WO2019230929A1 - Multi-layer plastic container comprising ethylene-vinyl alcohol copolymer - Google Patents

Multi-layer plastic container comprising ethylene-vinyl alcohol copolymer Download PDF

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Publication number
WO2019230929A1
WO2019230929A1 PCT/JP2019/021658 JP2019021658W WO2019230929A1 WO 2019230929 A1 WO2019230929 A1 WO 2019230929A1 JP 2019021658 W JP2019021658 W JP 2019021658W WO 2019230929 A1 WO2019230929 A1 WO 2019230929A1
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Prior art keywords
oxygen barrier
layer
ethylene
vinyl alcohol
alcohol copolymer
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PCT/JP2019/021658
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French (fr)
Japanese (ja)
Inventor
雄介 安齋
小松　威久男
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メビウスパッケージング株式会社
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Priority to JP2020522616A priority Critical patent/JP7311503B2/en
Publication of WO2019230929A1 publication Critical patent/WO2019230929A1/en

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Classifications

    • 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
    • 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
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • 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
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • 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
    • B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
    • B65D65/38—Packaging materials of special type or form
    • B65D65/40—Applications of laminates for particular packaging purposes

Definitions

  • the present invention relates to a multilayer plastic container having an oxygen barrier layer made of an ethylene / vinyl alcohol copolymer as an intermediate layer, and further to oxygen used as an adhesive for forming the multilayer structure of the plastic container. Also related to barrier reinforcement.
  • Olefin resins such as polyethylene and polypropylene are excellent in properties such as moldability, transparency, mechanical strength, and chemical resistance, and are particularly used as packaging materials for bottles and the like.
  • the barrier property against oxygen is enhanced by providing a multilayer structure in which an oxygen barrier layer is provided in the intermediate layer.
  • the resin used for forming the oxygen barrier layer is typically an ethylene / vinyl alcohol copolymer (saponified ethylene-vinyl acetate copolymer).
  • the ethylene / vinyl alcohol copolymer (EVOH) has a low resistance to moisture, and has a drawback that, for example, under a high humidity condition, the oxygen barrier property is greatly reduced.
  • the oxygen barrier layer made of EVOH is used as a multilayer structure sandwiched by a low hygroscopic resin layer such as an olefin resin as disclosed in Patent Document 1 and the like. Even in this case, deterioration of EVOH due to moisture cannot be sufficiently prevented. In particular, when the contents stored in the container are edible liquid substances such as beverages, this tendency is remarkable. In addition, EVOH has a problem of poor adhesion to olefinic resins. For this reason, in the multilayer structure described above, the oxygen barrier layer of EVOH has a layer structure bonded to the olefin resin layer using an adhesive layer.
  • Examples of the adhesive used for the adhesive layer as described above include, for example, Patent Document 1, an ethylene-acrylic acid copolymer, an ion-crosslinked olefin copolymer (ionomer), a maleic anhydride grafted polyolefin, an acrylic acid grafted polyolefin, Examples include ethylene-vinyl acetate copolymer.
  • burrs are generated when a container is formed by blow molding, and punching scraps are generated by cup molding.
  • Such scrap is generally mixed with a virgin resin to be reused as a regrind layer and as an intermediate layer of a multilayer container.
  • the regrind layer containing scrap generated when molding a container including an oxygen barrier layer of an ethylene / vinyl alcohol copolymer contains a large amount of olefin resin used for inner and outer layer resins. It has poor adhesion. Therefore, when such a regrind layer is provided, it is necessary to use the adhesive layer as described above between the virgin EVOH layer.
  • EVOH is contained in this regrind layer, it has received a thermal history and further dispersed in the layer, so it does not have sufficient oxygen barrier properties. Therefore, by providing the regrind layer, it is impossible to avoid a decrease in oxygen barrier property due to moisture.
  • an object of the present invention includes an inner and outer layer of an olefin resin and an oxygen barrier layer of an ethylene / vinyl alcohol copolymer provided as an intermediate layer, and a decrease in oxygen barrier property due to moisture is effectively avoided. It is to provide a multilayer plastic container. Another object of the present invention is to prevent deterioration of oxygen barrier properties due to moisture, and at the same time, improve the adhesion between the regrind layer and the ethylene / vinyl alcohol copolymer, and provide a regrind layer. Another object of the present invention is to provide a multi-layer plastic container in which exfoliation of the ethylene / vinyl alcohol copolymer is effectively prevented.
  • Still another object of the present invention is to provide an oxygen barrier that can effectively mitigate a decrease in oxygen barrier properties of an ethylene / vinyl alcohol copolymer due to moisture while being used as an adhesive with an ethylene / vinyl alcohol copolymer layer. It is to provide a reinforcing material.
  • the inventors of the present invention conducted a number of experiments on the adhesion of ethylene / vinyl alcohol copolymer and reduced oxygen barrier properties due to moisture, and as a result, ethylene / vinyl alcohol copolymer, low-density polyethylene, compatibilizer, In order to complete the present invention, it has been found that the composition blended with the composition exhibits not only high oxygen barrier properties by itself, but also excellent adhesion to olefin resin layers and regrind layers. It came.
  • a multilayer plastic container including an inner and outer layer made of an olefin resin and an oxygen barrier layer made of an ethylene / vinyl alcohol copolymer as an intermediate layer, An oxygen barrier reinforcing layer containing ethylene-vinyl alcohol copolymer and low-density polyethylene as main materials and further containing a compatibilizing agent is provided adjacent to at least the inner surface of the oxygen barrier layer.
  • a multilayer plastic container is provided.
  • the oxygen barrier reinforcing layer is provided adjacent to the container outer surface side of the oxygen barrier layer.
  • At least one regrind layer containing scrap generated during molding of a container containing ethylene / vinyl alcohol as an oxygen barrier resin is provided as an intermediate layer.
  • the oxygen barrier reinforcing layer is located between the regrind layer and the oxygen barrier layer.
  • the hygroscopic material is an ethylene / vinyl alcohol copolymer.
  • An ionomer is used as the compatibilizing agent.
  • the oxygen barrier reinforcing layer contains the ethylene / vinyl alcohol copolymer and the low-density polyethylene in a mass ratio of 95: 5 to 50:50.
  • the oxygen barrier reinforcing layer contains the compatibilizing agent in an amount of 1 to 49 parts by mass per 100 parts by mass of the total amount of the ethylene / vinyl alcohol copolymer and the low density polyethylene.
  • the ethylene / vinyl alcohol copolymer forming the oxygen barrier layer and the ethylene / vinyl alcohol copolymer used in the oxygen barrier reinforcing layer have an ethylene content of 20 to 60 mol%. Be in the range.
  • the oxygen barrier layer is present with a peel strength of 100 mN / 15 mm or more.
  • the body thickness is in the range of 10 to 1500 ⁇ m and the oxygen permeability is 100 cc / m 2 ⁇ day ⁇ atm or less.
  • (11) A direct blow bottle.
  • the oxygen barrier reinforcing material further comprising an ethylene / vinyl alcohol copolymer and low-density polyethylene as main materials, and further containing a compatibilizer, wherein the melt flow rate at 190 ° C. of the low-density polyethylene is An oxygen barrier reinforcing material characterized by being 0.3 to 30 g / 10 min is provided.
  • the ethylene / vinyl alcohol copolymer and the low density polyethylene are contained in a mass ratio of 95: 5 to 50:50, and the compatibilizing agent is an ethylene / vinyl alcohol copolymer and a low density polyethylene. It is included in an amount of 1 to 49 parts by mass per 100 parts by mass in total.
  • the compatibilizing agent is an ethylene / vinyl alcohol copolymer and a low density polyethylene. It is included in an amount of 1 to 49 parts by mass per 100 parts by mass in total.
  • the low density polyethylene has a melt flow rate at 190 ° C. of 1.0 to 20 g / 10 min.
  • An ionomer is used as the compatibilizer, Is preferred.
  • the multilayer plastic container of the present invention includes an oxygen barrier layer made of ethylene / vinyl alcohol copolymer (EVOH) as an intermediate layer together with inner and outer layers made of olefin resin, and is adjacent to the inner surface side of the oxygen barrier layer.
  • EVOH ethylene / vinyl alcohol copolymer
  • the oxygen barrier reinforcing layer includes a hygroscopic material and low density polyethylene (LDPE) as main materials, and is further formed of an oxygen barrier reinforcing material containing a compatibilizing agent.
  • Such an oxygen barrier reinforcing layer contains a large amount of a hygroscopic material as a main material.
  • a hygroscopic material for example, a substance containing a large amount of water such as a beverage or a seasoning liquid as a container content.
  • the hygroscopic material in the oxygen barrier reinforcing layer absorbs moisture, and effectively suppresses the decrease in oxygen barrier properties due to moisture in the adjacent oxygen barrier layer (EVOH layer). Sex can be reinforced.
  • LDPE and compatibilizing agent are also homogeneously distributed in the oxygen barrier reinforcing layer described above. Therefore, it has excellent adhesion to EVOH gas barrier layers and olefin resin layers.
  • this oxygen barrier reinforcing material when this oxygen barrier reinforcing material is provided as an adhesive layer adjacent to the oxygen barrier layer of EVOH, the peel strength of the oxygen barrier layer is 100 mN / 15 mm or more. It becomes. Therefore, in the present invention, it is possible to effectively avoid peeling of the oxygen barrier layer and the regrind layer without forming a special adhesive resin layer, and to change the die head of the extruder by forming the adhesive resin layer, etc.
  • the oxygen barrier property can be enhanced while avoiding the cost increase derived from the above.
  • the multilayer plastic container of the present invention has inner and outer layers formed of an olefin resin, and includes an oxygen barrier layer made of ethylene / vinyl alcohol copolymer (EVOH) as an intermediate layer, and further includes at least an oxygen barrier layer.
  • An oxygen barrier reinforcing layer is provided adjacent to the inner surface side, and a regrind layer is provided as necessary.
  • olefin resin used as the inner and outer layers low density polyethylene (LDPE), medium density polyethylene (MDPE), high density polyethylene (HDPE), linear low density polyethylene (LLDPE), linear ultra-low Polyethylene such as density polyethylene (LVLDPE), polypropylene, ethylene-propylene copolymer, polybutene-1, ethylene-butene-1 copolymer, propylene-butene-1 copolymer, ethylene-propylene-butene-1 copolymer Examples thereof include a copolymer, an ethylene-vinyl acetate copolymer, and an ion-crosslinked olefin copolymer (ionomer). Among these, polyethylene is most suitable because it has high adhesiveness with an oxygen barrier reinforcing layer described later.
  • the olefin-based resin for forming the inner and outer layers as described above may be of an extrusion grade or an injection grade conventionally used in the field of packaging materials.
  • the thickness of the inner and outer layers as described above is not particularly limited, and is appropriately set according to the application utilizing the characteristics of the olefin resin used for the inner and outer layers, but in general, the total thickness of each layer About 10 to 50% of the total thickness of a certain multilayer structure is set to be the total thickness of the inner layer and the outer layer.
  • a lubricant in the inner and outer layers, a lubricant, a modifier, a pigment, an ultraviolet absorber and the like may be blended as necessary.
  • ethylene-vinyl alcohol copolymer (EVOH) used for forming the oxygen barrier layer specifically, an ethylene-vinyl acetate copolymer having an ethylene content of 20 to 60 mol% is used.
  • This ethylene-vinyl alcohol copolymer (saponified ethylene-vinyl acetate copolymer) is generally 0.01 dl / g or more measured at 30 ° C. in a mixed solvent having a phenol / water mass ratio of 85/15. In particular, it has an intrinsic viscosity of 0.05 dl / g or more.
  • the above-mentioned EVOH has a higher oxygen barrier property as the ethylene content is smaller.
  • the oxygen barrier reinforcement layer mentioned later shows high adhesiveness with respect to EVOH. Therefore, in the present invention, it is desirable to use EVOH having a low ethylene content. For example, those having an ethylene content in the range of 20 to 60 mol% are used, but high barrier properties in the range of 20 to 38 mol% are used. It is further preferred to use EVOH.
  • Such an oxygen barrier layer formed of EVOH is not limited to one layer, and may be provided in two or more layers. In particular, it is preferable to provide a plurality of oxygen barrier layers in terms of ensuring oxygen barrier properties at a certain level or higher.
  • the thickness of the oxygen barrier layer is set to an appropriate thickness according to the number of oxygen barrier layers provided in the multilayer structure and the required oxygen barrier property provided in the container.
  • an oxygen barrier reinforcing layer is provided adjacent to at least the inner surface side of the oxygen barrier layer.
  • Such an oxygen barrier reinforcing layer includes a hygroscopic material and low density polyethylene (LDPE) as main materials, and further includes an oxygen barrier reinforcing material including a compatibilizing agent.
  • the low density polyethylene in the present application includes linear low density polyethylene.
  • the hygroscopic material include an ethylene / vinyl alcohol copolymer (EVOH) and a polyamide resin. These materials can be blended alone in the oxygen barrier layer.
  • hygroscopic materials include polysaccharides such as starch and cellulose; cellulose derivatives such as carboxymethyl cellulose and hydroxyethyl cellulose; poly ⁇ and ⁇ unsaturated carboxylic acids such as polyacrylic acid or sodium polyacrylate or ionic cross-linked products thereof. ; Polyalkylene oxide derivatives such as polyethylene oxide or polypropylene oxide; Organic compounds having hydrophilic groups such as polyester; Zeolite, silica gel, activated carbon, activated clay, activated aluminum oxide, clay, kaolin, talc, bentonite, sepiolite, aluminum silicate, oxidation Mention may also be made of inorganic compounds such as calcium, calcium chloride and magnesium sulfate. These materials are blended in EVOH and then blended into the oxygen barrier reinforcing layer. This is to ensure adhesion with the oxygen barrier layer made of EVOH.
  • Such an oxygen barrier reinforcing layer has a hygroscopic material and LDPE compatibilized by a compatibilizing agent and is homogeneously distributed. Excellent adhesiveness is exhibited. Furthermore, moisture entering from the container is absorbed by the hygroscopic material in the oxygen barrier reinforcing layer, and as a result, deterioration of the oxygen barrier layer (EVOH layer) adjacent to the oxygen barrier reinforcing layer is effectively mitigated. Thus, it is possible to effectively suppress a decrease in oxygen barrier property due to moisture, and to maintain a certain level of oxygen barrier property.
  • the hygroscopic material used as the main material in the oxygen barrier reinforcing material the same material as that used for forming the oxygen barrier layer described above may be used.
  • those having the ethylene content in the range of 20 to 60 mol% are used, and high barrier EVOH in the range of 20 to 38 mol% is more preferably used.
  • the LDPE used as the other main material in the oxygen barrier reinforcing material is polyethylene having a density in the range of 0.910 g / cm 3 or more and less than 0.930 g / cm 3 .
  • EVOH is used as the hygroscopic material
  • such LDPE generally has a melt flow rate at 190 ° C. (from the viewpoint of avoiding phase separation with EVOH during molding and preventing delamination).
  • the MFR) is preferably 0.3 g / 10 min or more, 30 g / 10 min or less, particularly 1.0 to 20 g / 10 min from the viewpoint of moldability.
  • the compatibilizing agent in the oxygen barrier reinforcing layer is used for compatibilizing EVOH and LDPE having poor adhesion to each other and preventing phase separation between them.
  • carboxylic acid such as maleic acid, itaconic acid, fumaric acid or its anhydride, maleic acid-polyethylene copolymer, maleic anhydride-polyethylene copolymer, amide, ester, etc.
  • Graft-modified olefin resin 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
  • examples thereof include ethylene-vinyl alcohol copolymer, hydrotalcite compound; ionomer (ion-crosslinked olefin copolymer).
  • ionomers are particularly preferably used.
  • the compatibilizer such as ionomer is preferably used in an amount of 1 to 49 parts by mass, particularly 5 to 30 parts by mass, per 100 parts by mass of the total amount of the main materials (EVOH and LDPE). If the compatibilizing agent is used in excess, not only the properties required for EVOH and LDPE used as the main material are impaired, but the cost is increased and there is no merit. Moreover, when there is too little usage-amount of a compatibilizing agent, EVOH and LDPE will isolate
  • the oxygen barrier reinforcing layer formed from the above-described oxygen barrier reinforcing material is provided adjacent to at least the inner surface side of the above-described oxygen barrier layer. That is, since the oxygen barrier reinforcing material layer exhibits excellent adhesion to the oxygen barrier layer and the inner layer of the olein resin, it is possible to effectively prevent delamination of the oxygen barrier layer. Further, since this oxygen barrier reinforcing material layer contains EVOH, it reinforces the oxygen barrier property. However, by providing the oxygen barrier reinforcing material layer on the inner surface side of the oxygen barrier layer, it absorbs moisture contained in the container contents, Deterioration due to moisture of EVOH forming the layer can be effectively suppressed.
  • the above oxygen barrier reinforcing material can be easily prepared by, for example, melt-kneading in a kneading part provided in an extruder or an injection machine.
  • the layer made of the above-mentioned oxygen barrier reinforcing material is usually formed with a thickness of 1 ⁇ m or more, particularly about 5 to 30 ⁇ m, to improve adhesion with the oxygen barrier layer (or a regrind layer described later).
  • the oxygen barrier layer or a regrind layer described later.
  • Such an oxygen barrier reinforcing material layer is not limited to a single layer but can be provided with a plurality of layers, provided that it is provided adjacent to at least the inner surface side of the oxygen barrier layer.
  • the oxygen barrier reinforcing material layer also functions as an adhesive layer with respect to the oxygen barrier layer, it is generally preferable that the oxygen barrier reinforcing material layer is also provided on the outer surface side of the oxygen barrier layer.
  • the multilayer plastic container of the present invention can be provided with a regrind layer, thereby enabling reuse of scrap. Can do.
  • Scraps can be used alone, but scraps such as burrs and punching scraps generated during the molding of containers have undergone a thermal history, and various physical properties have deteriorated. It is mixed with the virgin olefin resin used for forming and reused as a regrind layer.
  • the regrind layer may contain virgin olefin resin at a rate of 1% by mass or more of scrap. preferable.
  • the scrap generated by container molding can be directly mixed with a virgin olefin resin and applied to the formation of a regrind layer without performing, for example, a drying process for removing water.
  • Such a regrind layer is not limited to a single layer, but a plurality of regrind layers can be provided.
  • the total thickness of the regrind layer is the thickness of the container wall (total thickness of each layer).
  • the thickness of one regrind layer is preferably set to about 9 to 1350 ⁇ m.
  • the multilayer plastic container of the present invention having the inner and outer layers, the oxygen barrier layer, and the oxygen barrier reinforcing layer described above is provided that the oxygen barrier reinforcing layer is provided adjacent to the inner surface side of the oxygen barrier layer (EVOH layer).
  • EVOH layer oxygen barrier layer
  • Various layer configurations such as providing a regrind layer can be employed. Although such a layer structure is not limited to this, when the example is given, it is as follows.
  • the inner and outer olefin resin layers were abbreviated as PO, the oxygen barrier layer as EVOH, the regrind layer as RG, and the oxygen barrier reinforcing layer as ROB.
  • the peel strength of the EVOH layer is 100 mN / 15 mm or more, particularly 100 It can be ⁇ 900 mN / 15 mm.
  • the thickness of the container body having a multilayer structure is in the range of 10 to 1500 ⁇ m, and is 100 cc / m 2 ⁇ day ⁇ atm or less The oxygen permeability can be expressed.
  • the above-mentioned multilayer plastic container forms a tube-shaped or sheet-shaped preform by extrusion molding or injection molding using the resin or resin composition forming each layer, and then known as blow molding or plug assist molding.
  • a bottle or cup-shaped container is formed and used.
  • the oxygen barrier reinforcing material used in the present invention exhibits a high oxygen barrier property by itself and an excellent adhesiveness to EVOH and olefin-based resins. Therefore, in particular, an oxygen barrier layer (EVOH layer) and an olefin It can be suitably used for adhesion to a regrind layer containing a resin.
  • Oxygen permeability (cc / m 2 ⁇ day ⁇ atm) (V ⁇ (Cg / 100)) / (A ⁇ 0.209 ⁇ t)
  • V Inert gas filling amount (cc)
  • Cg Oxygen permeation amount (vol%)
  • oxygen permeability was evaluated according to the following criteria, based on Reference Example 1 in which a normal adhesive layer (maleic anhydride-modified polyethylene layer) was provided instead of the oxygen barrier reinforcing layer.
  • a normal adhesive layer maleic anhydride-modified polyethylene layer
  • Oxygen permeability is 3 cc / m 2 ⁇ day ⁇ atm as compared to Reference Example 1.
  • Smaller than + Oxygen permeability is 0.3 cc / m 2 ⁇ day ⁇ compared to Reference Example 1. atm or more but less than 3 cc / m 2 ⁇ day ⁇ atm small
  • EVOH-A Ethylene / vinyl alcohol copolymer Nihon Gosei Co., Ltd.
  • EVOH-B Ethylene / vinyl alcohol copolymer Kuraray Co., Ltd.
  • LDPE-A Low density polyethylene G801 manufactured by Sumitomo Chemical Co., Ltd. (Density 0.921 g / cm 3 , MFR 20 g / 10 min)
  • LDPE-B Low density polyethylene F218-0 manufactured by Sumitomo Chemical Co., Ltd.
  • LDPE-C Low density polyethylene LB420M manufactured by Nippon Polyethylene (Density 0.928 g / cm 3 , MFR 0.7 g / 10 min)
  • LDPE-D Low density polyethylene F101-1 manufactured by Sumitomo Chemical Co., Ltd. (Density 0.928 g / cm 3 , MFR 0.3 g / 10 min)
  • Compatibilizer-A High Milan 1601 manufactured by Mitsui DuPont Polychemical Co., Ltd.
  • Compatibilizer-B Nippon Polyethylene ET220X Regrind layer: 50 parts by mass of scrap when the container of Reference Example 1 was made, and the same material 5 as the low-density polyethylene used for the inner and outer layers What dry-blended 0 mass part was used.
  • Adhesive layer Maleic anhydride-modified polyethylene L522 manufactured by Mitsubishi Chemical Corporation
  • Example 2 A container was prepared in the same manner as in Experimental Example 1 except that the mass ratio of EVOH to LDPE of the oxygen barrier reinforcing material was 89:11, and the obtained container was measured for oxygen permeability and evaluated by the above method. It was. The results are shown in Table 1.
  • Example 3 A container was prepared in the same manner as in Experimental Example 1 except that the LDPE of the oxygen barrier reinforcing material was changed to LDPE-D of MFR 0.3 g / 10 min (190 ° C.), and the obtained container was subjected to oxygen permeation by the above method. The degree was evaluated. The results are shown in Table 1.
  • Reference Example 6 A container was prepared in the same manner as in Reference Example 5 except that the LDPE constituting the oxygen barrier reinforcing layer was changed to LDPE-D with MFR 0.3 g / 10 min (190 ° C.), and the obtained container was bonded by the above method. The strength was evaluated. The results are shown in Table 2.
  • Example 5 A container was prepared in the same manner as in Experimental Example 1 except that the LDPE constituting the oxygen barrier reinforcing material was changed to LDPE-B of MFR 1.0 g / 10 min (190 ° C.), and the obtained container was bonded by the above method. The strength was evaluated. The results are shown in Table 2.
  • Example 6 A container was prepared in the same manner as in Experimental Example 5 except that the compatibilizer-A constituting the oxygen barrier reinforcing material was changed to the compatibilizer-B, and the adhesive strength of the obtained container was evaluated by the above method. went. The results are shown in Table 2.
  • Example 7 A container was prepared in the same manner as in Experimental Example 1 except that the LDPE constituting the oxygen barrier reinforcing material was changed to LDPE-C having an MFR of 0.7 g / 10 min (190 ° C.), and the obtained container was bonded by the above method. The strength was evaluated. The results are shown in Table 2.
  • Example 8 A container was prepared in the same manner as in Experimental Example 1 except that the LDPE of the oxygen barrier reinforcing material was changed to LDPE-D of MFR 0.3 g / 10 min (190 ° C.). Was evaluated. The results are shown in Table 2.

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  • Mechanical Engineering (AREA)
  • Laminated Bodies (AREA)
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Abstract

The present invention provides a multi-layer plastic container which includes: inner and outer layers that are composed of an olefin-based resin; and an oxygen barrier layer which is provided as an intermediate layer and which comprises an ethylene-vinyl alcohol copolymer, the multi-layer plastic container being characterized by containing, as chief materials, a hygroscopic material and a low-density polyethylene, and by having a compatibilizing agent-containing oxygen barrier reinforcement layer that is provided contiguously at least to a container inner peripheral surface side of the oxygen barrier layer.

Description

エチレン・ビニルアルコール共重合体を含む多層プラスチック容器Multi-layer plastic container containing ethylene / vinyl alcohol copolymer
　本発明は、エチレン・ビニルアルコール共重合体からなる酸素バリア層を中間層として有する多層構造のプラスチック容器に関するものであり、さらには、該プラスチック容器の多層構造の形成に接着剤として使用される酸素バリア補強材にも関する。 The present invention relates to a multilayer plastic container having an oxygen barrier layer made of an ethylene / vinyl alcohol copolymer as an intermediate layer, and further to oxygen used as an adhesive for forming the multilayer structure of the plastic container. Also related to barrier reinforcement.
　ポリエチレンやポリプロピレンなどのオレフィン系樹脂は、成形性、透明性、機械的強度、耐薬品性などの特性に優れており、特にボトルなどの包装材料として使用されている。 Olefin resins such as polyethylene and polypropylene are excellent in properties such as moldability, transparency, mechanical strength, and chemical resistance, and are particularly used as packaging materials for bottles and the like.
　ところで、包装材料の分野では、内容物の酸化劣化を防止するために、酸素を遮断することが要求されるが、プラスチック製の包装材料は、ガラスや金属と比較して酸素に対するバリア性が低いため、一般に、中間層に酸素バリア層を設けた多層構造とすることにより酸素に対するバリア性を高めている。 By the way, in the field of packaging materials, it is required to block oxygen in order to prevent oxidative deterioration of the contents, but plastic packaging materials have a lower barrier property against oxygen than glass and metal. Therefore, in general, the barrier property against oxygen is enhanced by providing a multilayer structure in which an oxygen barrier layer is provided in the intermediate layer.
　上記のような多層構造において、酸素バリア層の形成に使用する樹脂（酸素バリア性樹脂）としては、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）が代表的であるが、このエチレン・ビニルアルコール共重合体（ＥＶＯＨ）は、湿分に対する耐性が低く、例えば高湿度条件下では、酸素バリア性が大きく低下するという欠点を有している。 In the multilayer structure as described above, the resin used for forming the oxygen barrier layer (oxygen barrier resin) is typically an ethylene / vinyl alcohol copolymer (saponified ethylene-vinyl acetate copolymer). The ethylene / vinyl alcohol copolymer (EVOH) has a low resistance to moisture, and has a drawback that, for example, under a high humidity condition, the oxygen barrier property is greatly reduced.
　従って、ＥＶＯＨからなる酸素バリア層は、特許文献１等に開示されているように、オレフィン系樹脂などの低吸湿性樹脂層にサンドイッチされた多層構造として使用されるが、このような多層構造とした場合にも、ＥＶＯＨの水分による劣化は十分に防止することができない。特に、容器に収容される内容物が、飲料等の食用の液状物質である場合は、この傾向が顕著である。
　また、ＥＶＯＨは、オレフィン系樹脂などに対して接着性が乏しいという問題もある。このため、上記の多層構造においては、ＥＶＯＨの酸素バリア層は、接着剤層を用いてオレフィン系樹脂層に接着された層構造となっている。 Therefore, the oxygen barrier layer made of EVOH is used as a multilayer structure sandwiched by a low hygroscopic resin layer such as an olefin resin as disclosed in Patent Document 1 and the like. Even in this case, deterioration of EVOH due to moisture cannot be sufficiently prevented. In particular, when the contents stored in the container are edible liquid substances such as beverages, this tendency is remarkable.
In addition, EVOH has a problem of poor adhesion to olefinic resins. For this reason, in the multilayer structure described above, the oxygen barrier layer of EVOH has a layer structure bonded to the olefin resin layer using an adhesive layer.
　上記のような接着剤層に用いる接着剤として、例えば、特許文献１には、エチレン－アクリル酸共重合体、イオン架橋オレフィン共重合体（アイオノマー）、無水マレイン酸グラフトポリオレフィン、アクリル酸グラフトポリオレフィン、エチレン－酢酸ビニル共重合体などが挙げられている。 Examples of the adhesive used for the adhesive layer as described above include, for example, Patent Document 1, an ethylene-acrylic acid copolymer, an ion-crosslinked olefin copolymer (ionomer), a maleic anhydride grafted polyolefin, an acrylic acid grafted polyolefin, Examples include ethylene-vinyl acetate copolymer.
　ところで、ブロー成形により容器を成形する際にはバリが発生し、カップ成形では、打ち抜きクズが発生する。このようなスクラップは、一般に、バージンの樹脂と混合してリグラインド層として、多層容器の中間層として再利用されるのが一般的である。 By the way, burrs are generated when a container is formed by blow molding, and punching scraps are generated by cup molding. Such scrap is generally mixed with a virgin resin to be reused as a regrind layer and as an intermediate layer of a multilayer container.
　しかるに、エチレン・ビニルアルコール共重合体の酸素バリア層を含む容器を成形する際に発生するスクラップを含むリグラインド層は、内外層樹脂に使用されるオレフィン系樹脂を多く含むため、バージンのＥＶＯＨに対して接着性が乏しい。このため、このようなリグラインド層を設ける場合には、バージンのＥＶＯＨ層との間に上記のような接着剤層を用いる必要がある。 However, the regrind layer containing scrap generated when molding a container including an oxygen barrier layer of an ethylene / vinyl alcohol copolymer contains a large amount of olefin resin used for inner and outer layer resins. It has poor adhesion. Therefore, when such a regrind layer is provided, it is necessary to use the adhesive layer as described above between the virgin EVOH layer.
　また、このリグラインド層中には、ＥＶＯＨが含まれているが、熱履歴を受けており、さらに、層中に分散しているために、十分な酸素バリア性を有さない。従って、リグラインド層を設けることにより、水分による酸素バリア性の低下を回避することはできない。 In addition, although EVOH is contained in this regrind layer, it has received a thermal history and further dispersed in the layer, so it does not have sufficient oxygen barrier properties. Therefore, by providing the regrind layer, it is impossible to avoid a decrease in oxygen barrier property due to moisture.
特開昭６０－１８０８１３号公報Japanese Patent Laid-Open No. 60-180813
　従って、本発明の目的は、オレフィン系樹脂の内外層と、中間層として設けられたエチレン・ビニルアルコール共重合体の酸素バリア層とを含み、水分による酸素バリア性の低下が有効に回避された多層プラスチック容器を提供することにある。
　本発明の他の目的は、水分による酸素バリア性の低下が防止されていると同時に、リグラインド層とエチレン・ビニルアルコール共重合体との接着性も改善され、リグラインド層を設けた場合にも、エチレン・ビニルアルコール共重合体の剥離が有効に防止された多層プラスチック容器を提供することにある。
　本発明のさらに他の目的は、エチレン・ビニルアルコール共重合体層との接着剤として使用されながら、湿分によるエチレン・ビニルアルコール共重合体の酸素バリア性の低下を有効に緩和し得る酸素バリア補強材を提供することにある。 Accordingly, an object of the present invention includes an inner and outer layer of an olefin resin and an oxygen barrier layer of an ethylene / vinyl alcohol copolymer provided as an intermediate layer, and a decrease in oxygen barrier property due to moisture is effectively avoided. It is to provide a multilayer plastic container.
Another object of the present invention is to prevent deterioration of oxygen barrier properties due to moisture, and at the same time, improve the adhesion between the regrind layer and the ethylene / vinyl alcohol copolymer, and provide a regrind layer. Another object of the present invention is to provide a multi-layer plastic container in which exfoliation of the ethylene / vinyl alcohol copolymer is effectively prevented.
Still another object of the present invention is to provide an oxygen barrier that can effectively mitigate a decrease in oxygen barrier properties of an ethylene / vinyl alcohol copolymer due to moisture while being used as an adhesive with an ethylene / vinyl alcohol copolymer layer. It is to provide a reinforcing material.
　本発明者等は、エチレン・ビニルアルコール共重合体の接着性や水分による酸素バリア性の低下について多くの実験を行い検討した結果、エチレン・ビニルアルコール共重合体と低密度ポリエチレンと相溶化剤とがブレンドされている組成物は、それ自体で高い酸素バリア性を示すばかりか、オレフィン系樹脂層やリグラインド層に対しても優れた接着性を示すという知見を見出し、本発明を完成させるに至った。 The inventors of the present invention conducted a number of experiments on the adhesion of ethylene / vinyl alcohol copolymer and reduced oxygen barrier properties due to moisture, and as a result, ethylene / vinyl alcohol copolymer, low-density polyethylene, compatibilizer, In order to complete the present invention, it has been found that the composition blended with the composition exhibits not only high oxygen barrier properties by itself, but also excellent adhesion to olefin resin layers and regrind layers. It came.
　即ち、本発明によれば、オレフィン系樹脂からなる内外層と、中間層として、エチレン・ビニルアルコール共重合体からなる酸素バリア層を含む多層プラスチック容器において、
　エチレン・ビニルアルコール共重合体と低密度ポリエチレンとを主材として含み、さらに相溶化剤を含む酸素バリア補強層が、前記酸素バリア層の少なくとも容器内面側に隣接して設けられていることを特徴とする多層プラスチック容器が提供される。 That is, according to the present invention, in a multilayer plastic container including an inner and outer layer made of an olefin resin and an oxygen barrier layer made of an ethylene / vinyl alcohol copolymer as an intermediate layer,
An oxygen barrier reinforcing layer containing ethylene-vinyl alcohol copolymer and low-density polyethylene as main materials and further containing a compatibilizing agent is provided adjacent to at least the inner surface of the oxygen barrier layer. A multilayer plastic container is provided.
　本発明の多層プラスチック容器においては、下記の構成が好適に採用される。
（１）前記酸素バリア層の容器外面側にも隣接して前記酸素バリア補強層が設けられていること。
（２）エチレン・ビニルアルコールを酸素バリア性樹脂として含む容器の成形時に発生するスクラップを含むリグラインド層が少なくとも一層、中間層として設けられていること。
（３）前記リグラインド層と前記酸素バリア層との間に前記酸素バリア補強層が位置していること。
（４）前記吸湿性材料がエチレン・ビニルアルコール共重合体であること。
（５）前記相溶化剤として、アイオノマーが使用されていること。
（６）前記酸素バリア補強層が、前記エチレン・ビニルアルコール共重合体と前記低密度ポリエチレンとを、９５：５～５０：５０の質量比で含んでいること。
（７）前記酸素バリア補強層が、前記相溶化剤を、前記エチレン・ビニルアルコール共重合体と前記低密度ポリエチレンとの合計量１００質量部当り１～４９質量部の量で含んでいること。
（８）前記酸素バリア層を形成している前記エチレン・ビニルアルコール共重合体及び前記酸素バリア補強層に使用されている前記エチレン・ビニルアルコール共重合体が、エチレン含有量が２０～６０モル％の範囲にあること。
（９）前記酸素バリア層は、１００ｍＮ／１５ｍｍ以上の剥離強度で存在していること。
（１０）胴部の厚みが１０～１５００μｍの範囲にあり、且つ１００ｃｃ／ｍ２・ｄａｙ・ａｔｍ以下の酸素透過度を示すこと。
（１１）ダイレクトブローボトルであること。 In the multilayer plastic container of the present invention, the following configuration is preferably employed.
(1) The oxygen barrier reinforcing layer is provided adjacent to the container outer surface side of the oxygen barrier layer.
(2) At least one regrind layer containing scrap generated during molding of a container containing ethylene / vinyl alcohol as an oxygen barrier resin is provided as an intermediate layer.
(3) The oxygen barrier reinforcing layer is located between the regrind layer and the oxygen barrier layer.
(4) The hygroscopic material is an ethylene / vinyl alcohol copolymer.
(5) An ionomer is used as the compatibilizing agent.
(6) The oxygen barrier reinforcing layer contains the ethylene / vinyl alcohol copolymer and the low-density polyethylene in a mass ratio of 95: 5 to 50:50.
(7) The oxygen barrier reinforcing layer contains the compatibilizing agent in an amount of 1 to 49 parts by mass per 100 parts by mass of the total amount of the ethylene / vinyl alcohol copolymer and the low density polyethylene.
(8) The ethylene / vinyl alcohol copolymer forming the oxygen barrier layer and the ethylene / vinyl alcohol copolymer used in the oxygen barrier reinforcing layer have an ethylene content of 20 to 60 mol%. Be in the range.
(9) The oxygen barrier layer is present with a peel strength of 100 mN / 15 mm or more.
(10) The body thickness is in the range of 10 to 1500 μm and the oxygen permeability is 100 cc / m 2 · day · atm or less.
(11) A direct blow bottle.
　本発明によれば、また、エチレン・ビニルアルコール共重合体と低密度ポリエチレンを主材として含み、さらに相溶化剤を含んだ酸素バリア補強材において、前記低密度ポリエチレンの１９０℃におけるメルトフローレートが０．３～３０ｇ／１０ｍｉｎであることを特徴とする酸素バリア補強材が提供される。 According to the present invention, the oxygen barrier reinforcing material further comprising an ethylene / vinyl alcohol copolymer and low-density polyethylene as main materials, and further containing a compatibilizer, wherein the melt flow rate at 190 ° C. of the low-density polyethylene is An oxygen barrier reinforcing material characterized by being 0.3 to 30 g / 10 min is provided.
　上記の酸素バリア補強材においては、
（１）前記エチレン・ビニルアルコール共重合体と低密度ポリエチレンとを、９５：５～５０：５０の質量比で含み、前記相溶化剤を、エチレン・ビニルアルコール共重合体と低密度ポリエチレンとの合計量１００質量部当り１～４９質量部の量で含んでいること、
（２）エチレン・ビニルアルコール共重合体による酸素バリア層を含む容器の成形時に発生するスクラップを含むリグラインド層と、エチレン・ビニルアルコール共重合体層との接着に使用すること、
（３）前記低密度ポリエチレンの、１９０℃におけるメルトフローレートが１．０～２０ｇ／１０ｍｉｎであること、
（４）前記相溶化剤として、アイオノマーが使用されていること、
が好適である。 In the above oxygen barrier reinforcement,
(1) The ethylene / vinyl alcohol copolymer and the low density polyethylene are contained in a mass ratio of 95: 5 to 50:50, and the compatibilizing agent is an ethylene / vinyl alcohol copolymer and a low density polyethylene. It is included in an amount of 1 to 49 parts by mass per 100 parts by mass in total.
(2) Use for adhesion between a regrind layer containing scrap generated during molding of a container including an oxygen barrier layer made of ethylene / vinyl alcohol copolymer and an ethylene / vinyl alcohol copolymer layer;
(3) The low density polyethylene has a melt flow rate at 190 ° C. of 1.0 to 20 g / 10 min.
(4) An ionomer is used as the compatibilizer,
Is preferred.
　本発明の多層プラスチック容器は、オレフィン系樹脂よりなる内外層と共に、エチレン・ビニルアルコール共重合体（ＥＶＯＨ）からなる酸素バリア層を中間層として含んでいるが、この酸素バリア層の内面側に隣接して酸素バリア補強層を有している点に新規な特徴を有するものである。
　この酸素バリア補強層は、主材として吸湿性材料と低密度ポリエチレン（ＬＤＰＥ）とを含み、さらに、相溶化剤を含有している酸素バリア補強材により形成されている。 The multilayer plastic container of the present invention includes an oxygen barrier layer made of ethylene / vinyl alcohol copolymer (EVOH) as an intermediate layer together with inner and outer layers made of olefin resin, and is adjacent to the inner surface side of the oxygen barrier layer. Thus, it has a novel feature in that it has an oxygen barrier reinforcing layer.
The oxygen barrier reinforcing layer includes a hygroscopic material and low density polyethylene (LDPE) as main materials, and is further formed of an oxygen barrier reinforcing material containing a compatibilizing agent.
　このような酸素バリア補強層は、吸湿性材料を主材として多量に含んでおり、この酸素バリア補強層を設けることにより、例えば、容器内容物として、飲料や調味液等の水分を多く含む物質が収容されている場合においても、酸素バリア補強層中の吸湿性材料が水分を吸収し、隣接する酸素バリア層（ＥＶＯＨ層）での水分による酸素バリア性の低下を有効に抑制し、酸素バリア性を補強することができる。
　また、上記の酸素バリア補強層は、吸湿性材料に加えて、ＬＤＰＥと相溶化剤も層中に均質に分布しているため、ＥＶＯＨによるガスバリア層やオレフィン系樹脂層に対して優れた接着性を示すばかりか、オレフィン系樹脂を多く含むリグラインド層に対しても優れた接着性を示す。即ち、後述する実施例にも示されているように、この酸素バリア補強材を接着剤層としてＥＶＯＨの酸素バリア層に隣接して設けたとき、酸素バリア層の剥離強度は、１００ｍＮ／１５ｍｍ以上となる。
　従って、本発明では、格別の接着剤樹脂層を形成することなく、酸素バリア層やリグラインド層の剥離を有効に回避することができ、接着剤樹脂層の形成による押出機のダイヘッドの変更等に由来するコストアップを回避しつつ、酸素バリア性を高めることができる。 Such an oxygen barrier reinforcing layer contains a large amount of a hygroscopic material as a main material. By providing this oxygen barrier reinforcing layer, for example, a substance containing a large amount of water such as a beverage or a seasoning liquid as a container content. Even when oxygen is contained, the hygroscopic material in the oxygen barrier reinforcing layer absorbs moisture, and effectively suppresses the decrease in oxygen barrier properties due to moisture in the adjacent oxygen barrier layer (EVOH layer). Sex can be reinforced.
In addition to the hygroscopic material, LDPE and compatibilizing agent are also homogeneously distributed in the oxygen barrier reinforcing layer described above. Therefore, it has excellent adhesion to EVOH gas barrier layers and olefin resin layers. In addition, it exhibits excellent adhesion to a regrind layer containing a large amount of olefin resin. That is, as shown in the examples described later, when this oxygen barrier reinforcing material is provided as an adhesive layer adjacent to the oxygen barrier layer of EVOH, the peel strength of the oxygen barrier layer is 100 mN / 15 mm or more. It becomes.
Therefore, in the present invention, it is possible to effectively avoid peeling of the oxygen barrier layer and the regrind layer without forming a special adhesive resin layer, and to change the die head of the extruder by forming the adhesive resin layer, etc. The oxygen barrier property can be enhanced while avoiding the cost increase derived from the above.
　本発明の多層プラスチック容器は、内外層がオレフィン系樹脂により形成され、中間層として、エチレン・ビニルアルコール共重合体（ＥＶＯＨ）よりなる酸素バリア層を中間層として含み、さらに、酸素バリア層の少なくとも内面側に隣接して酸素バリア補強層が設けられ、また、必要に応じてリグラインド層が設けられる。 The multilayer plastic container of the present invention has inner and outer layers formed of an olefin resin, and includes an oxygen barrier layer made of ethylene / vinyl alcohol copolymer (EVOH) as an intermediate layer, and further includes at least an oxygen barrier layer. An oxygen barrier reinforcing layer is provided adjacent to the inner surface side, and a regrind layer is provided as necessary.
＜内外層＞
　本発明において、内外層として使用されるオレフィン系樹脂としては、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）等のポリエチレンや、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）等を挙げることができる。
　これらの中でも、ポリエチレンは、後述する酸素バリア補強層との接着性が高いという点でもっとも好適である。 <Inner and outer layers>
In the present invention, as the olefin resin used as the inner and outer layers, low density polyethylene (LDPE), medium density polyethylene (MDPE), high density polyethylene (HDPE), linear low density polyethylene (LLDPE), linear ultra-low Polyethylene such as density polyethylene (LVLDPE), polypropylene, ethylene-propylene copolymer, polybutene-1, ethylene-butene-1 copolymer, propylene-butene-1 copolymer, ethylene-propylene-butene-1 copolymer Examples thereof include a copolymer, an ethylene-vinyl acetate copolymer, and an ion-crosslinked olefin copolymer (ionomer).
Among these, polyethylene is most suitable because it has high adhesiveness with an oxygen barrier reinforcing layer described later.
　また、上記のような内外層形成用のオレフィン系樹脂は、従来から包装材料の分野で使用されている押出グレード或いは射出グレードのものであってよい。 Further, the olefin-based resin for forming the inner and outer layers as described above may be of an extrusion grade or an injection grade conventionally used in the field of packaging materials.
　上記のような内外層の厚みは、特に制限されるものではなく、内外層に用いるオレフィン系樹脂の特性を活かした用途に応じて適宜設定されるが、一般には、各層の厚みの合計値である多層構造のトータル厚みの１０～５０％程度が内層及び外層の合計厚みとなるように設定される。 The thickness of the inner and outer layers as described above is not particularly limited, and is appropriately set according to the application utilizing the characteristics of the olefin resin used for the inner and outer layers, but in general, the total thickness of each layer About 10 to 50% of the total thickness of a certain multilayer structure is set to be the total thickness of the inner layer and the outer layer.
　尚、かかる内外層中には、必要により、滑剤、改質剤、顔料、紫外線吸収剤等が配合されていてもよい。 In addition, in the inner and outer layers, a lubricant, a modifier, a pigment, an ultraviolet absorber and the like may be blended as necessary.
＜酸素バリア層＞
　酸素バリア層の形成に使用されるエチレン－ビニルアルコール共重合体（ＥＶＯＨ）としては、具体的には、エチレン含有量が２０乃至６０モル％のエチレン－酢酸ビニル共重合体を、ケン化度が９６％以上、特に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が好適に使用される。このエチレン－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）は、一般に、フェノール／水の質量比が８５／１５の混合溶媒中、３０℃で測定して０．０１ｄｌ／ｇ以上、特に０．０５ｄｌ／ｇ以上の固有粘度を有している。 <Oxygen barrier layer>
As the ethylene-vinyl alcohol copolymer (EVOH) used for forming the oxygen barrier layer, specifically, an ethylene-vinyl acetate copolymer having an ethylene content of 20 to 60 mol% is used. A saponified copolymer obtained by saponification so as to be 96% or more, particularly 99 mol% or more is preferably used. This ethylene-vinyl alcohol copolymer (saponified ethylene-vinyl acetate copolymer) is generally 0.01 dl / g or more measured at 30 ° C. in a mixed solvent having a phenol / water mass ratio of 85/15. In particular, it has an intrinsic viscosity of 0.05 dl / g or more.
　ところで、上記のＥＶＯＨは、エチレン含量が少ないほど酸素バリア性が高くなるが、反面、他の樹脂層との接着性が低下する傾向がある。しかるに、本発明においては、後述する酸素バリア補強層がＥＶＯＨに対して高い接着性を示す。従って、本発明では、エチレン含量が少ないＥＶＯＨを使用することが望ましく、例えば、エチレン含量が２０乃至６０モル％の範囲のものが使用されるが、２０乃至３８モル％の範囲にある高バリア性ＥＶＯＨを使用することが更に好適である。 By the way, the above-mentioned EVOH has a higher oxygen barrier property as the ethylene content is smaller. However, in this invention, the oxygen barrier reinforcement layer mentioned later shows high adhesiveness with respect to EVOH. Therefore, in the present invention, it is desirable to use EVOH having a low ethylene content. For example, those having an ethylene content in the range of 20 to 60 mol% are used, but high barrier properties in the range of 20 to 38 mol% are used. It is further preferred to use EVOH.
　このようなＥＶＯＨにより形成される酸素バリア層は、１層に限定されるものではなく、２層或いはそれ以上の数で設けられていてよい。特に、一定レベル以上の酸素バリア性を確保するという点で、酸素バリア層を複数設けることが好適である。 Such an oxygen barrier layer formed of EVOH is not limited to one layer, and may be provided in two or more layers. In particular, it is preferable to provide a plurality of oxygen barrier layers in terms of ensuring oxygen barrier properties at a certain level or higher.
　また、かかる酸素バリア層の厚みは、多層構造中に設けられる酸素バリア層の数や、容器に設けられる要求される酸素バリア性の程度に応じて適宜の厚みに設定される。 The thickness of the oxygen barrier layer is set to an appropriate thickness according to the number of oxygen barrier layers provided in the multilayer structure and the required oxygen barrier property provided in the container.
＜酸素バリア補強層＞
　本発明においては、上記の酸素バリア層の少なくとも内面側に隣接して酸素バリア補強層が設けられる。
　かかる酸素バリア補強層は、吸湿性材料と低密度ポリエチレン（ＬＤＰＥ）とを主材として含み、さらに相溶化剤を含む酸素バリア補強材からなるものである。ここで本願における低密度ポリエチレンには、線状低密度ポリエチレンも含まれる。
　吸湿性材料としては、エチレン・ビニルアルコール共重合体（ＥＶＯＨ）やポリアミド樹脂等を挙げることができる。これらの材料は単独で酸素バリア層に配合することができる。
　また、吸湿性材料としては、でんぷん、セルロース等の多糖類；カルボキシメチルセルロース、ヒドロキシエチルセルロース等のセルロース誘導体；ポリアクリル酸、或いはポリアクリル酸ナトリウム等のポリα、β不飽和カルボン酸或いはそのイオン架橋物；ポリエチレンオキサイド或いはポリプロピレンオキサイド等のポリアルキレンオキサイド誘導体；ポリエステル等の親水基を有する有機化合物；ゼオライト、シリカゲル、活性炭、活性白土、活性酸化アルミニウム、クレー、カオリン、タルク、ベントナイト、セピオライト、珪酸アルミニウム、酸化カルシウム、塩化カルシウム、硫酸マグネシウム等の無機化合物を挙げることもできる。これらの材料はＥＶＯＨにブレンドした上で酸素バリア補強層に配合する。ＥＶＯＨから成る前記酸素バリア層との接着性を担保するためである。 <Oxygen barrier reinforcement layer>
In the present invention, an oxygen barrier reinforcing layer is provided adjacent to at least the inner surface side of the oxygen barrier layer.
Such an oxygen barrier reinforcing layer includes a hygroscopic material and low density polyethylene (LDPE) as main materials, and further includes an oxygen barrier reinforcing material including a compatibilizing agent. Here, the low density polyethylene in the present application includes linear low density polyethylene.
Examples of the hygroscopic material include an ethylene / vinyl alcohol copolymer (EVOH) and a polyamide resin. These materials can be blended alone in the oxygen barrier layer.
Examples of hygroscopic materials include polysaccharides such as starch and cellulose; cellulose derivatives such as carboxymethyl cellulose and hydroxyethyl cellulose; poly α and β unsaturated carboxylic acids such as polyacrylic acid or sodium polyacrylate or ionic cross-linked products thereof. ; Polyalkylene oxide derivatives such as polyethylene oxide or polypropylene oxide; Organic compounds having hydrophilic groups such as polyester; Zeolite, silica gel, activated carbon, activated clay, activated aluminum oxide, clay, kaolin, talc, bentonite, sepiolite, aluminum silicate, oxidation Mention may also be made of inorganic compounds such as calcium, calcium chloride and magnesium sulfate. These materials are blended in EVOH and then blended into the oxygen barrier reinforcing layer. This is to ensure adhesion with the oxygen barrier layer made of EVOH.
　このような酸素バリア補強層は、吸湿性材料及びＬＤＰＥが相溶化剤によって相溶化されて均質に分布しているため、ＬＤＰＥに由来して、内層のオレフィン系樹脂層や後述するリグラインド層に対して優れた接着性を示す。
　さらに、容器内から侵入する水分が酸素バリア補強層中の吸湿性材料により吸収され、この結果、この酸素バリア補強層に隣接している酸素バリア層（ＥＶＯＨ層）の水分による劣化が有効に緩和され、水分による酸素バリア性の低下を有効に抑制することができ、一定レベルの酸素バリア性を維持することが可能となる。 Such an oxygen barrier reinforcing layer has a hygroscopic material and LDPE compatibilized by a compatibilizing agent and is homogeneously distributed. Excellent adhesiveness is exhibited.
Furthermore, moisture entering from the container is absorbed by the hygroscopic material in the oxygen barrier reinforcing layer, and as a result, deterioration of the oxygen barrier layer (EVOH layer) adjacent to the oxygen barrier reinforcing layer is effectively mitigated. Thus, it is possible to effectively suppress a decrease in oxygen barrier property due to moisture, and to maintain a certain level of oxygen barrier property.
　この酸素バリア補強材中の主材として使用される吸湿性材料としては、前述した酸素バリア層の形成に使用されるものと同種のものを使用しても良い。特に、高い酸素バリア性を確保するために、前述したエチレン含量が２０～６０モル％の範囲のものが使用され、２０～３８モル％の範囲にある高バリアＥＶＯＨが更に好適に使用される。 As the hygroscopic material used as the main material in the oxygen barrier reinforcing material, the same material as that used for forming the oxygen barrier layer described above may be used. In particular, in order to ensure high oxygen barrier properties, those having the ethylene content in the range of 20 to 60 mol% are used, and high barrier EVOH in the range of 20 to 38 mol% is more preferably used.
　また、酸素バリア補強材中の他方の主材として使用されるＬＤＰＥは、密度が０．９１０ｇ／ｃｍ３以上、０．９３０ｇ／ｃｍ３未満の範囲にあるポリエチレンである。
　吸湿性材料にＥＶＯＨを使用する場合、このようなＬＤＰＥとしては、一般に、成形時でのＥＶＯＨとの相分離等を回避し、層間剥離を防止するという観点から、１９０℃でのメルトフローレート（ＭＦＲ）が、０．３ｇ／１０ｍｉｎ以上、成形性の観点から３０ｇ／１０ｍｉｎ以下、特に１．０～２０ｇ／１０ｍｉｎの範囲にあることが好適である。 The LDPE used as the other main material in the oxygen barrier reinforcing material is polyethylene having a density in the range of 0.910 g / cm 3 or more and less than 0.930 g / cm 3 .
When EVOH is used as the hygroscopic material, such LDPE generally has a melt flow rate at 190 ° C. (from the viewpoint of avoiding phase separation with EVOH during molding and preventing delamination). The MFR) is preferably 0.3 g / 10 min or more, 30 g / 10 min or less, particularly 1.0 to 20 g / 10 min from the viewpoint of moldability.
　このようなＥＶＯＨとＬＤＰＥとは、ＥＶＯＨ：ＬＤＰＥ＝９５：５～５０：５０、特に９０：１０～６０：４０の質量比で使用することが好適である。即ち、主材の中でもＥＶＯＨを多く使用することにより、ＥＶＯＨの酸素バリア性を活かして、優れた酸素バリア補強性を確保することができる。 Such EVOH and LDPE are preferably used in a mass ratio of EVOH: LDPE = 95: 5 to 50:50, particularly 90:10 to 60:40. That is, by using a large amount of EVOH among the main materials, it is possible to ensure excellent oxygen barrier reinforcement by utilizing the oxygen barrier properties of EVOH.
　さらに、酸素バリア補強層中の相溶化剤は、互いに接着性の乏しいＥＶＯＨとＬＤＰＥとを相溶化させ、両者の相分離を防止するために使用される。
　かかる相溶化剤としては、マレイン酸、イタコン酸、フマル酸等のカルボン酸もしくはその無水物、マレイン酸－ポリエチレン共重合体、無水マレイン酸－ポリエチレン共重合体、アミド、エステルなどでグラフト変性されたグラフト変性オレフィン樹脂；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）；などを例示することができる。本発明においては、特にアイオノマーが好適に使用される。 Furthermore, the compatibilizing agent in the oxygen barrier reinforcing layer is used for compatibilizing EVOH and LDPE having poor adhesion to each other and preventing phase separation between them.
As such a compatibilizing agent, carboxylic acid such as maleic acid, itaconic acid, fumaric acid or its anhydride, maleic acid-polyethylene copolymer, maleic anhydride-polyethylene copolymer, amide, ester, etc. Graft-modified olefin resin; 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 Examples thereof include ethylene-vinyl alcohol copolymer, hydrotalcite compound; ionomer (ion-crosslinked olefin copolymer). In the present invention, ionomers are particularly preferably used.
　また、アイオノマー等の相溶化剤は、主材（ＥＶＯＨとＬＤＰＥ）の合計量１００質量部当り、１～４９質量部、特に５～３０質量部の量で使用されることが好ましい。相溶化剤を過剰に使用した場合には、主材として使用されているＥＶＯＨやＬＤＰＥに要求される特性が損なわれてしまうばかりか、コストアップとなってしまい、メリットがない。また、相溶化剤の使用量が少な過ぎると、ＥＶＯＨとＬＤＰＥとが分離してしまい、酸素バリア層やリグラインド層（さらには内外層のオレフィン系樹脂）に対する接着性が損なわれてしまう。 Further, the compatibilizer such as ionomer is preferably used in an amount of 1 to 49 parts by mass, particularly 5 to 30 parts by mass, per 100 parts by mass of the total amount of the main materials (EVOH and LDPE). If the compatibilizing agent is used in excess, not only the properties required for EVOH and LDPE used as the main material are impaired, but the cost is increased and there is no merit. Moreover, when there is too little usage-amount of a compatibilizing agent, EVOH and LDPE will isolate | separate and the adhesiveness with respect to an oxygen barrier layer or a regrind layer (further olefin resin of inner and outer layers) will be impaired.
　本発明において、上述した酸素バリア補強材より形成される酸素バリア補強層は、少なくとも前述した酸素バリア層の内面側に隣接して設けられる。即ち、酸素バリア補強材層は、酸素バリア層やオレイン系樹脂の内層に対して優れた接着性を示すため、これにより、酸素バリア層の層間剥離を有効に防止することができる。また、この酸素バリア補強材層は、ＥＶＯＨを含有しているため、酸素バリア性を補強するが、酸素バリア層の内面側に設けることにより、容器内容物に含まれる水分を吸収し、酸素バリア層を形成しているＥＶＯＨの水分による劣化を有効に抑制することができる。 In the present invention, the oxygen barrier reinforcing layer formed from the above-described oxygen barrier reinforcing material is provided adjacent to at least the inner surface side of the above-described oxygen barrier layer. That is, since the oxygen barrier reinforcing material layer exhibits excellent adhesion to the oxygen barrier layer and the inner layer of the olein resin, it is possible to effectively prevent delamination of the oxygen barrier layer. Further, since this oxygen barrier reinforcing material layer contains EVOH, it reinforces the oxygen barrier property. However, by providing the oxygen barrier reinforcing material layer on the inner surface side of the oxygen barrier layer, it absorbs moisture contained in the container contents, Deterioration due to moisture of EVOH forming the layer can be effectively suppressed.
　尚、上記の酸素バリア補強材は、例えば押出機や射出機に設けられている混練部で溶融混練することにより容易に調製することができる。 The above oxygen barrier reinforcing material can be easily prepared by, for example, melt-kneading in a kneading part provided in an extruder or an injection machine.
　本発明において、上述した酸素バリア補強材からなる層は、通常、１μｍ以上、特に５～３０μｍ程度の厚みで形成されることが、酸素バリア層（或いは後述するリグラインド層）との接着性を確保し、吸湿性材料としてＥＶＯＨを用いた場合には、その高い酸素バリア性を効果的に発揮させることができる。 In the present invention, the layer made of the above-mentioned oxygen barrier reinforcing material is usually formed with a thickness of 1 μm or more, particularly about 5 to 30 μm, to improve adhesion with the oxygen barrier layer (or a regrind layer described later). When EVOH is used as the hygroscopic material, the high oxygen barrier property can be effectively exhibited.
　このような酸素バリア補強材層は、少なくとも酸素バリア層の内面側に隣接して設けられることを条件として、単層に限らず、複数層を設けることができる。特に、酸素バリア補強材層は、酸素バリア層に対して接着剤層としての機能も示すため、一般的には、酸素バリア層の外面側にも設けられていることが好適である。 Such an oxygen barrier reinforcing material layer is not limited to a single layer but can be provided with a plurality of layers, provided that it is provided adjacent to at least the inner surface side of the oxygen barrier layer. In particular, since the oxygen barrier reinforcing material layer also functions as an adhesive layer with respect to the oxygen barrier layer, it is generally preferable that the oxygen barrier reinforcing material layer is also provided on the outer surface side of the oxygen barrier layer.
＜リグラインド層＞
　上述した酸素バリア補強材は、オレフィン系樹脂やＥＶＯＨに対して高い接着性を示すため、本発明の多層プラスチック容器は、リグラインド層を設けることができ、これにより、スクラップの再利用を図ることができる。 <Regrind layer>
Since the above-mentioned oxygen barrier reinforcing material exhibits high adhesion to olefin-based resins and EVOH, the multilayer plastic container of the present invention can be provided with a regrind layer, thereby enabling reuse of scrap. Can do.
　スクラップは単独で使用することも可能であるが、容器の成形時に発生するバリや打ち抜きクズなどのスクラップは、熱履歴を経ているおり、各種の物性が劣化しているため、通常、内外層の形成に使用されるバージンのオレフィン系樹脂と混合して、リグラインド層として再利用される。例えば、成形性を維持しつつ、資源の再利用化を図るという観点から、リグラインド層中には、スクラップ量が１質量％以上となる割合でバージンのオレフィン系樹脂が配合されていることが好ましい。
　尚、容器成形により発生したスクラップは、例えば水分除去のための乾燥処理などを行うことなく、直接、バージンのオレフィン系樹脂と混合してリグラインド層の形成に適用することができる。 Scraps can be used alone, but scraps such as burrs and punching scraps generated during the molding of containers have undergone a thermal history, and various physical properties have deteriorated. It is mixed with the virgin olefin resin used for forming and reused as a regrind layer. For example, from the viewpoint of reusing resources while maintaining moldability, the regrind layer may contain virgin olefin resin at a rate of 1% by mass or more of scrap. preferable.
The scrap generated by container molding can be directly mixed with a virgin olefin resin and applied to the formation of a regrind layer without performing, for example, a drying process for removing water.
　このようなリグラインド層は、単層に限らず、複数設けることができるが、リグラインド層による性能低下を回避するため、リグラインド層のトータル厚みが、容器壁の厚み（各層のトータル厚み）の９０％以下とし、一つのリグラインド層の厚みは、９～１３５０μｍ程度に設定することが好適である。 Such a regrind layer is not limited to a single layer, but a plurality of regrind layers can be provided. In order to avoid performance degradation due to the regrind layer, the total thickness of the regrind layer is the thickness of the container wall (total thickness of each layer). The thickness of one regrind layer is preferably set to about 9 to 1350 μm.
＜層構成＞
　上述した内外層、酸素バリア層及び酸素バリア補強層を有する本発明の多層プラスチック容器は、酸素バリア補強層が酸素バリア層（ＥＶＯＨ層）の内面側に隣接して設けられていることを条件として、リグラインド層を設けるなど、種々の層構成を採用することができる。このような層構成は、これに限定されるものではないが、その一例を挙げると、次のとおりである。尚、内外層のオレフィン系樹脂層はＰＯ、酸素バリア層はＥＶＯＨ、リグラインド層はＲＧ、及び酸素バリア補強層はＲＯＢと略した。
　　（内）ＰＯ／ＲＯＢ／ＥＶＯＨ／ＲＯＢ／ＰＯ（外）
　　（内）ＰＯ／ＲＧ／ＲＯＢ／ＥＶＯＨ／ＲＯＢ／ＰＯ（外）
　　（内）ＰＯ／ＲＯＢ／ＥＶＯＨ／ＲＯＢ／ＲＧ／ＰＯ（外）
　　（内）ＰＯ／ＲＧ／ＲＯＢ／ＥＶＯＨ／ＲＯＢ／ＲＧ／ＰＯ（外） <Layer structure>
The multilayer plastic container of the present invention having the inner and outer layers, the oxygen barrier layer, and the oxygen barrier reinforcing layer described above is provided that the oxygen barrier reinforcing layer is provided adjacent to the inner surface side of the oxygen barrier layer (EVOH layer). Various layer configurations such as providing a regrind layer can be employed. Although such a layer structure is not limited to this, when the example is given, it is as follows. The inner and outer olefin resin layers were abbreviated as PO, the oxygen barrier layer as EVOH, the regrind layer as RG, and the oxygen barrier reinforcing layer as ROB.
(Inside) PO / ROB / EVOH / ROB / PO (Outside)
(Inside) PO / RG / ROB / EVOH / ROB / PO (Outside)
(Inside) PO / ROB / EVOH / ROB / RG / PO (Outside)
(Inside) PO / RG / ROB / EVOH / ROB / RG / PO (Outside)
　本発明においては、上記のような層構成において、酸素バリア補強層がＥＶＯＨ層やリグラインド層に対して高い接着性を示すことから、例えば、ＥＶＯＨ層の剥離強度を１００ｍＮ／１５ｍｍ以上、特に１００～９００ｍＮ／１５ｍｍとすることができる。
　また、酸素バリア層や酸素バリア補強層中の主材として高バリアＥＶＯＨを使用することにより、多層構造を有する容器胴部の厚みが１０～１５００μｍの範囲として、１００ｃｃ／ｍ２・ｄａｙ・ａｔｍ以下の酸素透過度を発現させることができる。 In the present invention, in the layer configuration as described above, since the oxygen barrier reinforcing layer exhibits high adhesion to the EVOH layer or the regrind layer, for example, the peel strength of the EVOH layer is 100 mN / 15 mm or more, particularly 100 It can be ˜900 mN / 15 mm.
Further, by using high barrier EVOH as a main material in the oxygen barrier layer or the oxygen barrier reinforcing layer, the thickness of the container body having a multilayer structure is in the range of 10 to 1500 μm, and is 100 cc / m 2 · day · atm or less The oxygen permeability can be expressed.
＜容器の成形＞
　上述した多層プラスチック容器は、各層を形成する樹脂もしくは樹脂組成物を用いての押出成形或いは射出成形により、チューブ状或いはシート状のプリフォームを成形し、次いで、ブロー成形或いはプラグアシスト成形等の公知の方法により、ボトル或いはカップ状の容器を成形し、使用に供される。
　かかる本発明によれば、容器成形時に発生するスクラップの有効利用を図ることができ、しかも水分除去のための乾燥などの格別の処理を行う必要がないため、生産性も高い。さらには、格別の接着剤層を設ける必要がないため、コストダウンを図ることもできる。
　また、本発明で用いる酸素バリア補強材は、それ自体で高い酸素バリア性を示し、且つＥＶＯＨやオレフィン系樹脂に対して優れた接着性を示すため、特に、酸素バリア層（ＥＶＯＨ層）とオレフィン系樹脂を含むリグラインド層との接着に好適に使用することができる。 <Molding of container>
The above-mentioned multilayer plastic container forms a tube-shaped or sheet-shaped preform by extrusion molding or injection molding using the resin or resin composition forming each layer, and then known as blow molding or plug assist molding. By this method, a bottle or cup-shaped container is formed and used.
According to the present invention, it is possible to effectively use scrap generated at the time of container forming, and it is not necessary to perform a special treatment such as drying for removing water, so that productivity is high. Furthermore, since it is not necessary to provide a special adhesive layer, the cost can be reduced.
In addition, the oxygen barrier reinforcing material used in the present invention exhibits a high oxygen barrier property by itself and an excellent adhesiveness to EVOH and olefin-based resins. Therefore, in particular, an oxygen barrier layer (EVOH layer) and an olefin It can be suitably used for adhesion to a regrind layer containing a resin.
　本発明を次の実験例によりさらに説明するが、本発明はこれらの実験例に規制されるものではない。各参考例及び実験例で得られた容器を以下の方法で評価した。 The present invention will be further described with reference to the following experimental examples, but the present invention is not limited to these experimental examples. The containers obtained in each reference example and experimental example were evaluated by the following methods.
［容器の胴部厚み、層構成の測定］
　多層ボトルの底から５０ｍｍの位置での胴部水平断面における層構成を偏光顕微鏡にて観察し、ボトルの胴部厚み、および層構成を求めた。断面に対し、０°、９０°、１８０°、２７０°の位置での層構成を観察し、４方向での平均値をボトルの胴部厚み、層構成とした。 [Measurement of container body thickness and layer structure]
The layer configuration in the horizontal section of the barrel at a position 50 mm from the bottom of the multilayer bottle was observed with a polarizing microscope, and the barrel thickness and the layer configuration of the bottle were determined. The layer configuration at the positions of 0 °, 90 °, 180 °, and 270 ° with respect to the cross section was observed, and the average value in the four directions was defined as the thickness of the body of the bottle and the layer configuration.
［酸素透過度の評価］
　容器をグローブボックス内に投入した後、グローブボックス内を脱気し、不活性ガス（窒素）で置換し、前記容器内にイオン交換水２ｍｌを入れ、アルミニウムシールで密封した。この容器を５本作製し、３０℃－８０％ＲＨの恒温恒湿器内に１週間保管した。
　その後、容器を恒温恒室器から取り出し、各容器内部の酸素濃度をガスクロマトグラフィー（Ｖａｒｉａｎ社製　ＣＰ－４９００）で測定した。この酸素濃度の値より、下記式によって酸素透過度を算出した。
　　酸素透過度（ｃｃ／ｍ２・ｄａｙ・ａｔｍ）
　　　　　　＝（Ｖ×（Ｃｇ／１００））／（Ａ×０．２０９×ｔ）
　　Ｖ　：不活性ガス充填量（ｃｃ）
　　Ｃｇ：酸素透過量（ｖｏｌ％）
　　Ａ　：樹脂製容器表面積（ｍ２）
　　ｔ　：保存期間（ｄａｙｓ（日数）） [Evaluation of oxygen permeability]
After putting the container into the glove box, the inside of the glove box was deaerated and replaced with an inert gas (nitrogen), and 2 ml of ion exchange water was put into the container and sealed with an aluminum seal. Five of these containers were prepared and stored for 1 week in a constant temperature and humidity chamber of 30 ° C.-80% RH.
Thereafter, the containers were taken out from the thermostatic chamber and the oxygen concentration inside each container was measured by gas chromatography (CP-4900 manufactured by Varian). From this oxygen concentration value, the oxygen permeability was calculated by the following formula.
Oxygen permeability (cc / m 2 · day · atm)
= (V × (Cg / 100)) / (A × 0.209 × t)
V: Inert gas filling amount (cc)
Cg: Oxygen permeation amount (vol%)
A: Resin container surface area (m 2 )
t: retention period (days (days))
　次に、得られた酸素透過度は、酸素バリア補強層の代わりに通常の接着剤層（無水マレイン酸変性ポリエチレンの層）が設けられている参考例１を基準として、以下の基準で評価した。
　　　＋＋：参考例１に比して酸素透過度が３ｃｃ／ｍ２・ｄａｙ・ａｔｍ
　　　　　　以上小さい
　　　＋　：参考例１に比して酸素透過度が０．３ｃｃ／ｍ２・ｄａｙ・
　　　　　　ａｔｍ以上３未満ｃｃ／ｍ２・ｄａｙ・ａｔｍ小さい Next, the obtained oxygen permeability was evaluated according to the following criteria, based on Reference Example 1 in which a normal adhesive layer (maleic anhydride-modified polyethylene layer) was provided instead of the oxygen barrier reinforcing layer. .
++: Oxygen permeability is 3 cc / m 2 · day · atm as compared to Reference Example 1.
Smaller than +: Oxygen permeability is 0.3 cc / m 2 · day · compared to Reference Example 1.
atm or more but less than 3 cc / m 2 · day · atm small
［接着強度の評価］
　容器の胴部から測定サンプルを１５ｍｍ幅で切り取り、テンシロン（株式会社オリエンテック製）を用いて剥離時の試験力を測定した。なお剥離面は、オレフィン系樹脂層（リグラインド層）と酸素バリア補強層の界面である。接着強度は、端部を剥離させたサンプルの、剥離面を境にした両側をそれぞれエアチャックで挟み、剥離角度９０度とし、荷重を２４．５１７Ｎに設定したロードセルを用い、２３℃－５０％ＲＨの雰囲気中において、３０ｍｍ／分の速度で５０ｍｍ剥離させた時の平均試験力（ｍＮ／１５ｍｍ）を算出した。該平均試験力に基づき、以下の基準で評価した。
　　　＋＋：接着強度が９００ｍＮ／１５ｍｍ以上
　　　＋　：接着強度が１００～９００ｍＮ／１５ｍｍ [Evaluation of adhesive strength]
A measurement sample was cut from the body of the container with a width of 15 mm, and the test force at the time of peeling was measured using Tensilon (manufactured by Orientec Co., Ltd.). The release surface is the interface between the olefin resin layer (regrind layer) and the oxygen barrier reinforcing layer. The adhesive strength was 23 ° C.-50% using a load cell in which both ends of the sample with the end peeled were sandwiched by air chucks, the peel angle was 90 degrees, and the load was set at 24.517 N In an RH atmosphere, an average test force (mN / 15 mm) when 50 mm was peeled off at a speed of 30 mm / min was calculated. Based on the average test force, evaluation was made according to the following criteria.
++: Adhesive strength is 900 mN / 15 mm or more +: Adhesive strength is 100 to 900 mN / 15 mm
　以下の参考例及び実験例において、容器の作成に用いた材料は、以下の通りである。
　　ＥＶＯＨ－Ａ：エチレン・ビニルアルコール共重合体
　　　　　　　日本合成（株）製　ＶＨ２７０４ＲＢ
　　　　　　　エチレン比率２７ｍｏｌ％
　　ＥＶＯＨ－Ｂ：エチレン・ビニルアルコール共重合体
　　　　　　　クラレ（株）製　Ｅ１０５Ｂ
　　　　　　　エチレン比率４４ｍｏｌ％
　　ＬＤＰＥ－Ａ：低密度ポリエチレン
　　　　　　　住友化学社製　Ｇ８０１
　　　　　　　（密度０．９２１ｇ／ｃｍ３、ＭＦＲ２０ｇ／１０ｍｉｎ）
　　ＬＤＰＥ－Ｂ：低密度ポリエチレン
　　　　　　　住友化学社製　Ｆ２１８－０
　　　　　　（密度０．９１９ｇ／ｃｍ３、ＭＦＲ１．０ｇ／１０ｍｉｎ）
　　ＬＤＰＥ－Ｃ：低密度ポリエチレン
　　　　　　　日本ポリエチレン社製　ＬＢ４２０Ｍ
　　　　　　　（密度０．９２８ｇ／ｃｍ３、ＭＦＲ０．７ｇ／１０ｍｉｎ）
　　ＬＤＰＥ－Ｄ：低密度ポリエチレン
　　　　　　　住友化学社製　Ｆ１０１－１
　　　　　　（密度０．９２８ｇ／ｃｍ３、ＭＦＲ０．３ｇ／１０ｍｉｎ）
　　相溶化剤－Ａ：三井・デュポンポリケミカル社製　ハイミラン１６０１
　　相溶化剤－Ｂ：日本ポリエチレン社製　ＥＴ２２０Ｘ
　　リグラインド層：参考例１の容器を作成した際のスクラップ５０質量部
　　　　　　　　　と、内外層に使用した低密度ポリエチレンと同じ材料５
　　　　　　　　　０質量部をドライブレンドしたものを用いた。
　　接着剤層：無水マレイン酸変性ポリエチレン
　　　　　　　三菱化学社製　Ｌ５２２ In the following reference examples and experimental examples, the materials used for preparing the containers are as follows.
EVOH-A: Ethylene / vinyl alcohol copolymer Nihon Gosei Co., Ltd. VH2704RB
Ethylene ratio 27mol%
EVOH-B: Ethylene / vinyl alcohol copolymer Kuraray Co., Ltd. E105B
Ethylene ratio 44 mol%
LDPE-A: Low density polyethylene G801 manufactured by Sumitomo Chemical Co., Ltd.
(Density 0.921 g / cm 3 , MFR 20 g / 10 min)
LDPE-B: Low density polyethylene F218-0 manufactured by Sumitomo Chemical Co., Ltd.
(Density 0.919 g / cm 3 , MFR 1.0 g / 10 min)
LDPE-C: Low density polyethylene LB420M manufactured by Nippon Polyethylene
(Density 0.928 g / cm 3 , MFR 0.7 g / 10 min)
LDPE-D: Low density polyethylene F101-1 manufactured by Sumitomo Chemical Co., Ltd.
(Density 0.928 g / cm 3 , MFR 0.3 g / 10 min)
Compatibilizer-A: High Milan 1601 manufactured by Mitsui DuPont Polychemical Co., Ltd.
Compatibilizer-B: Nippon Polyethylene ET220X
Regrind layer: 50 parts by mass of scrap when the container of Reference Example 1 was made, and the same material 5 as the low-density polyethylene used for the inner and outer layers
What dry-blended 0 mass part was used.
Adhesive layer: Maleic anhydride-modified polyethylene L522 manufactured by Mitsubishi Chemical Corporation
［参考例１］
　３つの押出機を用いて下記３種５層の多層パリソンを成形し、該多層パリソンを用いたダイレクトブロー成形により、下記３種５層の容器（内容積２００ｍｌ、質量２０ｇ）を作製した。
　　（内側）ＬＤＰＥ－Ａ（６５）／接着剤層（１）／ＥＶＯＨ－Ａ（２．
　　５）／接着剤層（１）／ＬＤＰＥ－Ａ（３０．５）（外側）（単位：質
　　量％）
　得られた容器について、前記方法により酸素透過度を測定した。結果を表１に示す。 [Reference Example 1]
The following 3 types and 5 layers of multi-layer parisons were formed using three extruders, and the following 3 types and 5 layers of containers (internal volume 200 ml, mass 20 g) were prepared by direct blow molding using the multi-layer parisons.
(Inside) LDPE-A (65) / Adhesive layer (1) / EVOH-A (2.
5) / Adhesive layer (1) / LDPE-A (30.5) (outside) (unit: mass%)
About the obtained container, the oxygen permeability was measured by the said method. The results are shown in Table 1.
［参考例２］
　４つの押出機を用いて下記４種７層の多層パリソンを成形し、該多層パリソンを用いたダイレクトブロー成形により、下記４種７層構成の容器（内容積２００ｍｌ、質量２０ｇ）を作製した。
　　（内側）ＬＤＰＥ－Ａ（１５）／リグラインド層（５３）／接着剤層（
　　１）／ＥＶＯＨ－Ａ（２．５）／接着剤層（１）／リグラインド層（１
　　２．５）／ＬＤＰＥ－Ａ（１５）（外側）（単位：質量％）
　得られた容器について、前記方法により酸素透過度を測定し評価を行った。結果を表１に示す。 [Reference Example 2]
The following 4 types and 7 layers of multilayer parison were molded using 4 extruders, and the following 4 types and 7 layers of containers (internal volume 200 ml, mass 20 g) were prepared by direct blow molding using the multilayer parison.
(Inside) LDPE-A (15) / Regrind layer (53) / Adhesive layer (
1) / EVOH-A (2.5) / adhesive layer (1) / regrind layer (1
2.5) / LDPE-A (15) (outside) (unit: mass%)
About the obtained container, oxygen permeability was measured and evaluated by the said method. The results are shown in Table 1.
［参考例３］
　前記酸素バリア層の比率を下記のように変更し、これに合わせて外層の比率を変更した以外は参考例１と同様にして容器を作製した。
　　（内側）ＬＤＰＥ－Ａ（６５）／接着剤層（１）／ＥＶＯＨ－Ａ（４．
　　５）／接着剤層（１）／ＬＤＰＥ－Ａ（２８．５）（外側）（単位：質
　　量％）
　得られた容器について、前記方法により酸素透過度を測定し評価を行った。結果を表１に示す。 [Reference Example 3]
A container was prepared in the same manner as in Reference Example 1 except that the ratio of the oxygen barrier layer was changed as follows and the ratio of the outer layer was changed accordingly.
(Inside) LDPE-A (65) / Adhesive layer (1) / EVOH-A (4.
5) / Adhesive layer (1) / LDPE-A (28.5) (outside) (unit: mass%)
About the obtained container, oxygen permeability was measured and evaluated by the said method. The results are shown in Table 1.
［参考例４］
（酸素バリア補強材の調整）
　この実験は、酸素バリア補強材の酸素バリア性を評価するために行ったものである。
　ＥＶＯＨとＬＤＰＥの質量比が７５：２５の混合物１００質量部に対し、相溶化剤－Ａを１０質量部添加したものをタンブラーによりドライブレンドし、公知の押出機で溶融混練、ペレット化し、酸素バリア補強材を得た。
　続いて、前記接着剤層と前記酸素バリア層を前記酸素バリア補強材から成る酸素バリア補強層に置き換えて下記の層構成とした以外は参考例１と同様にして容器を作製した。
　　（内側）ＬＤＰＥ－Ａ（６５）／酸素バリア補強層（１０）／ＬＤＰＥ
　　－Ａ（２５）（外側）（単位：質量％）
　得られた容器について、前記方法により酸素透過度を測定し評価を行った。結果を表１に示す。 [Reference Example 4]
(Adjustment of oxygen barrier reinforcement)
This experiment was conducted in order to evaluate the oxygen barrier property of the oxygen barrier reinforcing material.
10 parts by mass of compatibilizer-A is added to 100 parts by mass of a mixture of EVOH and LDPE having a mass ratio of 75:25 using a tumbler, melt-kneaded and pelletized with a known extruder, oxygen barrier A reinforcement was obtained.
Subsequently, a container was produced in the same manner as in Reference Example 1 except that the adhesive layer and the oxygen barrier layer were replaced with an oxygen barrier reinforcing layer made of the oxygen barrier reinforcing material to obtain the following layer structure.
(Inside) LDPE-A (65) / Oxygen barrier reinforcing layer (10) / LDPE
-A (25) (outside) (unit: mass%)
About the obtained container, oxygen permeability was measured and evaluated by the said method. The results are shown in Table 1.
［実験例１］
　前記接着剤層を前記酸素バリア補強材から成る酸素バリア補強層に置き換えて下記の層構成とした以外は参考例１と同様にして容器を作製した。
　　（内側）ＬＤＰＥ－Ａ（６５）／酸素バリア補強層（２）／ＥＶＯＨ
　　－Ａ（２．５）／酸素バリア補強層（２）／ＬＤＰＥ－Ａ（２８．５）
　　（外側）（単位：質量％）
　得られた容器について、前記方法により酸素透過度を測定し評価を行った。結果を表１に示す。 [Experimental Example 1]
A container was produced in the same manner as in Reference Example 1 except that the adhesive layer was replaced with an oxygen barrier reinforcing layer made of the oxygen barrier reinforcing material to obtain the following layer structure.
(Inside) LDPE-A (65) / Oxygen barrier reinforcing layer (2) / EVOH
-A (2.5) / oxygen barrier reinforcing layer (2) / LDPE-A (28.5)
(Outside) (Unit: mass%)
About the obtained container, oxygen permeability was measured and evaluated by the said method. The results are shown in Table 1.
［実験例２］
　前記酸素バリア補強材のＥＶＯＨとＬＤＰＥの質量比を８９：１１とした以外は実験例１と同様にして容器を作製し、得られた容器について、前記方法により酸素透過度を測定し評価を行った。結果を表１に示す。 [Experiment 2]
A container was prepared in the same manner as in Experimental Example 1 except that the mass ratio of EVOH to LDPE of the oxygen barrier reinforcing material was 89:11, and the obtained container was measured for oxygen permeability and evaluated by the above method. It was. The results are shown in Table 1.
［実験例３］
　前記酸素バリア補強材のＬＤＰＥをＭＦＲ０．３ｇ／１０ｍｉｎ（１９０℃）のＬＤＰＥ－Ｄに変更した以外は、実験例１と同様にして容器を作製し、得られた容器について、前記方法により酸素透過度の評価を行った。結果を表１に示す。 [Experiment 3]
A container was prepared in the same manner as in Experimental Example 1 except that the LDPE of the oxygen barrier reinforcing material was changed to LDPE-D of MFR 0.3 g / 10 min (190 ° C.), and the obtained container was subjected to oxygen permeation by the above method. The degree was evaluated. The results are shown in Table 1.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
［参考例５］
　前記酸素バリア層と前記酸素バリア補強層に使用するＥＶＯＨをエチレン比率４４ｍｏｌ％のＥＶＯＨ－Ｂに変更した以外は実験例１と同様にして容器を作製し、得られた容器について、前記方法により接着強度の評価を行った。結果を表２に示す。 [Reference Example 5]
A container was prepared in the same manner as in Experimental Example 1 except that EVOH used for the oxygen barrier layer and the oxygen barrier reinforcing layer was changed to EVOH-B having an ethylene ratio of 44 mol%, and the obtained container was bonded by the above method. The strength was evaluated. The results are shown in Table 2.
［参考例６］
　前記酸素バリア補強層を構成するＬＤＰＥをＭＦＲ０．３ｇ／１０ｍｉｎ（１９０℃）のＬＤＰＥ－Ｄに変更した以外は参考例５と同様にして容器を作製し、得られた容器について、前記方法により接着強度の評価を行った。結果を表２に示す。 [Reference Example 6]
A container was prepared in the same manner as in Reference Example 5 except that the LDPE constituting the oxygen barrier reinforcing layer was changed to LDPE-D with MFR 0.3 g / 10 min (190 ° C.), and the obtained container was bonded by the above method. The strength was evaluated. The results are shown in Table 2.
［実験例４］
　実験例１の容器について、前記方法により接着強度の評価を行った。結果を表２に示す。 [Experimental Example 4]
For the container of Experimental Example 1, the adhesive strength was evaluated by the above method. The results are shown in Table 2.
［実験例５］
　前記酸素バリア補強材を構成するＬＤＰＥをＭＦＲ１．０ｇ／１０ｍｉｎ（１９０℃）のＬＤＰＥ－Ｂに変更した以外は実験例１と同様にして容器を作成し、得られた容器について、前記方法により接着強度の評価を行った。結果を表２に示す。 [Experimental Example 5]
A container was prepared in the same manner as in Experimental Example 1 except that the LDPE constituting the oxygen barrier reinforcing material was changed to LDPE-B of MFR 1.0 g / 10 min (190 ° C.), and the obtained container was bonded by the above method. The strength was evaluated. The results are shown in Table 2.
［実験例６］
　前記酸素バリア補強材を構成する相溶化剤－Ａを相溶化剤－Ｂに変更した以外は実験例５と同様にして容器を作成し、得られた容器について、前記方法により接着強度の評価を行った。結果を表２に示す。 [Experimental Example 6]
A container was prepared in the same manner as in Experimental Example 5 except that the compatibilizer-A constituting the oxygen barrier reinforcing material was changed to the compatibilizer-B, and the adhesive strength of the obtained container was evaluated by the above method. went. The results are shown in Table 2.
［実験例７］
　前記酸素バリア補強材を構成するＬＤＰＥをＭＦＲ０．７ｇ／１０ｍｉｎ（１９０℃）のＬＤＰＥ－Ｃに変更した以外は実験例１と同様にして容器を作成し、得られた容器について、前記方法により接着強度の評価を行った。結果を表２に示す。 [Experimental Example 7]
A container was prepared in the same manner as in Experimental Example 1 except that the LDPE constituting the oxygen barrier reinforcing material was changed to LDPE-C having an MFR of 0.7 g / 10 min (190 ° C.), and the obtained container was bonded by the above method. The strength was evaluated. The results are shown in Table 2.
［実験例８］
　前記酸素バリア補強材のＬＤＰＥをＭＦＲ０．３ｇ／１０ｍｉｎ（１９０℃）のＬＤＰＥ－Ｄに変更した以外は、実験例１と同様にして容器を作製し、得られた容器について、前記方法により接着強度の評価を行った。結果を表２に示す。 [Experimental Example 8]
A container was prepared in the same manner as in Experimental Example 1 except that the LDPE of the oxygen barrier reinforcing material was changed to LDPE-D of MFR 0.3 g / 10 min (190 ° C.). Was evaluated. The results are shown in Table 2.
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002

Claims (17)

  1. 　オレフィン系樹脂からなる内外層と、中間層として、エチレン・ビニルアルコール共重合体からなる酸素バリア層を含む多層プラスチック容器において、
    　吸湿性材料と低密度ポリエチレンとを主材として含み、さらに相溶化剤を含む酸素バリア補強層が、前記酸素バリア層の少なくとも容器内面側に隣接して設けられていることを特徴とする多層プラスチック容器。     In a multilayer plastic container including an inner and outer layer made of an olefin resin and an oxygen barrier layer made of an ethylene / vinyl alcohol copolymer as an intermediate layer,
    A multilayer plastic comprising an oxygen barrier reinforcing layer containing a hygroscopic material and low density polyethylene as main materials, and further comprising a compatibilizing agent adjacent to at least the inner surface of the container. container.
  2. 　前記酸素バリア層の容器外面側にも隣接して前記酸素バリア補強層が設けられている請求項１に記載の多層プラスチック容器。 The multilayer plastic container according to claim 1, wherein the oxygen barrier reinforcing layer is provided adjacent to the container outer surface side of the oxygen barrier layer.
  3. 　エチレン・ビニルアルコールを酸素バリア性樹脂として含む容器の成形時に発生するスクラップを含むリグラインド層が少なくとも一層、中間層として設けられている請求項１に記載の多層プラスチック容器。 2. The multilayer plastic container according to claim 1, wherein at least one regrind layer containing scrap generated during molding of a container containing ethylene / vinyl alcohol as an oxygen barrier resin is provided as an intermediate layer.
  4. 　前記リグラインド層と前記酸素バリア層との間に前記酸素バリア補強層が位置している請求項３に記載の多層プラスチック容器。 The multilayer plastic container according to claim 3, wherein the oxygen barrier reinforcing layer is located between the regrind layer and the oxygen barrier layer.
  5. 　前記吸湿性材料がエチレン・ビニルアルコール共重合体である請求項１に記載の多層プラスチック容器。 The multilayer plastic container according to claim 1, wherein the hygroscopic material is an ethylene / vinyl alcohol copolymer.
  6. 　前記相溶化剤として、アイオノマーが使用されている請求項５に記載の多層プラスチック容器。 The multilayer plastic container according to claim 5, wherein an ionomer is used as the compatibilizing agent.
  7. 　前記酸素バリア補強層が、前記エチレン・ビニルアルコール共重合体と前記低密度ポリエチレンとを、９５：５～５０：５０の質量比で含んでいる請求項５に記載の多層プラスチック容器。 6. The multilayer plastic container according to claim 5, wherein the oxygen barrier reinforcing layer contains the ethylene / vinyl alcohol copolymer and the low density polyethylene in a mass ratio of 95: 5 to 50:50.
  8. 　前記酸素バリア補強層が、前記相溶化剤を、前記エチレン・ビニルアルコール共重合体と前記低密度ポリエチレンとの合計量１００質量部当り１～４９質量部の量で含んでいる請求項７に記載の多層プラスチック容器。 The oxygen barrier reinforcing layer includes the compatibilizing agent in an amount of 1 to 49 parts by mass per 100 parts by mass of the total amount of the ethylene / vinyl alcohol copolymer and the low density polyethylene. Multi-layer plastic container.
  9. 　前記酸素バリア層を形成している前記エチレン・ビニルアルコール共重合体及び前記酸素バリア補強層に使用されている前記エチレン・ビニルアルコール共重合体が、エチレン含有量が２０～６０モル％の範囲にある請求項５に記載の多層プラスチック容器。 The ethylene / vinyl alcohol copolymer forming the oxygen barrier layer and the ethylene / vinyl alcohol copolymer used in the oxygen barrier reinforcing layer have an ethylene content in the range of 20 to 60 mol%. The multilayer plastic container according to claim 5.
  10. 　前記酸素バリア層は、１００ｍＮ／１５ｍｍ以上の剥離強度で存在している請求項１に記載の多層プラスチック容器。 The multilayer plastic container according to claim 1, wherein the oxygen barrier layer is present with a peel strength of 100 mN / 15 mm or more.
  11. 　胴部の厚みが１０～１５００μｍの範囲にあり、且つ１００ｃｃ／ｍ２・ｄａｙ・ａｔｍ以下の酸素透過度を示す請求項１に記載の多層プラスチック容器。 The multilayer plastic container according to claim 1, wherein the thickness of the body portion is in the range of 10 to 1500 µm and the oxygen permeability is 100 cc / m 2 · day · atm or less.
  12. 　ダイレクトブローボトルである請求項１に記載の多層プラスチック容器。 The multilayer plastic container according to claim 1, which is a direct blow bottle.
  13. 　エチレン・ビニルアルコール共重合体と低密度ポリエチレンを主材として含み、さらに相溶化剤を含んだ酸素バリア補強材において、前記低密度ポリエチレンの１９０℃におけるメルトフローレートが０．３～３０ｇ／１０ｍｉｎであることを特徴とする酸素バリア補強材。 An oxygen barrier reinforcing material comprising ethylene / vinyl alcohol copolymer and low density polyethylene as main materials, and further comprising a compatibilizing agent, wherein the low density polyethylene has a melt flow rate at 190 ° C. of 0.3 to 30 g / 10 min. An oxygen barrier reinforcement characterized by being.
  14. 　前記エチレン・ビニルアルコール共重合体と低密度ポリエチレンとを、９５：５～５０：５０の質量比で含み、前記相溶化剤を、エチレン・ビニルアルコール共重合体と低密度ポリエチレンとの合計量１００質量部当り１～４９質量部の量で含んでいる請求項１３に記載の酸素バリア補強材。 The ethylene / vinyl alcohol copolymer and the low density polyethylene are contained in a mass ratio of 95: 5 to 50:50, and the compatibilizer is added in a total amount of 100 of the ethylene / vinyl alcohol copolymer and the low density polyethylene. The oxygen barrier reinforcing material according to claim 13, which is contained in an amount of 1 to 49 parts by mass per part by mass.
  15. 　エチレン・ビニルアルコール共重合体による酸素バリア層を含む容器の成形時に発生するスクラップを含むリグラインド層と、エチレン・ビニルアルコール共重合体層との接着に使用する請求項１３に記載の酸素バリア補強材。 The oxygen barrier reinforcement according to claim 13, which is used for adhesion between a regrind layer containing scrap generated during molding of a container including an oxygen barrier layer made of an ethylene / vinyl alcohol copolymer and an ethylene / vinyl alcohol copolymer layer. Wood.
  16. 　前記低密度ポリエチレンの、１９０℃におけるメルトフローレートが１．０～２０ｇ／１０ｍｉｎである請求項１３に記載の酸素バリア補強材。 The oxygen barrier reinforcing material according to claim 13, wherein the low density polyethylene has a melt flow rate at 190 ° C of 1.0 to 20 g / 10 min.
  17. 　前記相溶化剤として、アイオノマーが使用されている請求項１３に記載の酸素バリア補強材。 The oxygen barrier reinforcing material according to claim 13, wherein an ionomer is used as the compatibilizing agent.
PCT/JP2019/021658 2018-05-31 2019-05-31 Multi-layer plastic container comprising ethylene-vinyl alcohol copolymer WO2019230929A1 (en)

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