WO2003025048A1 - Method for producing oxygen-capturing packaging material and oxygen-capturing packaging material - Google Patents

Method for producing oxygen-capturing packaging material and oxygen-capturing packaging material Download PDF

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Publication number
WO2003025048A1
WO2003025048A1 PCT/JP2002/009322 JP0209322W WO03025048A1 WO 2003025048 A1 WO2003025048 A1 WO 2003025048A1 JP 0209322 W JP0209322 W JP 0209322W WO 03025048 A1 WO03025048 A1 WO 03025048A1
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WIPO (PCT)
Prior art keywords
oxygen
scavenging
resin
packaging material
layer
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Application number
PCT/JP2002/009322
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French (fr)
Japanese (ja)
Inventor
Peter Frisk
Tadakatsu Ikenoya
Hiroaki Ogita
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Tetra Laval Holdings & Finance S.A.
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Publication of WO2003025048A1 publication Critical patent/WO2003025048A1/en

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    • 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
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • 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
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • 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
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters

Definitions

  • the present invention relates to a method for producing an oxygen-scavenging packaging material excellent in oxygen barrier properties and suitable for packaging liquid foods, and an oxygen-scavenging packaging material.
  • paper containers for liquid foods such as juice, coffee, milk, and liquors
  • paper containers made of laminates of paper and thermoplastic resin have become widespread.
  • the outermost layer (the layer that contacts the outside air) and the innermost layer (the layer that contacts the liquid food) are usually made of a thermoplastic resin layer.
  • the material has poor oxygen barrier properties, and its contents degrade from the permeated oxygen and its quality is reduced.
  • a packaging material comprising a laminate in which a resin layer containing an oxygen scavenger is provided as an inner layer in order to prevent the quality of the content from being deteriorated due to oxygen permeation.
  • the resin in the resin layer include ethylene-vinyl alcohol copolymer and polyethylene terephthalate having good compatibility with the oxygen scavenger.
  • the packaging material thickens the oxygen scavenger-containing barrier layer. Does not have mechanical strength.
  • the oxygen scavenging agent's mechanism of oxygen scavenging causes oxygen Poor oxygen scavenging capacity based on the amount of scavenger, ethylene-vinyl alcohol copolymer and polyethylene terephthalate used; that is, use oxygen scavenger, ethylene-vinyl alcohol copolymer and polyethylene terephthalate However, its oxygen collection efficiency is inferior. Disclosure of the invention
  • An object of the present invention is to provide a method for producing an oxygen-scavenging packaging material having an excellent oxygen barrier property and capable of preventing a deterioration in the quality of contents caused by oxygen permeation even if the oxygen-scavenging layer is thin. It is to provide.
  • An object of the present invention is to provide an oxygen-scavenging packaging material that exhibits the maximum oxygen-scavenging ability of an oxygen-scavenging agent, an ethylene-pinyl alcohol copolymer and polyethylene terephthalate, and has an excellent oxygen-scavenging efficiency. To provide an oxygen-scavenging packaging material.
  • An object of the present invention is to provide a method for producing a strong oxygen-scavenging packaging material by thinning an oxygen-scavenging layer having no mechanical strength, and to provide an oxygen-scavenging packaging material.
  • the method for producing an oxygen-scavenging packaging material according to the present invention comprises the steps of blending an oxygen-scavenging agent with a carrier of an ethylene-vinyl alcohol copolymer or a polyethylene terephthalate barrier resin to form an oxygen-scavenging dispersion resin. Forming, dispersing the oxygen-scavenging dispersion resin in a polyolefin or polyamide matrix resin to form an oxygen-scavenging composite material, and forming a packaging material using the oxygen-scavenging composite material Including doing.
  • an adhesive resin having a polyolefin compatibility with an ethylene-vinyl alcohol copolymer or a polyethylene terephthalate carrier resin and an oxygen-scavenging resin are provided.
  • the packaging material is formed using the conductive composite material.
  • an oxygen-scavenging agent is blended with a carrier of a barrier resin such as an ethylene-vinyl alcohol copolymer or polyethylene terephthalate.
  • a barrier resin such as an ethylene-vinyl alcohol copolymer or polyethylene terephthalate.
  • a packaging material is formed by using the oxygen-scavenging composite material to form an opening device by injection molding.
  • the oxygen-scavenging packaging material comprises a paper layer and a thermoplastic resin layer on both sides thereof.
  • a packaging material formed from a laminate having: an oxygen-scavenging agent, an oxygen-scavenging agent comprising an ethylene-vinyl alcohol copolymer or polyethylene terephthalate and an adhesive resin, inside the paper layer.
  • Dispersed resin particles have an oxygen-scavenging composite layer dispersed in a polyolefin matrix.
  • the oxygen-scavenging composite material layer has an oxygen noria layer between the paper layer and the oxygen-scavenging composite material layer.
  • An oxygen-scavenging packaging material is a packaging material formed from a laminate having a paper layer and a thermoplastic resin layer on both sides thereof, wherein an oxygen-scavenger and ethylene-vinyl alcohol are contained inside the paper layer. It has an oxygen-scavenging composite material layer in which oxygen-scavenging dispersed resin particles of a polymer or polyethylene terephthalate are dispersed in a polyamide matrix.
  • the oxygen-scavenging agent is a sulfite.
  • the oxygen-scavenging packaging material according to the present invention is a packaging material formed from a laminate having a paper layer and thermoplastic resin layers on both sides thereof.
  • the basis weight is 50 to 35
  • the thermoplastic resin constituting one layer of the packaging material of the present invention includes polyolefin, polyamide, polyester, polychlorinated biel, polystyrene, methacrylic resin, and ethylene-unsaturated carboxylic acid copolymer, ionomer, and unsaturated monomer.
  • Carboxylic acid modification Examples include polyolefin, cyclic olefin copolymer, ethylene-vinyl alcohol copolymer, polyvinyl alcohol having a saponification degree of 95% or more, and acetyl cellulose.
  • the polyolefin include polyethylene, polypropylene, ethylene-propylene copolymer, and polybutene-1.
  • polyamide examples include polyamide 6, polyamide 6-6, polyamide-11, polyamide-12, and the like.
  • polyester examples include polyethylene terephthalate and polybutylene terephthalate. Of these, polyolefins are preferred.
  • polyethylene examples include high-density polyethylene, medium-density polyethylene, low-density polyethylene, linear low-density polyethylene (LLDPE), and linear low-density polyethylene (mL LDPE) produced by using a metallocene catalyst. No.
  • an oxygen-scavenging agent, and an oxygen-scavenging dispersed resin particle composed of an ethylene-vinyl alcohol copolymer or polyethylene terephthalate and an adhesive resin are formed of polyolefin inside the paper layer. It has an oxygen-scavenging composite material layer dispersed in a matrix.
  • Examples of the oxygen scavenger in the present invention include sulfites, reducing organic compounds, and reduced metals.
  • the sulfite is sodium sulfite, potassium sulfite, or the like.
  • the reducing organic compounds include ascorbic acids, polyvalent phenols, and catechins.
  • Ascorbic acid is a mixture thereof such as ascorbic acid, arapoascorbic acid and their salts (sodium salt, potassium salt, etc.).
  • Polyhydric phenols include pyrogallol, catechol, gallic acid, resorcinol, hydroquinone, and mixtures thereof.
  • Catechins are epicatechin, epiga mouth Catechin, epicatechin gallate, epigallocatechin gallate, etc., and mixtures thereof.
  • ascorbic acids and dextrins particularly ascorbic acid and arapoascorbic acid
  • the reduced metal is reduced iron.
  • oxygen scavengers sulfites, especially sodium sulfite, are preferred.
  • the content of the oxygen scavenger is 5 to 30% by mass based on the total of the ethylene-pinyl alcohol copolymer or polyethylene terephthalate and the oxygen scavenger in the oxygen-scavenging composite material layer. It is particularly preferably from 10 to 15% by mass.
  • the adhesive resin contained in the oxygen-scavenging dispersed resin particles of the present invention is used for preparing an oxygen-scavenging composite material layer by dispersing it in a polyolefin matrix.
  • the adhesive resin includes, for example, an acrylic resin adhesive resin, a modified polyolefin adhesive resin, an ethylene-vinyl acetate copolymer adhesive resin, a polyamide adhesive resin, an epoxy resin adhesive resin, and the like.
  • the acrylic resin-based adhesive resin includes a polymer or a copolymer of acrylic acid or methacrylic acid or an alkyl ester thereof.
  • Modified polyolefin-based adhesive resins include polyethylene, polypropylene, and other unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, nadic acid, and nadic anhydride or anhydrides thereof.
  • the product is obtained by grafting in the presence of an organic peroxide.
  • a modified polyolefin adhesive is particularly preferred.
  • the oxygen-scavenging packaging material is an oxygen-scavenging dispersing resin particle comprising an oxygen-scavenging agent and an ethylene-pier alcohol copolymer or polyethylene terephthalate in which oxygen-dispersing resin particles are dispersed in a polyamide matrix. It has a trapping composite material layer.
  • the polyamide of the matrix resin of the oxygen-scavenging composite material layer includes polyamide MXD6, polyhexamethylenediamine terephthalate (polyamide 6T), polyhexamethylenediamineisophthalamide, and a xylene group-containing polyamide.
  • aromatic polyamides such as polyamides, aliphatic polyamides such as polyamide 4-6, polyamide 6, polyamide 6-6, polyamide 6-10, polyamide 6-12, polyamide 11 and polyamide 12, and the like.
  • aromatic polyamides such as polyamides, aliphatic polyamides such as polyamide 4-6, polyamide 6, polyamide 6-6, polyamide 6-10, polyamide 6-12, polyamide 11 and polyamide 12, and the like.
  • an aromatic polyamide is preferable
  • the resin is polyethylene terephthalate, an aliphatic polyamide is preferable.
  • the content of polyamide in the oxygen-scavenging composite material layer is preferably 50% by mass or more, and particularly preferably 80 to 90% by mass. Therefore, the content of the ethylene-vinyl alcohol copolymer or polyethylene terephthalate containing the oxygen scavenger is preferably 50% by mass or less, particularly preferably 10 to 20% by mass.
  • the oxygen-scavenging composite material layer can contain an aliphatic polyamide.
  • the content of the aliphatic polyamide is preferably set to 10 to 20% by mass of the oxygen-scavenging composite material layer containing the aliphatic polyamide.
  • the oxygen scavenging composite material layer if made of polyethylene terephthalate tallates including aliphatic polyamides, the said layer, the further content of the aromatic polyamide during the 9 to Ru can contain aromatic polyamides, aromatic The content is preferably 10 to 20% by mass of the oxygen-scavenging composite material layer containing polyamide.
  • the oxygen-scavenging packaging material is An oxygen-scavenging agent is blended with a carrier of an alcohol copolymer or polyethylene terephthalate barrier resin to form an oxygen-scavenging dispersion resin, and the oxygen-scavenging dispersion resin is contained in a polyolefin or polyamide matrix resin. It is obtained by dispersing the collective dispersion resin to form an oxygen-collecting composite material, and forming a packaging material using the oxygen-collecting composite material.
  • Adhesive resin is mixed with a mixture of oxygen scavenger and ethylene-vinyl alcohol copolymer or polyethylene terephthalate, if necessary, and the resulting masterbatch of oxygen-scavenging dispersed resin is mixed with polyolefin matrix. And disperse.
  • the mixing ratio between the mixture and the adhesive resin is such that the mixture is 50 to 90% by mass, preferably 70 to 80% by mass, and the adhesive resin is 10 to 50% by mass, preferably 20 to 30% by mass.
  • a master batch of oxygen-scavenging dispersed resin obtained by mixing an adhesive resin with a mixture of the oxygen-scavenging agent and ethylene-vinyl alcohol copolymer or polyethylene terephthalate, and polyolefin, a blend of It can be obtained by mechanically blending with an ordinary kneader.
  • the blending ratio between the masterbatch and the polyolefin is 5 to 40% by mass, preferably 10 to 20% by mass for the masterbatch, and 60 to 95% by mass, preferably 80 to 90% by mass for the polyolefin. %.
  • a preferred embodiment of the oxygen-scavenging packaging material according to the present invention is a packaging material formed from a laminate having a paper layer and a thermoplastic resin layer on both sides thereof, wherein an oxygen-scavenger, ethylene Monovinyl alcohol copolymer or polyethylene
  • An oxygen-scavenging composite material layer in which oxygen-scavenging dispersed resin particles composed of a sheet and an adhesive resin are dispersed in a polyolefin matrix is a packaging material formed from a laminate having a paper layer and a thermoplastic resin layer on both sides thereof, wherein an oxygen-scavenger, ethylene Monovinyl alcohol copolymer or polyethylene
  • An oxygen-scavenging composite material layer in which oxygen-scavenging dispersed resin particles composed of a sheet and an adhesive resin are dispersed in a polyolefin matrix.
  • the oxygen-scavenging packaging material of the present invention can have a barrier layer between the paper layer and the oxygen-scavenging composite material or at a layer position.
  • the barrier layer is a barrier material alone or a multilayer containing a barrier material.
  • the barrier material is aluminum foil, silicon oxide-deposited polyethylene phthalate, ethylene-vinyl alcohol copolymer, polyamide resin, or the like.
  • the multilayer structure including barrier material is made of polyethylene film Z aluminum foil, adhesive polyethylene, silicon oxide vapor-deposited polyethylene terephthalate biaxially stretched film (Z adhesive), polyethylene film / adhesive / ethylene-pier alcohol Copolymer film / adhesive, polyamide resin film / adhesive, etc.
  • the thickness of the barrier layer is usually between 5 and 25 m.
  • the adhesive layer provided inside the oxygen-scavenging composite material layer includes, for example, an acrylic resin-based adhesive, a modified polyolefin-based adhesive, an ethylene-vinyl acetate copolymer, a polyamide-based adhesive, and an epoxy resin-based adhesive.
  • the acrylic resin adhesive is a polymer or copolymer of acrylic acid or methacrylic acid or an alkyl ester thereof.
  • Modified polyolefin adhesives include polyethylene, polypropylene, and other unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, nadic acid, and nadic acid anhydride or anhydrides thereof.
  • the adhesive layer is provided inside the layer of the oxygen-absorbing composite material containing the polyamide matrix. In particular, it is desirable to provide it in contact with the layer.
  • the thickness of this adhesive layer is usually 5 ⁇ 30m It is.
  • the number of thermoplastic resin layers provided outside the paper layer is not limited to one, and two or more thermoplastic resin layers can be provided.
  • the thermoplastic resin is preferably polyolefin.
  • polyethylene is particularly preferred.
  • the polyethylene is a high-density polyethylene, a medium-density polyethylene, a low-density polyethylene, a linear low-density polyethylene, a mLLDPE or the like, and preferably a low-density polyethylene and a linear low-density polyethylene.
  • thermoplastic resin layers provided inside the paper layer is not limited to one, and two or more thermoplastic resin layers can be provided.
  • the thermoplastic resin is preferably polyolefin.
  • polyethylene is particularly preferred.
  • Polyethylene is particularly preferably linear low-density polyethylene and mLLDP.
  • the thickness of these thermoplastic resin layers is usually 5 to 200 m.
  • the packaging material of the present invention comprises a laminate.
  • Laminating methods include laminating each layer using an adhesive, laminating a layer that can be melted by heat, and laminating with a layer that is in contact with it, and laminating layers that can be simultaneously extruded by simultaneous extrusion. And how to combine them.
  • an oxygen-scavenging dispersing resin is formed by blending an oxygen-scavenging agent into a barrier resin carrier, and the polyamide matrix resin includes: Disperse the oxygen-scavenging dispersion resin to form an oxygen-scavenging composite material, and extrude and laminate the oxygen-scavenging composite material directly on the paper layer to form a packaging material consisting of a paper laminate .
  • the container can be shaped like a parallelepiped, a parallel hexagonal prism, a parallel octagonal prism at the center of the body, a quadrilateral at the top and bottom, and a patch.
  • a packaging material is formed by injection molding using an oxygen-scavenging composite material to form an opening device such as a spat, a plug, a lid, a drinking spout, a spout, and a spout.
  • Sodium sulfite (Na 2 S0 3) which contained 15 wt% ethylene-vinyl ⁇ alcohol copolymer 70 parts by weight of polypropylene modified polyolefin obtained by grafting maleic anhydride melted and (adhesive resin) 30 parts by kneading Then, a master batch of the oxygen-scavenging dispersing resin was prepared. After blending 10 parts by mass of this mass and 90 parts by mass of polypropylene equivalent to 20 gZ of melt per mouth, the mixture is extruded, and the oxygen-scavenging composite material in which the oxygen-scavenging dispersion resin is dispersed in the matrix resin A pellet was formed.
  • Low-density polyethylene with a density of 0.924 gZcm 3 , paper (250 g / m 2 basis weight), polypropylene (PP) with a melt flow rate of 20 gZ, ethylene-vinyl alcohol copolymer (EVOH), A modified polyolefin-based adhesive obtained by grafting maleic anhydride on polypropylene, the pellet obtained above, and a linear low-density polyethylene (LLDPE) having a density of 0.910 g / cm 3 were prepared.
  • LDPE Low-density polyethylene
  • PP polypropylene
  • EVOH ethylene-vinyl alcohol copolymer
  • LLDPE linear low-density polyethylene
  • Push LDPE (thickness 15 m) (outermost layer) / paper / PP (thickness 10 m) / EVOH (thickness 10 m) / modified polyolefin adhesive (thickness 10)
  • a packaging material having a laminated configuration of the oxygen-scavenging composite material (thickness: 15 lim) ZLLDPE (thickness: 25 m) (innermost layer) of the pellet obtained in step (1) was manufactured.
  • a 200ml 1-prick type liquid food container was prepared and filled with a vitamin C solution.
  • the vitamin C concentration was 95% of the initial concentration.
  • the pellets were prepared in the same manner as in Example 11 except that polyethylene terephthalate containing 15% by mass of sodium sulfite was used instead of the ethylene-vinyl alcohol copolymer containing 15% by mass of sodium sulfite. Molded.
  • a packaging material was produced in the same manner as in Example 11-11, except that the pellets obtained above were used instead of the pellets used in Example 11-11.
  • a container was prepared and filled with a vitamin C solution in the same manner as in Example 1-1, and the change in the concentration of vitamin C in the container was observed. At 95% of the concentration.
  • a pellet was formed in the same manner as in Example 11 except that the modified polyolefin was not used as the adhesive resin, but the ethylene-vinyl alcohol copolymer containing sodium sulfite and the matrix resin, polypropylene, were uniformly kneaded. As a result, the obtained pellets could not be used as a material for producing a packaging material.
  • Example 11 In the same manner as in Example 11 except that the pellet used in Example 11 was replaced with an oxygen-trapping pellet obtained by uniformly mixing the oxygen-trapping resin in the matrix resin. To produce packaging materials. Using this packaging material, a container was prepared and a vitamin C solution was filled in the same manner as in Example 1-1, and the change in the concentration of vitamin C in the container was observed. It was 90% of the concentration. Moreover, this packaging material is inferior in strength to the packaging material obtained in Example 11-11.
  • LDPE Low-density polyethylene
  • LLDPE linear low density polyethylene
  • a 200ml 1-prick type liquid food container was prepared and filled with a vitamin C solution. Immediately after filling and at 23 ° C As a result of observing changes in the concentration of vitamin C in the container stored for 4 weeks, the concentration of vitamin C was 90% of the initial concentration.
  • Example 2-1 (outermost layer) No. Paper used in Example 2-1 Z Oxygen-scavenging property of the composition used in Example 2-1 containing 10% by mass of polyamide 6
  • a packaging material comprising a laminate of the modified polyolefin adhesive used in Example 2-1 / the LLDPE film (innermost layer) used in Example 1 was manufactured.
  • a container was prepared and a vitamin C solution was filled in the same manner as in Example 2-1, and the change in the concentration of vitamin C in the container was observed. It was 90% of the concentration.
  • LDPE film used in Example 2-1 (outermost layer) No. Composition containing 20% by mass of polyethylene terephthalate containing 10% by mass of sodium paper bisulfite and 80% by mass of polyamide 6 used in Example 2-1 Film (15 m) / modified polyolefin adhesive used in Example 2-1 Z density: 0.915 g / cm3, MI: 14 g / 10 min mL LDPE film (20 rn) (Innermost layer) packaging material was manufactured. Using this packaging material, a container was prepared and a vitamin C solution was filled in the same manner as in Example 2-1, and the change in the concentration of vitamin C in the container was observed. The concentration was 92%.
  • Example 3 A packaging material consisting of a laminate of the mLLDPE film (innermost layer) used in Step 1 was manufactured. Using this packaging material, a container was prepared and a vitamin C solution was filled in the same manner as in Example 2-1, and the change in the concentration of vitamin C in the container was observed. Was 93%.
  • Example 2 A packaging material consisting of the LLDPE film (innermost layer) used in 1 was manufactured. Using this packaging material, a container was prepared and a vitamin C solution was filled in the same manner as in Example 2-1, and the change in the concentration of vitamin C in the container was observed. 80%.
  • Example 2-1 outermost layer
  • paper used in Example 2-1 film consisting of polyethylene terephthalate (15 m) / mLLDPE film used in Example 2-3 (most An inner layer) was manufactured as a packaging material.
  • a packaging material Using this packaging material, a container was prepared and filled with Vimin C solution in the same manner as in Example 2-1, and the change in vitamin C concentration in the container was observed. The initial concentration was 70%.
  • the container molded using the packaging material of the example is It can be seen that the oxygen barrier property is superior to the container molded using the packaging material of the comparative example, and the strength of the packaging material is improved.
  • the present invention has the following effects.
  • the container molded using the packaging material of the present invention has excellent oxygen barrier properties, despite being substantially composed of a laminate of paper and polyolefin.
  • the container molded using the packaging material of the present invention has excellent oxygen barrier properties even when the oxygen barrier layer is thin, and can prevent the quality of contents from being deteriorated due to oxygen permeation.
  • the oxygen barrier layer can be made thin, the weight of the packaging container can be reduced.
  • the packaging material of the present invention has excellent mechanical strength. Industrial applicability
  • the method for producing an oxygen-scavenging packaging material and the oxygen-scavenging packaging material of the present invention are used for packaging liquid foods such as milk, distillery, sake, shochu, mineral water and other beverages.

Abstract

A method for producing an oxygen-capturing packaging material, which comprises blending an ethylene-vinyl alcohol copolymer or polyethylene terephthalate as a carrier of a barrier resin with an oxygen-capturing agent to form an oxygen-capturing resin for dispersion, dispersing the oxygen-capturing resin in a polyolefin or polyamide as a matrix resin to form an oxygen-capturing composite material, and forming a packaging material by the use of the oxygen-capturing composite material. A container formed by using the packaging material exhibits excellent oxygen-barrier properties and excellent mechanical strength with a thinner thickness, and thus may be reduced in weight.

Description

明 細書 酸素捕集性包装材料の製造法及び酸素捕集性包装材料 技術分野  Description Method for manufacturing oxygen-scavenging packaging materials and oxygen-scavenging packaging materials
本発明は、 酸素バリア性に優れ、 液体食品の包装に適した酸素捕集性包装材 料の製造法及び酸素捕集性包装材料に関する。 背景技術  The present invention relates to a method for producing an oxygen-scavenging packaging material excellent in oxygen barrier properties and suitable for packaging liquid foods, and an oxygen-scavenging packaging material. Background art
ジュース、 コーヒー、牛乳、 酒類等の液体食品の容器として紙及び熱可塑性樹 脂の積層物からなる紙容器が普及している。 その紙容器は、 通常、 その最外層 (外気に触れる層） 及び最内層 （液体食品に触れる層） が熱可塑性樹脂層から なっている。 その材料が、 酸素バリア性に乏しく、 その内容物が、 透過した酸 素より劣化し、 その品質が低下する。  As paper containers for liquid foods such as juice, coffee, milk, and liquors, paper containers made of laminates of paper and thermoplastic resin have become widespread. In the paper container, the outermost layer (the layer that contacts the outside air) and the innermost layer (the layer that contacts the liquid food) are usually made of a thermoplastic resin layer. The material has poor oxygen barrier properties, and its contents degrade from the permeated oxygen and its quality is reduced.
酸素透過による内容物の品質低下を防止するために、 酸素捕集剤を含有した 樹脂層をその内層に設けた積層物からなる包装材料は知られている。 この樹脂 層の樹脂の例は、 酸素捕集剤と相溶性が良いエチレン一ビニルアルコール共重 合体、 ポリエチレンテレフタレート等である。  There is known a packaging material comprising a laminate in which a resin layer containing an oxygen scavenger is provided as an inner layer in order to prevent the quality of the content from being deteriorated due to oxygen permeation. Examples of the resin in the resin layer include ethylene-vinyl alcohol copolymer and polyethylene terephthalate having good compatibility with the oxygen scavenger.
しかし、 従来の酸素捕集剤を含有したエチレン一ビエルアルコール共重合体 層やポリエチレンテレフタレ一ト層を包装積層材料として使用した場合、 酸素 捕集剤、 エチレン—ビニルアルコール共重合体やポリエチレンテレフタレ一ト が、 ポリオレフインなどのその他の積層材料と相溶性が良好ではなく、 酸素バ リア性を維持し相溶性を向上させるには酸素捕集剤含有バリア層を厚くする必 要があった。 However, when a conventional ethylene-vinyl alcohol copolymer layer or polyethylene terephthalate layer containing an oxygen scavenger is used as a packaging laminate material, the oxygen scavenger, ethylene-vinyl alcohol copolymer or polyethylene terephthalate The sauce is not compatible with other laminated materials such as polyolefins and oxygen In order to maintain compatibility and improve compatibility, it was necessary to increase the thickness of the barrier layer containing an oxygen scavenger.
酸素捕集剤を含有したエチレン一ビエルアルコール共重合体層ゃポリェチレ ンテレフ夕レート層を包装積層材料として使用した場合、 その包装材料は、 酸 素捕集剤含有バリア層を厚くするので、 良好な機械的強度を有していない。 酸素捕集剤を含むェチレン—ピエルアルコール共重合体層ゃポリエチレンテ レフ夕レート層を含む積層包装材料を、 紙容器に成形した場合、 酸素捕集剤の 酸素捕集の作用機序から、 酸素捕集剤、 エチレン一ビニルアルコール共重合体 及びポリエチレンテレフ夕レートの使用量に対する酸素捕集の能力が、 低く、 すなわち、 酸素捕集剤、 エチレン一ビニルアルコール共重合体及びポリェチレ ンテレフタレ一トを使用した割に、 その酸素捕集効率は、 劣っている。 発明の開示  When an ethylene-bier alcohol copolymer layer containing an oxygen scavenger and a polyethylene terephthalate layer are used as a packaging laminate material, the packaging material thickens the oxygen scavenger-containing barrier layer. Does not have mechanical strength. When a laminated packaging material containing an ethylene-pier alcohol copolymer layer containing an oxygen scavenger and a polyethylene terephthalate layer is molded into a paper container, the oxygen scavenging agent's mechanism of oxygen scavenging causes oxygen Poor oxygen scavenging capacity based on the amount of scavenger, ethylene-vinyl alcohol copolymer and polyethylene terephthalate used; that is, use oxygen scavenger, ethylene-vinyl alcohol copolymer and polyethylene terephthalate However, its oxygen collection efficiency is inferior. Disclosure of the invention
本発明の目的は、 酸素捕集層が薄くても酸素透過による内容物の品質低下を 防止することができる酸素バリァ性に優れた酸素捕集性包装材料の製造法及び 酸素捕集性包装材料を提供することである。  An object of the present invention is to provide a method for producing an oxygen-scavenging packaging material having an excellent oxygen barrier property and capable of preventing a deterioration in the quality of contents caused by oxygen permeation even if the oxygen-scavenging layer is thin. It is to provide.
本発明の目的は、 酸素捕集剤、 エチレン一ピニルアルコール共重合体及びポ リエチレンテレフタレートの酸素捕集の能力を最大限に発揮させ、 その酸素捕 集効率に優れた酸素捕集性包装材料の製造法及び酸素捕集性包装材料を提供す ることである。  An object of the present invention is to provide an oxygen-scavenging packaging material that exhibits the maximum oxygen-scavenging ability of an oxygen-scavenging agent, an ethylene-pinyl alcohol copolymer and polyethylene terephthalate, and has an excellent oxygen-scavenging efficiency. To provide an oxygen-scavenging packaging material.
本発明の目的は、 機械的強度のない酸素捕集層が薄くし、 強度のある酸素捕 集性包装材料の製造法及び酸素捕集性包装材料を提供することである。 この発明による酸素捕集性包装材料の製造法は、 エチレン一ビニルアルコ一 ル共重合体若しくはポリエチレンテレフ夕レートのバリァ榭脂のキヤリアに、 酸素捕集剤をプレンドして酸素捕集性分散樹脂を形成し、 ポリオレフィン又は ポリアミドのマトリックス用樹脂中に、 前記酸素捕集性分散樹脂を分散して、 酸素捕集性複合材料を形成し、 前記酸素捕集性複合材料を用いて、 包装材料を 形成することを含む。 An object of the present invention is to provide a method for producing a strong oxygen-scavenging packaging material by thinning an oxygen-scavenging layer having no mechanical strength, and to provide an oxygen-scavenging packaging material. The method for producing an oxygen-scavenging packaging material according to the present invention comprises the steps of blending an oxygen-scavenging agent with a carrier of an ethylene-vinyl alcohol copolymer or a polyethylene terephthalate barrier resin to form an oxygen-scavenging dispersion resin. Forming, dispersing the oxygen-scavenging dispersion resin in a polyolefin or polyamide matrix resin to form an oxygen-scavenging composite material, and forming a packaging material using the oxygen-scavenging composite material Including doing.
この発明による酸素捕集性包装材料の製造法の好ましい態様において、 ェチ レン—ビニルアルコール共重合体若しくはポリエチレンテレフタレートのパリ ァ樹脂のキヤリアに、 ポリオレフィンと相溶性を有する接着性樹脂及び酸素捕 集剤をブレンドして酸素捕集性分散樹脂を形成し、 ポリオレフインのマトリツ クス用樹脂中に、 前記酸素捕集性分散樹脂を分散して、 酸素捕集性複合材料を 形成し、 前記酸素捕集性複合材料を用いて、 包装材料を形成する。  In a preferred embodiment of the method for producing an oxygen-scavenging packaging material according to the present invention, an adhesive resin having a polyolefin compatibility with an ethylene-vinyl alcohol copolymer or a polyethylene terephthalate carrier resin and an oxygen-scavenging resin are provided. An oxygen-scavenging dispersing resin to form an oxygen-scavenging dispersed resin; dispersing the oxygen-scavenging dispersed resin in a polyolefin matrix resin to form an oxygen-scavenging composite material; The packaging material is formed using the conductive composite material.
この発明による酸素捕集性包装材料の製造法の別の好ましい態様において、 エチレン一ビニルアルコール共重合体若しくはポリエチレンテレフタレ一卜の バリア樹脂のキャリアに、 酸素捕集剤をブレンドして酸素捕集性分散樹脂を形 成し、 ポリアミドのマトリックス用樹脂中に、 前記酸素捕集性分散樹脂を分散 して、 酸素捕集性複合材料を形成し、 前記酸素捕集性複合材料を押出しラミネ 一トで紙層に直接積層して、 紙積層体からなる包装材料を形成する。  In another preferred embodiment of the method for producing an oxygen-scavenging packaging material according to the present invention, an oxygen-scavenging agent is blended with a carrier of a barrier resin such as an ethylene-vinyl alcohol copolymer or polyethylene terephthalate. Forming an oxygen-dispersing resin, dispersing the oxygen-scavenging dispersing resin in a polyamide matrix resin to form an oxygen-scavenging composite material, and extruding the oxygen-scavenging composite material. To form a packaging material consisting of a paper laminate.
この発明による酸素捕集性包装材料の製造法の別の好ましい態様において、 前記酸素捕集性複合材料を用いて、 射出成形で開封装置を成形して、 包装材料 を形成する。  In another preferred embodiment of the method for producing an oxygen-scavenging packaging material according to the present invention, a packaging material is formed by using the oxygen-scavenging composite material to form an opening device by injection molding.
この発明による酸素捕集性包装材料は、 紙層及びその両側に熱可塑性樹脂層 を有する積層物から形成される包装材において、 該紙層の内側に、 酸素捕集剤 と、 エチレン—ビニルアルコール共重合体若しくはポリエチレンテレフ夕レ一 トと接着性樹脂とからなる酸素捕集性分散樹脂粒がポリオレフインのマトリツ クス中に分散された酸素捕集性複合材料層を有する。 The oxygen-scavenging packaging material according to the present invention comprises a paper layer and a thermoplastic resin layer on both sides thereof. In a packaging material formed from a laminate having: an oxygen-scavenging agent, an oxygen-scavenging agent comprising an ethylene-vinyl alcohol copolymer or polyethylene terephthalate and an adhesive resin, inside the paper layer. Dispersed resin particles have an oxygen-scavenging composite layer dispersed in a polyolefin matrix.
この発明による酸素捕集性包装材料の好ましい態様において、 上記紙層と上 記酸素捕集性複合材料層の間に酸素ノ リア層を有する。  In a preferred embodiment of the oxygen-scavenging packaging material according to the present invention, the oxygen-scavenging composite material layer has an oxygen noria layer between the paper layer and the oxygen-scavenging composite material layer.
この発明による酸素捕集性包装材料は、 紙層及びその両側に熱可塑性樹脂層 を有する積層物から形成される包装材において、 該紙層の内側に、 酸素捕集剤 とエチレン—ビニルアルコール共重合体若しくはポリエチレンテレフタレート とからなる酸素捕集性分散樹脂粒がポリアミドのマトリックス中に分散されて いる酸素捕集性複合材料層を有する。  An oxygen-scavenging packaging material according to the present invention is a packaging material formed from a laminate having a paper layer and a thermoplastic resin layer on both sides thereof, wherein an oxygen-scavenger and ethylene-vinyl alcohol are contained inside the paper layer. It has an oxygen-scavenging composite material layer in which oxygen-scavenging dispersed resin particles of a polymer or polyethylene terephthalate are dispersed in a polyamide matrix.
この発明による酸素捕集性包装材料の好ましい態様において、 上記酸素捕集 剤は亜硫酸塩である。 発明を実施するための最良の形態  In a preferred embodiment of the oxygen-scavenging packaging material according to the present invention, the oxygen-scavenging agent is a sulfite. BEST MODE FOR CARRYING OUT THE INVENTION
この発明による酸素捕集性包装材料は、 紙層及びその両側に熱可塑性樹脂層 を有する積層物から形成される包装材である。  The oxygen-scavenging packaging material according to the present invention is a packaging material formed from a laminate having a paper layer and thermoplastic resin layers on both sides thereof.
この発明の包装材の一層を構成する紙としては、 例えば、 坪量が 5 0〜3 5 As the paper constituting one layer of the packaging material of the present invention, for example, the basis weight is 50 to 35
0 g /mz である紙容器用の紙、 板紙、 紙主体積層体が使用できる。 0 g / mz paper for paper containers, paperboard, and paper-based laminates can be used.
本発明の包装材の一層を構成する熱可塑性樹脂は、 ポリオレフイン、 ポリア ミド、 ポリエステル、 ポリ塩化ビエル、 ポリスチレン、 メタクリル樹脂、 ェチ レン一 0；—不飽和カルボン酸共重合体、 アイオノマー、 不飽和カルボン酸変性 ポリオレフイン、 環状ォレフィン共重合体、 エチレン一ビニルアルコール共重 合体、 けん化度 9 5 %以上のポリビニルアルコール、 ァセチルセルロース等が 挙げられる。 ポリオレフインとしては、 ポリエチレン、 ポリプロピレン、 ェチ レン一プロピレン共重合体、 ポリブテン— 1等が挙げられる。 ポリアミドとし ては、 ポリアミド 6、 ポリアミド 6— 6、 ポリアミド一 1 1、 ポリアミド一 1 2等が挙げられる。 ポリエステルとしては、 ポリエチレンテレフ夕レート、 ポ リブチレンテレフタレート等が挙げられる。 これらの中でもポリオレフィンが 好ましい。ポリエチレンとしては、高密度ポリエチレン、 中密度ポリエチレン、 低密度ポリエチレン、 直鎖状低密度ポリエチレン （L L D P E)、 メタ口セン触 媒を用いることにより製造される直鎖状低密度ポリエチレン （mL L D P E) 等が挙げられる。 The thermoplastic resin constituting one layer of the packaging material of the present invention includes polyolefin, polyamide, polyester, polychlorinated biel, polystyrene, methacrylic resin, and ethylene-unsaturated carboxylic acid copolymer, ionomer, and unsaturated monomer. Carboxylic acid modification Examples include polyolefin, cyclic olefin copolymer, ethylene-vinyl alcohol copolymer, polyvinyl alcohol having a saponification degree of 95% or more, and acetyl cellulose. Examples of the polyolefin include polyethylene, polypropylene, ethylene-propylene copolymer, and polybutene-1. Examples of the polyamide include polyamide 6, polyamide 6-6, polyamide-11, polyamide-12, and the like. Examples of the polyester include polyethylene terephthalate and polybutylene terephthalate. Of these, polyolefins are preferred. Examples of the polyethylene include high-density polyethylene, medium-density polyethylene, low-density polyethylene, linear low-density polyethylene (LLDPE), and linear low-density polyethylene (mL LDPE) produced by using a metallocene catalyst. No.
本発明の包装材は、 紙層の内側に、 酸素捕集剤と、 エチレン—ビニルアルコ ール共重合体若しくはポリエチレンテレフ夕レートと接着性樹脂とからなる酸 素捕集性分散樹脂粒がポリオレフインのマトリックス中に分散された酸素捕集 性複合材料層を有することを特徴とする。  In the packaging material of the present invention, an oxygen-scavenging agent, and an oxygen-scavenging dispersed resin particle composed of an ethylene-vinyl alcohol copolymer or polyethylene terephthalate and an adhesive resin are formed of polyolefin inside the paper layer. It has an oxygen-scavenging composite material layer dispersed in a matrix.
この発明における酸素捕集剤は、 亜硫酸塩、 還元性有機化合物、 還元金属等 が挙げられる。 亜硫酸塩は、 亜硫酸ナトリウム、 亜硫酸カリウム等である。 還 元性有機化合物は、 ァスコルビン酸類、 多価フエノール類、 カテキン類等が挙 げられる。 ァスコルビン酸類は、 ァスコルビン酸、 ァラポアスコルビン酸及び それらの塩類 （ナトリウム塩、 カリウム塩等） 等、 それらの混合物である。 多 価フエノール類は、 ピロガロール、 カテコール、 没食子酸、 レゾルシン、 ヒド ロキノン等、 それらの混合物を含む。 カテキン類は、 ェピカテキン、 ェピガ口 カテキン、 ェピカテキンガレート、 ェピガロカテキンガレ一ト等、 それらの混 合物である。 これらの還元性有機化合物の中で、 ァスコルビン酸類及び力テキ ン類、 特にァスコルビン酸及びァラポアスコルピン酸が望ましい。 又、 還元金 属は還元鉄である。 これらの酸素捕集剤の中で、 亜硫酸塩、 特に亜硫酸ナトリ ゥムが好ましい。 酸素捕集剤の含有量は、 上記ポ酸素捕集性複合材料層中のェ チレン一ピニルアルコール共重合体又はポリエチレンテレフ夕レートと酸素捕 集剤の合計に対して 5〜3 0質量％、 特に 1 0〜1 5質量％が好ましい。 Examples of the oxygen scavenger in the present invention include sulfites, reducing organic compounds, and reduced metals. The sulfite is sodium sulfite, potassium sulfite, or the like. The reducing organic compounds include ascorbic acids, polyvalent phenols, and catechins. Ascorbic acid is a mixture thereof such as ascorbic acid, arapoascorbic acid and their salts (sodium salt, potassium salt, etc.). Polyhydric phenols include pyrogallol, catechol, gallic acid, resorcinol, hydroquinone, and mixtures thereof. Catechins are epicatechin, epiga mouth Catechin, epicatechin gallate, epigallocatechin gallate, etc., and mixtures thereof. Among these reducing organic compounds, ascorbic acids and dextrins, particularly ascorbic acid and arapoascorbic acid, are preferred. The reduced metal is reduced iron. Of these oxygen scavengers, sulfites, especially sodium sulfite, are preferred. The content of the oxygen scavenger is 5 to 30% by mass based on the total of the ethylene-pinyl alcohol copolymer or polyethylene terephthalate and the oxygen scavenger in the oxygen-scavenging composite material layer. It is particularly preferably from 10 to 15% by mass.
この発明の酸素捕集性分散樹脂粒に含まれる接着性樹脂は、 ポリオレフィン のマトリックス中に分散して酸素捕集性複合材料層を調製する場合に用いられ る。 その接着性樹脂は、 例えば、 アクリル樹脂系接着性樹脂、 変性ポリオレフ イン系接着性樹脂、 エチレン一酢酸ビニル共重合体接着性樹脂、 ポリアミド系 接着性樹脂、 エポキシ樹脂系接着性樹脂等を含む。 アクリル樹脂系接着性樹脂 は、 アクリル酸若しくはメタクリル酸又はそのアルキルエステルの重合体、 共 重合体等を含む。 変性ポリオレフイン系接着性樹脂は、 ポリエチレン、 ポリプ ロピレン等にアクリル酸、 メタクリル酸、 マレイン酸、 無水マレイン酸、 フマ —ル酸、 ィタコン酸、 ナジック酸、 無水ナジック酸等の不飽和カルボン酸又は その無水物を有機過酸化物の存在下、 グラフトさせて得られる。 これらの接着 性樹脂の中でも、 変性ポリオレフイン系接着剤が特に好ましい。  The adhesive resin contained in the oxygen-scavenging dispersed resin particles of the present invention is used for preparing an oxygen-scavenging composite material layer by dispersing it in a polyolefin matrix. The adhesive resin includes, for example, an acrylic resin adhesive resin, a modified polyolefin adhesive resin, an ethylene-vinyl acetate copolymer adhesive resin, a polyamide adhesive resin, an epoxy resin adhesive resin, and the like. The acrylic resin-based adhesive resin includes a polymer or a copolymer of acrylic acid or methacrylic acid or an alkyl ester thereof. Modified polyolefin-based adhesive resins include polyethylene, polypropylene, and other unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, nadic acid, and nadic anhydride or anhydrides thereof. The product is obtained by grafting in the presence of an organic peroxide. Among these adhesive resins, a modified polyolefin adhesive is particularly preferred.
この発明による酸素捕集性包装材料は、 酸素捕集剤とエチレン—ピエルアル コール共重合体若しくはポリエチレンテレフ夕レートとからなる酸素捕集性分 散樹脂粒がポリアミドのマトリックス中に分散されている酸素捕集性複合材料 層を有する。 この態様における上記酸素捕集性複合材料層のマトリックス樹脂のポリアミ ドは、 ポリアミド MXD 6、 ポリへキサメチレンジアミンテレフタレート （ポ リアミド 6 T)、 ポリへキサメチレンジァミンイソフタルアミド、 キシレン基含 有ポリアミド等の芳香族ポリアミド、 ポリアミド 4— 6、 ポリアミド 6、 ポリ アミド 6— 6、 ポリアミド 6— 1 0、 ポリアミド 6— 1 2、 ポリアミド 1 1、 ポリアミド 1 2等の脂肪族ポリアミド等を含む。 これらの中でも、 上記酸素捕 集性複合材料層に含有させる樹脂が、 エチレン一ビニルアルコール共重合体の 場合は、芳香族ポリアミドが好ましく、ポリエチレンテレフ夕レートの場合は、 脂肪族ポリアミドが好ましい。 The oxygen-scavenging packaging material according to the present invention is an oxygen-scavenging dispersing resin particle comprising an oxygen-scavenging agent and an ethylene-pier alcohol copolymer or polyethylene terephthalate in which oxygen-dispersing resin particles are dispersed in a polyamide matrix. It has a trapping composite material layer. In this embodiment, the polyamide of the matrix resin of the oxygen-scavenging composite material layer includes polyamide MXD6, polyhexamethylenediamine terephthalate (polyamide 6T), polyhexamethylenediamineisophthalamide, and a xylene group-containing polyamide. Includes aromatic polyamides such as polyamides, aliphatic polyamides such as polyamide 4-6, polyamide 6, polyamide 6-6, polyamide 6-10, polyamide 6-12, polyamide 11 and polyamide 12, and the like. Among these, when the resin contained in the oxygen-scavenging composite material layer is an ethylene-vinyl alcohol copolymer, an aromatic polyamide is preferable, and when the resin is polyethylene terephthalate, an aliphatic polyamide is preferable.
上記酸素捕集性複合材料層のポリアミドの含有量は、 5 0質量％以上、 特に 8 0〜9 0質量％が好ましい。 従って、 上記酸素捕集剤を含有するエチレン— ビニルアルコール共重合体又はポリエチレンテレフタレートの含有量は、 5 0 質量％以下、 特に 1 0〜2 0質量％が好ましい。  The content of polyamide in the oxygen-scavenging composite material layer is preferably 50% by mass or more, and particularly preferably 80 to 90% by mass. Therefore, the content of the ethylene-vinyl alcohol copolymer or polyethylene terephthalate containing the oxygen scavenger is preferably 50% by mass or less, particularly preferably 10 to 20% by mass.
上記酸素捕集性複合材料層が、 エチレン一ビニルアルコール共重合体を含む 芳香族ポリアミドからなる場合、 上記酸素捕集性複合材料層に脂肪族ポリアミ ドを含ませることができる。 その際の脂肪族ポリアミドの含有量は、 脂肪族ポ リアミドを含ませた酸素捕集性複合材料層の 1 0〜 2 0質量％とするのが好ま しい。 酸素捕集性複合材料層が、 脂肪族ポリアミドを含むポリエチレンテレフ タレートからなる場合、 該層に、 更に芳香族ポリアミドを含ませることができ る 9 その際の芳香族ポリアミドの含有量は、 芳香族ポリアミドを含ませた上記 酸素捕集性複合材料層の 1 0〜2 0質量％とするのが好ましい。 When the oxygen-scavenging composite material layer is made of an aromatic polyamide containing an ethylene-vinyl alcohol copolymer, the oxygen-scavenging composite material layer can contain an aliphatic polyamide. In this case, the content of the aliphatic polyamide is preferably set to 10 to 20% by mass of the oxygen-scavenging composite material layer containing the aliphatic polyamide. The oxygen scavenging composite material layer, if made of polyethylene terephthalate tallates including aliphatic polyamides, the said layer, the further content of the aromatic polyamide during the 9 to Ru can contain aromatic polyamides, aromatic The content is preferably 10 to 20% by mass of the oxygen-scavenging composite material layer containing polyamide.
この発明による製造方法によって、 酸素捕集性包装材料は、 エチレンービニ ルアルコール共重合体若しくはポリエチレンテレフ夕レートのバリァ樹脂のキ ャリアに、 酸素捕集剤をブレンドして酸素捕集性分散樹脂を形成し、 ポリオレ フィン又はポリアミドのマトリックス用樹脂中に、 前記酸素捕集性分散樹脂を 分散して、 酸素捕集性複合材料を形成し、 前記酸素捕集性複合材料を用いて、 包装材料を形成することで、 得られる。 According to the production method of the present invention, the oxygen-scavenging packaging material is An oxygen-scavenging agent is blended with a carrier of an alcohol copolymer or polyethylene terephthalate barrier resin to form an oxygen-scavenging dispersion resin, and the oxygen-scavenging dispersion resin is contained in a polyolefin or polyamide matrix resin. It is obtained by dispersing the collective dispersion resin to form an oxygen-collecting composite material, and forming a packaging material using the oxygen-collecting composite material.
酸素捕集剤とエチレン—ビニルアルコール共重合体又はポリエチレンテレフ タレートとの混合物に、 必要に応じて、 接着性樹脂を混合させ、 得られた酸素 捕集性分散樹脂のマスターバッチに、 マトリックスのポリオレフインをプレン ドして分散させる。  Adhesive resin is mixed with a mixture of oxygen scavenger and ethylene-vinyl alcohol copolymer or polyethylene terephthalate, if necessary, and the resulting masterbatch of oxygen-scavenging dispersed resin is mixed with polyolefin matrix. And disperse.
該混合物と接着性樹脂との混合割合は、 該混合物が 5 0〜9 0質量％、 好ま しくは 7 0〜8 0質量％であり、 接着性樹脂が 1 0〜5 0質量％、 好ましくは 2 0〜3 0質量％である。  The mixing ratio between the mixture and the adhesive resin is such that the mixture is 50 to 90% by mass, preferably 70 to 80% by mass, and the adhesive resin is 10 to 50% by mass, preferably 20 to 30% by mass.
上記酸素捕集剤とエチレン一ビニルアルコール共重合体又はポリェチレンテ レフタレ一トとの混合物に接着性樹脂を混合させて得た酸素捕集性分散樹脂の マスタ一バッチと、 ポリオレフインと、 のブレンドは、 通常の混練機を用いて 機械的にブレンドすることにより得られる。 マスターバッチとポリオレフィン とのブレンド割合は、 マスターバッチが 5〜4 0質量％、 好ましくは 1 0〜2 0質量％であり、 ポリオレフインが 6 0〜 9 5質量％、 好ましくは 8 0〜9 0 質量％である。  A master batch of oxygen-scavenging dispersed resin obtained by mixing an adhesive resin with a mixture of the oxygen-scavenging agent and ethylene-vinyl alcohol copolymer or polyethylene terephthalate, and polyolefin, a blend of It can be obtained by mechanically blending with an ordinary kneader. The blending ratio between the masterbatch and the polyolefin is 5 to 40% by mass, preferably 10 to 20% by mass for the masterbatch, and 60 to 95% by mass, preferably 80 to 90% by mass for the polyolefin. %.
この発明による酸素捕集性包装材料の好ましい態様は、 紙層及びその両側に 熱可塑性樹脂層を有する積層物から形成される包装材において、 該紙層の内側 に、 酸素捕集剤と、 エチレン一ビニルアルコール共重合体若しくはポリエチレ ートと接着性樹脂とからなる酸素捕集性分散樹脂粒がポリオレフ ィンのマトリックス中に分散された酸素捕集性複合材料層を有する。 A preferred embodiment of the oxygen-scavenging packaging material according to the present invention is a packaging material formed from a laminate having a paper layer and a thermoplastic resin layer on both sides thereof, wherein an oxygen-scavenger, ethylene Monovinyl alcohol copolymer or polyethylene An oxygen-scavenging composite material layer in which oxygen-scavenging dispersed resin particles composed of a sheet and an adhesive resin are dispersed in a polyolefin matrix.
本発明の酸素捕集性包装材料は、 紙層と酸素捕集性複合材料の間に、 若しく は層位置にバリァ層を有することができる。  The oxygen-scavenging packaging material of the present invention can have a barrier layer between the paper layer and the oxygen-scavenging composite material or at a layer position.
そのバリア層は、 バリア性材料単独、 または、 バリア性材料を含む多層であ る。バリア性材料は、 アルミニウム箔、酸化珪素蒸着ポリエチレンフタレート、 エチレン一ビニルアルコール共重合体、 ポリアミド樹脂等である。 バリア性材 料を含む多層構造は、 ポリエチレンフィルム Zアルミニウム箔、 接着性ポリエ チレン Z酸化珪素蒸着ポリエチレンテレフ夕レートの 2軸延伸フィルム （Z接 着剤）、 ポリエチレンフィルム/接着剤/エチレン—ピエルアルコール共重合体 フィルム/接着剤、 ポリアミド樹脂フィルム/接着剤等である。 バリア層の厚 さは、 通常、 5〜2 5 mである。  The barrier layer is a barrier material alone or a multilayer containing a barrier material. The barrier material is aluminum foil, silicon oxide-deposited polyethylene phthalate, ethylene-vinyl alcohol copolymer, polyamide resin, or the like. The multilayer structure including barrier material is made of polyethylene film Z aluminum foil, adhesive polyethylene, silicon oxide vapor-deposited polyethylene terephthalate biaxially stretched film (Z adhesive), polyethylene film / adhesive / ethylene-pier alcohol Copolymer film / adhesive, polyamide resin film / adhesive, etc. The thickness of the barrier layer is usually between 5 and 25 m.
酸素捕集性複合材料層の内側に設ける接着層は、 例えば、 アクリル樹脂系接 着剤、 変性ポリオレフイン系接着剤、 エチレン—酢酸ビニル共重合体、 ポリア ミド系接着剤、 エポキシ樹脂系接着剤等である。 アクリル樹脂系接着剤は、 ァ クリル酸若しくはメタクリル酸又はそのアルキルエステルの重合体、 共重合体 等である。 変性ポリオレフイン系接着剤は、 ポリエチレン、 ポリプロピレン等 にアクリル酸、 メタクリル酸、 マレイン酸、 無水マレイン酸、 フマ一ル酸、 ィ タコン酸、 ナジック酸、 無水ナジック酸等の不飽和カルボン酸又はその無水物 を有機過酸化物の存在下、 グラフトさせて得た樹脂である。 この接着層は、 ポ リアミドマトリックス含有酸素捕集性複合材料層層の内側に設けられる。 特に その層に接して設けるのが望ましい。 この接着層の厚さは、 通常 5〜3 0 m である。 The adhesive layer provided inside the oxygen-scavenging composite material layer includes, for example, an acrylic resin-based adhesive, a modified polyolefin-based adhesive, an ethylene-vinyl acetate copolymer, a polyamide-based adhesive, and an epoxy resin-based adhesive. It is. The acrylic resin adhesive is a polymer or copolymer of acrylic acid or methacrylic acid or an alkyl ester thereof. Modified polyolefin adhesives include polyethylene, polypropylene, and other unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, nadic acid, and nadic acid anhydride or anhydrides thereof. Is a resin obtained by grafting in the presence of an organic peroxide. The adhesive layer is provided inside the layer of the oxygen-absorbing composite material containing the polyamide matrix. In particular, it is desirable to provide it in contact with the layer. The thickness of this adhesive layer is usually 5 ~ 30m It is.
上記紙層の外側に設けられる熱可塑性樹脂層は、 1層に限らず、 2層以上設 けることができる。 その際の熱可塑性樹脂はポリオレフインが好ましい。 その 層が包装材の最外層の場合は、特にポリエチレンが好ましい。ポリエチレンは、 高密度ポリエチレン、 中密度ポリエチレン、 低密度ポリエチレン、 直鎖状低密 度ポリエチレン、 mL L D P E等、 好ましくは、 低密度ポリエチレン及び直鎖 状低密度ポリエチレンである。  The number of thermoplastic resin layers provided outside the paper layer is not limited to one, and two or more thermoplastic resin layers can be provided. In that case, the thermoplastic resin is preferably polyolefin. When that layer is the outermost layer of the packaging material, polyethylene is particularly preferred. The polyethylene is a high-density polyethylene, a medium-density polyethylene, a low-density polyethylene, a linear low-density polyethylene, a mLLDPE or the like, and preferably a low-density polyethylene and a linear low-density polyethylene.
紙層の内側に設けられる熱可塑性樹脂層は、 1層に限らず、 2層以上設ける ことができる。 その際の熱可塑性樹脂はポリオレフインが好ましい。 その層が 包装材の最内層の場合は、 特にポリエチレンが好ましい。 ポリエチレンは、 特 に直鎖状低密度ポリェチレン及び m L L D P Eが好ましい。 これら熱可塑性樹 脂層の厚さは、 通常 5〜2 0 0 mである。  The number of thermoplastic resin layers provided inside the paper layer is not limited to one, and two or more thermoplastic resin layers can be provided. In that case, the thermoplastic resin is preferably polyolefin. When that layer is the innermost layer of the packaging material, polyethylene is particularly preferred. Polyethylene is particularly preferably linear low-density polyethylene and mLLDP. The thickness of these thermoplastic resin layers is usually 5 to 200 m.
本発明の包装材は、 積層物からなる。 積層方法は、 接着剤を用いて各層を貼 り合わせる方法、 熱溶融が可能な層を熱溶融してそれと接する層と貼り合わせ る方法、 同時押し出し成形が可能な層を同時押し出し成形して積層する方法、 それらを組み合わせる方法等である。  The packaging material of the present invention comprises a laminate. Laminating methods include laminating each layer using an adhesive, laminating a layer that can be melted by heat, and laminating with a layer that is in contact with it, and laminating layers that can be simultaneously extruded by simultaneous extrusion. And how to combine them.
この発明による酸素捕集性包装材料の製造法の好ましい態様において、 バリ ァ樹脂のキヤリァに、 酸素捕集剤をプレンドして酸素捕集性分散樹脂を形成し、 ポリアミドのマトリックス用樹脂中に、 酸素捕集性分散樹脂を分散して、 酸素 捕集性複合材料を形成し、 酸素捕集性複合材料を押出しラミネートで紙層に直 接積層して、 紙積層体からなる包装材料を形成する。  In a preferred embodiment of the method for producing an oxygen-scavenging packaging material according to the present invention, an oxygen-scavenging dispersing resin is formed by blending an oxygen-scavenging agent into a barrier resin carrier, and the polyamide matrix resin includes: Disperse the oxygen-scavenging dispersion resin to form an oxygen-scavenging composite material, and extrude and laminate the oxygen-scavenging composite material directly on the paper layer to form a packaging material consisting of a paper laminate .
本発明の包装材からは、 ブリック形状、 ゲ一ブルトップ形状、 立方体、 円筒 形、 平行 6角柱体、 胴部中央部が平行 8角柱で頂部及び底部が 4角形の形状、 パゥチ形状等の容器を形成することができる。 Brick shape, gable top shape, cube, cylinder The container can be shaped like a parallelepiped, a parallel hexagonal prism, a parallel octagonal prism at the center of the body, a quadrilateral at the top and bottom, and a patch.
別の好ましい態様において、 酸素捕集性複合材料を用いて、 射出成形で、 ス パゥト、 栓、 ふた、 飲み口、 注出栓、 注ぎ口などの開封装置を成形して、 包装 材料を形成する。 実施例  In another preferred embodiment, a packaging material is formed by injection molding using an oxygen-scavenging composite material to form an opening device such as a spat, a plug, a lid, a drinking spout, a spout, and a spout. . Example
以下、 本発明を実施例により、 詳細に説明する。 Hereinafter, the present invention will be described in detail with reference to Examples.
(実施例 1一 1)  (Example 11)
亜硫酸ナトリウム （Na2 S03) を 15質量％含有するエチレンービニルァ ルコール共重合体 70質量部とポリプロピレンに無水マレイン酸をグラフトさ せた変性ポリオレフィン (接着性樹脂） 30質量部とを溶融混練し、 酸素捕集性 分散樹脂のマスターバッチを調製した。 このマス夕一バッチ 10質量部とメル トフ口一レート 20 gZ分のポリプロピレン 90質量部をブンレンドした後、 押出して、 マトリックス用樹脂中に酸素捕集性分散樹脂が分散した酸素捕集性 複合材料ペレツトを成形した。 Sodium sulfite (Na 2 S0 3) which contained 15 wt% ethylene-vinyl § alcohol copolymer 70 parts by weight of polypropylene modified polyolefin obtained by grafting maleic anhydride melted and (adhesive resin) 30 parts by kneading Then, a master batch of the oxygen-scavenging dispersing resin was prepared. After blending 10 parts by mass of this mass and 90 parts by mass of polypropylene equivalent to 20 gZ of melt per mouth, the mixture is extruded, and the oxygen-scavenging composite material in which the oxygen-scavenging dispersion resin is dispersed in the matrix resin A pellet was formed.
密度 0. 924 gZcm3 の低密度ポリエチレン （LDPE)、 紙 （坪量 25 0 g/m2)、 メルトフローレート 20 gZ分のポリプロピレン (PP)、 ェチレ ン—ビニルアルコール共重合体 （EVOH)、 ポリプロピレンに無水マレイン酸 をグラフ卜させた変性ポリオレフィン系接着剤、 上記で得たペレツ卜及び密度 0. 910 g/cm3の線状低密度ポリエチレン （LLDPE) を準備した。 押 出しラミネート及び共押出しによって、 LDPE (厚さ 15 m) (最外層） / 紙/ PP (厚さ 1 0 m) /EVOH (厚さ 10 m) /変性ポリオレフイン 系接着剤 （厚さ 10) Z上記で得たペレツトの酸素捕集性複合材料 （厚さ 1 5 lim) ZLLDPE (厚さ 25 m) (最内層） の積層構成を有する包装材料を 製造した。 Low-density polyethylene (LDPE) with a density of 0.924 gZcm 3 , paper (250 g / m 2 basis weight), polypropylene (PP) with a melt flow rate of 20 gZ, ethylene-vinyl alcohol copolymer (EVOH), A modified polyolefin-based adhesive obtained by grafting maleic anhydride on polypropylene, the pellet obtained above, and a linear low-density polyethylene (LLDPE) having a density of 0.910 g / cm 3 were prepared. Push LDPE (thickness 15 m) (outermost layer) / paper / PP (thickness 10 m) / EVOH (thickness 10 m) / modified polyolefin adhesive (thickness 10) A packaging material having a laminated configuration of the oxygen-scavenging composite material (thickness: 15 lim) ZLLDPE (thickness: 25 m) (innermost layer) of the pellet obtained in step (1) was manufactured.
上記で製造した包装材料を用い、 200m 1入りのプリック型液体食品容器 を作製し、 これにビタミン C溶液を充填した。 充填した直後とそれを 23°Cで 4週間保管した容器中のビタミン Cの濃度変化を観察した結果、 ビタミン Cの 濃度は、 最初の濃度の 95%であった。  Using the packaging material produced above, a 200ml 1-prick type liquid food container was prepared and filled with a vitamin C solution. As a result of observing the change in vitamin C concentration immediately after filling and in the container where it was stored at 23 ° C for 4 weeks, the vitamin C concentration was 95% of the initial concentration.
(実施例 1一 2)  (Examples 1-2)
亜硫酸ナトリウムを 1 5質量％含有するエチレン一ビニルアルコール共重合 体の代りに、 亜硫酸ナトリウムを 1 5質量％含有するポリエチレンテレフタレ —トを用いる以外は、 実施例 1一 1と同様にしてペレットを成形した。 実施例 1一 1で用いたペレットの代りに、 上記で得たペレットを用いた以外は、 実施 例 1一 1と同様にして包装材料を製造した。 この包装材料を用い、 実施例 1一 1と同様にして、 容器の作製とビタミン C溶液の充填を行い、 容器中のビタミ ン Cの濃度変化を観察した結果、 ビタミン Cの濃度は、 最初の濃度の 95%で めった。  The pellets were prepared in the same manner as in Example 11 except that polyethylene terephthalate containing 15% by mass of sodium sulfite was used instead of the ethylene-vinyl alcohol copolymer containing 15% by mass of sodium sulfite. Molded. A packaging material was produced in the same manner as in Example 11-11, except that the pellets obtained above were used instead of the pellets used in Example 11-11. Using this packaging material, a container was prepared and filled with a vitamin C solution in the same manner as in Example 1-1, and the change in the concentration of vitamin C in the container was observed. At 95% of the concentration.
(比較例 1一 1)  (Comparative Example 1-1)
接着性樹脂としての変性ポリオレフィンを用いずに実施例 1一 1と同様にし てペレツトを成形したが、 亜硫酸ナトリウムを含有するエチレン—ビニルアル コール共重合体とマトリックス樹脂であるポリプロピレンとは均質に混練する ことができず、 得られたペレットは、 包装材料を製造する際の材料として用い ることができなかった。 A pellet was formed in the same manner as in Example 11 except that the modified polyolefin was not used as the adhesive resin, but the ethylene-vinyl alcohol copolymer containing sodium sulfite and the matrix resin, polypropylene, were uniformly kneaded. As a result, the obtained pellets could not be used as a material for producing a packaging material.
(比較例 1— 2)  (Comparative Example 1-2)
実施例 1一 1で用いたべレットの代りに、 マトリックス用樹脂中に酸素捕集 性樹脂が均一に混合して得た酸素捕集性ペレットを用いた以外は、 実施例 1一 1と同様にして包装材料を製造した。 この包装材料を用い、 実施例 1—1と同 様にして、 容器の作製とビタミン C溶液の充填を行い、 容器中のビタミン Cの 濃度変化を観察した結果、 ビタミン Cの濃度は、最初の濃度の 90%であった。 しかも、 この包装材料は、 実施例 1一 1で得られた包装材料に比べて、 強度が 劣っている。  Example 11 In the same manner as in Example 11 except that the pellet used in Example 11 was replaced with an oxygen-trapping pellet obtained by uniformly mixing the oxygen-trapping resin in the matrix resin. To produce packaging materials. Using this packaging material, a container was prepared and a vitamin C solution was filled in the same manner as in Example 1-1, and the change in the concentration of vitamin C in the container was observed. It was 90% of the concentration. Moreover, this packaging material is inferior in strength to the packaging material obtained in Example 11-11.
(実施例 2— 1)  (Example 2-1)
密度 0. 924 g/cm3 の低密度ポリエチレン （LDPE) フィルム （厚 さ 15 m) (最外層） Z紙 （坪量 250 gZm2 ) ノ 亜硫酸ナトリウムLow-density polyethylene (LDPE) film with a density of 0.924 g / cm 3 (thickness 15 m) (outermost layer) Z paper (basis weight 250 gZm 2 )
(Na2 S03 ) を 15質量％含有するエチレン一ビエルアルコール共重合体 を 10質量％及びポリアミド MXD6を 90質量％含有する酸素捕集性複合材 料からなるフィルム （15 m) ノポリプロピレンに無水マレイン酸をグラフ トさせた変性ポリオレフイン系接着剤 （厚さ 10 m) Z密度 0. 915 g/ cm3 の線状低密度ポリエチレン （LLDPE) フィルム （厚さ 25 /m) (最 内層） の積層構成を有する包装材料を製造した。 A film composed of an oxygen-scavenging composite material containing 10% by mass of an ethylene-bier alcohol copolymer containing 15% by mass of (Na2S03) and 90% by mass of polyamide MXD6 (15 m) the graph Sorted not modified polyolefin-based adhesive laminate construction of (thickness 10 m) Z density 0. 915 g / cm 3 of linear low density polyethylene (LLDPE) film (thickness 25 / m) (innermost layer) A packaging material was produced.
上記で製造した包装材料を用い、 200m 1入りのプリック型液体食品容器 を作製し、 これにビタミン C溶液を充填した。 充填した直後とそれを 23°Cで 4週間保管した容器中のビタミン Cの濃度変化を観察した結果、 ビタミン Cの 濃度は、 最初の濃度の 90%であった。 Using the packaging material produced above, a 200ml 1-prick type liquid food container was prepared and filled with a vitamin C solution. Immediately after filling and at 23 ° C As a result of observing changes in the concentration of vitamin C in the container stored for 4 weeks, the concentration of vitamin C was 90% of the initial concentration.
(実施例 2— 2)  (Example 2-2)
実施例 2— 1で用いた LDPEフィルム （最外層） ノ実施例 2— 1で用いた 紙 Z実施例 2— 1で用いた組成物にポリアミド 6を 1 0質量％含有させた酸素 捕集性複合材料からなるフィルム （15 zm) ノ実施例 2— 1で用いた変性ポ リオレフイン系接着剤/実施例 1で用いた LLDPEフィルム （最内層） の積 層からなる包装材料を製造した。 この包装材料を用い、 実施例 2— 1と同様に して、 容器の作製とビタミン C溶液の充填を行い、 容器中のビタミン Cの濃度 変化を観察した結果、 ビタミン Cの濃度は、 最初の濃度の 90%であった。  LDPE film used in Example 2-1 (outermost layer) No. Paper used in Example 2-1 Z Oxygen-scavenging property of the composition used in Example 2-1 containing 10% by mass of polyamide 6 A film made of a composite material (15 zm) A packaging material comprising a laminate of the modified polyolefin adhesive used in Example 2-1 / the LLDPE film (innermost layer) used in Example 1 was manufactured. Using this packaging material, a container was prepared and a vitamin C solution was filled in the same manner as in Example 2-1, and the change in the concentration of vitamin C in the container was observed. It was 90% of the concentration.
(実施例 2— 3)  (Example 2-3)
実施例 2— 1で用いた LDPEフィルム （最外層） ノ実施例 2— 1で用いた 紙ノ亜硫酸ナトリウムを 10質量％含有するポリエチレンテレフタレートを 2 0質量％及びポリアミド 6を 80質量％含有する組成物からなるフィルム （1 5 m) /実施例 2— 1で用いた変性ポリオレフイン系接着剤 Z密度： 0. 9 1 5 g/cm3、 MI ： 14 g/10分の mL L D P Eフィルム (20 rn) (最 内層） の積層からなる包装材料を製造した。 この包装材料を用い、 実施例 2— 1と同様にして、 容器の作製とビタミン C溶液の充填を行い、 容器中のビタミ ン Cの濃度変化を観察した結果、 ビタミン Cの濃度は、 最初の濃度の 92%で めった。  LDPE film used in Example 2-1 (outermost layer) No. Composition containing 20% by mass of polyethylene terephthalate containing 10% by mass of sodium paper bisulfite and 80% by mass of polyamide 6 used in Example 2-1 Film (15 m) / modified polyolefin adhesive used in Example 2-1 Z density: 0.915 g / cm3, MI: 14 g / 10 min mL LDPE film (20 rn) (Innermost layer) packaging material was manufactured. Using this packaging material, a container was prepared and a vitamin C solution was filled in the same manner as in Example 2-1, and the change in the concentration of vitamin C in the container was observed. The concentration was 92%.
(実施例 2— 4)  (Example 2-4)
実施例 2— 1で用いた LDPEフィルム （最外層） Z実施例 2— 1で用いた紙 Z実施例 2— 3で用いた組成物にポリアミド MXD6を 20質量％含有させた 組成物からなるフィルム （15 ^m) Z実施例 2— 1で用いた変性ポリオレフ イン系接着剤/実施例 3で用いた mLLDPEフィルム （最内層） の積層から なる包装材料を製造した。 この包装材料を用い、 実施例 2— 1と同様にして、 容器の作製とビタミン C溶液の充填を行い、 容器中のビタミン Cの濃度変化を 観察した結果、 ビタミン Cの濃度は、 最初の濃度の 93%であった。 LDPE film used in Example 2-1 (outermost layer) Z Paper used in Example 2-1 Z Film consisting of a composition containing 20% by mass of polyamide MXD6 in the composition used in Example 2-3 (15 ^ m) Z Modified polyolefin-based adhesive used in Example 2-1 / Example 3 A packaging material consisting of a laminate of the mLLDPE film (innermost layer) used in Step 1 was manufactured. Using this packaging material, a container was prepared and a vitamin C solution was filled in the same manner as in Example 2-1, and the change in the concentration of vitamin C in the container was observed. Was 93%.
(比較例 2— 1)  (Comparative Example 2-1)
実施例 2— 1で用いた LDPEフィルム （最外層） 実施例 2— 1で用いた 紙 Z亜硫酸ナトリウムを 15質量％含有するェチレン—ビエルアルコール共重 合体からなるフィルム （15 xm) Z実施例 2— 1で用いた LLDPEフィル ム （最内層） の積層からなる包装材料を製造した。 この包装材料を用い、 実施 例 2— 1と同様にして、 容器の作製とビタミン C溶液の充填を行い、 容器中の ビタミン Cの濃度変化を観察した結果、 ビタミン Cの濃度は、 最初の濃度の 80 %であった。  LDPE film used in Example 2-1 (outermost layer) Paper used in Example 2-1 Film made of ethylene-Biel alcohol copolymer containing 15% by mass of sodium sulfite (15 xm) Z Example 2 — A packaging material consisting of the LLDPE film (innermost layer) used in 1 was manufactured. Using this packaging material, a container was prepared and a vitamin C solution was filled in the same manner as in Example 2-1, and the change in the concentration of vitamin C in the container was observed. 80%.
(比較例 2— 2)  (Comparative Example 2-2)
実施例 2— 1で用いた LDPEフィルム （最外層） /実施例 2— 1で用いた 紙/ポリエチレンテレフタレ一卜からなるフィルム （15 m) / 実施例 2— 3で用いた mLLDPEフィルム （最内層） の積層からなる包装材料を製 造した。 この包装材料を用い、 実施例 2— 1と同様にして、 容器の作製とビ夕 ミン C溶液の充填を行い、 容器中のビタミン Cの濃度変化を観察した結果、 ビ 夕ミン Cの濃度は、 最初の濃度の 70%であった。  LDPE film used in Example 2-1 (outermost layer) / paper used in Example 2-1 / film consisting of polyethylene terephthalate (15 m) / mLLDPE film used in Example 2-3 (most An inner layer) was manufactured as a packaging material. Using this packaging material, a container was prepared and filled with Vimin C solution in the same manner as in Example 2-1, and the change in vitamin C concentration in the container was observed. The initial concentration was 70%.
上記の結果から明らかのように、 実施例の包装材料を用いて成形した容器は、 比較例の包装材料を用いて成形した容器に比べて酸素バリァ性に優れ、 包装材 料の強度が改善されていることが判る。 利点 As is clear from the above results, the container molded using the packaging material of the example is It can be seen that the oxygen barrier property is superior to the container molded using the packaging material of the comparative example, and the strength of the packaging material is improved. advantage
上記実施例から具体化され、 明らかなように、 本発明によって、 次のような 効果を奏する。  As embodied and evident from the above embodiment, the present invention has the following effects.
本発明の包装材料を用いて成形した容器は、 実質紙とポリオレフィンの積層 体からなるにも関わらず、 酸素バリァ性に優れている。  The container molded using the packaging material of the present invention has excellent oxygen barrier properties, despite being substantially composed of a laminate of paper and polyolefin.
本発明の包装材料を用いて成形した容器は、 酸素バリア層が薄くても酸素バ リア性に優れており、 酸素透過による内容物の品質低下を防止することができ る。  The container molded using the packaging material of the present invention has excellent oxygen barrier properties even when the oxygen barrier layer is thin, and can prevent the quality of contents from being deteriorated due to oxygen permeation.
酸素バリア層を薄くすることができるために、 包装容器を軽量にすることが できる。  Since the oxygen barrier layer can be made thin, the weight of the packaging container can be reduced.
本発明の包装材料は、 機械的強度に優れている。 産業上の利用可能性  The packaging material of the present invention has excellent mechanical strength. Industrial applicability
この発明の酸素捕集性包装材料の製造法及び酸素捕集性包装材料は、 牛乳、 ジ ユース、 清酒、 焼酎、 ミネラルウォーター及びその他飲料の液体食品を包装す るために用いられる。 The method for producing an oxygen-scavenging packaging material and the oxygen-scavenging packaging material of the present invention are used for packaging liquid foods such as milk, distillery, sake, shochu, mineral water and other beverages.

Claims

請求の範囲  The scope of the claims
エチレン一ビニルアルコール共重合体若 )  Ethylene-vinyl alcohol copolymer)
ートのバリア樹脂のキャリアに、 酸素捕集剤をブ 酸素捕集性分散樹 脂を形成し、 An oxygen scavenger is added to the carrier of the barrier resin to form an oxygen-scavenging dispersed resin.
ポリオレフイン又はポリアミドのマトリックス用樹脂中に、 前記酸素捕集性分 散樹脂を分散して、 酸素捕集性複合材料を形成し、 Dispersing the oxygen-scavenging dispersing resin in a polyolefin or polyamide matrix resin to form an oxygen-scavenging composite material,
前記酸素捕集性複合材料を用いて、 包装材料を形成する Forming a packaging material using the oxygen-scavenging composite material
ことを含む酸素捕集性包装材料の製造法。 And a method for producing an oxygen-scavenging packaging material.
2 . エチレン一ビエルアルコール共重合体若しくはポリエチレンテレフタレ ートのバリァ樹脂のキヤリアに、 ポリオレフィンと相溶性を有する接着性樹脂 及び酸素捕集剤をプレンドして酸素捕集性分散樹脂を形成し、  2. An oxygen-scavenging dispersed resin is formed by blending an adhesive resin and an oxygen-scavenging agent compatible with polyolefin on a carrier of a barrier resin of ethylene-biel alcohol copolymer or polyethylene terephthalate,
ポリオレフィンのマトリックス用樹脂中に、 前記酸素捕集性分散樹脂を分散し て、 酸素捕集性複合材料を形成し、 Dispersing the oxygen-scavenging dispersion resin in a polyolefin matrix resin to form an oxygen-scavenging composite material;
前記酸素捕集性複合材料を用いて、 包装材料を形成する Forming a packaging material using the oxygen-scavenging composite material
請求の範囲第 1項による製造法。 A method according to claim 1.
3 . エチレン一ビニルアルコール共重合体若 i  3. Ethylene-vinyl alcohol copolymer i
ートのバリア樹脂のキャリアに、 酸素捕集剤を 酸素捕集性分散樹 脂を形成し、 An oxygen scavenger is formed on the carrier of the barrier resin to form an oxygen-scavenging dispersed resin.
ポリアミドのマトリックス用樹脂中に、 前記酸素捕集性分散樹脂を分散して、 酸素捕集性複合材料を形成し、 Dispersing the oxygen-scavenging dispersion resin in a polyamide matrix resin to form an oxygen-scavenging composite material,
前記酸素捕集性複合材料を押出しラミネートで紙層に直接積層して、 紙積層体 からなる包装材料を形成する 請求の範囲第 1項による製造法。 The oxygen-scavenging composite material is directly laminated on a paper layer by extrusion lamination to form a packaging material composed of a paper laminate. A method according to claim 1.
4. 前記酸素捕集性複合材料を用いて、 射出成形で開封装置を成形して、 包 装材料を形成する  4. Using the oxygen-scavenging composite material to form an opening device by injection molding to form a packaging material
請求の範囲第 2項による製造法。 A manufacturing method according to claim 2.
5 . 紙層及びその両側に熱可塑性樹脂層を有する積層物から形成される包装 材において、 該紙層の内側に、 酸素捕集剤と、 エチレン—ビニルアルコール共 重合体若しくはポリエチレンテレフ夕レートと接着性樹脂とからなる酸素捕集 性分散樹脂粒がポリオレフィンのマトリックス中に分散された酸素捕集性複合 材料層を有する酸素捕集性包装材料。 5. A packaging material formed from a laminate having a paper layer and a thermoplastic resin layer on both sides thereof, wherein an oxygen scavenger, an ethylene-vinyl alcohol copolymer or polyethylene terephthalate is provided inside the paper layer. An oxygen-scavenging packaging material having an oxygen-scavenging composite material layer in which oxygen-scavenging dispersed resin particles composed of an adhesive resin are dispersed in a polyolefin matrix.
6 . 上記紙層と上記酸素捕集性複合材料層の間に酸素パリア層を有する、 請 求の範囲第 5項の酸素捕集性包装材料。 6. The oxygen-scavenging packaging material according to claim 5, having an oxygen barrier layer between said paper layer and said oxygen-scavenging composite material layer.
7 . 紙層及びその両側に熱可塑性樹脂層を有する積層物から形成される包装 材において、 該紙層の内側に、 酸素捕集剤とエチレン一ビニルアルコール共重 合体若しくはポリエチレンテレフタレートとからなる酸素捕集性分散樹脂粒が ポリアミドのマトリックス中に分散されている酸素捕集性複合材料層を有する 酸素捕集性包装材料。  7. A packaging material formed of a laminate having a paper layer and a thermoplastic resin layer on both sides thereof, wherein oxygen formed of an oxygen scavenger and an ethylene-vinyl alcohol copolymer or polyethylene terephthalate is provided inside the paper layer. An oxygen-scavenging packaging material having an oxygen-scavenging composite material layer in which scavenging dispersed resin particles are dispersed in a polyamide matrix.
8 . 上記酸素捕集剤は亜硫酸塩である、 請求の範囲第 7項の酸素捕集性包装 材料。  8. The oxygen-scavenging packaging material according to claim 7, wherein the oxygen-scavenging agent is a sulfite.
PCT/JP2002/009322 2001-09-18 2002-09-12 Method for producing oxygen-capturing packaging material and oxygen-capturing packaging material WO2003025048A1 (en)

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