30 liters, which has a threaded insert metal opening on the top to which a lid can be attached.
) using a two-shaft rotary molding machine equipped with a medium-density polyethylene for the outer layer (manufactured by Mitsui Petrochemical Industries, Ltd., Neozex 254OR1 density = 0.925. M to 4
．． 0.62kg (particle size: 30m2) was added, and the outer layer was formed by rotating and heating at 270'C using a direct flame heating method. Molding of the outer layer proceeds in the order of powder flow, sintering, melting, and smoothing, but in the middle of this smoothing (7 minutes after heating starts), the rotation is stopped and the polyethylene adhesive resin for the middle layer (Mitsui Petrochemical Manufactured by Kogyo Co., Ltd., Atmer N R106, density = 0.93, M I ” 9.0
, particle size: 30 mesh) and restart rotating heating. Forming of the intermediate layer is also possible through powder flow, sintering, melting,
The process proceeds in the order of smoothing, but this middle stage of smoothing (
6 minutes after resuming heating, the rotation was stopped and EVOH powder (manufactured by Kuraray Co., Ltd., EVAL EP-2105, ethylene content 44 mol%, degree of saponification 99.5 mol%, density = 114
, M I = 5.5, grain size 40 mesh) 0.78
kg, and restart rotating heating. M I of this system
tV/MIAo=0,61. Molding of the inner layer also proceeds in the order of powder flow, sintering, melting, and smoothing, but once the smoothing of the EVOH layer is completed,
Stop the heating with a filter (9 minutes after adding EVOH), and immediately cool down to 40'(40') in 2 minutes with one cold water shower.
Outer layer + middle layer average thickness 3.0, inner layer average thickness 1.5I,
A rotomolded container having an average thickness of 4.5 mm in all layers was obtained. The inner layer surface of the obtained container is smooth and has the gloss characteristic of EVOH,
A completely continuous layer was formed with no pinholes, and the outer layer and middle layer, as well as the middle layer and inner layer, were strongly adhered and could not be peeled off by hand. Also, regarding the obtained container, 2
After filling the container with 7 liters of water and screwing on the opening, the container was dropped from a height of 2 meters onto a concrete surface with the bottom facing down, but there was no delamination or cracks in the inner layer. . In addition, the average values measured at three cross-sectional locations on the flat bottom part are: outer layer + middle layer thickness: 2.6111111% inner layer thickness: 1.3 m1 m, total layer thickness: 3.9 mff1, and the unevenness of the interface between the middle layer and the inner layer is 0. It was 32 mm. On the other hand, the average values measured at three cross sections in the direction perpendicular to the circumference of the side cylindrical part are: outer layer + middle layer thickness: 3.2cm, inner layer thickness: 1.
, 6 mm, total layer thickness 4, 8 mm, and the unevenness of the interface between the outer layer and the inner layer was 0.33 mm.
実施例７
外層用の中密度ポリエチレンの投入量０．８２ｋｇ、中
間層用のポリエチレン系接着性樹脂の投入量を０．８２
ｋｇ、内層用（７）ＥＶＯＨ（７）投入量を１．０４ｋ
ｇとし、外、ｇ成形の加熱時間８分、中間層成形の加熱
時間７分、内層用ＥＶＯＨ投入後の加熱時間１１分、冷
却時間３分を要した以外は、実施例６と同装置、同条件
で容器を作成し、外層＋中間層の平均厚み４．０ｍｍ、
内層の平均厚み２．０ｍｍ、全層の平均厚み６．０ｍｍ
の容器を得た。得られた容器の内層表面は平滑でＥＶＯ
Ｈ特有の光沢を有し、ピンホールもなく完全な連続層を
形成しており、また外層と中間層、および中間層と内層
は強固に接着しており、実・施例６と同様に落下テスト
を実施したが、眉間剥離はなく、内層に亀裂は生じなか
った。底面平坦部の断面３ケ所について測定した平均値
は、外層＋中間層厚み３．５■、内層厚み１．７ｍｍ、
全層厚み５．２ｍｍ、中間層と内層が作る界面の凹凸は
ＯＪ４ｍｍであった。一方側面円筒部の円周と直角方向
の断面３ケ所について測定した平均値は、外層＋中間層
厚み４ 、３ｍｍ、内層厚み２．１ｍｌ１１、全層厚み
６ 、４ ｍ’ｍ ｓ中間層と内層が作る界面の凹凸は
３． ｌｆｆ１ｍであった。Example 7 The amount of medium density polyethylene for the outer layer was 0.82 kg, and the amount of polyethylene adhesive resin for the middle layer was 0.82 kg.
kg, inner layer (7) EVOH (7) input amount 1.04k
The same apparatus as Example 6 was used, except that the heating time for outer and g molding was 8 minutes, the heating time for intermediate layer molding was 7 minutes, the heating time was 11 minutes after charging the EVOH for the inner layer, and the cooling time was 3 minutes. A container was made under the same conditions, and the average thickness of the outer layer + middle layer was 4.0 mm.
Average thickness of inner layer 2.0mm, average thickness of all layers 6.0mm
I got a container of. The inner layer surface of the obtained container was smooth and EVO
It has the unique gloss of H, and forms a completely continuous layer with no pinholes. Also, the outer layer and the middle layer, and the middle layer and the inner layer are strongly bonded, and as in Example 6, it does not fall off. Tests were performed and there was no glabellar peeling and no cracks in the inner layer. The average values measured at three cross-sectional locations on the flat bottom part were: outer layer + middle layer thickness 3.5 mm, inner layer thickness 1.7 mm,
The total thickness was 5.2 mm, and the unevenness at the interface between the intermediate layer and the inner layer was OJ 4 mm. On the other hand, the average values measured at three cross sections in the direction perpendicular to the circumference of the side cylindrical part are: outer layer + intermediate layer thickness 4.3 mm, inner layer thickness 2.1 ml11, total layer thickness 6.4 mm s intermediate layer and inner layer. The unevenness of the interface created by 3. It was lff1m.
比較例５
冷却を空気冷却方式を角いて冷却に２０分を要した以外
は実施例６と同装置、同条件で容器を作成した。得られ
た容器は、内層表面は平滑でＥＶＯＨ特有の光沢を有し
ていたが、接着性樹脂層の空洞につながるＥＶＯＨ眉の
ピンホールが・側面円筒部に多発して、ＥＶＯＨ層の連
続的形成が出来ていなかった。なお外層と中間層、およ
び中間層と内層は強固に接着しており手で剥離できなか
った。Comparative Example 5 A container was produced using the same apparatus and under the same conditions as in Example 6, except that the air cooling method was changed and cooling took 20 minutes. The obtained container had a smooth inner layer surface and a gloss characteristic of EVOH, but there were many pinholes in the EVOH eyebrows that connected to the cavities in the adhesive resin layer and in the cylindrical side surface, and the EVOH layer was continuous. It was not possible to form. Note that the outer layer and the intermediate layer, and the intermediate layer and the inner layer were strongly adhered to each other and could not be peeled off by hand.
底面平坦部の断面３ケ所で中間層と内層を作る界面の凹
凸を測定したところ、平均０．３５ｍｍであった。The unevenness of the interface between the intermediate layer and the inner layer was measured at three locations on the cross section of the flat bottom portion, and the average was 0.35 mm.
またピンホールを避けて採取した側面円筒部の円周と直
両方向の断面３ケ所で中間層と内層が作る界面の凹凸を
測定したところ平均０．４８ｍｍであった。In addition, the unevenness of the interface between the intermediate layer and the inner layer was measured at three locations in the cross section in the direction perpendicular to the circumference of the side cylindrical portion, which was sampled while avoiding pinholes, and found that the average was 0.48 mm.
比較例６
外層用ポリエチレンの投入量０．４１ｋｇ、外層成形ス
ムージング中期迄の加熱時間約６分、中間層用接着性樹
脂の投入量０．４１ｋｇ、中間層成形スムージング中期
迄の加熱時間約４分、内層用ＥＶＯＨの投入量１．０４
ｋｇ、 Ｅ Ｖ ＯＨ投入後内層スムージング完了迄の
加熱時間１１分、空気空冷方式を用いて冷却に１８分を
要した以外は実施例６と同装置、同条件を用いて容器を
作成し、外層＋中間層の平均厚み２０ｓ量、内層平均厚
み２．０ｍｍ、全層厚み４．０園鋼の容器を得た。得ら
れた容器は、内層表面は平滑でＥＶＯＨ特有の光沢を有
していたが、側面円筒部にピンホールが散見され、完全
な連続層を形成していなかった。なお外層と中間層、お
よび中間層と内層は強固に接着しており手で剥離できな
かった。また実施例６と同様に落下テストを実施したが
、眉間剥離はなく、内層に亀裂は生じなかった。Comparative Example 6 Input amount of polyethylene for outer layer: 0.41 kg, heating time until the middle stage of outer layer molding smoothing: about 6 minutes, input amount of adhesive resin for middle layer: 0.41 kg, heating time until middle stage of middle layer molding smoothing: about 4 minutes , Input amount of EVOH for inner layer 1.04
A container was made using the same equipment and under the same conditions as in Example 6, except that the heating time was 11 minutes until the smoothing of the inner layer was completed after the addition of EV OH, and the cooling time was 18 minutes using the air cooling method. + A container made of steel with an average intermediate layer thickness of 20 seconds, an inner layer average thickness of 2.0 mm, and a total thickness of 4.0 mm was obtained. The obtained container had a smooth inner layer surface and a gloss characteristic of EVOH, but pinholes were found here and there in the cylindrical side surface, and a completely continuous layer was not formed. Note that the outer layer and the intermediate layer, and the intermediate layer and the inner layer were strongly adhered to each other and could not be peeled off by hand. Further, a drop test was conducted in the same manner as in Example 6, but there was no peeling between the eyebrows and no cracks were generated in the inner layer.
底面平坦部の断面３ケ所で中間層と内層が作る界面の凹
凸を測定したところ、平均０．２８ｍｒＰｌであった。When the unevenness of the interface between the intermediate layer and the inner layer was measured at three locations on the cross section of the flat bottom portion, the average was 0.28 mrPl.
またピンホールから離れた側面円筒部の円周と直角方向
の断面３ケ所で中間層と内層が作る界面の凹凸を測定し
たところ平均０３０ＩＩＩＩであった。Further, when the unevenness of the interface between the intermediate layer and the inner layer was measured at three locations in the cross section in the direction perpendicular to the circumference of the side cylindrical portion away from the pinhole, the average was 030III.
比較例７
接着性樹脂の添加時期を外層のスムージング終了後に（
外層加熱時間１０分）、ＥＶＯ）ｌの添加時期を中間層
のスムージング終了後に変更（中間層加熱時間９分）し
た以外は実施例６と同装置、同条件で容器を作成した。Comparative Example 7 The adhesive resin was added after the smoothing of the outer layer (
A container was prepared using the same apparatus and under the same conditions as in Example 6, except that the outer layer heating time was 10 minutes) and the timing of addition of EVO) was changed after smoothing of the intermediate layer was completed (intermediate layer heating time was 9 minutes).
得られた容器の内層表面は平滑でＥＶＯＨ特有の光沢を
有し、穴、ピンホール等らなく完全な連続層を形成して
おり、外層と中間層の接着は強固であったが、中間層と
内層の層間接着力は弱く、手で引っ張ると剥離可能で、
実施例６と同様の落下テストで簡単に剥離が生じ、ＥＶ
ＯＨＩ＊の１部に亀裂が生じた。底面平坦部の断面３ケ
所および側面円筒部の円周と直角方向の断面３ケ所で中
間層と内層が作る界面の凹凸を測定したところ、どちら
も、０．０５ｍｍ以下であった。The surface of the inner layer of the obtained container was smooth and had the characteristic luster of EVOH, and formed a completely continuous layer with no holes or pinholes.Although the adhesion between the outer layer and the middle layer was strong, the middle layer The adhesion between the inner and outer layers is weak and can be peeled off by hand.
In the same drop test as in Example 6, peeling occurred easily, and the EV
A crack appeared in a part of OHI*. The unevenness of the interface between the intermediate layer and the inner layer was measured at three locations on the cross section of the flat bottom portion and at three locations on the cross section in the direction perpendicular to the circumference of the side cylindrical portion, and both were found to be 0.05 mm or less.
実施例８
内層にエチレン含有率４８モル％、鹸化度９９５モル％
、ＭＩ＝１４、粒度４０メツシユのＥｖＯＨ（株式会社
クラレ製、エパールＥ Ｐ −Ｇ １１０）を用いた以
外は、実施例６と同条件で容器を作成した。Example 8 Ethylene content in inner layer: 48 mol%, saponification degree: 995 mol%
A container was prepared under the same conditions as in Example 6, except that EvOH (manufactured by Kuraray Co., Ltd., Epal EP-G 110) having a particle size of 40 mesh and MI=14 was used.
この系のＭ ｌ ｇ ｖ ／ Ｍ Ｉ Ａ Ｄ ＝ １
、６である。得られた容器の内層表面は平滑でＥＶＯ
Ｈ特有の光沢を有し、穴、ピンホール等もなく完全な連
続層を形成しており、また中間層と内層は強固に接着し
ており手で剥離できなかった。また実施例６と同様に落
下テストを実施したが、眉間剥離はなく、内層に亀裂は
生じなかった。底面平坦部の断面３ケ所について測定し
た平均値は、外層＋中間層厚み２．６ＩＩ１１、内層厚
み１．１ｍｍ、全層厚み３．１ｍｍ、中間層と内層が作
る界面の凹凸は０．３５ｍｍであった。一方側面円筒部
の円周と直角方向の断面３ケ所について測定した平均値
は、外−十中間層厚み３．２ｍＩ＋＋、内層厚み１．７
１、全層厚み４．９ｍｍ、中間層と内層が作る界面の凹
凸は０．３２ｍ＋ａであった。M l g v / M I A D = 1 for this system
, 6. The inner layer surface of the obtained container was smooth and EVO
It had the characteristic gloss of H, and formed a completely continuous layer with no holes or pinholes, and the intermediate layer and inner layer were strongly adhered to each other and could not be peeled off by hand. Further, a drop test was conducted in the same manner as in Example 6, but there was no peeling between the eyebrows and no cracks were generated in the inner layer. The average value measured at three cross-sectional locations on the flat part of the bottom is: outer layer + middle layer thickness: 2.6II11, inner layer thickness: 1.1 mm, total layer thickness: 3.1 mm, and the unevenness of the interface between the middle layer and the inner layer is 0.35 mm. there were. On the other hand, the average values measured at three cross sections in the direction perpendicular to the circumference of the side cylindrical part were as follows: outer layer thickness: 3.2 mI++, inner layer thickness: 1.7 mI++.
1. The total layer thickness was 4.9 mm, and the unevenness of the interface between the intermediate layer and the inner layer was 0.32 m+a.
比較例７
内層にエチレン含有率３２モル％、鹸化度９９，５モル
％、Ｍ Ｉ ＝ １．３、粒度４０メツシユノＥＶｏＨ
（株式会社クラレ製、エバールＥ Ｐ −Ｆ １０１）
ヲ用いた以外は、実施例６と同条件で容器を作成した
。この系のＭ Ｉ ｔ ｖ ／ Ｍ Ｉ Ａｂ＝ ０
、１４である。得られた容器は内層表面が凹凸で、かっ
ＥＶＯＨが連続層を形成しておらず、耐薬品性、ガスバ
リヤ−性能が期待できないものであった。Comparative Example 7 Ethylene content in inner layer: 32 mol%, saponification degree: 99.5 mol%, M I = 1.3, particle size: 40 mesh EVoH
(Manufactured by Kuraray Co., Ltd., EVAL EP-F 101)
A container was produced under the same conditions as in Example 6, except that . M I tv / M I Ab of this system = 0
, 14. The resulting container had an uneven inner layer surface, EVOH did not form a continuous layer, and chemical resistance and gas barrier performance could not be expected.
〈発明の効果〉
本発明により、ＥＶＯＨの使用量を最少に押さえた、耐
薬品性、ガスバリヤ−性にすぐれたポリオレフィンとＥ
ＶＯＨの二層構成の大型容器を、少量生産においても低
コストで供給可能となる。<Effects of the Invention> According to the present invention, polyolefin and E
Large containers with a two-layer structure for VOH can be supplied at low cost even in small quantity production.
また本発明の容器は各種工業薬品用の容器またはドラム
缶、自動車用ガソリンタンク等の２０〜２５０リツトル
容器をはじめ、１０００リットル以上の耐薬品性の装置
用タンク、輸送用コンテナータンク等に適している。In addition, the container of the present invention is suitable for containers or drums for various industrial chemicals, 20-250 liter containers such as gasoline tanks for automobiles, chemical-resistant equipment tanks of 1000 liters or more, transportation container tanks, etc. .
第１図は本発明の容器例の縦断面図であり、第２図は第
１図の底部断面（Ａ）の拡大図である。また、第３図は
比較例１の容器の内層のピンホールとこれにつながる外
層の空洞の断面図である。
稟４図は本発明の容器例の縦断面図であり、第５図は第
４図の底部断面（Ａ）の拡大図である。また、第６図は
比較例５の容器の内層のピンホールとこれにつながる中
間層の空洞の断面図である。
１・・・外 層
２・・・中間層
３・・・内 層
４・・・内層とこれと隣接する層とが作る界面線５・・
・界面線の中心
６・・・ピンホール
７・・・空 洞FIG. 1 is a longitudinal sectional view of an example of the container of the present invention, and FIG. 2 is an enlarged view of the bottom section (A) of FIG. 1. Moreover, FIG. 3 is a sectional view of a pinhole in the inner layer of the container of Comparative Example 1 and a cavity in the outer layer connected thereto. Figure 4 is a longitudinal cross-sectional view of an example of the container of the present invention, and Figure 5 is an enlarged view of the bottom cross-section (A) of Figure 4. Further, FIG. 6 is a sectional view of a pinhole in the inner layer of the container of Comparative Example 5 and a cavity in the intermediate layer connected thereto. 1... Outer layer 2... Intermediate layer 3... Inner layer 4... Interface line 5 formed between the inner layer and the adjacent layer...
・Center of interface line 6...Pinhole 7...Cavity
Claims (1)
ビニル共重合体けん化物層の少なくとも二層からなり、
かつ内層が連続層であり、内層とこれと隣接する層の界
面により 形成される凹凸が０．１１ｍｍ以上である回転成形容器
。 （２）外層がポリオレフィン層、中間層が接着性樹脂層
、内層がエチレン−酢酸ビニル共重合体けん化物層から
なり、かつ内層が連続層であり、中間層と内層の界面に
より形成 される凹凸が０．１ｍｍ以上である回転成形容器。 （３）ポリオレフィン層が、ポリオレフィンおよび接着
性樹脂との混合物層である請求項１または２記載の回転
成形容器。 （４）全層厚みが２ｍｍ以上、内層厚みが０．５ｍｍ〜
全層厚みの１／２である請求項１〜３より選ばれた１つ
の項に記載の回転成形容器。 （５）接着性樹脂が不飽和カルボン酸またはその誘導体
により変性されたポリオレフィンである請求項１〜４か
ら選ばれる１つの項に記載の回転成形容器。 （６）ポリオレフィンが、ポリエチレンである請求項１
〜５から選ばれる１つの項に記載の回転成形容器。 （７）ポリオレフィン粉末またはポリオレフィン粉末と
接着性樹脂粉末との混合物、およびＥＶＯＨ粉末を、順
次金型に導入して、加熱回転により外層にポリオレフィ
ン層、内層にＥＶＯＨ層を成形して回転成形容器を製造
するに際し、下記式を満足する、ポリオレフィン粉末お
よびＥＶＯＨ粉末を使用し、 ０．５≦（Ｍｌ＿Ｅ＿Ｖ／Ｍｌ＿Ｐ＿Ｏ）≦３．０Ｍｌ
＿Ｅ＿Ｖ：ＥＶＯ層のメルトインデツクス（１９０℃、
２１６０ｇ荷重下に測定した値）Ｍｌ＿Ｐ＿Ｏ：ポリオ
レフイン層のメルトインデックス（１９０℃、２１６０
ｇ荷重下に測定した値）さらにＥＶＯＨ粉末を、金型に
、ポリオレフィン層のスムージングの初期〜完了前に導
入し、かつ外層および内層を成形後、急速冷却すること
を特徴とする回転成形容器の製造法。 （８）ポリオレフィン粉末、接着性樹脂粉末、およびＥ
ＶＯＨ粉末を順次金型に導入して、加熱回転により外層
にポリオレフィン層、中間層に接着性樹脂層、内層にＥ
ＶＯＨ層を成形して回転成形容器を製造するに際し、下
記式を満足する、接着性樹脂粉末およびＥＶＯＨ粉末を
使用し、 ０．５≦（Ｍｌ＿Ｅ＿Ｖ／Ｍｌ＿Ａ＿Ｄ）≦３．０Ｍｌ
＿Ｅ＿Ｖ：ＥＶＯＨ層のメルトインデックス（１９０℃
、２１６０ｇ荷重下に測定した値）Ｍｌ＿Ａ＿Ｄ：接着
性樹脂層のメルトインデックス（１９０℃、２１６０ｇ
荷重下に測定した値）さらにＥＶＯＨ粉末を、金型に、
接着性樹脂層のスムージングの初期〜完了前に導入し、
かつ外層、中間層、および内層を成形後、急速冷却する
ことを特徴とする回転成形容器の製造法。[Claims] (1) The outer layer is a polyolefin layer, and the inner layer is a saponified ethylene-vinyl acetate copolymer layer.
and a rotomolded container in which the inner layer is a continuous layer, and the unevenness formed by the interface between the inner layer and an adjacent layer is 0.11 mm or more. (2) The outer layer is a polyolefin layer, the intermediate layer is an adhesive resin layer, and the inner layer is a saponified ethylene-vinyl acetate copolymer layer, and the inner layer is a continuous layer, with unevenness formed by the interface between the intermediate layer and the inner layer. A rotomolded container having a diameter of 0.1 mm or more. (3) The rotomolded container according to claim 1 or 2, wherein the polyolefin layer is a mixture layer of polyolefin and adhesive resin. (4) Total layer thickness is 2 mm or more, inner layer thickness is 0.5 mm or more
The rotomolded container according to one of claims 1 to 3, which has a thickness of 1/2 of the total thickness. (5) The rotomolded container according to one of claims 1 to 4, wherein the adhesive resin is a polyolefin modified with an unsaturated carboxylic acid or a derivative thereof. (6) Claim 1 wherein the polyolefin is polyethylene.
The rotomolded container according to one item selected from 5 to 5. (7) Polyolefin powder or a mixture of polyolefin powder and adhesive resin powder, and EVOH powder are sequentially introduced into a mold, and heated and rotated to form a polyolefin layer as an outer layer and an EVOH layer as an inner layer to form a rotary molded container. When manufacturing, use polyolefin powder and EVOH powder that satisfy the following formula, 0.5≦(Ml_E_V/Ml_P_O)≦3.0Ml
_E_V: Melt index of EVO layer (190°C,
Value measured under a load of 2160g) Ml_P_O: Melt index of polyolefin layer (190°C, 2160g)
g load) Furthermore, EVOH powder is introduced into the mold from the beginning to the completion of smoothing of the polyolefin layer, and after the outer layer and the inner layer are molded, the rotary molding container is rapidly cooled. Manufacturing method. (8) Polyolefin powder, adhesive resin powder, and E
VOH powder is sequentially introduced into a mold, and heated and rotated to form a polyolefin layer on the outer layer, an adhesive resin layer on the middle layer, and an E layer on the inner layer.
When manufacturing a rotary molded container by molding a VOH layer, adhesive resin powder and EVOH powder that satisfy the following formula are used: 0.5≦(Ml_E_V/Ml_A_D)≦3.0Ml
_E_V: Melt index of EVOH layer (190℃
, value measured under a load of 2160g) Ml_A_D: Melt index of adhesive resin layer (190°C, 2160g
(Value measured under load) Furthermore, EVOH powder was added to the mold,
Introduced from the beginning to the completion of smoothing of the adhesive resin layer,
A method for producing a rotary molded container, which comprises rapidly cooling the outer layer, middle layer, and inner layer after molding.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1140198A JP2826125B2 (en) | 1989-05-31 | 1989-05-31 | Rotationally molded container and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1140198A JP2826125B2 (en) | 1989-05-31 | 1989-05-31 | Rotationally molded container and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH032009A true JPH032009A (en) | 1991-01-08 |
| JP2826125B2 JP2826125B2 (en) | 1998-11-18 |
Family
ID=15263196
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1140198A Expired - Lifetime JP2826125B2 (en) | 1989-05-31 | 1989-05-31 | Rotationally molded container and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2826125B2 (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06269653A (en) * | 1993-03-16 | 1994-09-27 | Nippon Spindle Mfg Co Ltd | Modification of surface of powder |
| US5512523A (en) * | 1993-02-03 | 1996-04-30 | Asahi Glass Company Ltd. | Monolithic refractory powder mixture |
| US6381662B1 (en) | 1993-09-01 | 2002-04-30 | Sandisk Corporation | Removable mother/daughter peripheral card |
| JP2002361657A (en) * | 2001-06-08 | 2002-12-18 | Nippon Synthetic Chem Ind Co Ltd:The | Rotary molding container |
| WO2004065495A2 (en) | 2003-01-24 | 2004-08-05 | Showa Denko K. K. | Surface modification method for inorganic oxide powder, powder produced by the method and use of the powder |
| US7247268B2 (en) * | 2000-08-30 | 2007-07-24 | Commissariat A L'energie Atomique | Method for making a part with clearance volume by rotational moulding and resulting part |
| US7258794B2 (en) | 2002-10-09 | 2007-08-21 | Daicel Chemical Industries, Ltd. | Process for producing packing for resolving optical isomers |
| JP2007270540A (en) * | 2006-03-31 | 2007-10-18 | Taiheiyo Cement Corp | Block for sound insulation wall |
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| KR102046895B1 (en) * | 2017-12-18 | 2019-12-04 | 김문호 | Hollow articles for container and manufacturing process thereof |
-
1989
- 1989-05-31 JP JP1140198A patent/JP2826125B2/en not_active Expired - Lifetime
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5512523A (en) * | 1993-02-03 | 1996-04-30 | Asahi Glass Company Ltd. | Monolithic refractory powder mixture |
| JPH06269653A (en) * | 1993-03-16 | 1994-09-27 | Nippon Spindle Mfg Co Ltd | Modification of surface of powder |
| US6381662B1 (en) | 1993-09-01 | 2002-04-30 | Sandisk Corporation | Removable mother/daughter peripheral card |
| US7247268B2 (en) * | 2000-08-30 | 2007-07-24 | Commissariat A L'energie Atomique | Method for making a part with clearance volume by rotational moulding and resulting part |
| JP4833497B2 (en) * | 2000-08-30 | 2011-12-07 | コミッサリア ア レネルジー アトミーク エ オ ゼネルジ ザルタナテイヴ | Method for forming a cylindrical member by rotational molding and member obtained thereby |
| JP2002361657A (en) * | 2001-06-08 | 2002-12-18 | Nippon Synthetic Chem Ind Co Ltd:The | Rotary molding container |
| US7258794B2 (en) | 2002-10-09 | 2007-08-21 | Daicel Chemical Industries, Ltd. | Process for producing packing for resolving optical isomers |
| WO2004065495A2 (en) | 2003-01-24 | 2004-08-05 | Showa Denko K. K. | Surface modification method for inorganic oxide powder, powder produced by the method and use of the powder |
| JP2007270540A (en) * | 2006-03-31 | 2007-10-18 | Taiheiyo Cement Corp | Block for sound insulation wall |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2826125B2 (en) | 1998-11-18 |
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