JP2008081525A - Resin composition, coextruded multilayer barrier sealant film, and packaging material, packaging bag and packaged product produced by using the film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin composition effective for preventing the intrusion of oxygen, water vapor, etc., from outside through a packaging material and suitable for sufficiently capturing oxygen existing in a packaging container or generated in the packaging container, a coextruded multilayer barrier sealant film containing a layer composed of the resin composition, and a packaging material, packaging bag and packaged product produced by using the film. <P>SOLUTION: The resin composition contains an ethylene-vinyl alcohol copolymer developing passive barrier effect, an oxidizable resin having active barrier effect and a transition metal catalyst. The layer composed of the resin composition develops drastic barrier effect having all functions in a single layer and keeps high oxygen barrier effect even in a high-humidity environment. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a resin composition, a barrier coextrusion multilayer sealant film, a packaging material and a packaging product using the film, and more particularly, in a packaging product formed by filling the contents and sealing the mouth. Or a resin composition suitable for forming a barrier oxygen absorbing layer that captures oxygen generated in a packaged product, blocks oxygen from entering from the outside, and has an oxygen absorbing function, and the resin composition. The present invention relates to a barrier co-extruded multilayer sealant film including a layer, a packaging material using the film, a packaging bag comprising the packaging material, and a packaging product.

Conventionally, materials such as plastic films, paper base materials, metal foils or vapor-deposited films thereof are used, and these materials are combined and laminated to produce packaging materials having various layer configurations. After that, for example, various foods and drinks, chemical products such as liquid detergents, cosmetics, pharmaceuticals, miscellaneous goods, industrial members, and other various articles are filled in the packaging bag. Various forms of packaged products with sealed mouths have been developed and proposed.
Thus, the above-mentioned packaged products are required to have excellent heat sealability and sufficiently satisfy the sealability from the demands for protecting the quality of contents and extending the storage period.
Further, depending on the contents filled in the packaging bag, for example, it is required to have a gas barrier property that prevents permeation of oxygen gas, water vapor, or the like, or to have an aroma retaining property that protects the odor of the content. .
Further, it may be required to have a light blocking property or a light blocking property that blocks sunlight, fluorescent light, and the like.
Therefore, in recent years, packaging materials having various layer configurations using various materials, materials, and the like have been developed, and various forms of packaging bags, packaging products, and the like have been developed and proposed.
Moreover, in the barrier film produced by the coextrusion film forming machine, a barrier film such as an ethylene-vinyl alcohol copolymer is used for the intermediate layer, and the effect of protecting the contents is exhibited from the barrier property against oxygen. (For example, refer to Patent Document 1).
Further, for example, a polymer main chain suitable as a container for preventing oxidation of the contents in the container by removing oxygen from the container and preventing oxygen from entering the container from outside the container. In addition, a multilayer film, a packaging container, and the like including a layer made of an oxygen scavenging composition containing a cyclic olefin pendant group, a linking group that binds the olefin pendant group to the main chain, and a transition metal catalyst have also been proposed (see, for example, Patent Document 2). ).
JP 61-162539 A Special table 2003-521552 gazette

However, the EVOH barrier described in Patent Document 1 only prevents the permeation of oxygen and only functions as a passive barrier. Oxidation of the package contents due to oxygen remaining in the packaging bag cannot be prevented. In addition, the barrier property decreases rapidly under high humidity.
Moreover, if the layer made of the oxygen scavenging composition described in Patent Document 2 is completely exposed to oxygen, the layer will deteriorate quickly and it will be difficult to maintain the oxygen absorption function for a long time.
Moreover, when the packaging material containing the layer which consists of an oxygen scavenging composition of patent document 2 uses the base film containing a biaxial stretching polyester-type resin film as the base film, a biaxial stretching polyester film is Because it absorbs near-ultraviolet light from 350 nm, the packaging material is irradiated with ultraviolet light, through a transition metal catalyst, for example, a radical is attacked to the unsaturated bond part of the cyclohexene ring as an oxidizing resin, and from the chain reaction. There is a problem that it is difficult to sufficiently exhibit an oxygen scavenging function of binding to oxygen and absorbing oxygen.
In addition, the packaging product is provided with a base printing layer on the base film of the packaging material for displaying, explaining, etc. the packaging contents, and a printed pattern layer composed of, for example, letters, designs, symbols, etc. is provided thereon. Provided. However, by providing an underprint layer, the transmission of ultraviolet light is inhibited, radicals are attacked to the unsaturated bond part of the cyclohexene ring, combined with oxygen from the chain reaction, and has an oxygen scavenging function of absorbing oxygen. There is a problem that it is not played sufficiently.
The problems to be solved by the present invention are to prevent oxygen, water vapor, etc. from entering from the outside through the packaging material, and to sufficiently capture oxygen existing in the packaging container or oxygen generated in the packaging container. And a barrier co-extruded multilayer sealant film comprising a layer comprising the resin composition, a packaging material, a packaging bag and a packaged product using the film.

  The invention described in claim 1 solves the above-mentioned problems relating to the resin composition, and is summarized in a resin composition containing an ethylene-vinyl alcohol copolymer, an oxidizing resin, and a transition metal catalyst.

  The resin composition according to the present invention includes an ethylene-vinyl alcohol copolymer that exhibits passive barrier properties (passive barrier properties) and an oxidizing resin that exhibits active barrier properties (active barrier properties). By the composition, it is possible to form a barrier layer having a dramatic barrier property in which all functions are imparted to one layer.

  In the present invention, as the oxidizing resin, an ethylenically unsaturated hydrocarbon polymer, a main chain ethylenically unsaturated hydrocarbon, a polyether unit polymer, a copolymer of ethylene and cyclic alkylene, a copolymer of ethylene and distorted cyclic alkylene, a polyamide resin, Resins composed of one or two of acid-modified polybutadiene and hydroxyaldehyde can be applied.

  In the present invention, an ethylene / methyl acrylate / methyl cyclohexene-methyl acrylate copolymer, which is a copolymer of ethylene and cyclic alkylene, is particularly effective as the oxidizing resin.

  The above oxidizing resin continuously absorbs oxygen when radicals are generated by some energy such as ultraviolet light. However, in order to positively control, it is preferable to add a transition metal catalyst and a radical photopolymerization initiator. In that case, for example, cobalt 2-ethylhexanoate can be used as the transition metal catalyst. Further, as the radical photopolymerization initiator, for example, 1-hydroxy-hexyl-phenyl ketone can be used.

  Since the blending ratio of the thermoplastic ethylene-vinyl alcohol copolymer (EVOH) and the oxidizing resin is preferably EVOH as a matrix (sea), if EVOH is less than 50 parts by weight, passive barrier properties On the other hand, when EVOH exceeds 90 parts by weight, the amount of the oxidizing resin becomes 10 parts by weight or less, and the oxygen scavenging function is lowered. Therefore, both the passive barrier property of EVOH and the active barrier property of the oxidizing resin are reduced. In order to give physical properties, it is necessary to set EVOH to 50 to 90 parts by weight.

  EVOH is weak to water and its barrier property is drastically lowered under high humidity. However, by adding an oxidizing resin to EVOH, high oxygen barrier property is maintained even under high humidity.

  The ethylene molar concentration of EVOH is desirably 30 molar.

  In the present invention, the above-described resin composition is used and is a coextruded multilayer sealant film comprising at least five layers, wherein the first layer constituting the surface layer and the fifth layer constituting the back layer are composed of an olefin resin layer. The second layer and the fourth layer are made of an adhesive resin layer, and the third layer is made of a barrier oxygen absorbing layer made of an ethylene-vinyl alcohol copolymer, a resin composition containing the above resin composition and a transition metal catalyst. A barrier coextrusion multilayer sealant film can be produced.

  A packaging bag is formed using a packaging material formed by laminating the above-mentioned co-extruded multilayer sealant film on a base film, and the inside of the packaging bag is irradiated with ultraviolet light, and then the contents are filled in the packaging bag. The packaged product of the present invention can be manufactured by sealing the opening of the packaging bag.

In this packaged product, the barrier oxygen absorbing layer prevents oxygen from entering the outside of the packaging bag, and the ultraviolet light irradiated from the inside of the packaging bag is easily applied to the barrier oxygen absorbing layer. The transition metal catalyst contained in the barrier oxygen absorption layer acts on the oxidizing resin, and the oxidizing resin is contained in the oxygen contained in the head space in the packaging bag, or in the oxygen contained in the contents or in the contents. It has an oxygen collecting function of absorbing the generated oxygen. As a result, the quality, freshness, etc. of the contents can be maintained almost as it is or when it is packed and packaged. Even when performing storage, storage and display for a period of time, there is almost no change in the quality of the contents such as color and smell, and the quality and freshness of the contents can be maintained very well. Improve the shell To enable awe of the extension.
Further, the packaging product of the present invention is a barrier co-extruded multilayer sealant film in which the packaging bag is composed of a base film, and the first layer constituting the surface layer and the fifth layer constituting the back layer are olefinic resin layers. Since it is made of a packaging material containing, it is excellent in heat sealability at the time of bag making, and can be sufficiently satisfied with its sealability, has an easy-opening property, and further has excellent rigidity, strength, etc., and It has excellent shape retention and self-supporting properties, and further contributes to reducing the environmental burden by reducing the volume and volume of packaging materials.

The resin composition according to the present invention includes an ethylene-vinyl alcohol copolymer that exhibits passive barrier properties (passive barrier properties) and an oxidizing resin that exhibits active barrier properties (active barrier properties). By the composition, it is possible to form a barrier layer having a dramatic barrier property in which all functions are imparted to one layer. In particular, ethylene-vinyl alcohol copolymer is weak against water, and its barrier property is drastically lowered at high humidity. However, by blending an oxidizing resin with ethylene-vinyl alcohol copolymer, high oxygen concentration can be obtained even at high humidity. Barrier property is maintained.
Using this resin composition, a coextruded multilayer sealant film consisting of at least 5 layers, wherein the first layer constituting the surface layer and the fifth layer constituting the back layer are composed of an olefin-based resin layer, The fourth layer comprises an adhesive resin layer, and the third layer produces a barrier coextrusion multilayer sealant film comprising an ethylene-vinyl alcohol copolymer, the above resin composition, and a barrier oxygen absorbing layer containing a transition metal catalyst. be able to.
A packaging bag is formed using a packaging material formed by laminating the above-mentioned co-extruded multilayer sealant film on a base film, and the inside of the packaging bag is irradiated with ultraviolet light, and then the contents are filled in the packaging bag. The packaged product of the present invention can be manufactured by sealing the opening of the packaging bag.
In this packaged product, the barrier oxygen absorbing layer prevents oxygen from entering the outside of the packaging bag, and the ultraviolet light irradiated from the inside of the packaging bag is easily applied to the barrier oxygen absorbing layer. The transition metal catalyst contained in the barrier oxygen absorption layer acts on the oxidizing resin, and the oxidizing resin is contained in the oxygen contained in the head space in the packaging bag, or in the oxygen contained in the contents or in the contents. It has an oxygen collecting function of absorbing the generated oxygen. As a result, the quality, freshness, etc. of the contents can be maintained almost as it is or when it is packed and packaged. Even during storage, storage and display for a period of time, there is almost no change in the quality of the contents such as color and smell, and the quality and freshness of the contents can be maintained very well. Improvement, sheller To enable the extension of full.
In the packaging product of the present invention, the packaging bag includes a barrier co-extruded multilayer sealant film in which the first layer constituting the base film and the surface layer and the fifth layer constituting the back surface layer are composed of an olefin resin layer. It is made of packaging material, has excellent heat sealability at the time of bag making, can sufficiently satisfy its sealability, has easy-openability, and has excellent rigidity, strength, etc. and high retention. It is excellent in formability and independence, and further contributes to reducing the environmental burden by reducing the volume and volume of packaging materials.

  Hereinafter, the resin composition of the present invention, the barrier co-extruded multilayer sealant film, the packaging material using the film, the packaging bag, and the packaged product will be described in detail.

  The resin composition of the present invention comprises an ethylene-vinyl alcohol copolymer, an oxidizing resin, and a transition metal catalyst, and exhibits an passive barrier property (passive barrier property) and an ethylene-vinyl alcohol copolymer and an active barrier. Because it contains an oxidative resin that exhibits the property (active barrier property), this resin composition forms a barrier oxygen absorbing layer that exhibits a dramatic barrier property in which all functions are imparted to one layer. Is featured.

  In the present invention, for example, a thermoplastic ethylene-vinyl alcohol copolymer and a thermoplastic resin that can be easily kneaded as exemplified below can be used as the oxidizing resin. -A material close to the polarity of the vinyl alcohol copolymer is preferred.

(1) Ethylenically unsaturated hydrocarbon polymer: ethylenically unsaturated hydrocarbon polymer having a molecular weight of at least 1,000, atactic-1,2-polybutadiene, ethylene-propylene rubber (EDPM), polyoctenamer, 1,4-polybutadiene, Syndiotactic-1,2-polybutadiene, partially polymerized unsaturated fatty acids and esters, block or graft copolymers, hydrosite-like materials can be used.
The oxygen-absorbing anion is an ascorbate anion, a thiolate anion, a phenolate anion, or a mixture thereof, bisulfite, dithionic acid or a mixture thereof, and the carrier of these oxygen-absorbing polymers is polyethylene, polyolefin, ethylene / vinyl acetate copolymer, Uses a thermoplastic resin selected from the group consisting of butyl rubber, styrene / butadiene rubber, styrene / butadiene / styrene block copolymer, styrene / ethylene / butylene / styrene block copolymer, vinyl chloride homopolymer, vinyl chloride polymer and blends thereof. can do.

(2) Main chain ethylenically unsaturated hydrocarbon polymer: Number average molecular weight is in the range of 1,000 to 500,000, and contains carbon-carbon double bonds at a rate of 0.0001 eq / g or more. Thermoplastic resin of the formula.
Structural Formula —CH ₂ —CH—
│
C-R ₁
‖
R ₂ —C—R ₃
In the above structural formula, R ₁ , R ₂ and R ₃ are a methyl group or a hydrogen atom.

(3) Polyether unit polymer: A polymer containing 0.001 to 10 parts by weight of an oxidation catalyst with respect to 1000 parts by weight of a polymer having a polyether unit.
A multi-block copolymer in which a polyether unit has a polyalkylene glycol ether segment as a soft segment and at least one hard segment selected from the group consisting of polyester, polyamide, and polyurethane segments.
The polymer having a polyether unit may be a polymer containing an aromatic polyether unit, a polyalkylene ether unit (aliphatic polyether unit) or other generally known polyether unit as the polyether unit. A single polymer or a copolymer may be used.
Examples of the polymer having an aromatic polyether unit include poly (2,6-dimethyl-1,4-phenylene ether), polyphenylene ether represented by poly (2,6-diethyl-1,4-phenylene ether) and the like. Or a copolymer containing these.
Examples of the polymer having a polyalkylene ether unit include polymethylene glycol, polyethylene glycol, poly (1,2-propylene glycol), poly (1,3-propylene glycol), polytetramethylene glycol, and polymethylene (1,3-propylene. Glycol), polytetramethylene glycol, poly (1,2-butylene glycol), polyhexamethylene glycol, and other linear and branched aliphatic ethers, cyclohexanediol condensates and cyclohexanedimethanol condensates Examples thereof include a single polymer or a copolymer of alicyclic ethers.
Moreover, the random copolymer in these ether units is also contained in the polyether unit polymer of this invention.
A polymer having a polyalkylene ether unit is particularly preferably used. Among them, a multi-block copolymer having a polyalkylene ether unit can be preferably used.
These multiblock copolymers include polyester ether block copolymers (polyester thermoplastic elastomers) using aromatic polyesters and polyalkylene ethers, and multiblock copolymers using aliphatic polyesters and polyalkylene ethers. , Polyurethane-based thermoplastic elastomer having a hard segment composed of a polymer of a short-chain glycol and a diisocyanate and a soft segment composed of a polymer of a diisocyanate and a polyalkylene ether, a polyamide polyether copolymer using a polyamide and a polyalkylene ether Examples thereof include block copolymers (block copolyether amide, block copolyether ester amide, block copolyether ester amide, etc.).
When the segment copolymerized with the polyalkylene ether has crystallinity, these copolymers are generally elastic bodies.
Examples of the polyalkylene ether unit contained in these copolymers include alkylene ethers having a number average molecular weight of 400 to 6,000 (eg, polyethylene glycol, poly (1,2- and 1,3-propylene glycol), polytetramethylene. Glycol, polyhexamethylene glycol and the like) are preferred.
As the polyalkylene ether unit, those having a number average molecular weight of 400 to 6,000 are usually used, but those having 600 to 4,000 are preferred, and those having 1,000 to 3,000 are particularly preferred.
In this case, if the number average molecular weight is less than 400, sufficient oxygen absorption performance cannot be exhibited.
On the other hand, those having a number average molecular weight exceeding 6000 tend to cause phase separation in the system, and the physical properties of the polymer obtained by copolymerization or the like tend to be lowered.

(4) Copolymer of ethylene and cyclic alkylene: A typical example is an ethylene / methyl acrylate / methylcyclohexene-methyl acrylate copolymer.

(5) Copolymers of ethylene and strained cyclic alkylene: Cyclic alkylene includes cyclopentene, cyclobutene, cycloptene, cyclooctene, cyclononene nesexene.

(6) Polyamide resin: nylon 6-6, poly-m-xylylene adipamide, poly-m-xylylene sebacamide and poly-m-xylylene speramide as examples of homopolymers, m as examples of copolymers -Xylylene / p-xylylene adipamide copolymer, m-xylylene / p-xylylene piperamide copolymer, m-xylylene / p-xylylene azelamide copolymer.
Examples of aliphatic diamines include hexamethylene diamine, examples of cyclic diamines, piperazine, examples of aromatic diamines, p-bis (2-aminoethyl) benzene, examples of aromatic dicarboxylic acids include terephthal .
In addition, benzylamine, 3-methylbenzylamine, metaxylylenediamine, paraxylylenediamine, N, N′-dimethylmetaxylylenediamine, N, N, N ′, N′-tetramethylmetaxylylenediamine, N , N′-dimethylparaxylylenediamine, N, N, N ′, N′-tetramethyl parameter xylylenediamine, N, N′-diethylmetaxylylenediamine, N, N, N ′, N′-tetraethylmeta Xylylene, N, N′-diethylparaxylylenediamine, N, N, N ′, N′-tetraethylparaxylenediamine, 1,3,5-tris (aminomethyl) benzene, metaxylylenediamine or paraxylylene and organic Carboxylic acids, for example, monocarboxylic acids such as stearic acid, oleic acid, lauric acid, tall oil fatty acid and adipic acid, Salts and amides with dicarboxylic acids such as vasic acid and dimer acid, and metaxylylenediamine or paraxylylene widely used as epoxy resin curing agents, Mannich base, metaxylylenediamine or paraxylylene obtained by reaction of formaldehyde and phenol And adducts of acrylo with vinyl compounds such as tolyl and methyl methacrylate, adducts of metaxylylenediamine or paraxylylenediamine with epoxy compounds such as bisphenol A epoxy resin, bisphenol F epoxy resin, butyl glycidyl ether, etc. , And epoxy resin cured products cured with these curing agents, amino group-containing epoxy compounds represented by tetraglycidyl metaxylylene resin, metaxylylene diisocyanate, paraxylylene diene It can be exemplified polyurethane or the like which are derived from each with an isocyanate compound represented by the represented by the isocyanate in isocyanate, although it is also possible to use by blending plural kinds of these things.

(7) Acid-modified polybutadiene: acrylate or polyterpene produced by transesterification of polybutadiene, polyisoprene, styrene-butadiene block copolymer, poly (ethylene-methyl acrylate)

(8) Hydroxyaldehyde polymer: As glycol aldehyde and glyceraldehyde-aliphatic aldehyde, aliphatic unsaturated aldehydes such as formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, isobutyraldehyde, and aliphatic unsaturations such as acrylic aldehyde and fumaraldehyde Hydroxyaldehydes such as aldehyde, glycol aldehyde, glyceraldehyde, alkoxy aldehydes such as 2-methoxyethanal, oxoaldehydes such as 2-oxopropanal, aminoaldehydes such as 2-aminoethanal, 2-chloroethanal, etc. 1 to 2 or more kinds of aldehydes such as halogen-substituted aldehydes, cycloaliphatic aldehydes such as cyclohexanecarbaldehyde, aldehydes substituted with aromatic rings such as 2-phenylethanal, etc. It is possible to use mer.
Thus, in the present invention, the above-described oxidizing resin mainly has an unsaturated heavy bond unit in the main chain and the skeleton or in the side chain, and the heavy bond portion is linked to, for example, a radical chain. Oxygen absorption function is achieved by becoming saturated by interaction with oxygen due to reaction or the like.

  In the present invention, specific examples of the oxidizing resin include ethylene / methyl acrylate / cyclohexenyl methyl acrylate terpolymer, cyclohexenyl methyl acrylate / ethylene copolymer, cyclohexenyl methyl acrylate / styrene copolymer, and cyclohexenyl acrylate homopolymer. Alternatively, a methyl acrylate / cyclohexenyl methyl acrylate copolymer can be used.

Next, as the transition metal catalyst, for example, a transition metal selected from Sc, Ti, V, Cr, Mn, Co, Ni, Sn, Cu, or a mixture thereof can be used.
A composition in which the transition metal is selected from Co, Cu, or a mixture thereof, and a Group VIII metal component of the periodic table is preferable, but in addition, a Group I metal: a Group IV metal such as tin, titanium, zirconium, It is possible to use a group V metal such as vanadium, a group VI such as chromium, a group VI such as manganese, or a group VII metal such as manganese in the form of an inorganic acid salt, organic acid salt or complex salt of a transition metal. it can.
Examples of inorganic acid salts include halides such as chlorides, sulfur oxyacid salts such as sulfates, nitrogen oxyacid salts such as nitrates, phosphorus oxyacid salts such as phosphates, and silicates.
As the organic acid salt, a carboxylic acid, a sulfonic acid salt, a phosphonic acid salt, or the like can be used.
Specific examples of the transition metal catalyst include acetic acid, propionic acid, isopropionic acid, butanoic acid, isobutanoic acid, pentanoic acid, isopentanoic acid, hexanoic acid, heptanoic acid, isoheptanoic acid, octanoic acid, 2-ethylhexanoic acid, and nonane. Acid 3,5,5-trimethylhexanoic acid, decanoic acid, neodecanoic acid, undecanoic acid, lauric acid, myristic acid, palmitic acid, margaric acid, stearic acid, arachidic acid, lindelic acid, tuzuic acid, petroceric acid, Examples thereof include transition metal salts such as oleic acid, linoleic acid, linolenic acid, arachidonic acid, formic acid, oxalic acid, sulfamic acid, and naphthenic acid.
Specifically, it is preferable to use cobalt neodecanoate, cobalt 2-ethylhexanoate, cobalt oleate, and cobalt cobalt stearate as the transition metal catalyst as described above.
The transition metal catalyst as described above is one in which radical decomposition reaction is promoted mainly by applying energy such as ultraviolet light (UV) and oxidative absorption of the above-described oxidizing resin is started.

  In the present invention, regarding the blending ratio of the oxidizing resin and the transition metal catalyst, it is preferable to blend the transition metal catalyst in a ratio of 0.001 to 10 parts by weight with respect to 100 parts by weight of the oxidizing resin. If the transition metal catalyst is less than 0.001, it is not preferable because the catalytic action is low and the oxidation reaction does not proceed, and if it exceeds 10 parts by weight, the amount of catalyst is too large, and the oxidation reaction Although it progresses, it is not preferable because of the occurrence of other side reactions or an increase in cost.

Further, in the present invention, together with the thermoplastic ethylene-vinyl alcohol copolymer, a thermoplastic resin as a binder, for example, melted by heat, can be extruded from a T-die extruder such as an extruder, and further thermally welded to each other. It is possible to use a mixture of one or more thermoplastic resins.
Specifically, for example, low density polyethylene (LDPE), linear (linear) low density polyethylene (polymerized using a multisite catalyst, LLDPE), polymerization using a metallocene catalyst (single site catalyst). Ethylene-α / olefin polymer, medium density polyethylene (MDPE), high density polyethylene (HDPE), polypropylene resin, ethylene-vinyl acetate copolymer, ionomer resin, ethylene-acrylic acid copolymer, ethylene-acrylic acid Ethylene copolymers, ethylene-methacrylic acid copolymers, ethylene-methacrylic acid copolymers, ethylene-propylene copolymers, methylpentene polymers, polybutene polymers, olefinic resins such as polyethylene or polypropylene, acrylic acid, methacrylic acid , Maleic acid, maleic anhydride Use one or more thermoplastic resins such as acid-modified olefin resins modified with unsaturated carboxylic acids such as acid, fumaric acid, and itaconic acid, polyvinyl acetate resins, and poly (meth) acrylic resins. be able to.
Therefore, in the present invention, it is desirable to use a polymer ethylene-α / olefin copolymer as a main component of the vehicle using a metallocene catalyst (single site catalyst) as the thermoplastic resin.
The thermoplastic resin as described above mainly has a certain degree of affinity for the oxidizing resin.

  Since the blending ratio of the thermoplastic ethylene-vinyl alcohol copolymer (EVOH) and the oxidizing resin is preferably EVOH as a matrix (sea), if EVOH is less than 50 parts by weight, passive barrier properties On the other hand, when EVOH exceeds 90 parts by weight, the amount of the oxidizing resin becomes 10 parts by weight or less, and the oxygen scavenging function is lowered. Therefore, both the passive barrier property of EVOH and the active barrier property of the oxidizing resin are reduced. In order to give physical properties, it is necessary to set EVOH to 50 to 90 parts by weight.

  EVOH is weak to water and its barrier property is drastically lowered under high humidity. However, by adding an oxidizing resin to EVOH, high oxygen barrier property is maintained even under high humidity.

  The ethylene molar concentration of EVOH is desirably 30 molar.

It is preferable to further add a radical photopolymerization initiator to the resin composition of the present invention.
Examples of the radical photopolymerization initiator include benzoin such as benzoin, acetonaphthenequinone, benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether and alkyl ethers thereof; acetophenone, methyl ethyl ketone, valerophenone, hexaphenone, 2,2- Dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 1-hydroxychlorophenyl phenyl ketone, 2-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- ( Acetophenones such as methylthio) phenyl] -2-morpholino-propan-1-one; anthraquinones such as 2,4-methylanthraquinone and 2-amylanthraquinone; 2 Thioxanthones such as 4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, and 2,4-diisopropylthioxanthone; Ketals such as acetophenone dimethyl ketal and benzyldimethyl ketal; Benzophenones such as benzophenone or xanthones What is generally known as a photoinitiator can be used.
These radical photopolymerization initiators can be used in combination with one or more known and commonly used photopolymerization accelerators of benzoic acid type or tertiary amine type.
Moreover, at least 1 type selected from the alpha-ketocarbonyl compound, the amine compound, the transition metal and its compound, and the halogen compound can be used.
Examples of the α-ketocarbonyl compound include α-diketone, α-ketoaldehyde, α-ketocarboxylic acid, α-ketocarboxylic acid ester, specifically, diacetyl, 2,3-pentanedione, 2,3-hexanedione, Α such as benzyl, 4,4-methoxybenzyl, 4,4-oxybenzyl, 4,4-dichlorobenzyl, 4-nitrobenzyl, α-naphthyl, β-naphthyl, camphorquinone, 1,2-cyclohexanedione, etc. Α-Ketoaldehyde such as diketone, methylglyoxal, phenylglyoxal, pyruvic acid, benzoylformic acid, phenylpyruvic acid, methyl pyruvate, ethyl benzoylformate, methyl phenylpyruvate, butyl phenylpyruvate can be used.
Acetyltetralone, Linderic acid, Margaric acid, Stearic acid, Adipic acid, Diacetylbenzoin, Distearoylmethane, Dibivaloylmethane, and the like can also be used.
In the present invention, it is particularly desirable to use benzophenone, benzoin methyl ether or the like as the radical photopolymerization initiator.
The above-mentioned radical photopolymerization initiator mainly serves as an auxiliary function of a transition metal catalyst used as a catalyst, and serves to dramatically enhance the oxidation reaction of an oxidizing resin and to force it to proceed. is there.

Moreover, in this invention, when adding a radical type photoinitiator to a resin composition, it mix | blends a radical type polymerization initiator in the ratio of 0.001-10 weight part with respect to 100 weight part of oxidizing resins. Is preferred.
If the radical polymerization initiator is less than 0.001, its action is lowered, which is not preferable. If it exceeds 10 parts by weight, the oxidation reaction is promoted, but other side reactions occur, or the cost is increased. It is not preferable for reasons such as rising.

  Next, the barrier coextruded multilayer sealant film of the present invention will be described. FIG. 1 is a sectional view showing the layer structure of the barrier coextrusion multilayer sealant film of the present invention.

  The barrier co-extruded multilayer sealant film 1 of the present invention includes a first layer 2 constituting a surface layer made of an olefin resin, a fifth layer 6 constituting a back layer when made of an olefin resin, and a first layer made of an adhesive resin. A barrier oxygen-absorbing layer comprising a resin composition comprising two layers 3, a fourth layer 5 also comprising an adhesive resin, and the above-described thermoplastic ethylene-vinyl alcohol copolymer (EVOH), an oxidizing resin and a transition metal catalyst The third layer 4 made of is coextruded.

As the olefin resin constituting the first layer 2 and the fifth layer 6, for example, a low density polyethylene resin 1 that can be melted by heat, extruded from an extrusion die such as an extruder, and further thermally welded to each other. Two or more species can be used.
Specifically, for example, low density polyethylene (LDPE) by high pressure polymerization method, linear (linear) low density polyethylene (LLDPE) polymerized using multi-site Ziegler Natta catalyst, polymerization using single site metallocene catalyst Ethylene-α / olefin copolymer and the like can be used.
Furthermore, a functional polypropylene block copolymer can also be used as an olefin resin.
As the low-density polyethylene resin, ethylene or a homopolymer or copolymer of ethylene and α-olefin can be used. The density of the low density polyethylene resin is preferably 0.930 or less.

Next, the adhesive resin constituting the second layer 3 and the fourth layer 4 will be described. As this adhesive resin, it is possible to use one or more kinds of medium density to high density polyethylene resins which are melted by heat and can be extruded from an extrusion die of an extruder or the like, and further thermally welded to each other.
Specifically, a medium density polyethylene resin (MDPE) or a high density polyethylene resin (HDPE) having a density of 0.930 or more, preferably 0.935 to 0.970 can be used.
In addition, as the medium density to high density polyethylene resin, ethylene or a homopolymer or copolymer of ethylene and α-olefin can be used.

  For the first layer 2, the second layer 3, the fourth layer 5 and the fifth layer 6, for example, a polypropylene resin, an ethylene-vinyl acetate copolymer, an ionomer resin are used to modify the film quality and the like. , Ethylene-acrylic acid copolymer, ethylene-ethyl acrylate copolymer, ethylene-methacrylic acid copolymer, ethylene-methyl methacrylate copolymer, ethylene-propylene copolymer, methylpentene polymer, polybutene polymer, polyethylene Or an acid-modified polyolefin resin obtained by modifying a polyolefin resin such as polypropylene with an unsaturated carboxylic acid such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid or itaconic acid, polyvinyl acetate resin, poly (meth) Acrylic resin, polyvinyl chloride resin, thermoplastic polyester resin, thermoplastic poly One thermoplastic resin such as bromide resins or by addition of two or more kinds may be used.

The first layer 2 and the fifth layer 6 mainly exhibit heat sealing performance, in particular, can be heat sealed at low temperatures and exhibit stable sealing strength.
In addition, the second layer 3 and the fourth layer 5 have heat sealing performance similar to the first layer 2 and the fifth layer 6, and assist the heat sealing performance of the second layer 3 and the fourth layer 5, It has rigidity, strength, etc., and exhibits physical properties such as impact resistance, self-sustainability, and shape retention.
Further, the third layer 4 constituting the center layer prevents oxygen from entering the packaging bag from the outside of the packaging bag, and in the state where the contents are filled and packaged in the packaging bag, for example, It absorbs and captures oxygen present in the package, such as oxygen present in the head space or oxygen contained in the contents such as liquid, and oxygen generated from the contents.

The barrier oxygen-absorbing layer constituting the third layer 4 includes the thermoplastic ethylene-vinyl alcohol copolymer (EVOH), the oxidizing resin, and the transition metal catalyst as described above. It consists of a resin film of a resin composition containing a photopolymerization initiator and other additives. The oxygen absorption performance of the barrier oxygen absorbing layer 4 is 300 cc / m ² · day · atm after irradiation with 1000 mJ / cm ² of ultraviolet light when the thickness of the barrier oxygen absorbing layer 4 is about 10 μm or more. As described above, it preferably exhibits an oxygen absorption performance of 500 cc / m ² · day · atm or more.

A method for producing the barrier co-extruded multilayer sealant film 1 of the present invention will be described.
The olefin-based resin constituting the first layer 2 and the fifth layer 6 is the main component of the vehicle, and if necessary, for example, film forming, heat resistance, weather resistance, and mechanical properties when forming the film. 1 to 2 of various plastic compounding agents and additives for the purpose of improving dimensional stability, antioxidation, slipperiness, releasability, flame retardancy, anti-glare property, electrical properties, strength, etc. A seed or more is optionally added, and further, if necessary, a solvent, a diluent and the like are added and kneaded sufficiently to prepare a first resin composition for forming the barrier coextruded multilayer sealant film 1.
Further, the adhesive resin constituting the second layer 3 and the fourth layer 5 is a main component of the vehicle, and if necessary, for example, when forming the film, for example, film workability, heat resistance, weather resistance For the purpose of improving mechanical properties, dimensional stability, antioxidant properties, slipperiness, mold release properties, flame retardancy, anti-glare properties, electrical properties, strength, etc., various plastic compounding agents and additives, etc. 1st or 2 or more types are optionally added, and further, if necessary, a solvent, a diluent and the like are added and kneaded sufficiently to form the barrier co-extruded multilayer sealant film 1. To prepare.
Further, it includes a resin composition containing a thermoplastic ethylene-vinyl alcohol copolymer (EVOH) constituting the third layer 4, an oxidizing resin and a transition metal catalyst, and if necessary, forming a film thereof. At the same time, for example, improving the processability, heat resistance, weather resistance, mechanical properties, dimensional stability, antioxidant properties, slipperiness, mold release properties, flame retardancy, resistance properties, electrical properties, strength, etc. of the film For this purpose, one or more kinds of various plastic compounding agents and additives are arbitrarily added, and further, if necessary, a solvent, a diluent, etc. are added, and kneaded sufficiently to share the barrier property. A third resin composition for forming the extruded multilayer sealant film 1 is prepared.
Examples of the above plastic compounding agents and additives include, for example, lubricants, crosslinking agents, antioxidants, light stabilizers, fillers, reinforcing agents, antistatic agents, flame retardants, flameproofing agents, foaming agents, antifungal agents, pigments, Dyes, dispersants, surfactants, antiblocking agents and the like can be used, and modified resins can also be used. Furthermore, the addition amount can be arbitrarily set from a very small amount to several tens of weight% according to the purpose.

  Next, the above-described first to third resin compositions are used, and these are co-extruded using, for example, a T-die co-extruder or an inflation co-extruder to form the barrier co-extrusion multilayer of the present invention. A sealant film can be produced.

The film thickness of the barrier coextruded multilayer sealant film 1 of the present invention is about 45 μm to 450 μm, preferably 70 μm to 270 μm in total thickness.
Thus, in the barrier coextruded multilayer sealant film of the present invention, the thickness of the barrier oxygen absorbing layer constituting the third layer 4 is 5 μm to 50 μm, preferably 10 μm to 30 μm.
Next, the film thickness of the olefin resin layer constituting the first layer 2 and the fifth layer 6 is 10 μm to 100 μm, preferably 15 μm to 60 μm.
The layer thickness of the adhesive resin constituting the second layer 3 and the fourth layer 5 is 10 μm to 100 μm, preferably 15 μm to 60 μm.

In the present invention, if the film thickness of the barrier coextrusion multilayer sealant film 1 is 70 μm, and further less than 45 μm, it becomes difficult to form the film itself, and the strength is reduced, such as tearing and scratches. It is not preferred for reasons such as the occurrence of defects, and if it exceeds 270 μm, and more than 450 μm, there is no problem with respect to the strength of the film, but it is not preferred from the viewpoint of environment and cost.
Furthermore, if the film thickness of the third layer 4 is 10 μm, more preferably less than 5 μm, it is not preferable because the required oxygen absorption performance is not sufficiently exhibited, and it is not preferable. If it exceeds 1, there is no problem with respect to the sealing strength, but it is not preferable from the viewpoint of cost increase and environmental aspects.
Furthermore, if the film thickness of the second layer 3 and the fourth layer 5 is 15 μm, and further less than 10 μm, the function as the adhesive layer is lowered, and the adhesive strength may be insufficient. Further, if it exceeds 60 μm, and further 100 μm, there is no problem with respect to the adhesive strength, but it is not preferable from the viewpoint of cost increase and environment.

  The barrier co-extruded multilayer sealant film 1 can be dry laminated with a single layer or multilayer base film to form a packaging material having a barrier property and an oxygen absorbing property.

FIG. 2 shows a first embodiment of the packaging material. The packaging material 7 according to the first embodiment is obtained by dry laminating a single-layer base film 8 on a barrier coextrusion multilayer sealant film 1 via a dry laminate layer 9.
FIG. 3 shows a second embodiment of the packaging material. A packaging material 10 according to the second embodiment includes a multilayer base film 12 obtained by dry laminating a first base film 8a and a second base film 8b via a dry laminate layer 11, and a barrier. It is formed by dry-laminating the adhesive co-extruded multilayer sealant film 1 through the dry laminate layer 9.

In the packaging material of the first embodiment, the base film 8 has excellent mechanical, physical and chemical strength, and is excellent in puncture resistance and the like, and in addition, in heat resistance, moisture resistance and the like. An excellent resin film or sheet can be used, and it is particularly preferable to use a resin film or sheet having printability.
Specifically, as the base film 8, for example, a polyethylene resin, a polypropylene resin, a cyclic polyolefin resin, a polystyrene resin, an acrylonitrile-styrene copolymer (AS resin), an acrylonitrile-butadiene-styrene copolymer ( ABS resin), polyvinyl chloride resin, fluororesin, poly (meth) acrylic resin, polycarbonate resin, polyester resin such as polyethylene terephthalate and polyethylene naphthalate, various polyamide resins such as nylon, polyimide resin , Polyamideimide resin, polyaryl phthalate resin, silicone resin, polysulfone resin, polyphenylene sulfide resin, polyethersulfone resin, polyurethane resin, acetal resin, cellulose resin, etc. It can be used film or sheet of the kind of the resin.
As the resin film or sheet, any of an unstretched film or a stretched film stretched in a uniaxial direction or a biaxial direction can be used.
The thickness of the resin film or sheet may be any thickness that can maintain strength, puncture resistance, and the like to the minimum necessary. If it is too thick, there is a disadvantage that the cost increases. Conversely, if it is too thin, strength, puncture resistance and the like are lowered, which is not preferable.
For the above reasons, the thickness of the base film 8 is about 3 μm to 100 μm, preferably about 5 μm to 50 μm.
In the present invention, as the base film 8, it is desirable to use a biaxially stretched polyethylene terephthalate film having a thickness of 5 to 12 μm from the viewpoint of strength and the like.

Furthermore, a barrier-type base film can also be used as the base film 8. As such a base material film having a barrier property, a material that blocks permeation of oxygen gas, water vapor, and the like, specifically, a resin film that blocks permeation of oxygen, water vapor, etc., a resin film having a metal foil or a metal vapor deposition film, Or the resin film etc. which have the vapor deposition film | membrane of an inorganic oxide can be used.
For example, as a resin film for preventing permeation of oxygen gas, water vapor and the like, for example, a resin film such as polyvinylidene chloride resin, polyvinyl alcohol resin, saponified ethylene-vinyl acetate copolymer, nylon MXD6 alone or co-extrusion Or a sheet can be used.
The film thickness of the resin film or sheet is several μm to several tens of μm, specifically 3 to 50 μm, and preferably 7 μm to 10 μm.
Moreover, although metal foil, such as aluminum foil, copper foil, and various alloy foils, can also be used as the base film 8, it is generally preferable to use aluminum foil. The thickness of the metal foil is 6 μm to 20 μm, preferably 7 μm to 10 μm.

Further, as the base film 8, a resin film having a metal vapor deposition film, a metal is applied to one surface of the resin film, for example, a physical vapor such as a vacuum vapor deposition method, a sputtering method, an ion plating method, an ion cluster beam method or the like. A vapor-deposited metal-deposited resin film can be used using the phase growth method.
For example, aluminum, nickel, tin, bismuth, indium, cadmium, lead, or other metals can be used as the resin film having the metal vapor deposition film.
Therefore, in the present invention, it is preferable to use aluminum in consideration of versatility, economy and the like.
The thickness of the deposited metal film is 200 to 1000 mm, preferably 300 to 800 mm.
Moreover, the resin film thru | or sheet | seat which comprises the above-mentioned base film as a resin film can be used similarly.
Specifically, polyethylene resins, polypropylene resins, polystyrene resins, polyvinyl chloride resins, polycarbonate resins, polyester resins such as polyethylene terephthalate and polyethylene naphthalate, polyamide resins such as various nylons, and other transparent materials Or a translucent film or sheet can be used.
The film thickness is 3 μm to 50 μm, preferably 5 μm to 30 μm.

Further, as a base film 8, a resin film having an inorganic oxide vapor deposition film, for example, physical vapor deposition such as vacuum vapor deposition, sputtering, ion plating, ion cluster beam, etc. on one surface of the resin film. For example, an inorganic oxide vapor-deposited resin film on which an inorganic oxide such as aluminum oxide or silicon oxide is vapor-deposited can be used. For example, an inorganic oxide vapor-deposited resin film in which an inorganic oxide such as aluminum oxide or silicon oxide is vapor-deposited can be used. Specifically, a metal or metal oxide is used as a metal raw material, the raw material is heated and vaporized, and vapor deposition is performed on a resin film surface, or a metal or metal oxide is used as a raw material and oxygen Inorganic oxide vapor-deposited resin film in which a vapor-deposited film of inorganic oxide is formed by oxidation reaction vapor deposition method that oxidizes and vapor-deposits, plasma-assisted oxidation reaction vapor deposition method that promotes oxidation reaction with plasma, etc. is used be able to.
In this case, for example, a resistance heating method, a high frequency induction heating method, an electron beam heating method (EB), or the like can be used as a heating method for the vapor deposition material.
In the present invention, an inorganic oxide such as silicon oxide is applied to the surface of the resin film by chemical vapor deposition such as plasma chemical vapor deposition, thermal chemical vapor deposition, or photochemical vapor deposition. A resin film on which a deposited film is formed can be used.
Specifically, a vapor deposition monomer such as an organosilicon compound is used as a raw material on the surface of the resin film, an inert gas such as argon gas or helium gas is used as a carrier gas, and oxygen gas is used as an oxygen supply gas. And an inorganic oxide vapor deposition film such as silicon oxide can be formed by low temperature plasma chemical vapor deposition using a low temperature plasma generator. In that case, as a low temperature plasma generator, generators, such as high frequency plasma, pulse wave plasma, and microwave plasma, can be used, for example.

In the resin film having the inorganic oxide vapor-deposited film, the inorganic oxide vapor-deposited film may be formed by arbitrarily selecting the film thickness within a range of, for example, 50 to 2000 mm, preferably 100 to 1000 mm. desirable.
In that case, as the resin film, a polyethylene resin, a polypropylene resin, a polystyrene resin, a polyvinyl chloride resin, a polycarbonate resin, a polyester resin such as polyethylene terephthalate and polyethylene naphthalate, a polyamide resin such as various nylons, etc. Transparent or translucent films of various resins can be used. Moreover, the film thickness is 3 micrometers-50 micrometers, Preferably they are 5 micrometers-30 micrometers.

  In the present invention, the base film 8 can be provided with a desired printed pattern. For example, one or more of normal ink vehicles are the main components, and if necessary, plasticizers, stabilizers, antioxidants, light stabilizers, UV absorbers, curing agents, crosslinking agents, lubricants, electrification Add one or more additives such as an inhibitor, add a colorant such as a dye or pigment, and knead thoroughly with a solvent, an imperial agent, etc. to prepare an ink composition; Using the ink composition, the printed pattern is printed on the surface of the base film 8 and / or by a printing method such as gravure printing, offset printing, letterpress printing, screen printing, transfer printing, flexographic printing, etc. It can be formed on the back side.

  As the ink vehicle, known ones such as linseed oil, tung oil, soybean oil, hydrocarbon oil, rosin, rosin ester, rosin modified resin, shellac, alkyd resin, phenolic resin, maleic resin, natural resin, carbonized Hydrogen resin, polyvinyl chloride resin, polyvinyl acetate resin, polystyrene resin, polyvinyl butyral resin, acrylic or methacrylic resin, polyamide resin, polyester resin, polyurethane resin, epoxy resin, urea resin, melamine resin, One or more aminoalkyd resins, nitrocellulose, ethylcellulose, chlorinated rubber, cyclized rubber and the like can be used.

Next, the dry laminate is made of, for example, a polyvinyl acetate adhesive, a homopolymer such as ethyl acrylate, butyl, 2-ethylhexyl ester, or a copolymer of these with methyl methacrylate, acrylonitrile, styrene, or the like. Polyacrylic acid ester adhesive, cyanoacrylate adhesive, ethylene and vinyl acetate, ethyl acrylate, acrylic acid, methacrylic acid copolymer, etc. ethylene copolymer adhesive, cellulose adhesive, Polyester adhesive, polyamide adhesive, polyimide adhesive, amino resin adhesive consisting of melamine resin, phenol resin adhesive, epoxy adhesive, polyurethane adhesive, reactive (meth) acrylic Adhesive, chloroprene rubber, nitrile rubber, styrene-butadiene Rubber adhesives made of rubber or the like, silicone - emissions based adhesive, an alkali metal silicate, may be used an inorganic adhesive or other adhesive made of such low-melting glass.
The composition system of the above-mentioned adhesive may be in the form of any composition such as an aqueous type, a solvent type, an emulsion type, and a dispersion type, and the property may be any of a film sheet, powder, and solid. It may be in the form of
The adhesive can be coated by a coating method such as a roll coating method, a gravure roll coating method, or a kiss coating method. The coating amount in that case is preferably about 0.1 to 5.0 g / m ² (dry state).

  Instead of the above-mentioned dry lamination, a melt resin extrusion laminating method in which various resins are laminated while being melt extruded through an anchor coating agent layer can be employed.

In this case, as the anchor coating agent, for example, organic titanium-based, isocyanate-based, polyethyleneimine-based, polybutadiene-based, such as alkyl titanate, and other water-based or oil-based various anchor coating agents can be used.
The anchor coating agent can be coated using, for example, a roll coating method, a gravure roll coating method, and other coating methods, and the coating amount is 0.1 to 5.0 g / m ² (dry state). ) Is desirable.

Examples of the melt-extruded resin in the melt-resin extrusion laminating method include, for example, polyethylene resins, polypropylene resins, acid-modified polyethylene resins, acid-modified polypropylene resins, ethylene-acrylic acid or methacrylic acid copolymers, and Surlyn-based resins. One or more of resin, ethylene-vinyl acetate copolymer, polyvinyl acetate resin, ethylene-acrylic acid ester or methacrylic ester copolymer, polystyrene resin, polyvinyl chloride resin, and other thermoplastic resins Can be used.
In the above melt resin extrusion laminating method, it is desirable to laminate the melt extruded resin through an anchor coating agent layer in order to obtain stronger adhesive strength.
Moreover, for example, corona discharge treatment, flame treatment, plasma treatment, and other pretreatments can be performed on the surface of the base film or the like to be laminated.

  Next, in the second embodiment, the same material as the base film 8 in the first embodiment as described above is used as the first base film 8a and the second base film 8b. Can do.

  Moreover, the adhesive agent similar to the dry laminate layer 9 can be used as a material of the dry laminate layer 11 between the 1st base film 8a and the 2nd base film 8b.

  Further, in the same manner as in the first embodiment, instead of dry lamination, a laminate of the base film 8, 8a, 8b and the barrier coextrusion multilayer sealant film 1 is melt-extruded through an anchor coat layer, for example. A molten resin extrusion laminating method for laminating resin layers can be employed.

  Further, as in the first embodiment, a printing layer can be provided on the front surface or the back surface of the first base film 8a.

4 and FIG. 5 show a multilayer substrate on the lower 207 or barrier co-extruded multilayer sealant film 1 formed by using the packaging material 10 in which the barrier co-extruded multilayer sealant film 1 and the base film 8 are laminated. FIG. 4 is a side view and FIG. 5 is a cross-sectional view showing a packaging bag 12 made by using packaging materials 7 and 10 formed by dry laminating a material film 10. Although not shown, the packaging bag can be made in a form such as a pillow packaging form, a gusset packaging form, or a standing (self-standing) pouch packaging form. In addition, as the form of the seal at the time of bag making, side seal type, two-side seal type, three-side seal type, four-side seal type, envelope sticker seal type, joint sticker seal type, pleated seal type, flat bottom seal type, square seal Various sealing forms such as a mold can be adopted. As a method for sealing the end portion of the packaging bag, for example, a known method such as a bar seal, a rotary roll seal, a belt seal, an impulse seal, a high frequency seal, or an ultrasonic seal can be used.
In addition, for example, a one-piece type, a two-piece type or other spout, or an opening zipper can be arbitrarily attached to the packaging bag.

Next, a method for manufacturing a packaged product using the packaging bag shown in FIGS. 4 and 5 will be described.
First, as shown in FIG. 6, for example, an ultraviolet irradiation device 15 is inserted from the opening 13 of the packaging bag 12, and the ultraviolet irradiation device 15 is moved in the vertical direction as indicated by the arrow P, while the ultraviolet light is emitted from the packaging bag. 13, and then, as shown in FIG. 7, in the packaging bag 12, chemicals such as foods and beverages, adhesives, adhesives, cosmetics, detergents, agricultural chemicals or pharmaceuticals, electronic device chemical warmers, miscellaneous goods, etc. And then the opening 13 of the packaging bag 12 is heat-sealed to form a sealed portion 16 to produce the packaged product of the present invention.

  Further, after filling the packaging bag 12 with the contents, an ultraviolet irradiation device is inserted into the packaging bag to irradiate the inner surface of the packaging bag with ultraviolet light, and then the packaging bag 12 is sealed to thereby provide the packaging product of the present invention. Can be manufactured. In addition, the packaging product of the present invention is manufactured by irradiating the inner surface of the packaging bag with ultraviolet light by the ultraviolet irradiation device at the same time as filling the contents in the packaging bag 13 and then sealing the packaging bag 13. Can do.

  Instead of the above packaging product manufacturing method, the barrier co-extruded multilayer sealant film side of the packaging material is irradiated with ultraviolet light and then a bag is made to create a packaging bag, the packaging bag is filled with the contents, and the packaging is made. The packaged product of the present invention can be manufactured by a method of sealing the opening of the bag.

In the above method for manufacturing a packaged product, an ultraviolet irradiation device that irradiates ultraviolet light, an ultraviolet light irradiation method, and irradiation conditions will be described.
First, as an ultraviolet irradiation device, for example, an ultraviolet (UV) irradiation device using a high mercury lamp (manufactured by Eye Graphics Co., Ltd., model name: ECX-401GX) can be used.
Thus, in the present invention, as described above, as the ultraviolet irradiation method, the inner surface of the packaging bag can be irradiated before, after, or simultaneously with the filling of the contents into the packaging bag. As the irradiation condition, with respect to the intensity of ultraviolet light, an accumulated amount of ^{light, 500mJ / cm 2 ~2000mJ / cm} 2, preferably ^{500mJ / cm 2 ~1000mJ / cm 2} . The irradiation time of the ultraviolet rays is a time that satisfies the above integrated light quantity in correlation with the lamp light quantity, for example, 10 seconds to 80 seconds.

  The present invention is not only a flexible packaging container such as a packaging bag as described above, but also a lid having an oxygen collecting function formed by laminating the barrier coextrusion multilayer sealant film of the present invention with a bottle base material, A gasket for sealing using a barrier coextrusion multilayer sealant film and a molding material obtained by laminating the barrier multilayer sealant film of the present invention and a base film are thermoformed to form a multilayer molded container having an oxygen scavenging function. You can also.

In this packaged product, the barrier oxygen-absorbing layer prevents oxygen from entering from the outside to the inside of the packaging bag, and ultraviolet light irradiated from the inside of the barrier-packaging bag is applied to the barrier oxygen-absorbing layer. The transition metal catalyst that is easily reached and contained in the barrier oxygen-absorbing layer acts on the oxidizing resin, and the oxidizing resin is contained in the head space in the packaging bag, or the oxygen or the content contained in the content. It absorbs the oxygen generated inside, and as a result, maintains the quality, freshness, etc. of the contents as they are when they are filled and packaged, almost as they are or more. Even when storing, storing, displaying, etc. for a long period of time, there is almost no change in the quality of the contents such as color and smell, and the quality, freshness, etc. of the contents can be maintained very well, Quality improvement, To enable the extension of the Ruraifu.
In the packaging product of the present invention, the packaging bag includes a barrier co-extruded multilayer sealant film in which the first layer constituting the base film and the surface layer and the fifth layer constituting the back surface layer are composed of an olefin resin layer. It is made of packaging material, has excellent heat sealability at the time of bag making, can sufficiently satisfy its sealability, has easy-openability, and has excellent rigidity, strength, etc. and high retention. Excellent shape and independence, and further contributes to reducing environmental impact by reducing packaging material volume and volume.

  Next, the above invention will be described in detail with reference to examples.

A barrier coextruded multilayer sealant film was produced by the following method.
First, the following resin composition was prepared.
(I) As a resin composition for the first layer, an ethylene-α / olefin copolymer (Evolu SP2020 manufactured by Mitsui Chemicals, Ltd., density = 0.916 g / cm) polymerized using a single-site catalyst (metallocene catalyst) ³ and melt flow rate (MFR) = 1.5 g / 10 min) were prepared.
(B) As a resin composition for the second layer, maleic anhydride-modified adhesive polyethylene (Admer NF528 manufactured by Mitsui Chemicals, Inc.) was prepared.
(C) As the resin composition for the third layer, an ethylene-vinyl alcohol copolymer (Eval F101B, Kuraray Co., Ltd., density = 1.19 g / cm ³ , MFR = 1.6 g / 10 min, melting point = 183 ° C., Ethylene molar concentration = 32%) 55 parts by weight, oxidizing resin: ethylene / methyl acrylate / methylcyclohexene-methyl acrylate copolymer 45.0 parts by weight, transition metal catalyst: 0.01 parts by weight of cobalt 2-ethylhexanoate And radical photopolymerization initiator: 0.001 part by weight of 1-hydroxy-cyclohexyl phenyl ketone was sufficiently kneaded to prepare an oxygen-absorbing resin composition.
(D) As the resin composition for the fourth layer, maleic anhydride-modified adhesive polyethylene (Admer NF528 manufactured by Mitsui Chemicals, Inc.) was prepared.
(E) As a resin composition for the fifth layer, an ethylene-α-olefin copolymer polymerized using a single-site catalyst (metallocene catalyst) (Evolution SP2020 manufactured by Mitsui Chemicals, density = 0.916 g / cm) ³ , MFR = 1.5 g / 10 minutes) 100.0 parts by weight, 0.05 parts by weight of synthetic silica, 0.05 parts by weight of erucic acid amide, 0.05 parts by weight of ethylenebisoleic acid amide are sufficiently kneaded. A resin composition was prepared.

  Using a five-type five-layer top blown inflation co-extrusion machine, the first layer is composed of a resin composition layer 20 μm shown in (a) above, and the second layer is a resin composition layer shown in (b) above. 5 μm, the third layer consists of a resin composition layer 10 μm shown in (c) above, the fourth layer consists of a resin composition layer 5 μm shown in (d) above, and the fifth layer A five-layer barrier coextrusion multilayer sealant film 60 μm comprising a resin layer 20 μm shown in (e) was produced.

When the obtained barrier co-extruded multilayer sealant film was irradiated with 500 mJ / cm ^{2 of} 254 nm ultraviolet light using an ultraviolet irradiation device [model name, ECS-401GX, manufactured by Eye Graphics Co., Ltd.], I started to breathe oxygen.

  Further, when the oxygen barrier property was measured, a high oxygen barrier property not found in a normal barrier sealant was found. In particular, a behavior peculiar to an ethylene-vinyl alcohol copolymer which decreases under high humidity was not observed, and high oxygen barrier properties were maintained even at 40 ° C. to 90% RH.

Next, the surface of the ethylene-α / olefin copolymer of the first layer of the barrier coextruded multilayer sealant film is subjected to corona treatment, and a two-component curable urethane adhesive (main component: polyester polyol, curing agent) is applied to the surface. : Aliphatic isocyanate) by a gravure coating method to a thickness of 4.0 g / m ² (dry state) to form an adhesive layer for dry lamination, and then on the surface of the adhesive layer for dry lamination A laminate of a biaxially stretched polyester resin film (E5100, Toyobo Co., Ltd., 12 μm) and a biaxially stretched polyamide resin film (Toyobo Harden N1102, 15 μm) is a biaxially stretched polyester resin film (E5100, manufactured by Toyobo Co., Ltd.). , 12 μm) / 2-axis stretched polyamide resin film (Toyobo Harden N1102, 15 μ) ) / Barrier coextruded laminated so that the order of the multi-layer sealant films created the packaging material.

After irradiating the above packaging material with ultraviolet light of 254 nm in an integrated light amount of 500 mJ / cm ² from the barrier co-extrusion multi-layer sealant film side, using this barrier co-extrusion multi-layer sealant film, A sealed flat pouch bag was made, and “seasoned bonito” was enclosed in the created four-side sealed flat pouch bag.

  A three-month storage test was conducted on a packaged product in which “bonito” was encapsulated in a four-side sealed flat pouch bag. Neither discoloration, fragrance reduction nor odor deterioration was observed.

The surface of the ethylene-α / olefin copolymer of the first layer of the barrier co-extruded multilayer sealant film of Example 1 was subjected to corona treatment, and a two-component curable urethane adhesive (main agent: polyester polyol, curing agent) was applied to the surface. : Aliphatic isocyanate) by a gravure coating method to a thickness of 4.0 g / m ² (dry state) to form an adhesive layer for dry lamination, and then on the surface of the adhesive layer for dry lamination A laminate of an inorganic vapor-deposited stretched polyester resin film (IB-PET-RB manufactured by Dai Nippon Printing Co., Ltd., 12 μm) and a biaxially stretched polyamide-based resin film (Toyobo Harden N1102, 15 μm) (IB-PET-RB, manufactured by Dai Nippon Printing Co., Ltd., 12 μm) / 2-axis stretched polyamide resin film Toyobo Harden N1102,15μm) / barrier coextruded multilayer sealant film bonded so that the order of creating the packaging material.

After irradiating the above packaging material with ultraviolet light of 254 nm in an integrated light amount of 500 mJ / cm ² from the barrier co-extrusion multi-layer sealant film side, using this barrier co-extrusion multi-layer sealant film, A sealed flat pouch bag was made, and “seasoned bonito” was enclosed in the created four-side sealed flat pouch bag.

  A three-month storage test was conducted on a packaged product in which “bonito” was encapsulated in a four-side sealed flat pouch bag. Neither discoloration, fragrance reduction nor odor deterioration was observed.

A barrier coextruded multilayer sealant film was produced by the following method.
First, the following resin composition was prepared.
(A) As a resin composition for the first layer, a functional polypropylene block copolymer (PC380A manufactured by Sun Allomer Co., Ltd., density = 0.9 g / cm ² , MFR = 1.0 g / 10 minutes) was prepared.
(B) As the second layer resin composition, maleic anhydride-modified adhesive polyethylene (Modic AP-P604V manufactured by Mitsui Chemicals, Inc.) was prepared.
(C) As the resin composition for the third layer, an ethylene-vinyl alcohol copolymer (Eval H171B, Kuraray Co., Ltd., density = 1.17 g / cm ³ , MFR = 1.6 g / 10 min, melting point = 175 ° C., (Ethylene molar concentration = 38%) 65 parts by weight, oxidizing resin: 35.0 parts by weight of ethylene / methyl acrylate / methylcyclohexene-methyl acrylate copolymer, transition metal catalyst: 0.01 parts by weight of cobalt 2-ethylhexanoate And radical photopolymerization initiator: 0.001 part by weight of 1-hydroxy-cyclohexyl phenyl ketone was sufficiently kneaded to prepare an oxygen-absorbing resin composition.
(D) As the resin composition for the fourth layer, maleic anhydride modified adhesive polyethylene (Modic AP-P604V manufactured by Mitsui Chemicals, Inc.) was prepared.
(E) As a resin composition for the fifth layer, a functional polypropylene block copolymer (PC380A manufactured by Sun Allomer Co., Ltd., density = 0.9 g / cm ² , MFR = 1.0 g / 10 min) 100.0 parts by weight, synthetic silica A resin composition was prepared by sufficiently kneading 0.05 parts by weight, 0.05 parts by weight of erucic acid amide, and 0.05 parts by weight of ethylene bisoleic acid amide.

  Using a five-type five-layer top blown inflation co-extrusion machine, the first layer is composed of a resin composition layer 20 μm shown in (a) above, and the second layer is a resin composition layer shown in (b) above. 5 μm, the third layer consists of a resin composition layer 10 μm shown in (c) above, the fourth layer consists of a resin composition layer 5 μm shown in (d) above, and the fifth layer A five-layer barrier coextrusion multilayer sealant film 60 μm comprising a resin layer 20 μm shown in (e) was produced.

When the obtained barrier co-extruded multilayer sealant film was irradiated with 500 mJ / cm ^{2 of} 254 nm ultraviolet light using an ultraviolet irradiation device [model name, ECS-401GX, manufactured by Eye Graphics Co., Ltd.], I started to breathe oxygen.

  Further, when the oxygen barrier property was measured, a high oxygen barrier property not found in a normal barrier sealant was found. In particular, a behavior peculiar to an ethylene-vinyl alcohol copolymer which decreases under high humidity was not observed, and a high oxygen barrier property was maintained even at 40 ° C. to 90% RH.

Next, the surface of the ethylene-α / olefin copolymer of the first layer of the barrier coextruded multilayer sealant film is subjected to corona treatment, and a two-component curable urethane adhesive (main component: polyester polyol, curing agent) is applied to the surface. : Aliphatic isocyanate) by a gravure coating method to a thickness of 4.0 g / m ² (dry state) to form an adhesive layer for dry lamination, and then on the surface of the adhesive layer for dry lamination A biaxially stretched polyester resin film (E5100, 12 μm manufactured by Toyobo Co., Ltd.) and an inorganic vapor-deposited stretched polyamide resin film (IB-ON-FRC 15 μm manufactured by Dai Nippon Printing Co., Ltd.) (Toyobo Co., Ltd. E5100, 12 μm) / Inorganic vapor-deposited stretched polyamide resin film (Dainippon Ink Have created a packaging material by bonding to be the order of the IB-ON-FRC15μm) / barrier coextruded multilayer sealant film Co., Ltd..

After irradiating the above packaging material with ultraviolet light of 254 nm in an integrated light amount of 500 mJ / cm ² from the barrier co-extrusion multi-layer sealant film side, using this barrier co-extrusion multi-layer sealant film, A sealed flat pouch bag was made, and “seasoned bonito” was enclosed in the created four-side sealed flat pouch bag.

  A packaging product in which “bonito” is enclosed in a four-side sealed flat pouch bag is subjected to a storage test for 3 months after a retort sterilization treatment at 120 ° C. for 30 minutes. Even in the storage test for 3 months, no discoloration of the product, no decrease in fragrance, and no deterioration in odor were observed.

The surface of the ethylene-α / olefin copolymer of the first layer of the barrier co-extruded multilayer sealant film of Example 1 was subjected to corona treatment, and a two-component curable urethane adhesive (main agent: polyester polyol, curing agent) was applied to the surface. : Aliphatic isocyanate) by a gravure coating method to a thickness of 4.0 g / m ² (dry state) to form an adhesive layer for dry lamination, and then on the surface of the adhesive layer for dry lamination A laminate of an inorganic vapor-deposited stretched polyester resin film (IB-PET-RB, manufactured by Dai Nippon Printing Co., Ltd., 12 μm) and an inorganic vapor-deposited stretched amide-based resin (IB-ON-FRC, produced by Dai Nippon Printing Co., Ltd., 15 μm) Inorganic vapor-deposited stretched polyester resin film (IB-PET-RB, 12 μm, manufactured by Dai Nippon Printing Co., Ltd.) / Inorganic vapor-deposited stretched amide-based resin Dai Nippon Printing Co., Ltd. IB-ON-FRC, 15μm) / barrier coextruded laminated so that the order of the multi-layer sealant films created the packaging material.

After irradiating the above packaging material with ultraviolet light of 254 nm in an integrated light amount of 500 mJ / cm ² from the barrier co-extrusion multi-layer sealant film side, using this barrier co-extrusion multi-layer sealant film, A sealed flat pouch bag was made, and “seasoned bonito” was enclosed in the created four-side sealed flat pouch bag.

  A three-month storage test was conducted on a packaged product in which “bonito” was encapsulated in a four-side sealed flat pouch bag. Neither discoloration, fragrance reduction nor odor deterioration was observed.

[Experimental Example 1]
The barrier properties coextruded multilayer sealant film of Example 1, Example 2, and Example 3 and the packaging material using the same were measured for oxygen permeability. The oxygen permeability was measured under conditions of 23 ° C. and 90% RH by MOCON method according to JIS-K7126B method.
The results are shown in Table 1 below.

  As shown in Table 1 above, it has been found that the barrier co-extruded multilayer sealant film of the present invention and the packaging material using the same show excellent oxygen barrier properties.

[Experiment 2]
The barrier co-extruded multilayer sealant films of Example 1, Example 2, and Example 3 were examined for oxygen permeability under conditions of high temperature and high humidity of 40 ° C.-90% RH.
The results are shown in Table 2 below.

  As shown in Table 2 above, it has been found that the barrier co-extruded multilayer sealant film of the present invention exhibits extremely good oxygen barrier properties even under conditions of high temperature and high humidity.

The present invention has an oxygen collecting function of absorbing oxygen present in the head space or the like in the packaged product, oxygen contained in the contents or generated oxygen, and as a result, from outside the packaged product. Oxygen that permeates inside is combined with the permeation prevention function by the base material film of barrier properties, chemicals such as food and drink, adhesives, adhesives, cosmetics, detergents, agricultural chemicals or pharmaceuticals, electronic devices, chemical warmers, Maintain the quality, freshness, etc. of the contents of miscellaneous goods etc., for example, in the state of filling and packaging almost as it is or more, and further, the contents of the packaged products are stored, stored and displayed for a long period of time. Almost no change in quality such as color, taste, smell, etc. is observed, the quality, freshness, etc. of the contents can be protected very well, and further, the appearance of the contents is not impaired. , Excellent in its beautification resistance, compatible with the above content protection performance, further, which also allows to prolong the product life of the contents, but applicable to packaging products in various forms.
Further, the present invention is not only a soft packaging container such as a packaging bag, but also a lid having an oxygen collecting function formed by laminating the barrier coextrusion multilayer sealant film of the present invention with a bottle base material. In addition to flexible packaging containers such as packaging bags, a lid having an oxygen scavenging function formed by laminating the barrier coextrusion multilayer sealant film of the present invention with a bottle base material, the barrier coextrusion multilayer of the present invention The present invention can also be used as a sealing gasket using a sealant film and a multilayer molded container having an oxygen collecting function formed by thermoforming a molding material obtained by laminating a barrier multilayer sealant film of the present invention and a base film.

It is sectional drawing of the barrier property coextrusion multilayer sealant film of this invention. It is sectional drawing of 1st embodiment of the packaging material of this invention. It is sectional drawing of 2nd embodiment of the packaging material of this invention. It is a side view of the packaging bag formed using the packaging material of this invention. It is sectional drawing of the packaging bag shown in FIG. It is the schematic which shows the state which inserts an ultraviolet irradiation device from the opening part of the packaging material shown in FIG. 4, and irradiates ultraviolet light inside the packaging bag. It is the schematic which shows the state which filled the content in the packaging bag.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Barrier coextrusion multilayer sealant film 2 First layer of barrier coextrusion multilayer sealant film 3 Second layer of barrier coextrusion multilayer sealant film 4 Third layer of barrier coextrusion multilayer sealant film 5 Barrier coextrusion multilayer 4th layer of sealant film 6 5th layer of barrier coextrusion multilayer sealant film 7 packaging material 8 substrate film 8a substrate film 8b substrate film 9 dry laminate layer 10 packaging material 11 dry laminate layer 12 packaging bag 13 opening 14 Contents 15 UV irradiation device 16 Sealing part

Claims (11)

  A resin composition comprising an ethylene-vinyl alcohol copolymer, an oxidizing resin, and a transition metal catalyst.   2. The resin composition according to claim 1, comprising 50 to 90 parts by weight of an ethylene-vinyl alcohol copolymer and 10 to 50 parts by weight of an oxidizing resin.   The resin composition according to claim 1 or 2, wherein the molar concentration of the ethylene-vinyl alcohol copolymer is 30 mol% or more.   The resin composition according to any one of claims 1 to 3, wherein the oxidizing resin has a polarity that is relatively close to that of the ethylene-vinyl alcohol copolymer.   The resin composition according to any one of claims 1 to 3, wherein the oxidizing resin is ethylene / methyl acrylate / methylcyclohexene-methyl acrylate.   The resin composition according to any one of claims 1 to 5, further comprising a radical photopolymerization initiator.   A coextruded multilayer film comprising at least five layers, wherein the first layer constituting the surface layer and the second layer constituting the back layer are composed of an olefin resin layer, and the second layer and the fourth layer are composed of an adhesive resin layer. And the third layer contains an ethylene-vinyl alcohol copolymer, an oxidizing resin and a transition metal catalyst, and further contains a radical photopolymerization initiator, a barrier coextrusion multilayer sealant film.   A packaging material comprising a laminate of the barrier coextruded multilayer sealant film according to claim 7 and a base film.   A packaging bag formed by using the packaging material according to claim 8 so that the surface of the barrier coextrusion multilayer sealant film constitutes the inner wall of the packaging bag.   A package formed by inserting an ultraviolet irradiation device into the packaging bag according to claim 9, irradiating the inner wall of the packaging bag with ultraviolet light, then filling the packaging bag with the contents, and sealing the opening of the packaging bag Product. The packaging bag according to claim 9 is filled with the contents, and then an ultraviolet irradiation device is inserted into the packaging bag, the inner wall of the packaging bag is irradiated with ultraviolet light, and then the opening of the packaging bag is sealed. Packaging product that will be.

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