WO2020017487A1 - Container and method for manufacturing same - Google Patents

Container and method for manufacturing same Download PDF

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Publication number
WO2020017487A1
WO2020017487A1 PCT/JP2019/027863 JP2019027863W WO2020017487A1 WO 2020017487 A1 WO2020017487 A1 WO 2020017487A1 JP 2019027863 W JP2019027863 W JP 2019027863W WO 2020017487 A1 WO2020017487 A1 WO 2020017487A1
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Prior art keywords
resin
container
layer
volume
base material
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PCT/JP2019/027863
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French (fr)
Japanese (ja)
Inventor
小松　威久男
訓之 開発
江里子 藤田
智啓 田口
Original Assignee
メビウスパッケージング株式会社
東洋製罐株式会社
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Publication of WO2020017487A1 publication Critical patent/WO2020017487A1/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C49/00—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor
    • B29C49/22—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor using multilayered preforms or parisons
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D1/00—Containers having bodies formed in one piece, e.g. by casting metallic material, by moulding plastics, by blowing vitreous material, by throwing ceramic material, by moulding pulped fibrous material, by deep-drawing operations performed on sheet material
    • B65D1/02—Bottles or similar containers with necks or like restricted apertures, designed for pouring contents

Definitions

  • the present invention relates to a container and a method for producing the container.
  • a tube-shaped container made of a laminate of various resin layers is used as a container for storing viscous foods such as wasabi, ginger, mustard, ketchup, mayonnaise, jam, chocolate, toothpaste, cosmetics, etc.
  • the container is generally provided with a gas barrier layer as an intermediate layer in order to prevent gas such as oxygen from passing through the container wall.
  • the container has an outer layer in contact with the outside and an inner layer in contact with the contents.
  • the container is generally provided with an adhesive layer between these layers.
  • the container can be manufactured, for example, by manufacturing a parison in which the respective layers are laminated, and blow-molding the parison in a mold (Patent Documents 1 to 3).
  • the parison flexes or blows at the time of blow molding, so that a part of the parison touches the inner surface of the mold, and there is a case where a pocket is generated in the portion. is there.
  • the presence of a meat reservoir on the surface of the container impairs the appearance of the container.
  • the container is required to have high transparency.
  • a method for manufacturing a container according to the present invention includes a step of manufacturing a parison including a base material layer including a base material and an adhesive layer including a mixture of resin A and resin B, and forming a container by blow molding the parison.
  • the melt flow rate (g / 10 min) of the base material at 210 ° C. under a load of 2.16 kg is 0.4 to 1.6 times the melt flow rate (g / 10 min) of the base material;
  • the melt tension Y (mN) at 210 ° C. of the following formula is Y> X-35
  • X is a melt tension (mN) at 210 ° C. of the base material.
  • the container according to the present invention is a container including a base material layer including a base material and an adhesive layer including a mixture of resin A and resin B.
  • the ratio of the volume of the adhesive layer to the volume of the wall of the container exceeds 0.2% by volume.
  • the value of the melt flow rate (g / 10 min) (hereinafter also referred to as MFR) of the resin A at 210 ° C. and a load of 2.16 kg is the melt flow rate of the base material at 210 ° C. and a load of 2.16 kg. (G / 10 min) is 0.4 to 1.6 times the value of (g / 10 min).
  • the melt tension Y (mN) at 210 ° C. of the mixture is represented by the following formula: Y> X-35 In the formula, X is a melt tension (mN) at 210 ° C. of the base material.
  • the present inventors have proposed that the transparency of the container is improved by the fact that the MFR value of the resin A used as the material of the adhesive layer is in the range of 0.4 to 1.6 times the MFR value of the base material. It has been found that it can be improved.
  • the MFR of the resin A is close to the MFR of the base material, disturbance at the time of joining of the base material layer and the adhesive layer is suppressed, the integrity at the interface is improved, and the transparency of the container can be improved. Further, by suppressing the disturbance at the time of merging, the parison is stabilized, and the moldability of the container is also improved.
  • the base layer may contain a lubricant, an ultraviolet absorber, a pigment, a dye, various fillers, and the like, depending on the application, in an amount such that the basic characteristics of the container are not impaired. .
  • the ratio of the volume of the base material layer to the volume of the container wall is not particularly limited.
  • the volume ratio of the outer layer to the volume of the container wall can be, for example, 10 to 20% by volume.
  • the volume ratio of the inner layer to the volume of the container wall can be, for example, 10 to 80% by volume.
  • the wall of the container may be the side of the body of the container.
  • the adhesive layer contains a mixture of resin A and resin B.
  • the resin A and the resin B have an MFR value of the resin A of 0.4 to 1.6 times the MFR value of the base material, and a melt tension Y (mN) at 210 ° C. of the mixture of the base material.
  • the relationship is not particularly limited as long as Y> X ⁇ 35 is satisfied in relation to the melt tension X (mN) at 210 ° C.
  • Resin A is preferably a base material of the base material layer from the viewpoint of further improving the integration with the base material layer and further improving the transparency of the container. That is, the resin A is preferably the same material as the base material of the base layer. In this case, the MFR of the resin A is the same as the MFR of the base material.
  • a material having adhesiveness can be used.
  • graft-modified polyolefin ethylene- (meth) acrylic acid copolymer, ethylene-vinyl acetate copolymer, saponified ethylene-vinyl acetate copolymer having a saponification degree of 20 to 100%, ethylene content of 85% or more
  • ethylene-vinyl alcohol copolymers hydrotalcite compounds, ionomers (ion-crosslinked olefin copolymers), and the like. It is preferable to use a graft-modified polyolefin from the viewpoint of adhesiveness and melt tension.
  • the graft-modified polyolefin examples include those obtained by graft-modifying a polyolefin with a carboxylic acid such as maleic acid, itaconic acid, or fumaric acid, or an anhydride, amide, or ester thereof.
  • the resin B is preferably an acid-modified polyolefin, and more preferably a maleic acid-modified polyolefin.
  • the maleic acid-modified polyolefin include maleic anhydride-modified low-density polyethylene, maleic anhydride-modified ethylene-butene 1 copolymer, and the like. These may be used alone or in combination of two or more.
  • the MFR value of the resin A is 0.4 to 1.6 times the MFR value of the base material.
  • the MFR value of the resin A is in the range of 0.4 to 1.6 times the MFR value of the base material, the integrity at the interface between the base material layer and the adhesive layer is improved, and the transparency of the container is improved. Can be improved.
  • the MFR value of the mixture of the resin A and the resin B is also 0.2 to 1.8 times the MFR value of the base material from the viewpoint of further improving the integrity at the interface between the base material layer and the adhesive layer. It is preferred that
  • the MFR of the resin A is preferably 0.1 to 3.0 g / 10 min, similarly to the MFR of the base material.
  • the MFR of the resin B is preferably 0.5 to 5.0 g / 10 min.
  • the MFR of the mixture of the resin A and the resin B is preferably 0.1 to 3.0 g / 10 min.
  • the melt tension Y (mN) of the mixture of the resin A and the resin B preferably satisfies Y> X-35 and Y> X-20 in relation to the melt tension X (mN) of the base material.
  • > X-10 is more preferable, and Y> X is more preferable.
  • the melt tension of the resin A is preferably from 50 to 500 mN, more preferably from 100 to 400 mN, even more preferably from 150 to 300 mN.
  • the melt tension of the resin B is preferably from 100 to 500 mN, more preferably from 150 to 400 mN, even more preferably from 180 to 300 mN.
  • the melt tension Y of the mixture of the resin A and the resin B is preferably from 100 to 500 mN, more preferably from 150 to 400 mN, even more preferably from 190 to 300 mN.
  • the melt tension of the resin can be increased by widening the molecular weight distribution. This is thought to be due to an increase in entanglement between molecules.
  • the ratio of the resin B to the total of the resin A and the resin B in the mixture is preferably 40% by mass or more, and more preferably 50% by mass or more and 90% by mass or less from the viewpoints of adhesion and appearance of the container. preferable.
  • the ratio of the volume of the adhesive layer to the volume of the container wall exceeds 0.2% by volume. When the ratio exceeds 0.2% by volume, a sufficient adhesive strength can be secured.
  • the proportion is preferably more than 0.2% by volume and less than 3.5% by volume, more preferably 0.3 to 3.0% by volume, and more preferably 0.5 to 2.5% by volume. Is more preferable. When the ratio is less than 3.5% by volume, it is possible to further suppress the occurrence of a pool in blow molding.
  • the average thickness of the adhesive layer is preferably from 0.5 to 20 ⁇ m, more preferably from 1.0 to 15 ⁇ m, and still more preferably from 1.5 to 10 ⁇ m.
  • the container according to the present invention is preferably composed of three or more layers.
  • the additional layer includes the above-described base layer, but may be a layer other than the base layer and the adhesive layer. Examples of the other layer include a gas barrier layer and a scrap layer.
  • the gas barrier layer is a layer that can inhibit the transmission of a gas such as oxygen.
  • a gas such as oxygen.
  • the gas barrier layer has, for example, an oxygen permeability coefficient (PO2) of preferably 5.5 ⁇ 10 ⁇ 12 cc ⁇ cm / cm 2 sec ⁇ cmHg or less, more preferably 4.5 ⁇ 10 ⁇ 12 cc ⁇ cm / cm 2 sec.
  • PO2 oxygen permeability coefficient
  • -It can be a layer of cmHg or less.
  • Examples of the material of the gas barrier layer include aromatic polyamides such as ethylene-vinyl alcohol copolymer (saponified ethylene-vinyl acetate copolymer) and polymethaxylylene adipamide (MXD6).
  • aromatic polyamides such as ethylene-vinyl alcohol copolymer (saponified ethylene-vinyl acetate copolymer) and polymethaxylylene adipamide (MXD6).
  • an ethylene-vinyl alcohol copolymer is preferred from the viewpoint of high oxygen barrier properties.
  • the ethylene content of the ethylene-vinyl alcohol copolymer is preferably from 20 to 60 mol%, more preferably from 25 to 50 mol%.
  • the ethylene-vinyl alcohol copolymer for example, the ethylene-vinyl acetate copolymer having the above-mentioned ethylene content is saponified so that the saponification degree is preferably 96 mol% or more, more preferably 99 mol% or more.
  • the obtained saponified copolymer can be used.
  • the temperature at the time of blow molding is determined by the melting point of the base material and the mixture, and is set, for example, to 190 to 230 ° C. when an olefin resin is used.
  • MFR MFR was measured under the conditions of a temperature of 210 ° C. and a load of 2.16 kg based on JIS K 7210-1.
  • the pellets of the LDPE-1, the ethylene-vinyl alcohol copolymer, and the mixture are charged into three extruders, respectively, and an outer layer (base layer) / adhesive layer / gas barrier layer / adhesive layer / inner layer (base A multi-layer parison having a five-layer structure was formed.
  • the multilayer parison was subjected to direct blow molding to obtain a tube-shaped bottle having the following structure shown in FIG.
  • the inner volume of the bottle was 80 ml
  • the outer shape of the mouth was 9.6 mm
  • the body diameter was 33 mm
  • the height was 150 mm
  • the average thickness was 0.33 mm.
  • Example 2 A bottle was prepared in the same manner as in Example 1, except that a mixture of LDPE-1 as resin A and AD-1 as resin B in a mass ratio of 40:60 was used as a material for the two adhesive layers. Manufactured and evaluated. Table 1 shows the results.
  • Example 6 As a material for the two adhesive layers, low-density polyethylene as resin A (trade name: F101-1, manufactured by Sumitomo Chemical Co., Ltd., melt tension: 272 mN (210 ° C.), MFR: 0.3 g / 10 min (210 ° C., 2.16 kg load) (hereinafter also referred to as “LDPE-2”) and AD-1 as the resin B in a weight ratio of 40:60, except that a mixture was used. Manufactured and evaluated. Table 1 shows the results.
  • Example 8 A bottle was prepared in the same manner as in Example 1 except that a mixture of LDPE-1 as resin A and AD-2 as resin B in a mass ratio of 50:50 was used as a material for the two adhesive layers. Manufactured and evaluated. Table 1 shows the results.
  • Example 9 A bottle was prepared in the same manner as in Example 1, except that a mixture of LDPE-2 as resin A and AD-2 as resin B at a mass ratio of 40:60 was used as a material for the two adhesive layers. Manufactured and evaluated. Table 1 shows the results.
  • Example 10 A bottle was prepared in the same manner as in Example 1 except that a mixture of LDPE-1 as resin A and AD-1 as resin B in a mass ratio of 60:40 was used as a material for the two adhesive layers. Manufactured and evaluated. Table 1 shows the results.
  • Example 11 As a material (base material) for the inner layer and the outer layer, low density polyethylene (trade name: LB420M, manufactured by JPE Co., Ltd., melt tension: 162 mN (210 ° C.), MFR: 0.7 g / 10 min (210 ° C., 2.16 kg) Load), hereinafter also referred to as “LDPE-3”), and a mixture of LDPE-3 as resin A and AD-1 as resin B at a mass ratio of 40:60 is used as a material for the adhesive layer.
  • LDPE-3 low density polyethylene
  • a and AD-1 as resin B at a mass ratio of 40:60
  • a maleic anhydride-modified ethylene-butene 1 copolymer (trade name: Admer NF307, manufactured by Mitsui Chemicals, Inc., melt tension: 83 mN (210 ° C.), MFR: 1.6 g / 10 min (210 ° C.) , 2.16 kg load) (hereinafter also referred to as “AD-3”), and a bottle was manufactured and evaluated in the same manner as in Example 1. Table 1 shows the results.
  • Example 4 A bottle was manufactured and evaluated in the same manner as in Example 2, except that the thickness of each layer of the bottle was changed as follows. Table 1 shows the results. Outer layer 1 (average thickness: 49.5 ⁇ m) / adhesive layer 2 (average thickness: 0.7 ⁇ m, volume ratio: 0.2% by volume) / gas barrier layer 3 (average thickness: 33 ⁇ m) / adhesive layer 4 (average thickness: 0) 0.7 ⁇ m, volume ratio: 0.2% by volume) / inner layer 5 (average thickness: 246.1 ⁇ m)

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Ceramic Engineering (AREA)
  • Containers Having Bodies Formed In One Piece (AREA)
  • Laminated Bodies (AREA)
  • Blow-Moulding Or Thermoforming Of Plastics Or The Like (AREA)

Abstract

Provided is a container with favorable appearance and high transparency. The container is provided with a substrate layer including a substrate and an adhesive layer containing a mixture of a resin A and a resin B, wherein: the proportion of the volume of the adhesive layer to the volume of a wall of the container exceeds 0.2% by volume; the value of the melt flow rate (g/10 min) of the resin A at 210°C with a load of 2.16 kg is 0.4–1.6 times the value of the melt flow rate (g/10 min) of the substrate at 210°C with a load of 2.16 kg; and the melt tension Y (mN) of the mixture at 210°C satisfies the expression Y > X − 35, where X is the melt tension (mN) of the substrate at 210°C.

Description

容器およびその製造方法Container and manufacturing method thereof
　本発明は容器およびその製造方法に関する。 (4) The present invention relates to a container and a method for producing the container.
　わさび、しょうが、からし、ケチャップ、マヨネーズ、ジャム、チョコレート等の粘性食品、練歯磨、化粧品等を収容するための容器には、種々の樹脂層の積層体からなるチューブ状の容器が用いられる。該容器には、酸素などのガスが容器壁を透過するのを防ぐために、一般的に中間層としてガスバリア層が設けられている。また、該容器には、外部と接する外層と、内容物と接する内層とが設けられている。また、各層をそれぞれ接着させるために、該容器には一般的にこれらの層間に接着層が設けられている。該容器は、例えば前記各層が積層されたパリソンを製造し、該パリソンを型内でブロー成形することにより製造することができる（特許文献１～３）。 As a container for storing viscous foods such as wasabi, ginger, mustard, ketchup, mayonnaise, jam, chocolate, toothpaste, cosmetics, etc., a tube-shaped container made of a laminate of various resin layers is used. The container is generally provided with a gas barrier layer as an intermediate layer in order to prevent gas such as oxygen from passing through the container wall. The container has an outer layer in contact with the outside and an inner layer in contact with the contents. In order to bond the respective layers, the container is generally provided with an adhesive layer between these layers. The container can be manufactured, for example, by manufacturing a parison in which the respective layers are laminated, and blow-molding the parison in a mold (Patent Documents 1 to 3).
特開平１－１３９３４７号公報JP-A-1-139347 特開２００１－２５３４２６号公報JP 2001-253426 A 特開２００３－９５２４０号公報JP-A-2003-95240
　しかしながら、ブロー成形により前記容器を製造する場合、ブロー成形時にパリソンがたわんだり、振れたりすることで、型の内表面にパリソンの一部が触れてしまい、その部分に肉溜りが発生する場合がある。容器の表面に肉溜りが存在すると、容器の外観を損なう。また、内容物の視認性の観点から、容器の透明性が高いことが求められる。 However, when the container is manufactured by blow molding, the parison flexes or blows at the time of blow molding, so that a part of the parison touches the inner surface of the mold, and there is a case where a pocket is generated in the portion. is there. The presence of a meat reservoir on the surface of the container impairs the appearance of the container. In addition, from the viewpoint of the visibility of the contents, the container is required to have high transparency.
　本発明は、外観が良好であり、かつ透明性の高い容器を提供することを目的とする。 An object of the present invention is to provide a container having good appearance and high transparency.
　本発明に係る容器は、基材を含む基材層と、樹脂Ａおよび樹脂Ｂの混合物を含む接着層と、を備える容器であって、前記容器の壁の体積に対する前記接着層の体積の割合が０．２体積％を超え、前記樹脂Ａの２１０℃、２．１６ｋｇ荷重でのメルトフローレート（ｇ／１０ｍｉｎ）の値が、前記基材の２１０℃、２．１６ｋｇ荷重でのメルトフローレート（ｇ／１０ｍｉｎ）の値の０．４～１．６倍であり、前記混合物の２１０℃での溶融張力Ｙ（ｍＮ）が下記式、
　　Ｙ＞Ｘ－３５
　式中、Ｘは前記基材の２１０℃での溶融張力（ｍＮ）である、を満足する。 The container according to the present invention is a container including a base material layer including a base material and an adhesive layer including a mixture of the resin A and the resin B, and a ratio of a volume of the adhesive layer to a volume of a wall of the container. Exceeds 0.2% by volume, and the value of the melt flow rate (g / 10 min) of the resin A at 210 ° C. and a load of 2.16 kg is equal to the melt flow rate of the base material at 210 ° C. and a load of 2.16 kg. (G / 10 min), which is 0.4 to 1.6 times the melt tension Y (mN) of the mixture at 210 ° C.
Y> X-35
In the formula, X is a melt tension (mN) at 210 ° C. of the base material.
　本発明に係る容器の製造方法は、基材を含む基材層と、樹脂Ａおよび樹脂Ｂの混合物を含む接着層と、を備えるパリソンを製造する工程と、前記パリソンをブロー成形して容器を製造する工程と、を含む容器の製造方法であって、前記容器の壁の体積に対する前記接着層の体積の割合が０．２体積％を超え、前記樹脂Ａの２１０℃、２．１６ｋｇ荷重でのメルトフローレート（ｇ／１０ｍｉｎ）の値が、前記基材の２１０℃、２．１６ｋｇ荷重でのメルトフローレート（ｇ／１０ｍｉｎ）の値の０．４～１．６倍であり、前記混合物の２１０℃での溶融張力Ｙ（ｍＮ）が下記式、
　　Ｙ＞Ｘ－３５
　式中、Ｘは前記基材の２１０℃での溶融張力（ｍＮ）である、を満足する。 A method for manufacturing a container according to the present invention includes a step of manufacturing a parison including a base material layer including a base material and an adhesive layer including a mixture of resin A and resin B, and forming a container by blow molding the parison. Producing a container, wherein a ratio of a volume of the adhesive layer to a volume of a wall of the container exceeds 0.2% by volume, and the resin A is heated at 210 ° C. under a load of 2.16 kg. The melt flow rate (g / 10 min) of the base material at 210 ° C. under a load of 2.16 kg is 0.4 to 1.6 times the melt flow rate (g / 10 min) of the base material; The melt tension Y (mN) at 210 ° C. of the following formula is
Y> X-35
In the formula, X is a melt tension (mN) at 210 ° C. of the base material.
　本発明によれば、外観が良好であり、かつ透明性の高い容器を提供することができる。 According to the present invention, a container having good appearance and high transparency can be provided.
本発明に係る容器の層構成の一例を示す断面図である。It is sectional drawing which shows an example of the layer structure of the container which concerns on this invention.
　［容器］
　本発明に係る容器は、基材を含む基材層と、樹脂Ａおよび樹脂Ｂの混合物を含む接着層と、を備える容器である。ここで、前記容器の壁の体積に対する前記接着層の体積の割合は０．２体積％を超える。また、前記樹脂Ａの２１０℃、２．１６ｋｇ荷重でのメルトフローレート（ｇ／１０ｍｉｎ）（以下、ＭＦＲとも示す）の値は、前記基材の２１０℃、２．１６ｋｇ荷重でのメルトフローレート（ｇ／１０ｍｉｎ）の値の０．４～１．６倍である。また、前記混合物の２１０℃での溶融張力Ｙ（ｍＮ）は下記式、
　　Ｙ＞Ｘ－３５
　式中、Ｘは前記基材の２１０℃での溶融張力（ｍＮ）である、を満足する。 [container]
The container according to the present invention is a container including a base material layer including a base material and an adhesive layer including a mixture of resin A and resin B. Here, the ratio of the volume of the adhesive layer to the volume of the wall of the container exceeds 0.2% by volume. The value of the melt flow rate (g / 10 min) (hereinafter also referred to as MFR) of the resin A at 210 ° C. and a load of 2.16 kg is the melt flow rate of the base material at 210 ° C. and a load of 2.16 kg. (G / 10 min) is 0.4 to 1.6 times the value of (g / 10 min). The melt tension Y (mN) at 210 ° C. of the mixture is represented by the following formula:
Y> X-35
In the formula, X is a melt tension (mN) at 210 ° C. of the base material.
　本発明者等は、ブロー成形時に発生する肉溜りを抑制するために鋭意検討した結果、接着層を構成する材料の溶融張力が、肉溜りの発生に影響を与えていることを見出した。具体的には、接着層を構成する樹脂Ａおよび樹脂Ｂの混合物の溶融張力Ｙ（ｍＮ）が、内層、外層などの基材層を構成する基材の溶融張力Ｘ（ｍＮ）との間で、Ｙ＞Ｘ－３５を満たすようにすることで、多層構造を有するパリソンの中間層において溶融張力を高くすることができる。これにより、ブロー成形時にパリソンが多少たわんだり、振れたりしても、張力によりパリソンが中央部に戻りやすくなる。したがって、ブロー成形時に型の内表面にパリソンの一部が触れることを抑制することができ、容器表面における肉溜りの発生を低減することができる。また、肉溜りの発生を低減することで、容器の壁厚が均一となるため容器の搬送性が向上し、結果として容器の生産性が向上する。 The present inventors have conducted intensive studies in order to suppress the accumulation of meat occurring during blow molding, and as a result, have found that the melt tension of the material forming the adhesive layer affects the occurrence of accumulation of meat. Specifically, the melt tension Y (mN) of the mixture of the resin A and the resin B forming the adhesive layer is between the melt tension X (mN) of the base material forming the base layer such as the inner layer and the outer layer. , Y> X-35, the melt tension in the intermediate layer of the parison having a multilayer structure can be increased. This makes it easier for the parison to return to the center due to tension, even if the parison flexes or swings slightly during blow molding. Therefore, it is possible to suppress a part of the parison from touching the inner surface of the mold at the time of blow molding, and it is possible to reduce the occurrence of the accumulation of meat on the container surface. Further, by reducing the occurrence of the accumulation of meat, the wall thickness of the container becomes uniform, so that the transportability of the container is improved, and as a result, the productivity of the container is improved.
　さらに、本発明者等は、接着層の材料として用いられる樹脂ＡのＭＦＲの値が基材のＭＦＲの値の０．４～１．６倍の範囲内であることにより、容器の透明性を向上させることができることを見出した。樹脂ＡのＭＦＲが基材のＭＦＲに近いことで、基材層と接着層の合流時の乱れが抑制され、界面における一体性が向上し、容器の透明性を向上させることができる。また、合流時の乱れが抑制されることにより、パリソンが安定化し、容器の成形性も向上する。 Furthermore, the present inventors have proposed that the transparency of the container is improved by the fact that the MFR value of the resin A used as the material of the adhesive layer is in the range of 0.4 to 1.6 times the MFR value of the base material. It has been found that it can be improved. When the MFR of the resin A is close to the MFR of the base material, disturbance at the time of joining of the base material layer and the adhesive layer is suppressed, the integrity at the interface is improved, and the transparency of the container can be improved. Further, by suppressing the disturbance at the time of merging, the parison is stabilized, and the moldability of the container is also improved.
　本発明に係る容器は、密閉可能であり、基材層と接着層とを少なくとも備えれば特に限定されない。該容器は、基材層と接着層とからなってもよく、他の層をさらに備えてもよい。基材層が内層、外層である場合、他の層としては例えば後述するガスバリア層、スクラップ層（リプロ層）などが挙げられる。前記容器は、例えば、外層（基材層）／接着層／内層（基材層）の３層構成を有していてもよく、外層（基材層）／接着層／ガスバリア層／接着層／内層（基材層）の５層構成を有していてもよく、外層（基材層）／接着層／ガスバリア層／接着層／スクラップ層／内層（基材層）の６層構成を有していてもよい。一例として、図１に、外層１（基材層）／接着層２／ガスバリア層３／接着層４／内層５（基材層）の５層構成を有する容器を示す。基材層と接着層とは互いに接することができる。 容器 The container according to the present invention is not particularly limited as long as it is sealable and includes at least a base layer and an adhesive layer. The container may include a base layer and an adhesive layer, and may further include another layer. When the base material layer is an inner layer or an outer layer, examples of the other layers include a gas barrier layer and a scrap layer (repro layer) described later. The container may have, for example, a three-layer structure of outer layer (base layer) / adhesive layer / inner layer (base layer), and outer layer (base layer) / adhesive layer / gas barrier layer / adhesive layer / It may have a five-layer structure of an inner layer (base layer), and has a six-layer structure of an outer layer (base layer) / adhesive layer / gas barrier layer / adhesive layer / scrap layer / inner layer (base layer). May be. As an example, FIG. 1 shows a container having a five-layer structure of outer layer 1 (base layer) / adhesive layer 2 / gas barrier layer 3 / adhesive layer 4 / inner layer 5 (base layer). The base layer and the adhesive layer can be in contact with each other.
　容器の厚みは特に限定されないが、容器の厚みが薄い場合、ブロー成形時にパリソンがたわんだり、振れたりしやすく、型の内表面にパリソンの一部が触れやすいため、肉溜りが発生しやすい。このため、本発明の構成による効果がより得られる観点から、容器の平均厚みは０．５ｍｍ以下であることが好ましい。なお、本発明において平均厚みは容器シール部から５ｍｍ高さ位置における周方向４箇所の平均により算出される値である。本発明に係る容器は肉溜りが低減されているため、容器の壁厚が均一であり、容器をつぶしやすい。このため、該容器は特にチューブ容器に好適である。 厚 み The thickness of the container is not particularly limited, but if the thickness of the container is small, the parison is likely to bend or swing during blow molding, and a portion of the parison is likely to touch the inner surface of the mold, so that a meat pocket is likely to occur. For this reason, from the viewpoint that the effect of the configuration of the present invention can be further obtained, the average thickness of the container is preferably 0.5 mm or less. In the present invention, the average thickness is a value calculated by averaging four locations in the circumferential direction at a height of 5 mm from the container seal portion. Since the container according to the present invention has a reduced thickness, the wall thickness of the container is uniform and the container is easily crushed. For this reason, the container is particularly suitable for a tube container.
　（基材層）
　基材層は基材を含む。基材はベース樹脂であることができ、基材層はベース樹脂を含む樹脂層であることができる。基材層は、例えば外部と接する外層、内容物と接する内層であることができる。基材層が外層または内層である場合、基材としては例えばオレフィン系樹脂が好ましい。 (Base material layer)
The substrate layer includes a substrate. The base material can be a base resin, and the base material layer can be a resin layer containing the base resin. The base layer can be, for example, an outer layer in contact with the outside and an inner layer in contact with the contents. When the substrate layer is an outer layer or an inner layer, the substrate is preferably, for example, an olefin-based resin.
　オレフィン系樹脂の例としては、低密度ポリエチレン（ＬＤＰＥ）、中密度ポリエチレン（ＭＤＰＥ）、高密度ポリエチレン（ＨＤＰＥ）、線状低密度ポリエチレン（ＬＬＤＰＥ）、線状超低密度ポリエチレン（ＬＶＬＤＰＥ）等のポリエチレン、ポリプロピレン、エチレン－プロピレン共重合体、ポリブテン－１、エチレン－ブテン－１共重合体、プロピレン－ブテン－１共重合体、エチレン－プロピレン－ブテン－１共重合体、エチレン－酢酸ビニル共重合体、イオン架橋オレフィン共重合体（アイオノマー）等が挙げられる。また、非環状オレフィンと環状オレフィンとの非晶質乃至低結晶性の共重合体（ＣＯＣ）も使用することができる。これらは一種を用いてもよく、二種以上を併用してもよい。これらの中でも、基材としては後述するＭＦＲ、溶融張力の観点から低密度ポリエチレン（ＬＤＰＥ）が好ましい。 Examples of the olefin resin include polyethylene such as low density polyethylene (LDPE), medium density polyethylene (MDPE), high density polyethylene (HDPE), linear low density polyethylene (LLDPE), and linear ultra low density polyethylene (LVLDPE). , Polypropylene, ethylene-propylene copolymer, polybutene-1, ethylene-butene-1 copolymer, propylene-butene-1 copolymer, ethylene-propylene-butene-1 copolymer, ethylene-vinyl acetate copolymer And ion-crosslinked olefin copolymers (ionomers). In addition, an amorphous or low-crystalline copolymer (COC) of an acyclic olefin and a cyclic olefin can also be used. These may be used alone or in combination of two or more. Among these, low density polyethylene (LDPE) is preferable as the base material from the viewpoint of MFR and melt tension described later.
　基材のＭＦＲとしては、０．１～３．０ｇ／１０ｍｉｎであることが好ましい。基材の溶融張力としては、５０～３００ｍＮであることが好ましく、１００～２５０ｍＮであることがより好ましい。 Ｍ The MFR of the base material is preferably 0.1 to 3.0 g / 10 min. The melt tension of the substrate is preferably 50 to 300 mN, more preferably 100 to 250 mN.
　なお、本発明においてＭＦＲはＪＩＳ　Ｋ　７２１０－１に基づき、温度２１０℃、荷重２．１６ｋｇの条件において測定される値である。また、本発明において溶融張力はＪＩＳ　Ｋ　７１９９に基づき、温度２１０℃、引っ張り速度６．５ｍ／ｍｉｎの条件において測定される値である。 In the present invention, the MFR is a value measured under the conditions of a temperature of 210 ° C. and a load of 2.16 kg based on JIS K 7210-1. In the present invention, the melt tension is a value measured at a temperature of 210 ° C. and a tensile speed of 6.5 m / min based on JIS K7199.
　基材層が外層または内層である場合、基材層は、用途に応じて、滑剤、紫外線吸収剤、顔料、染料、各種充填材等を、容器の基本特性が損なわれない量で含んでもよい。 When the base layer is an outer layer or an inner layer, the base layer may contain a lubricant, an ultraviolet absorber, a pigment, a dye, various fillers, and the like, depending on the application, in an amount such that the basic characteristics of the container are not impaired. .
　容器の壁の体積に対する基材層の体積の割合は特に限定されない。基材層が外層または内層である場合、容器の壁の体積に対する外層の体積割合は、例えば１０～２０体積％であることができる。また、容器の壁の体積に対する内層の体積割合は、例えば１０～８０体積％であることができる。なお、本発明において容器の壁は容器の胴部側面であることができる。 割 合 The ratio of the volume of the base material layer to the volume of the container wall is not particularly limited. When the base layer is an outer layer or an inner layer, the volume ratio of the outer layer to the volume of the container wall can be, for example, 10 to 20% by volume. Further, the volume ratio of the inner layer to the volume of the container wall can be, for example, 10 to 80% by volume. In the present invention, the wall of the container may be the side of the body of the container.
　（接着層）
　接着層は、樹脂Ａおよび樹脂Ｂの混合物を含む。樹脂Ａと樹脂Ｂは、樹脂ＡのＭＦＲの値が基材のＭＦＲの値の０．４～１．６倍であり、かつ、混合物の２１０℃での溶融張力Ｙ（ｍＮ）が、基材の２１０℃での溶融張力Ｘ（ｍＮ）との関係で、Ｙ＞Ｘ－３５を満たせば、特に限定されない。 (Adhesive layer)
The adhesive layer contains a mixture of resin A and resin B. The resin A and the resin B have an MFR value of the resin A of 0.4 to 1.6 times the MFR value of the base material, and a melt tension Y (mN) at 210 ° C. of the mixture of the base material. The relationship is not particularly limited as long as Y> X−35 is satisfied in relation to the melt tension X (mN) at 210 ° C.
　樹脂Ａとしては、基材層との一体性がより向上し、容器の透明性がより向上する観点から、基材層の基材であることが好ましい。すなわち、樹脂Ａは基材層の基材と同一の材料であることが好ましい。この場合、樹脂ＡのＭＦＲは基材のＭＦＲと同一である。 Resin A is preferably a base material of the base material layer from the viewpoint of further improving the integration with the base material layer and further improving the transparency of the container. That is, the resin A is preferably the same material as the base material of the base layer. In this case, the MFR of the resin A is the same as the MFR of the base material.
　樹脂Ｂとしては、接着性を有する材料を用いることができる。例えば、グラフト変性ポリオレフィン、エチレン－（メタ）アクリル酸共重合体、エチレン－酢酸ビニル共重合体、ケン化度２０～１００％であるエチレン－酢酸ビニル共重合体ケン化物、エチレン含量８５％以上であるエチレン－ビニルアルコール共重合体、ハイドロタルサイト化合物、アイオノマー（イオン架橋オレフィン系共重合体）等が挙げられる。接着性および溶融張力の観点からグラフト変性ポリオレフィンを用いることが好ましい。グラフト変性ポリオレフィンとしては、例えばマレイン酸、イタコン酸、フマル酸等のカルボン酸又はその無水物、アミド、エステルなどを用いて、ポリオレフィンをグラフト変性したものが挙げられる。これらの中でも、樹脂Ｂとしては接着性および溶融張力の観点から、酸変性ポリオレフィンが好ましく、マレイン酸変性ポリオレフィンがより好ましい。マレイン酸変性ポリオレフィンとしては、例えば（無水）マレイン酸変性低密度ポリエチレン、（無水）マレイン酸変性エチレン－ブテン１共重合体等が挙げられる。これらは一種を用いてもよく、二種以上を併用してもよい。 As the resin B, a material having adhesiveness can be used. For example, graft-modified polyolefin, ethylene- (meth) acrylic acid copolymer, ethylene-vinyl acetate copolymer, saponified ethylene-vinyl acetate copolymer having a saponification degree of 20 to 100%, ethylene content of 85% or more Certain ethylene-vinyl alcohol copolymers, hydrotalcite compounds, ionomers (ion-crosslinked olefin copolymers), and the like. It is preferable to use a graft-modified polyolefin from the viewpoint of adhesiveness and melt tension. Examples of the graft-modified polyolefin include those obtained by graft-modifying a polyolefin with a carboxylic acid such as maleic acid, itaconic acid, or fumaric acid, or an anhydride, amide, or ester thereof. Among these, from the viewpoint of adhesiveness and melt tension, the resin B is preferably an acid-modified polyolefin, and more preferably a maleic acid-modified polyolefin. Examples of the maleic acid-modified polyolefin include maleic anhydride-modified low-density polyethylene, maleic anhydride-modified ethylene-butene 1 copolymer, and the like. These may be used alone or in combination of two or more.
　樹脂ＡのＭＦＲの値は、基材のＭＦＲの値の０．４～１．６倍である。樹脂ＡのＭＦＲの値が基材のＭＦＲの値の０．４～１．６倍の範囲内であることにより、基材層と接着層との界面における一体性が向上し、容器の透明性を向上させることができる。また、樹脂Ａおよび樹脂Ｂの混合物のＭＦＲの値についても、基材層と接着層との界面における一体性がより向上する観点から、基材のＭＦＲの値の０．２～１．８倍であることが好ましい。 (4) The MFR value of the resin A is 0.4 to 1.6 times the MFR value of the base material. When the MFR value of the resin A is in the range of 0.4 to 1.6 times the MFR value of the base material, the integrity at the interface between the base material layer and the adhesive layer is improved, and the transparency of the container is improved. Can be improved. Further, the MFR value of the mixture of the resin A and the resin B is also 0.2 to 1.8 times the MFR value of the base material from the viewpoint of further improving the integrity at the interface between the base material layer and the adhesive layer. It is preferred that
　樹脂ＡのＭＦＲは、基材のＭＦＲと同様に、０．１～３．０ｇ／１０ｍｉｎであることが好ましい。樹脂ＢのＭＦＲは、０．５～５．０ｇ／１０ｍｉｎであることが好ましい。樹脂Ａおよび樹脂Ｂの混合物のＭＦＲは、０．１～３．０ｇ／１０ｍｉｎであることが好ましい。 The MFR of the resin A is preferably 0.1 to 3.0 g / 10 min, similarly to the MFR of the base material. The MFR of the resin B is preferably 0.5 to 5.0 g / 10 min. The MFR of the mixture of the resin A and the resin B is preferably 0.1 to 3.0 g / 10 min.
　樹脂Ａおよび樹脂Ｂの混合物の溶融張力Ｙ（ｍＮ）は、基材の溶融張力Ｘ（ｍＮ）との関係で、Ｙ＞Ｘ－３５を満たし、Ｙ＞Ｘ－２０を満たすことが好ましく、Ｙ＞Ｘ－１０を満たすことがより好ましく、Ｙ＞Ｘを満たすことがさらに好ましい。Ｙ＞Ｘ－３５を満たすことで、容器表面における肉溜りの発生を低減でき、容器の外観が良好となる。 The melt tension Y (mN) of the mixture of the resin A and the resin B preferably satisfies Y> X-35 and Y> X-20 in relation to the melt tension X (mN) of the base material. > X-10 is more preferable, and Y> X is more preferable. By satisfying Y> X-35, the occurrence of meat accumulation on the surface of the container can be reduced, and the appearance of the container can be improved.
　樹脂Ａの溶融張力は、５０～５００ｍＮであることが好ましく、１００～４００ｍＮであることがより好ましく、１５０～３００ｍＮであることがさらに好ましい。樹脂Ｂの溶融張力は、１００～５００ｍＮであることが好ましく、１５０～４００ｍＮであることがより好ましく、１８０～３００ｍＮであることがさらに好ましい。樹脂Ａと樹脂Ｂの混合物の溶融張力Ｙは、１００～５００ｍＮであることが好ましく、１５０～４００ｍＮであることがより好ましく、１９０～３００ｍＮであることがさらに好ましい。なお、樹脂の溶融張力は、分子量分布を広くすることで大きくすることができる。これは分子同士の絡み合いが増加することによるものと考えられている。 溶 融 The melt tension of the resin A is preferably from 50 to 500 mN, more preferably from 100 to 400 mN, even more preferably from 150 to 300 mN. The melt tension of the resin B is preferably from 100 to 500 mN, more preferably from 150 to 400 mN, even more preferably from 180 to 300 mN. The melt tension Y of the mixture of the resin A and the resin B is preferably from 100 to 500 mN, more preferably from 150 to 400 mN, even more preferably from 190 to 300 mN. The melt tension of the resin can be increased by widening the molecular weight distribution. This is thought to be due to an increase in entanglement between molecules.
　混合物中における樹脂Ａと樹脂Ｂとの合計に対する樹脂Ｂの割合は、接着性と容器の外観の観点から４０質量％以上であることが好ましく、５０質量％以上９０質量％以下であることがより好ましい。 The ratio of the resin B to the total of the resin A and the resin B in the mixture is preferably 40% by mass or more, and more preferably 50% by mass or more and 90% by mass or less from the viewpoints of adhesion and appearance of the container. preferable.
　容器の壁の体積に対する接着層の体積の割合は０．２体積％を超える。該割合が０．２体積％を超えることで、十分な接着強度を確保することができる。該割合は０．２体積％を超えて３．５体積％未満であることが好ましく、０．３～３．０体積％であることがより好ましく、０．５～２．５体積％であることがさらに好ましい。該割合が３．５体積％未満であることにより、ブロー成形時における肉溜りの発生をより抑制することができる。接着層の平均厚みは０．５～２０μｍであることが好ましく、１．０～１５μｍであることがより好ましく、１．５～１０μｍであることがさらに好ましい。 割 合 The ratio of the volume of the adhesive layer to the volume of the container wall exceeds 0.2% by volume. When the ratio exceeds 0.2% by volume, a sufficient adhesive strength can be secured. The proportion is preferably more than 0.2% by volume and less than 3.5% by volume, more preferably 0.3 to 3.0% by volume, and more preferably 0.5 to 2.5% by volume. Is more preferable. When the ratio is less than 3.5% by volume, it is possible to further suppress the occurrence of a pool in blow molding. The average thickness of the adhesive layer is preferably from 0.5 to 20 μm, more preferably from 1.0 to 15 μm, and still more preferably from 1.5 to 10 μm.
　（他の層）
　接着層は容器の最外層および最内層でないことが好ましいため、本発明に係る容器は三層以上で構成されることが好ましい。追加の層としては前記基材層が挙げられるが、基材層および接着層以外の他の層であってもよい。該他の層としてはガスバリア層、スクラップ層等が挙げられる。 (Other layers)
Since the adhesive layer is preferably not the outermost layer and the innermost layer of the container, the container according to the present invention is preferably composed of three or more layers. The additional layer includes the above-described base layer, but may be a layer other than the base layer and the adhesive layer. Examples of the other layer include a gas barrier layer and a scrap layer.
　＜ガスバリア層＞
　ガスバリア層は酸素などのガスの透過を阻害できる層である。ガスバリア層を設けることにより、例えば外部からの酸素透過による内容物の酸化劣化を有効に抑制することができる。ガスバリア層は、例えば酸素透過係数（ＰＯ２）が、好ましくは５．５×１０－１２ｃｃ・ｃｍ／ｃｍ２　ｓｅｃ・ｃｍＨｇ以下、より好ましくは４．５×１０－１２ｃｃ・ｃｍ／ｃｍ２　ｓｅｃ・ｃｍＨｇ以下の層であることができる。 <Gas barrier layer>
The gas barrier layer is a layer that can inhibit the transmission of a gas such as oxygen. By providing the gas barrier layer, for example, the oxidative deterioration of the content due to permeation of oxygen from the outside can be effectively suppressed. The gas barrier layer has, for example, an oxygen permeability coefficient (PO2) of preferably 5.5 × 10 −12 cc · cm / cm 2 sec · cmHg or less, more preferably 4.5 × 10 −12 cc · cm / cm 2 sec. -It can be a layer of cmHg or less.
　前記ガスバリア層の材料としては、例えばエチレン－ビニルアルコール共重合体（エチレン－酢酸ビニル共重合体ケン化物）、ポリメタキシリレンアジパミド（ＭＸＤ６）等の芳香族ポリアミドが挙げられる。これらの中でも、高い酸素遮断性を有する観点から、エチレン－ビニルアルコール共重合体が好ましい。 材料 Examples of the material of the gas barrier layer include aromatic polyamides such as ethylene-vinyl alcohol copolymer (saponified ethylene-vinyl acetate copolymer) and polymethaxylylene adipamide (MXD6). Among these, an ethylene-vinyl alcohol copolymer is preferred from the viewpoint of high oxygen barrier properties.
　エチレン－ビニルアルコール共重合体のエチレン含有量は、２０～６０ｍｏｌ％が好ましく、２５～５０ｍｏｌ％がより好ましい。エチレン－ビニルアルコール共重合体としては、例えば前記エチレン含有量のエチレン－酢酸ビニル共重合体を、ケン化度が好ましくは９６モル％以上、より好ましくは９９モル％以上となるようにケン化して得られる共重合体ケン化物を用いることができる。 The ethylene content of the ethylene-vinyl alcohol copolymer is preferably from 20 to 60 mol%, more preferably from 25 to 50 mol%. As the ethylene-vinyl alcohol copolymer, for example, the ethylene-vinyl acetate copolymer having the above-mentioned ethylene content is saponified so that the saponification degree is preferably 96 mol% or more, more preferably 99 mol% or more. The obtained saponified copolymer can be used.
　ガスバリア層は、ガスの遮断性が大きく損なわれない範囲で、前記材料以外の他の材料を含むことができる。前記他の材料としては、例えばポリオレフィンやアイオノマーなど、他の層との間の接着性を付与する樹脂等が挙げられる。ガスバリア層は、前記他の材料を例えば３０質量％以下含むことができる。 The gas barrier layer may contain other materials other than the above materials as long as the gas barrier properties are not significantly impaired. Examples of the other material include a resin that imparts adhesiveness to another layer, such as a polyolefin and an ionomer. The gas barrier layer may contain the other material, for example, in an amount of 30% by mass or less.
　容器の壁の体積に対するガスバリア層の体積の割合は特に限定されないが、例えば５～２０体積％であることができる。 割 合 The ratio of the volume of the gas barrier layer to the volume of the container wall is not particularly limited, but may be, for example, 5 to 20% by volume.
　＜スクラップ層＞
　スクラップ層はリプロ層とも呼ばれ、成形開始時に排出される樹脂やバリなどの容器以外の部分を粉砕したスクラップ樹脂を含む層である。該スクラップ樹脂を再利用することにより、樹脂使用量を低減でき、製造コストを低下させることができる。容器の壁の体積に対するスクラップ層の体積の割合は特に限定されないが、例えば３０～６０体積％であることができる。 <Scrap layer>
The scrap layer is also called a repro layer, and is a layer containing scrap resin obtained by pulverizing a portion other than the container such as resin and burrs discharged at the start of molding. By reusing the scrap resin, the amount of resin used can be reduced, and the manufacturing cost can be reduced. The ratio of the volume of the scrap layer to the volume of the container wall is not particularly limited, but may be, for example, 30 to 60% by volume.
　［容器の製造方法］
　本発明に係る容器の製造方法は、基材を含む基材層と、樹脂Ａおよび樹脂Ｂの混合物を含む接着層と、を備えるパリソンを製造する工程と、前記パリソンをブロー成形して容器を製造する工程と、を含む。ここで、容器の壁の体積に対する接着層の体積の割合は０．２体積％を超える。樹脂ＡのＭＦＲの値は基材のＭＦＲの値の０．４～１．６倍である。また、前記混合物の２１０℃での溶融張力Ｙ（ｍＮ）は、前記基材の２１０℃での溶融張力Ｘ（ｍＮ）との関係で、Ｙ＞Ｘ－３５を満足する。該方法によれば、本発明に係る容器を好適に製造することができる。 [Container manufacturing method]
A method for manufacturing a container according to the present invention includes a step of manufacturing a parison including a base material layer including a base material and an adhesive layer including a mixture of resin A and resin B, and forming a container by blow molding the parison. Manufacturing. Here, the ratio of the volume of the adhesive layer to the volume of the wall of the container exceeds 0.2% by volume. The MFR value of the resin A is 0.4 to 1.6 times the MFR value of the base material. The melt tension Y (mN) at 210 ° C. of the mixture satisfies Y> X−35 in relation to the melt tension X (mN) at 210 ° C. of the base material. According to the method, the container according to the present invention can be suitably manufactured.
　まず、基材を含む基材層と、樹脂Ａおよび樹脂Ｂの混合物を含む接着層と、を備えるパリソンを製造する。例えば、容器を構成する各層の材料を、多層多重ダイスを使用して共押出しすることでパリソンを製造することができる。次に、前記パリソンをブロー成形して容器を製造する。例えば、単頭又は多頭の押出ブロー成形機、多数個金型が回転しながら連続的に押出成形するロータリーブロー成形機などを用い、前記パリソンを溶融押出して割金型内に供給し、その内部に流体を吹き込んで膨張させることで、容器を成形することができる。 First, a parison including a base material layer including a base material and an adhesive layer including a mixture of a resin A and a resin B is manufactured. For example, a parison can be manufactured by co-extruding the material of each layer constituting the container using a multi-layer die. Next, the parison is blow molded to produce a container. For example, using a single-head or multi-head extrusion blow molding machine, a rotary blow molding machine that continuously extrudes while rotating a large number of dies, melt-extrudes the parison and supplies it into a split mold, and the The container can be formed by blowing a fluid into and expanding the fluid.
　ブロー成形時の温度は、基材や前記混合物の融点により決定され、オレフィン系樹脂を使用する場合は例えば１９０～２３０℃に設定される。 温度 The temperature at the time of blow molding is determined by the melting point of the base material and the mixture, and is set, for example, to 190 to 230 ° C. when an olefin resin is used.
　以下、本発明を実施例により更に具体的に説明するが、本発明はこれらの実施例によって限定されるものではない。各材料のＭＦＲおよび溶融張力を以下の方法により測定した。また、各実施例、比較例で得られたボトルの外観、透明性および接着強度を、以下の方法により評価した。 Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples. The MFR and the melt tension of each material were measured by the following methods. Further, the appearance, transparency and adhesive strength of the bottles obtained in each of the examples and comparative examples were evaluated by the following methods.
　［ＭＦＲ］
　ＭＦＲをＪＩＳ　Ｋ　７２１０－１に基づき、温度２１０℃、荷重２．１６ｋｇの条件で測定した。 [MFR]
MFR was measured under the conditions of a temperature of 210 ° C. and a load of 2.16 kg based on JIS K 7210-1.
　［溶融張力］
　溶融張力をＪＩＳ　Ｋ　７１９９に基づき、温度２１０℃、引っ張り速度６．５ｍ／ｍｉｎの条件において測定した。 [Melting tension]
The melt tension was measured based on JIS K 7199 under the conditions of a temperature of 210 ° C. and a tensile speed of 6.5 m / min.
　［外観］
　ボトルの外観を以下の基準で評価した。
Ａ：肉溜まり、縦スジの両方とも発生しない。
Ｂ：肉溜まりが発生するが、縦スジは発生しない。
Ｃ：肉溜まり、縦スジの両方とも発生する。 [appearance]
The appearance of the bottle was evaluated according to the following criteria.
A: Neither meat accumulation nor vertical stripes occur.
B: Meat accumulation occurs, but no vertical streak occurs.
C: Both meat accumulation and vertical streaks occur.
　［透明性］
　ボトルの胴部から縦４０ｍｍ×横４０ｍｍの試験片を切り出した。前記試験片について、濁度計（商品名：ＮＤＨ１００１、日本電色工業（株）製）を用いてＨａｚｅ（％）を測定した。透明性を以下の基準で評価した。
Ａ：Ｈａｚｅが２０％未満である。
Ｂ：Ｈａｚｅが２０％以上４０％未満である。
Ｃ：Ｈａｚｅが４０％以上である。 [transparency]
A test piece having a length of 40 mm and a width of 40 mm was cut out from the body of the bottle. Haze (%) of the test piece was measured using a turbidimeter (trade name: NDH1001, manufactured by Nippon Denshoku Industries Co., Ltd.). The transparency was evaluated according to the following criteria.
A: Haze is less than 20%.
B: Haze is 20% or more and less than 40%.
C: Haze is 40% or more.
　［接着強度］
　ボトルの胴部から幅５ｍｍ、長さ５０ｍｍの短冊状の試験片を切り出した。前記試験片の一方の端部の幅約１０ｍｍをジメチルスルホキシドに浸漬させ、ガスバリア層を溶解させた。内層、外層に分かれた部分をテンシロンの上下にチャッキングして、引張速度３０ｍｍ／ｍｉｎで剥離強度を測定した。接着強度を以下の基準で評価した。
Ａ：剥離強度が２Ｎ以上である。
Ｂ：剥離強度が１Ｎ以上２Ｎ未満である。
Ｃ：剥離強度が１Ｎ未満である（ジメチルスルホキシドに浸漬させなくても手で剥がせる）。 [Adhesive strength]
A strip-shaped test piece having a width of 5 mm and a length of 50 mm was cut out from the body of the bottle. About 10 mm width of one end of the test piece was immersed in dimethyl sulfoxide to dissolve the gas barrier layer. The portion divided into the inner layer and the outer layer was chucked above and below Tensilon, and the peel strength was measured at a tensile speed of 30 mm / min. The adhesive strength was evaluated according to the following criteria.
A: Peel strength is 2N or more.
B: Peel strength is 1N or more and less than 2N.
C: Peel strength is less than 1N (can be peeled off by hand without being immersed in dimethyl sulfoxide).
　［実施例１］
　内層および外層用の材料（基材）として、低密度ポリエチレン（商品名：ＮＵＣ８３２３、ダウ・ケミカル日本（株）製、溶融張力：１８２ｍＮ（２１０℃）、ＭＦＲ：０．７ｇ／１０ｍｉｎ（２１０℃、２．１６ｋｇ荷重）、以下「ＬＤＰＥ－１」とも示す）を準備した。ガスバリア層用の材料として、エチレン－ビニルアルコール共重合体（商品名：エバールＦ１０１Ｂ、（株）クラレ製）を準備した。接着層の材料として、樹脂ＡとしてのＬＤＰＥ－１と、樹脂Ｂとしての無水マレイン酸変性低密度ポリエチレン（商品名：アドマーＬＦ３００、三井化学（株）製、溶融張力：２０７ｍＮ（２１０℃）、ＭＦＲ：１．２ｇ／１０ｍｉｎ（２１０℃、２．１６ｋｇ荷重）、以下「ＡＤ－１」とも示す）とを５０：５０の質量比で配合した混合物を準備した。３つの押出機にそれぞれ、前記ＬＤＰＥ－１、前記エチレン－ビニルアルコール共重合体、および前記混合物のペレットを投入し、外層（基材層）／接着層／ガスバリア層／接着層／内層（基材層）の５層構造を有する多層パリソンを成形した。 [Example 1]
As a material (substrate) for the inner layer and the outer layer, low-density polyethylene (trade name: NUC8323, manufactured by Dow Chemical Japan Co., Ltd., melt tension: 182 mN (210 ° C.), MFR: 0.7 g / 10 min (210 ° C., 2.16 kg load), hereinafter also referred to as “LDPE-1”. As a material for the gas barrier layer, an ethylene-vinyl alcohol copolymer (trade name: EVAL F101B, manufactured by Kuraray Co., Ltd.) was prepared. As the material for the adhesive layer, LDPE-1 as resin A and maleic anhydride-modified low-density polyethylene as resin B (trade name: Admer LF300, manufactured by Mitsui Chemicals, Inc., melt tension: 207 mN (210 ° C.), MFR : 1.2 g / 10 min (210 ° C, 2.16 kg load), hereinafter also referred to as “AD-1” at a mass ratio of 50:50. The pellets of the LDPE-1, the ethylene-vinyl alcohol copolymer, and the mixture are charged into three extruders, respectively, and an outer layer (base layer) / adhesive layer / gas barrier layer / adhesive layer / inner layer (base A multi-layer parison having a five-layer structure was formed.
　次いで、前記多層パリソンをダイレクトブロー成形することにより、図１に示される下記構成を有するチューブ形状のボトルを得た。前記ボトルの内容量は８０ｍｌ、口部外形は９．６ｍｍ、胴径は３３ｍｍ、高さは１５０ｍｍ、平均厚みは０．３３ｍｍであった。
　　外層１（平均厚み：４９．５μｍ）／接着層２（平均厚み：８．３μｍ、体積割合：２．５体積％）／ガスバリア層３（平均厚み：３３μｍ）／接着層４（平均厚み：８．３μｍ、体積割合：２．５体積％）／内層５（平均厚み：２３０．９μｍ） Then, the multilayer parison was subjected to direct blow molding to obtain a tube-shaped bottle having the following structure shown in FIG. The inner volume of the bottle was 80 ml, the outer shape of the mouth was 9.6 mm, the body diameter was 33 mm, the height was 150 mm, and the average thickness was 0.33 mm.
Outer layer 1 (average thickness: 49.5 μm) / adhesive layer 2 (average thickness: 8.3 μm, volume ratio: 2.5 vol%) / gas barrier layer 3 (average thickness: 33 μm) / adhesive layer 4 (average thickness: 8) 0.3 μm, volume ratio: 2.5% by volume) / inner layer 5 (average thickness: 230.9 μm)
　前記ボトルについて、前記方法により外観、透明性および接着強度を評価した。結果を表１に示す。 外 観 The bottle was evaluated for appearance, transparency and adhesive strength by the above-mentioned method. Table 1 shows the results.
　［実施例２］
　２つの接着層の材料として、樹脂ＡとしてのＬＤＰＥ－１と、樹脂ＢとしてのＡＤ－１とを４０：６０の質量比で配合した混合物を用いた以外は、実施例１と同様にボトルを製造し、評価した。結果を表１に示す。 [Example 2]
A bottle was prepared in the same manner as in Example 1, except that a mixture of LDPE-1 as resin A and AD-1 as resin B in a mass ratio of 40:60 was used as a material for the two adhesive layers. Manufactured and evaluated. Table 1 shows the results.
　［実施例３］
　２つの接着層の材料として、樹脂ＡとしてのＬＤＰＥ－１と、樹脂ＢとしてのＡＤ－１とを２０：８０の質量比で配合した混合物を用いた以外は、実施例１と同様にボトルを製造し、評価した。結果を表１に示す。 [Example 3]
A bottle was prepared in the same manner as in Example 1, except that a mixture of LDPE-1 as resin A and AD-1 as resin B in a mass ratio of 20:80 was used as a material for the two adhesive layers. Manufactured and evaluated. Table 1 shows the results.
　［実施例４］
　ボトルの各層の厚みを以下のように変更した以外は、実施例２と同様にボトルを製造し、評価した。結果を表１に示す。
　　外層１（平均厚み：４９．５μｍ）／接着層２（平均厚み：３．３μｍ、体積割合：１．０体積％）／ガスバリア層３（平均厚み：３３μｍ）／接着層４（平均厚み：３．３μｍ、体積割合：１．０体積％）／内層５（平均厚み：２４０．９μｍ） [Example 4]
A bottle was manufactured and evaluated in the same manner as in Example 2, except that the thickness of each layer of the bottle was changed as follows. Table 1 shows the results.
Outer layer 1 (average thickness: 49.5 μm) / adhesion layer 2 (average thickness: 3.3 μm, volume ratio: 1.0% by volume) / gas barrier layer 3 (average thickness: 33 μm) / adhesion layer 4 (average thickness: 3) 0.3 μm, volume ratio: 1.0% by volume) / Inner layer 5 (average thickness: 240.9 μm)
　［実施例５］
　ボトルの各層の厚みを以下のように変更した以外は、実施例２と同様にボトルを製造し、評価した。結果を表１に示す。
　　外層１（平均厚み：４９．５μｍ）／接着層２（平均厚み：１．７μｍ、体積割合：０．５体積％）／ガスバリア層３（平均厚み：３３μｍ）／接着層４（平均厚み：１．７μｍ、体積割合：０．５体積％）／内層５（平均厚み：２４４．１μｍ） [Example 5]
A bottle was manufactured and evaluated in the same manner as in Example 2, except that the thickness of each layer of the bottle was changed as follows. Table 1 shows the results.
Outer layer 1 (average thickness: 49.5 μm) / adhesive layer 2 (average thickness: 1.7 μm, volume ratio: 0.5% by volume) / gas barrier layer 3 (average thickness: 33 μm) / adhesive layer 4 (average thickness: 1) 0.7 μm, volume ratio: 0.5% by volume) / inner layer 5 (average thickness: 244.1 μm)
　［実施例６］
　２つの接着層の材料として、樹脂Ａとしての低密度ポリエチレン（商品名：Ｆ１０１－１、住友化学（株）製、溶融張力：２７２ｍＮ（２１０℃）、ＭＦＲ：０．３ｇ／１０ｍｉｎ（２１０℃、２．１６ｋｇ荷重）、以下「ＬＤＰＥ－２」とも示す）と、樹脂ＢとしてのＡＤ－１とを４０：６０の質量比で配合した混合物を用いた以外は、実施例１と同様にボトルを製造し、評価した。結果を表１に示す。 [Example 6]
As a material for the two adhesive layers, low-density polyethylene as resin A (trade name: F101-1, manufactured by Sumitomo Chemical Co., Ltd., melt tension: 272 mN (210 ° C.), MFR: 0.3 g / 10 min (210 ° C., 2.16 kg load) (hereinafter also referred to as “LDPE-2”) and AD-1 as the resin B in a weight ratio of 40:60, except that a mixture was used. Manufactured and evaluated. Table 1 shows the results.
　［実施例７］
　２つの接着層の材料として、樹脂ＡとしてのＬＤＰＥ－１と、樹脂Ｂとしての無水マレイン酸変性低密度ポリエチレン（商品名：アドマーＬＢ５４０、三井化学（株）製、溶融張力：１４７ｍＮ（２１０℃）、ＭＦＲ：１．５ｇ／１０ｍｉｎ（２１０℃、２．１６ｋｇ荷重）、以下「ＡＤ－２」とも示す）とを４０：６０の質量比で配合した混合物を用いた以外は、実施例１と同様にボトルを製造し、評価した。結果を表１に示す。 [Example 7]
LDPE-1 as resin A and maleic anhydride-modified low density polyethylene as resin B (trade name: ADMER LB540, manufactured by Mitsui Chemicals, Inc., melt tension: 147 mN (210 ° C.) as a material for the two adhesive layers , MFR: 1.5 g / 10 min (210 ° C., 2.16 kg load, hereinafter also referred to as “AD-2”) at a mass ratio of 40:60, and the same as Example 1 Was manufactured and evaluated. Table 1 shows the results.
　［実施例８］
　２つの接着層の材料として、樹脂ＡとしてのＬＤＰＥ－１と、樹脂ＢとしてのＡＤ－２とを５０：５０の質量比で配合した混合物を用いた以外は、実施例１と同様にボトルを製造し、評価した。結果を表１に示す。 Example 8
A bottle was prepared in the same manner as in Example 1 except that a mixture of LDPE-1 as resin A and AD-2 as resin B in a mass ratio of 50:50 was used as a material for the two adhesive layers. Manufactured and evaluated. Table 1 shows the results.
　［実施例９］
　２つの接着層の材料として、樹脂ＡとしてのＬＤＰＥ－２と、樹脂ＢとしてのＡＤ－２とを４０：６０の質量比で配合した混合物を用いた以外は、実施例１と同様にボトルを製造し、評価した。結果を表１に示す。 [Example 9]
A bottle was prepared in the same manner as in Example 1, except that a mixture of LDPE-2 as resin A and AD-2 as resin B at a mass ratio of 40:60 was used as a material for the two adhesive layers. Manufactured and evaluated. Table 1 shows the results.
　［実施例１０］
　２つの接着層の材料として、樹脂ＡとしてのＬＤＰＥ－１と、樹脂ＢとしてのＡＤ－１とを６０：４０の質量比で配合した混合物を用いた以外は、実施例１と同様にボトルを製造し、評価した。結果を表１に示す。 [Example 10]
A bottle was prepared in the same manner as in Example 1 except that a mixture of LDPE-1 as resin A and AD-1 as resin B in a mass ratio of 60:40 was used as a material for the two adhesive layers. Manufactured and evaluated. Table 1 shows the results.
　［実施例１１］
　内層および外層用の材料（基材）として、低密度ポリエチレン（商品名：ＬＢ４２０Ｍ、ＪＰＥ（株）製、溶融張力：１６２ｍＮ（２１０℃）、ＭＦＲ：０．７ｇ／１０ｍｉｎ（２１０℃、２．１６ｋｇ荷重）、以下「ＬＤＰＥ－３」とも示す）を用い、接着層の材料として、樹脂ＡとしてのＬＤＰＥ－３と、樹脂ＢとしてのＡＤ－１を４０：６０の質量比で配合した混合物を用いた以外は、実施例１と同様にボトルを製造し、評価した。結果を表１に示す。 [Example 11]
As a material (base material) for the inner layer and the outer layer, low density polyethylene (trade name: LB420M, manufactured by JPE Co., Ltd., melt tension: 162 mN (210 ° C.), MFR: 0.7 g / 10 min (210 ° C., 2.16 kg) Load), hereinafter also referred to as “LDPE-3”), and a mixture of LDPE-3 as resin A and AD-1 as resin B at a mass ratio of 40:60 is used as a material for the adhesive layer. A bottle was manufactured and evaluated in the same manner as in Example 1 except for the presence of the bottle. Table 1 shows the results.
　［比較例１］
　接着層の材料として、無水マレイン酸変性エチレン－ブテン１共重合体（商品名：アドマーＮＦ３０７、三井化学（株）製、溶融張力：８３ｍＮ（２１０℃）、ＭＦＲ：１．６ｇ／１０ｍｉｎ（２１０℃、２．１６ｋｇ荷重）、以下「ＡＤ－３」とも示す）を用いた以外は、実施例１と同様にボトルを製造し、評価した。結果を表１に示す。 [Comparative Example 1]
As a material for the adhesive layer, a maleic anhydride-modified ethylene-butene 1 copolymer (trade name: Admer NF307, manufactured by Mitsui Chemicals, Inc., melt tension: 83 mN (210 ° C.), MFR: 1.6 g / 10 min (210 ° C.) , 2.16 kg load) (hereinafter also referred to as “AD-3”), and a bottle was manufactured and evaluated in the same manner as in Example 1. Table 1 shows the results.
　［比較例２］
　接着層の材料としてＡＤ－２を用いた以外は、実施例１と同様にボトルを製造し、評価した。結果を表１に示す。 [Comparative Example 2]
A bottle was manufactured and evaluated in the same manner as in Example 1 except that AD-2 was used as a material for the adhesive layer. Table 1 shows the results.
　［比較例３］
　ボトルの各層の厚みを以下のように変更した以外は、比較例２と同様にボトルを製造し、評価した。結果を表１に示す。
　　外層１（平均厚み：４９．５μｍ）／接着層２（平均厚み：１１．６μｍ、体積割合：３．５体積％）／ガスバリア層３（平均厚み：３３μｍ）／接着層４（平均厚み：１１．６μｍ、体積割合：３．５体積％）／内層５（平均厚み：２２４．３μｍ） [Comparative Example 3]
A bottle was manufactured and evaluated in the same manner as in Comparative Example 2 except that the thickness of each layer of the bottle was changed as follows. Table 1 shows the results.
Outer layer 1 (average thickness: 49.5 μm) / adhesive layer 2 (average thickness: 11.6 μm, volume ratio: 3.5 vol%) / gas barrier layer 3 (average thickness: 33 μm) / adhesive layer 4 (average thickness: 11) 0.6 μm, volume ratio: 3.5% by volume) / inner layer 5 (average thickness: 224.3 μm)
　［比較例４］
　ボトルの各層の厚みを以下のように変更した以外は、実施例２と同様にボトルを製造し、評価した。結果を表１に示す。
　　外層１（平均厚み：４９．５μｍ）／接着層２（平均厚み：０．７μｍ、体積割合：０．２体積％）／ガスバリア層３（平均厚み：３３μｍ）／接着層４（平均厚み：０．７μｍ、体積割合：０．２体積％）／内層５（平均厚み：２４６．１μｍ） [Comparative Example 4]
A bottle was manufactured and evaluated in the same manner as in Example 2, except that the thickness of each layer of the bottle was changed as follows. Table 1 shows the results.
Outer layer 1 (average thickness: 49.5 μm) / adhesive layer 2 (average thickness: 0.7 μm, volume ratio: 0.2% by volume) / gas barrier layer 3 (average thickness: 33 μm) / adhesive layer 4 (average thickness: 0) 0.7 μm, volume ratio: 0.2% by volume) / inner layer 5 (average thickness: 246.1 μm)
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
１　　外層
２　　接着層
３　　ガスバリア層
４　　接着層
５　　内層
  1 outer layer 2 adhesive layer 3 gas barrier layer 4 adhesive layer 5 inner layer

Claims (7)

  1. 　基材を含む基材層と、樹脂Ａおよび樹脂Ｂの混合物を含む接着層と、を備える容器であって、
    　前記容器の壁の体積に対する前記接着層の体積の割合が０．２体積％を超え、
    　前記樹脂Ａの２１０℃、２．１６ｋｇ荷重でのメルトフローレート（ｇ／１０ｍｉｎ）の値が、前記基材の２１０℃、２．１６ｋｇ荷重でのメルトフローレート（ｇ／１０ｍｉｎ）の値の０．４～１．６倍であり、
    　前記混合物の２１０℃での溶融張力Ｙ（ｍＮ）が下記式、
    　　Ｙ＞Ｘ－３５
    　式中、Ｘは前記基材の２１０℃での溶融張力（ｍＮ）である、
    を満足する容器。     A container comprising a base material layer including a base material and an adhesive layer including a mixture of resin A and resin B,
    The ratio of the volume of the adhesive layer to the volume of the container wall exceeds 0.2% by volume,
    The value of the melt flow rate (g / 10 min) of the resin A at 210 ° C. and a load of 2.16 kg is 0 of the value of the melt flow rate (g / 10 min) of the base material at 210 ° C. and a load of 2.16 kg. 0.4 to 1.6 times,
    The melt tension Y (mN) at 210 ° C. of the mixture is represented by the following formula:
    Y> X-35
    Wherein X is the melt tension (mN) of the substrate at 210 ° C.
    To satisfy the container.
  2. 　前記容器の壁の体積に対する前記接着層の体積の割合が３．５体積％未満である請求項１に記載の容器。 The container according to claim 1, wherein the ratio of the volume of the adhesive layer to the volume of the wall of the container is less than 3.5% by volume.
  3. 　前記混合物中における前記樹脂Ａと前記樹脂Ｂとの合計に対する前記樹脂Ｂの割合が４０質量％以上である請求項１または２に記載の容器。 The container according to claim 1 or 2, wherein the ratio of the resin B to the total of the resin A and the resin B in the mixture is 40% by mass or more.
  4. 　前記樹脂Ａが前記基材である請求項１から３のいずれか一項に記載の容器。 容器 The container according to any one of claims 1 to 3, wherein the resin A is the base material.
  5. 　前記樹脂Ｂがグラフト変性ポリオレフィンである請求項１から４のいずれか一項に記載の容器。 The container according to any one of claims 1 to 4, wherein the resin B is a graft-modified polyolefin.
  6. 　前記容器の平均厚みが０．５ｍｍ以下である請求項１から５のいずれか一項に記載の容器。 The container according to any one of claims 1 to 5, wherein the container has an average thickness of 0.5 mm or less.
  7. 　基材を含む基材層と、樹脂Ａおよび樹脂Ｂの混合物を含む接着層と、を備えるパリソンを製造する工程と、
    　前記パリソンをブロー成形して容器を製造する工程と、
    を含む容器の製造方法であって、
    　前記容器の壁の体積に対する前記接着層の体積の割合が０．２体積％を超え、
    　前記樹脂Ａの２１０℃、２．１６ｋｇ荷重でのメルトフローレート（ｇ／１０ｍｉｎ）の値が、前記基材の２１０℃、２．１６ｋｇ荷重でのメルトフローレート（ｇ／１０ｍｉｎ）の値の０．４～１．６倍であり、
    　前記混合物の２１０℃での溶融張力Ｙ（ｍＮ）が下記式、
    　　Ｙ＞Ｘ－３５
    　式中、Ｘは前記基材の２１０℃での溶融張力（ｍＮ）である、
    を満足する容器の製造方法。
          A step of manufacturing a parison comprising: a base material layer including a base material; and an adhesive layer including a mixture of resin A and resin B.
    Blow molding the parison to produce a container,
    A method for producing a container comprising:
    The ratio of the volume of the adhesive layer to the volume of the container wall exceeds 0.2% by volume,
    The value of the melt flow rate (g / 10 min) of the resin A at 210 ° C. and a load of 2.16 kg is 0 of the value of the melt flow rate (g / 10 min) of the base material at 210 ° C. and a load of 2.16 kg. 0.4 to 1.6 times,
    The melt tension Y (mN) at 210 ° C. of the mixture is represented by the following formula:
    Y> X-35
    Wherein X is the melt tension (mN) of the substrate at 210 ° C.
    A container manufacturing method that satisfies the following.
PCT/JP2019/027863 2018-07-17 2019-07-16 Container and method for manufacturing same WO2020017487A1 (en)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH02107437A (en) * 1988-10-17 1990-04-19 Nippon Petrochem Co Ltd Hollow vessel
JPH1059343A (en) * 1996-08-12 1998-03-03 Kishimoto Akira Multilayer plastic container and its manufacture
JPH1112321A (en) * 1997-06-24 1999-01-19 Nippon Polyolefin Kk Ethylene (co)polymer, laminate and blow molded product using the same
JP2000072818A (en) * 1993-09-21 2000-03-07 Mitsubishi Chemicals Corp Ethylenic polymer
JP2000326461A (en) * 1999-05-21 2000-11-28 Mitsui Chemicals Inc Polyethylenic multilayered laminated container
JP2003182744A (en) * 2001-12-19 2003-07-03 Toyo Seikan Kaisha Ltd Multilayer blow pack having improved clarity and its production method

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH02107437A (en) * 1988-10-17 1990-04-19 Nippon Petrochem Co Ltd Hollow vessel
JP2000072818A (en) * 1993-09-21 2000-03-07 Mitsubishi Chemicals Corp Ethylenic polymer
JPH1059343A (en) * 1996-08-12 1998-03-03 Kishimoto Akira Multilayer plastic container and its manufacture
JPH1112321A (en) * 1997-06-24 1999-01-19 Nippon Polyolefin Kk Ethylene (co)polymer, laminate and blow molded product using the same
JP2000326461A (en) * 1999-05-21 2000-11-28 Mitsui Chemicals Inc Polyethylenic multilayered laminated container
JP2003182744A (en) * 2001-12-19 2003-07-03 Toyo Seikan Kaisha Ltd Multilayer blow pack having improved clarity and its production method

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