JP2000071395A - Packing laminated film and laminated film for deposition packing - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a packing film excellent in environmental properties, work environment properties, transparency and gas barrier capacity and suitable for various gas barrier packing uses. SOLUTION: In a laminated film, an anchor coat agent and an ethylene/vinyl alcohol copolymer resin form a laminating film. In this case, the anchor coat agent is a polyester type urethane resin dispersed or dissolved in water and/or an alcohol soln. and the ethylene/vinyl alcohol copolymer resin is a resin dispersed or dissolved in water and/or an alcohol soln. and contains 25-50 mol.% ethylene.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a laminated film for packaging which is excellent in environmental properties and working environment, and is excellent in heat resistance, adhesion, transparency and gas barrier properties. The present invention relates to a laminated film for packaging having excellent characteristics.

[0002]

2. Description of the Related Art Conventionally, polyester and polypropylene films have been widely used for packaging because of their excellent film-forming properties, transparency, moldability and moisture-proof properties. These films are laminated with an unstretched polyolefin-based film and used as a base film of a packaging material.

In order to improve the gas barrier performance of packaging materials, polyvinylidene chloride (hereinafter referred to as “PVD”) is used.
A film such as a polyester film or a polypropylene film on which a coat layer is laminated is generally used as a part of the structure of the packaging material. More specifically, base film / PVDC / adhesive layer / unstretched polyolefin film or base film /
Configurations such as print layer / adhesive layer / PVDC or aluminum metal / base film / adhesive layer / unstretched polyolefin film are known.

However, since the PVDC contains chlorine in the resin in the constituent film using PVDC, the problem of environmental pollution at the time of disposal and incineration has recently been raised, and it has been desired to use a resin film containing no chlorine. I have.

As a method for improving the above, a film in which a film made of a polyvinyl alcohol resin and a metal oxide is provided on a base film has been proposed in Japanese Patent Application Laid-Open No. 56-4563. It is large, and the gas barrier property is remarkably deteriorated under high humidity, which is not yet a satisfactory level.

Further, a film having a gas barrier layer comprising an inorganic layered compound and a high hydrogen bonding compound has been proposed in JP-A-6-93133 and JP-A-7-41685, etc. For this purpose, drying or heat treatment for a long time is required in the process of forming gas barrier properties, which is disadvantageous in terms of productivity, and the adhesion between the coating material and the substrate is low. If the adhesion to the base material is low, a stable packaging material cannot be obtained because the packaging bag is broken or deformed when processed into a packaging bag or the like.

[0007]

An object of the present invention is to apply an anchor coating agent which cannot be achieved by the prior art and which can be dispersed or dissolved in water and / or an alcohol solution without using an organic solvent, and further apply chlorine onto the coating. Is a gas barrier resin that disperses or dissolves in water and / or alcohol solution containing no water, forms a laminated film, and is excellent in environmental properties and work environment, and has excellent adhesiveness, transparency and gas barrier properties. The purpose is to provide.

Another object is to apply an anchor coating agent which is dispersed or dissolved in a water and / or alcohol solution not using an organic solvent, and does not contain chlorine thereon.
A laminated film is formed from a gas-barrier resin that disperses or dissolves in water and / or an alcohol solution to provide a laminated film for vapor-deposition packaging having excellent environmental properties and work environment properties, and excellent adhesion, transparency, and gas barrier properties. It is in.

[0009]

According to the present invention, there is provided a laminated film for packaging according to the present invention, comprising, on at least one surface of a base film, an anchor coating agent dispersed or dissolved in water and / or an alcohol solution, and water and / or water. Or in a laminated film for packaging formed with a laminated film of an ethylene-vinyl alcohol copolymer resin dispersed or dissolved in an alcohol solution, the ethylene-vinyl alcohol copolymer resin contains 25 to 50 mol% of ethylene. It is a laminated film for packaging.

Further, the laminated film for vapor-deposited packaging according to the present invention is characterized in that an inorganic thin film is vapor-deposited on the substrate film of the laminated film for packaging or on the laminated surface of an ethylene-vinyl alcohol copolymer resin dispersed or dissolved in water and / or an alcohol solution. It is characterized by having been done.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the laminated film for packaging and the laminated film for vapor deposition packaging of the present invention will be described in more detail.

In the present invention, the anchor coating agent and the ethylene-vinyl alcohol copolymer resin need to be dispersed or dissolved in water and / or an alcohol solution. The alcohol solution in the present invention is a mixture of a lower alcohol and water.

The lower alcohol is an alcoholic compound having a straight-chain branched aliphatic group having 1 to 3 carbon atoms. For example, methanol, ethanol, n- or iso-propanol is preferably used.

In order to impart coatability to the base film, another water-soluble organic compound may be added to the mixture if the stability of the dispersion or solution is maintained. Is also good. Examples of the water-soluble organic compound, for example, alcohols such as methanol, ethanol, n- or iso-propanol, ethylene glycol, glycols such as propylene glycol, methyl cellosolve, ethyl cellosolve, glycol derivatives such as n- butyl cellosolve,
Examples thereof include polyhydric alcohols such as glycerin and waxes, ethers such as dioxane, esters such as ethyl acetate, and ketones such as methyl ethyl ketone. Of these, lower alcohols are preferable from the viewpoint of working environment. Water and / or
Alternatively, an alcohol solution is preferable because it is superior in terms of working environment and environmental pollution as compared with an organic solvent. It is not preferable to use a gas barrier resin other than the ethylene-vinyl alcohol copolymer resin, for example, polyvinylidene chloride containing chlorine, because of the problem of environmental pollution during disposal and incineration.

The ethylene-vinyl alcohol copolymer resin used in the present invention must contain 25 to 50 mol% of ethylene. 25 ethylene content
If it is less than mol%, there is a humidity dependence of gas barrier properties,
It is not preferred because it tends to decrease over time. Conversely, 50 mol%
Exceeding the gas barrier property is not preferred because the gas barrier properties rapidly decrease.

The anchor coating agent used in the present invention is not particularly limited, but is preferably a urethane resin produced by a reaction between a polyol and an isocyanate compound. Examples of the polyol component include polyester-based, polyether-based, and polycarbonate-based polymers, and examples of the isocyanate compound include a diisocyanate compound. Polyester is preferred in terms of heat resistance and adhesion.
A polyester urethane resin that dissolves in an organic solvent may be used, but a polyester urethane resin that disperses or dissolves in water and / or an alcohol solution is more preferable in terms of working environment and environmental characteristics. The polyester-based urethane may be a one-part curing type or a two-part curing type. The polyester-based urethane resin is produced by reacting a polyester polyol with a polyisocyanate by a conventional method. In addition, a chain extender may be used if necessary.

The polyester polyol is obtained by reacting a dicarboxylic acid and a glycol by a conventional method. As the dicarboxylic acid component, terephthalic acid, isophthalic acid, aromatic dicarboxylic acids such as 2,6-naphthalenedicarboxylic acid, adipic acid, aliphatic dicarboxylic acids such as sebacic acid, oxycarboxylic acids such as oxybenzoic acid,
And their ester-forming derivatives. Glycol components include ethylene glycol, 1,4-butanediol, diethylene glycol,
Aromatic diols such as triethylene glycol, and poly (oxyalkylene) glycols such as polyethylene glycol, polypropylene glycol, and polytetramethylene glycol can be used. Although these have a linear structure, they can be made into a branched polyester by using a trivalent or higher valent ester forming component.

Examples of the polyisocyanate compound include aliphatic diisocyanates such as tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, dodecamethylene diisocyanate, trimethylhexamethylene diisocyanate, and lysine diisocyanate.
1,3-cyclohexylene diisocyanate, 1,4-
Cyclohexylene diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate,
4,4′-dicyclohexylmethane diisocyanate,
Alicyclic diisocyanates such as 3,3′-dimethyl-4,4′-dicyclohexylmethane diisocyanate and 1,5-tetrahydronaphthalenediisocyanate;
-Tolylene diisocyanate 2,6-tolylene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 2,2'-diphenylmethane diisocyanate, 3,3 '-Dimethyl-4,4'-diphenylene diisocyanate, aromatic diisocyanates such as 1,5-naphthalene diisocyanate, araliphatic diisocyanates such as xylylene diisocyanate, tetramethyl xylylene diisocyanate, 2,4,6-triisocyanate toluene, Triisocyanates such as 2,4,6-triisocyanate diphenyl ether, tri (isocyanatephenyl) methane, and tri (isocyanatephenyl) thiophosphite , Polyisocyanate derived from 3 moles of diisocyanate and 1 mole of water, isocyanurate-type polyisocyanate formed by trimerization of diisocyanate, and poly by-produced during production of diphenylmethane-4,4'-diisocyanate Methylene polyphenyl polyisocyanate, and glycols, triols or polyester polyols, polyisocyanates such as adduct-type polyisocyanates and isocyanate prepolymers obtained by adding the above polyisocyanates to polyether polyols and the like, and mixtures thereof. No. In particular, it is preferable to use diisocyanate.

The chain extender optionally used in the present invention includes pendant carboxyl group-containing diols such as ethylene glycol, diethylene glycol, propylene glycol, 1,4-butanediol, hexamethylene glycol, neopentyl glycol. Glycols such as, or ethylenediamine,
Diamines such as propylenediamine, hexamethylenediamine, phenylenediamine, tolylenediamine, diphenyldiamine, diaminodiphenylmethane, diaminodiphenylmethane, diaminocyclohexylmethane, and the like.

In order to improve the adhesion to the ethylene-vinyl alcohol copolymer resin layer, in addition to the polyester-based urethane resin, other aqueous resins such as polyvinyl chloride resin, urethane acrylic resin, silicone acrylic resin, acetic acid Vinyl acrylic resin, acrylic resin, latex,
For example, styrene butadiene copolymer latex, acrylonitrile butadiene copolymer latex, methyl methacrylate butadiene copolymer latex,
Chloroprene latex, rubber-based latex of polybutadiene latex, polyacrylate latex, polyvinylidene chloride latex, polybutadiene latex, or carboxyl-modified or water-soluble substances of these latexes, for example, polyvinyl alcohol,
A water-soluble ethylene-vinyl acetate copolymer, polyethylene oxide, aqueous acrylic resin, aqueous epoxy resin, aqueous cellulose derivative, aqueous polyester and aqueous lignin derivative may be added, but the adhesion to the base film is not impaired. You may add in the range. The aqueous solution resin has an organic acid group such as a carboxyl group or a sulfonic acid group, and may be dispersed by forming a salt with a basic substance such as an amine or an alkali metal. It may have a functional group capable of reacting with an isocyanate group such as a group or a carboxyl group.

The crosslinking agent for the two-component polyester-based urethane resin is not particularly limited as long as it has reactivity with at least one or more of the polyester-based urethane resins. Among them, isocyanate-based crosslinking agents, melamine-based crosslinking agents, epoxy-based crosslinking agents, and the like are preferably used.
Further, a silane coupling agent can be added to the polyester-based urethane resin in order to improve adhesion and transparency after the boiling treatment. As a silane coupling agent,
For example, chlorosilanes such as phenyltrichlorosilane and diphenyldichlorosilane, alkoxysilanes such as trimethoxysilane and tetramethoxysilane, acyloxysilane, N-2- (aminoethyl) 3-aminopropyltrimethoxysilane, γ- (2- Aminosilane such as aminoethyl) aminopropylmethyldimethoxysilane, 3-aminopropyltriethoxysilane, γ- (2-aminoethyl) aminopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 2- (3,4 −
Epoxysilanes such as (epoxycyclohexyl) ethyltrimethoxysilane, acrylic silanes, and the like. Preferably, aminosilane, epoxysilane, acrylsilane and the like are preferable from the viewpoint of adhesiveness. The amount of addition depends on the solubility of the organic functional groups of the silane in water and the pH of the aqueous solution,
Usually, it is in the range of 0.1 to 5.0% by weight.

The base film used in the present invention is preferably a base film of a biaxially stretched film of a polyolefin resin, a nylon resin, a polyethylene terephthalate resin, or a polyethylene naphthalate resin, particularly in view of cost, heat resistance and gas barrier properties. It is preferable to use a polyester film such as polyethylene terephthalate and a polyolefin film such as polyethylene and polypropylene. In particular, in order to obtain a laminated film for packaging excellent in both oxygen and water vapor barrier properties, the base film is preferably a polypropylene resin. The substrate film may be any of non-stretched, uniaxially stretched and biaxially stretched, but it is particularly preferable to use a biaxially stretched film from the viewpoint of dimensional stability and mechanical properties.

The mesopentad fraction of the polypropylene resin in the present invention reflects the stereoregularity of polypropylene. General polypropylene has an isotactic structure, and the structure of adjacent repeating units of polypropylene is stereochemically meso (me).
so). Then, the isotactic stereoregularity can be evaluated by measuring the polypropylene-based resin by 13C-NMR. Generally, 5 in the polypropylene molecular chain
Conformation (pentad, penta)
d), and is expressed by a meso pentad fraction (hereinafter abbreviated as “mmmm”) in which the above meso structures are arranged. In addition, mmmm is T.E. HAYASHHI et al. [POLYMER, vol. 29, 138 to 143 (1
988)] to obtain from 13C-NMR. The polypropylene film in the present invention is preferably a polypropylene resin having a mmmm of 98% or more. It is preferably at least 98.5%, more preferably at least 99%. If the mmmm of the polypropylene resin is less than 98%, the tensile strength and the thermal dimensional stability are inferior, so cracks and wrinkles are likely to occur during secondary processing such as vapor deposition processing, slit processing, lamination processing, and problems such as print misalignment are likely to occur. Further, the gas barrier property tends to deteriorate, which is not preferable.

If necessary, a low-density polyethylene, a medium-density polyethylene, a high-density polyethylene, a linear low-density polyethylene (LLD-PE) may be used as long as the effects of the present invention are not impaired in the polypropylene resin. One or more polyolefin resins such as ethyl acrylate copolymer, ethylene-vinyl acetate copolymer, ethylene-methyl methacrylate copolymer, ethylene-n-butyl acrylate copolymer, and polypropylene may be added. it can.

In order to smoothly apply the anchor coating agent to the surface of the substrate film, a corona discharge treatment can be preferably applied to the surface of the substrate film as a preliminary treatment. The atmosphere gas at the time of the corona discharge treatment may be any of air, carbon dioxide gas, or a mixed system of nitrogen / carbon dioxide gas, particularly a mixed gas of carbon dioxide gas or nitrogen / carbon dioxide gas (volume ratio = 95/5 to 50/50). It is preferable to carry out corona treatment in the above).

Further, additives may be added to the base film as needed in a bag surrounding the effect of the present invention is not impaired. For example, antiblocking agents, nucleating agents,
UV absorber, heat stabilizer, antioxidant, weather stabilizer,
It can contain additives usually used in addition to resins, such as antistatic agents and inorganic and organic fillers. As the antiblocking agent, inorganic particles and / or crosslinked organic particles or a mixture thereof is more preferable. Examples of the inorganic particles include, but are not particularly limited to, calcium carbonate, kaolin, talc, magnesium carbonate, barium carbonate, calcium sulfate, barium sulfate, lithium phosphate, calcium phosphate, magnesium phosphate, aluminum oxide, silicon oxide, titanium oxide, and zirconium oxide. , Lithium fluoride or the like can be used. As the organic particles, terephthalates such as calcium oxalate, calcium, barium, zinc, manganese, and magnesium can be used. As crosslinked polymer particles, divinylbenzene,
A homo- or copolymer of a vinyl monomer such as styrene, acrylic acid, methacrylic acid, acrylic acid, and methacrylic acid may be used. In addition, organic fine particles such as polytetrafluoroethylene, benzoguanamine resin, thermosetting epoxy resin, unsaturated polyester resin, thermosetting urea resin, and thermosetting phenol resin are also preferably used. The particle shape is preferably spherical, and the particle size is preferably in the range of 1 to 6 μm.

[0027] The laminated film for packaging in the present invention preferably forms a laminated film of an ethylene-vinyl alcohol copolymer resin and an inorganic layered compound mainly dispersed or dissolved in water and / or an alcohol solution.

In the present invention, the inorganic layered compound is an inorganic compound in which ultrathin unit crystal layers overlap to form one layered particle, and those which swell and cleave in a solvent are preferable. Among these, a viscosity compound having a swelling property in a solvent is particularly preferably used.

The clay compound having swelling property to solvent in the present invention is a clay compound having coordinated water unit crystal layers very thin, the property of absorbing and swelling, generally, Si ⁴⁺
Is coordinated to O ^2- and forms a tetrahedral structure and A
l ³⁺ , Mg ²⁺ , Fe ²⁺ , Fe ^3+, etc. are coordinated with O ²⁻ and OH ⁻ to form a layer forming an octahedral structure in a one-to-one or two-to-one combination and stacked. It has a layered structure and may be natural or synthetic. Representative examples are halloysite, kaolinite, montmorillonite, vercurite, dickalite, nacrite, antigolite, pyrophyllite, hectorite, hyderite, margarite, talc, tetrasilicic mica, muscovite, and gold. Mica, chlorite and the like. The size of the layered compound is preferably 5 μm or less in average particle size and 500 nm or less in thickness.

The mixing ratio of the ethylene-vinyl alcohol copolymer resin / inorganic layered compound in the present invention is preferably in the range of 10/90 to 95/5 by weight. 10/9
If it is less than 0, the strength, elongation and flexibility of the laminated film are poor, and if it is more than 95/5, the gas barrier property at high humidity is greatly reduced.

The thickness of the laminated film in the present invention is not particularly limited.
10 to 10 μm, more preferably 0.3 to 6 μm
It is.

Further, various additives may be contained in the laminated film as long as the gas barrier property is not impaired. For example, antioxidants, weathering agents, heat stabilizers, lubricants,
It is a nucleating agent, an ultraviolet absorber, and a coloring agent. Further, as long as the transparency is not impaired, the above-mentioned inorganic or organic particles may be contained.

Further, in order to enhance the interaction between the inorganic layered compound and the polymer, between the polymers or between the inorganic layered compounds, etc. in forming the laminated film, a divalent or higher valent metal salt, a catalyst component and the like are added. You may. It is preferable to use an acetate, a sulfate, a nitrate, or the like containing calcium, magnesium, aluminum, or the like because moisture resistance is improved. The amount is 1 to 10 with respect to the laminated coating.
It is about 000 ppm.

Next, it is preferable to deposit an inorganic thin film on the base film of the laminated film for packaging or the laminated film surface of the ethylene-vinyl alcohol copolymer resin in the present invention.

The structure for forming an inorganic thin film by vapor deposition is as follows.
(1) Anchor coating agent, ethylene-
In the configuration in which the laminated thin film is formed in the order of the vinyl alcohol copolymer resin and then the inorganic thin film is deposited, (2) after the inorganic thin film is deposited on the base film, the anchor coating agent and the ethylene-vinyl alcohol copolymer resin are sequentially formed. Either of the configurations of forming a laminated film may be used. Further, after forming a laminated film of the ethylene-vinyl alcohol copolymer resin of the above method (2) for the purpose of improving gas barrier properties, an inorganic thin film may be further deposited, but in terms of transparency and cost. The configuration of the above (1) or (2) is preferable.

As the inorganic thin film of the laminated film for vapor deposition and packaging in the present invention, an aluminum thin film and / or a metal oxide such as aluminum, silicon, zinc, or magnesium can be preferably used. It can be more preferably used in terms of gas barrier performance and cost. These metal oxides may be used alone or in combination of two or more, and may be one in which a metal component partially remains.

As a method for forming these inorganic thin films by vapor deposition, ordinary vacuum vapor deposition can be used, but ion plating, sputtering, or a method of activating vapors by plasma can also be used.

As a method of forming a metal oxide, a method of depositing a metal oxide by direct evaporation and a method of reactive evaporation in an oxidizing atmosphere can be more preferably employed from the viewpoint of productivity. Chemical vapor deposition (so-called “CVD”
Method)) can be used as a vapor deposition method in a broad sense.

The oxidizing atmosphere refers to an atmosphere in which a required amount of oxygen gas alone or oxygen gas diluted with an inert gas is introduced into a vacuum evaporation machine. The inert gas refers to a rare gas such as argon and helium, a nitrogen gas, and a mixed gas thereof. Reactive deposition is a technique in which a metal or metal oxide is evaporated from an evaporation source in an oxidizing atmosphere as described above to cause an oxidation reaction in the vicinity of the substrate film to form on the substrate film. Examples of the evaporation source for these include a board type of resistance heating system, a crucible type by radiation or high frequency heating, and a system by electron beam heating, but are not particularly limited.

When the inorganic thin film is a metal oxide, it is most preferable that it is completely transparent. However, in general, when an attempt is made to form a complete oxide, there is a high probability that an excessively oxidized portion will be formed. Is inferior in gas barrier performance, and it is difficult to obtain high gas barrier performance as a whole. Therefore, an incomplete oxide film in which some metal components remain may be used. The light transmittance of the laminated film for vapor-deposition packaging of the present invention is preferably 70% or more, more preferably 80% or more, and more preferably 85% or more. It is preferable for confirmation. The upper limit of the light transmittance is limited by the light transmittance of the polypropylene resin film of the present invention used as the base film, and the upper limit of the light transmittance of the base film of the present invention is 92%. The upper limit of the light transmittance is 92%.

As the thickness of the inorganic thin film, in the case of an aluminum thin film, a thickness of generally 20 to 50 nm is used, and a film having an optical density (logarithm of the reciprocal of light transmittance) of about 1.5 to 3 is deposited. In the case of a metal oxide, it is preferably 5 to 100 in terms of gas barrier performance and flexibility.
nm, more preferably in the range of 8 to 50 nm. If the thickness is less than 5 nm, the gas barrier performance is not sufficient, and if the thickness exceeds 100 nm, the latent surface of the film is melted by the latent heat of aggregation of the metal oxide during the deposition, causing the film to lose its heat and whitening, and the flexibility of the deposited film. This is not preferable because cracking and peeling of the deposited film are likely to occur due to bending of the film.

The surface of the substrate film and / or
Alternatively, the lamination surface of the ethylene-vinyl alcohol copolymer resin is subjected to a corona discharge treatment so that the surface wetting tension is 35 mN /
It is preferable to increase the value to m or more because the adhesion of the deposited inorganic thin film is improved. Atmosphere gas at the time of the corona discharge treatment at this time may be any of air, carbon dioxide gas, or a mixed system of nitrogen / carbon dioxide gas, and particularly, a carbon dioxide gas or a mixed gas of nitrogen / carbon dioxide gas (volume ratio = 95).
/ 5/50/50) is preferable because the wet tension on the film surface increases to 35 mN / m or more.

In the laminated film for vapor deposition and packaging in the present invention, it is preferable that another film is laminated on the laminated surface of the ethylene-vinyl alcohol copolymer resin or the vapor deposited surface of the inorganic thin film. As the other film, a film of a polyolefin resin, a nylon resin, a polyethylene terephthalate resin, or the like is preferable, and a biaxially stretched film or a non-stretched film may be used. When laminating as a heat seal layer, a non-stretched film of a polyolefin resin is preferable, and these films are preferably laminated by an extrusion laminating method or an adhesive. The laminated film for packaging and the laminated film for vapor-deposited packaging are sealed by overlapping the heat-sealing layers and used as a packaging bag.

Next, the method for producing the laminated film for packaging and the laminated film for vapor-deposited packaging of the present invention will be described by way of an example in which a base film / anchor coating agent / polyethylene-vinyl alcohol copolymer resin / inorganic thin film is laminated in this order. Although described, it goes without saying that the present invention is not limited to this example.

The base film may be subjected to various adhesion promoting treatments before coating with the anchor coat agent, for example, a corona discharge treatment in air or other atmosphere, a flame treatment, an ultraviolet treatment, or the like.

The anchor coating agent may be applied to a commercially available substrate film, or may be applied to a substrate formed in-line.

The method of forming a film of ethylene-vinyl alcohol copolymer resin on the anchor coat surface is not particularly limited, and extrusion lamination and melt coating may be used, but the film can be coated at high speed. It is preferable to apply a gravure coat, a reverse coat, a spray coat, a kiss coat, a die coat, or a metaling bar coat to a solution in which the components of the coating are dispersed or dissolved in a water and / or alcohol solution.

The method of drying the anchor coating agent and the ethylene-vinyl copolymer resin film is not particularly limited, and a hot roll contact method, a heat medium (air, oil, etc.) contact method, an infrared heating method, a microwave heating method, etc. are used. it can. The drying of the coating
From the viewpoint of gas barrier properties, the drying is preferably performed in the range of 100 to 170 ° C, and the drying time is 1 to 60.
Seconds.

The coating agent containing the ethylene-vinyl alcohol copolymer resin is preferably a solution in which the ethylene-vinyl alcohol copolymer resin is dissolved or dispersed in a solvent and the inorganic layered compound is uniformly dispersed or swelled. Water and a mixed solution of water / lower alcohol are used as the solvent.

Next, various adhesion promoting treatments, for example, a corona discharge treatment in air or other atmosphere, a flame treatment, and the like, are performed on the surface of the obtained packaging film on which the packaging film is to be deposited.
UV treatment or the like may be performed.

Next, the laminated film for packaging is set in a vacuum evaporation apparatus equipped with a film traveling device, and is run through a cooling metal drum. At this time, vapor deposition is performed while heating and evaporating the aluminum metal. Alternatively, an oxygen gas was supplied to the evaporating vapor point, and aluminum was oxidized to be agglomerated and deposited on the running film surface to form an aluminum oxide vapor-deposited layer to form a laminated film for roll-up vapor deposition packaging. By changing the ratio between the amount of aluminum evaporated and the amount of supplied oxygen gas at this time, the light transmittance of the aluminum oxide deposited film can be changed. After the vapor deposition, the inside of the vacuum vapor deposition apparatus is returned to normal pressure, the wound film is slit, and the film is aged at a temperature of 30 ° C. or more for 1 day or more, because the gas barrier property is stabilized, which is preferable.

[0052]

EXAMPLES Next, the effects of the present invention will be described with reference to examples, but the present invention is not limited to these examples. First, measurement and evaluation methods are described below.

[Method of Measuring Characteristic Value] The characteristic value of the present invention is as follows.
The following measurement method is used.

(1) Mesopentad fraction (mmmm) 13C-NMR is measured using 1,2,4-trichlorobenzene as a measuring solvent. For the assignment of the obtained spectra and the calculation of mmmm, see T.W. Hayas
hi et al. [Polymer, 29, 138 (198)
8)] and expressed as a percentage. In addition, about a laminated film, the surface layer was peeled off or it was shaved off, and it measured by the same method as the above.

(2) Light Transmittance The laminated film for packaging was coated with a spectrophotometer 324 manufactured by Hitachi, Ltd.
The transmittance was measured at a wavelength of 550 nm using a mold.

(3) Transparency (Haze) of Film The laminated film for packaging was measured according to STM D1003-52.

(4) Adhesive Strength Under High Humidity Polyurethane adhesive manufactured by Takeda Pharmaceutical Co., Ltd. (base agent “Takelac” A-971 / hardener “Takenate” A-3 = 9/1) was applied to the laminated film for packaging. Is coated with a coating bar to a thickness of about 4 μm, and a 25 μm-thick non-stretched polypropylene film (CPP, T3529, manufactured by Toray Synthetic Film Co., Ltd.) is laminated to the laminated coating surface, and then is laminated at 40 ° C. for 2 days. After the aging, the sample was further left at 90% relative humidity for 3 days.

Then, each surface opposite to the surface in contact with the adhesive was reinforced with cellophane tape, cut out to a width of 15 mm, and the tensile speed was measured using Orientec Co., Ltd. UCT-100 type "Tensilon". The force required for 180-degree peeling of the CPP film and this film at 300 mm / min was evaluated as the adhesion between the coating and the substrate.

When the adhesion was 1.3 N / cm or more, it was evaluated as “「 ”, when it was 0.65 N / cm or less, as“ x ”, and when it was intermediate, as“ Δ ”. Separation is 23 ° C
In an atmosphere with a relative humidity of 65%.

(5) Gas Barrier Property Water vapor permeability (moisture proof) Water vapor permeability meter “PERMA” manufactured by Modern Control
The value measured using TRAN "W3 / 31 at a temperature of 37.8 ° C. and a relative humidity of 100% is shown in units of g / m ² · day.

B. Oxygen permeability Oxygen permeability meter “OXTRA” manufactured by Modern Control
The values measured using N ″ -100 under the conditions of a temperature of 23 ° C. and a relative humidity of 5%, and a temperature of 23 ° C. and a relative humidity of 80% are shown in units of ml / m ² · day · MPa.

(6) Structure of Film Thickness and Thickness of Inorganic Thin Film Layer A cross section of the film was photographed with a transmission electron microscope (TEM) under the following conditions, and the thickness of the inorganic thin film layer was measured.

Apparatus: JEM-1200EX manufactured by JEOL Ltd. Observation magnification: Film thickness configuration = 1000 times Thickness of inorganic thin film layer = 400,000 times Acceleration electron: 100 kV (7) Melt flow index (MFI) JIS K- 6758 polypropylene test method (23
(0 ° C., 21.2 N).

(8) Melting Point When a 5 mg sample was heated at a heating rate of 20 ° C./min from room temperature using a thermal analyzer SII manufactured by Seiko Instrument, a melting endothermic peak accompanying the melting of the crystal. The temperature at the position was taken as the melting point.

(9) Comprehensive evaluation Regarding coatability, environmental workability, film properties, and practicality as a packaging film, a more excellent one was evaluated as “◎”, an excellent one as “○”, and a slightly inferior one as “△”. And inferior were evaluated as "x".

Next, the effects of the present invention will be described with reference to examples.

Example 1 A polypropylene resin having a mesopentad fraction (mmmm) of 99.1% (MFI = 3.7 g / 10 min, melting point: 163 ° C.) was used as a base film of the packaging laminated film of the present invention.
Is fed to an extruder and melted at a temperature of 270 ° C.
After the filtration filter was obtained, it was formed into a sheet shape with a slit-shaped die, and the sheet was wound around a metal drum kept at 30 ° C. and cooled and solidified to form a sheet shape.

This sheet was heated to a temperature of 135 ° C., stretched 5 times in the longitudinal direction, cooled and then led to a tenter-type stretching machine, heated to a temperature of 165 ° C., stretched 9 times in the width direction, and pulled up to 165 ° C. The film was heat-treated for 6 seconds while giving 10% relaxation in the width direction at a temperature of 100 ° C., followed by blowing normal temperature air onto the film, cooling the film to a temperature of 40 ° C., and fixing the surface to be anchor-coated in air or nitrogen / carbon dioxide gas. The sheet was subjected to a corona discharge treatment in a mixed gas atmosphere, the free energy of the sheet surface was adjusted to 45 mN / m or more, and the sheet was wound into a roll.

Next, a two-pack type water-soluble polyester-based urethane resin was used as an anchor coat agent, a water-soluble polyester-based urethane resin was used as a main agent at 50% by weight, and a water-soluble polyester isocyanate group content of 19% by weight was used as a curing agent. Pure water is added to a liquid prepared by mixing a reactive polyisocyanate compound (aliphatic isocyanate obtained from 1,6-hexamethylene diisocyanate and methoxypolyethylene ether glycol) with a solid content of 50% by weight, and a 5% by weight aqueous solution is prepared using a roll coater. Then, the film was applied to the corona discharge treated surface of the film, dried at 100 ° C. for 30 seconds, and an anchor coating agent having a thickness of about 0.4 μm was applied. Thereafter, as an inorganic layered compound, montmorillonite ("Kunipia-F" manufactured by Kunimine Industries Co., Ltd.) was dispersed in water so as to have a concentration of 5% by weight, and an ethylene-vinyl alcohol copolymer resin having an ethylene content of 32 mol% was used. Was mixed with a 5% by weight solution obtained by adding a 50/50 weight ratio of pure water / isopropanol to a coating agent, and a roll coater was used on the anchor coat surface.
It was coated and dried at 100 ° C. for 30 seconds to obtain a laminated film for packaging having a coating thickness of about 4 μm of an ethylene-vinyl alcohol copolymer resin and an inorganic layered compound.

Next, the obtained laminated film for packaging was
A film of nitrogen / carbon dioxide mixed gas (nitrogen / carbon dioxide = 85/15) is applied to the film surface through a rubber roll heated to ° C.
The film was subjected to a corona discharge treatment under a treatment condition of 40 W · min / m ² in the atmosphere described above, and the film was wound into a roll with a wet tension of 45 mN / m or more. The temperature of the film at that time was 30 ° C., and the film was allowed to stand for 10 hours and slit into a small width.

Next, the film slit to a small width is set in a vacuum evaporation apparatus equipped with a film traveling device.
After a high vacuum of 1.00 × 10 ⁻² Pa, the sample was run through a cooling metal drum at −20 ° C. At this time, while heating and evaporating the aluminum metal, oxygen gas is supplied to the evaporating steam point, and while oxidizing the aluminum metal, the aluminum metal is coagulated and deposited on the corona discharge treated surface of the running film to form a vapor-deposited thin film layer of aluminum oxide. I took it. After the vapor deposition, the inside of the vacuum vapor deposition device was returned to normal pressure, the wound film was rewound, and aged at a temperature of 40 ° C. for 2 days to obtain a laminated film for vapor deposition packaging.

Example 2 A laminate film for packaging and a laminate for vapor deposition packaging were prepared in the same manner as in Example 1 except that the ethylene-vinyl alcohol copolymer resin of Example 1 to which no inorganic layered compound was added was used as a coating agent. A film was obtained.

Example 3 A polypropylene resin having a mesopentad fraction (mmmm) of 98.6% (MFI = 3.9 g / 10 min, melting point: 162 ° C.) was used as a base film of the packaging laminated film of the present invention.
Synthetic mica ("Tetrasilicic mica" NA- manufactured by Topy Industries, Ltd.)
A laminated film for packaging and a laminated film for vapor deposition packaging were obtained in the same manner as in Example 1 except that TS) was used.

Example 4 The procedure of Example 1 was repeated, except that a polypropylene film “Trefane” type YB22 (22 μm thick) manufactured by Toray Industries, Inc. was used as the base film of the laminated film for packaging of the present invention. A laminated film for packaging and a laminated film for vapor deposition packaging were obtained.

Example 5 As a base film of a laminated film for packaging according to the present invention, a polypropylene film “Trefane” type YB22 (22 μm thick) manufactured by Toray Industries, Inc. was passed through a rubber roll heated to 50 ° C. In an atmosphere of a mixed gas of nitrogen / carbon dioxide (nitrogen / carbon dioxide = 85/15).
The corona discharge treatment is performed under the treatment condition of W · min / m ² ,
The film was wound into a roll with a wet tension of 45 mN / m or more.

The temperature of the film at that time was 30 ° C. After leaving the film for 10 hours, the film was slit into a small width. next,
The film slit to a small width is set in a vacuum evaporation apparatus equipped with a film traveling device, and 1.00 × 10 ^-2 Pa
And then run through a cooled metal drum at -20 ° C. At this time, while heating and evaporating the aluminum metal, oxygen gas is supplied to the evaporating steam point, and while oxidizing the aluminum metal, the aluminum metal is coagulated and deposited on the corona discharge treated surface of the running film to form a vapor-deposited thin film layer of aluminum oxide. I took it. After the evaporation, the inside of the vacuum evaporation apparatus was returned to normal pressure, the wound film was rewound, and aged at a temperature of 40 ° C. for 2 days to obtain an evaporation film.

Next, a two-pack type polyester urethane resin was used as an anchor coating agent, a water-soluble polyester-based urethane resin was used as a main agent at 50% by weight, and a water-soluble polyisocyanate having an isocyanate group content of 19% by weight was used as a curing agent. Pure water is added to a solution prepared by mixing a compound (aliphatic isocyanate obtained from 1,6-hexamethylene diisocyanate and methoxypolyethylene ether glycol) with 50% by weight as a solid content to form a 5% by weight aqueous solution. Is applied to the corona-discharge treated surface, dried at 100 ° C. for 30 seconds, and has a thickness of about 0.4 μm.
Was applied. Thereafter, as an inorganic layered compound, montmorillonite ("Kunipia-F" manufactured by Kunimine Industries Co., Ltd.) was dispersed in water so as to have a concentration of 5% by weight, and an ethylene-vinyl alcohol copolymer resin having an ethylene content of 32 mol% was used. Was mixed with a 5% by weight solution obtained by adding 50/50 by weight of pure water / isopropanol to obtain a coating agent. The coating was applied to the anchor coat surface using a roll coater.
After drying at 00 ° C. for 30 seconds, a laminated film for packaging having a coating thickness of about 4 μm of an ethylene-vinyl alcohol copolymer resin and an inorganic layered compound was obtained.

Comparative Example 1 Instead of the ethylene-vinyl alcohol copolymer resin of the laminated film for packaging according to the present invention according to Example 1, a polyvinyl alcohol resin (“POVAL” EV manufactured by Kuraray Co., Ltd.) was used.
A laminated film for packaging was obtained in the same manner as in Example 1 except that A-105) was used.

Comparative Example 2 The procedure of Example 1 was repeated except that the ethylene-vinyl alcohol copolymer resin having an ethylene content of 55 mol% was used instead of the ethylene content of 32 mol% in the laminated film for packaging according to the present invention. In the same manner as in Example 1, a laminated film for packaging was obtained.

Comparative Example 3 A high-crystalline polypropylene resin having a mesopentad fraction (mmmm) of 99.1% of Example 1 was used as a base film, and a biaxially stretched film was obtained in the same manner as in Example 1. After performing corona discharge treatment and slitting to a small width, the film slit to a small width is set in a vacuum vapor deposition device equipped with a film traveling device, and after applying a high vacuum of 1.00 × 10 ⁻² Pa, at −20 ° C. Through a cooling metal drum.

At this time, while heating and evaporating the aluminum metal, oxygen gas is supplied to the evaporating vapor, and the aluminum metal is oxidized to be coagulated and deposited on the corona discharge treated surface of the running film to form a deposited thin film layer of aluminum oxide. And wound up. After the vapor deposition, the inside of the vacuum vapor deposition apparatus was returned to normal pressure, and the wound film was rewound.
After aging for days, a film for vapor deposition packaging was obtained.

Table 1 summarizes the quality evaluation results of the above-mentioned laminated film for packaging and laminated film for vapor-deposited packaging.

[0083]

[Table 1] From Table 1, the laminated films for packaging and laminated films for vapor deposition packaging obtained in Examples 1 to 5 were excellent in transparency and gas barrier properties.

That is, in order to obtain a laminated film for packaging and a laminated film for vapor-deposited packaging having excellent transparency, adhesion and gas barrier properties, an anchor coating agent dispersed or dissolved in water and / or an alcohol solution and an ethylene content of 2
It has been found that it is necessary to form a laminated film of 5 to 50 mol% of an ethylene-vinyl alcohol copolymer resin.

On the other hand, in Comparative Examples 1 and 2, the oxygen permeability under particularly high humidity was significantly inferior, and in Comparative Example 3, both the water vapor permeability and the oxygen permeability were inferior.

[0086]

According to the laminated film for packaging obtained by the present invention, by using an ethylene-vinyl alcohol copolymer resin as a gas barrier resin, environmental pollution during disposal and incineration can be prevented. -By using water and / or an alcohol solution as a dispersion medium for a vinyl alcohol copolymer resin, it is possible to provide a film having excellent environmental properties and working environment properties, and further having excellent transparency and gas barrier properties and suitable for various packaging applications. be able to.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) B65D 65/40 B65D 65/40 D C08J 7/06 CER C08J 7/06 CERZ F-term (Reference) 3E086 AD01 BA04 BA15 BA24 BA40 BB01 BB22 BB41 BB51 BB87 BB90 4F006 AA12 AA19 AA35 AA37 AA38 AB20 AB37 AB73 BA00 BA05 CA07 DA01 DA04 4F100 AA01C AA17C AA19C AC03 J07 BA02B02 BA01 BAO BAB BAB BAB

Claims (8)

[Claims] 1. A lamination of an anchor coating agent dispersed or dissolved in a water and / or alcohol solution and an ethylene-vinyl alcohol copolymer resin dispersed or dissolved in a water and / or alcohol solution on at least one surface of a substrate film. In a laminated film for packaging formed a coating,
The ethylene-vinyl alcohol copolymer resin is 25 to 5;
A laminated film for packaging, characterized by containing 0 mol% of ethylene. 2. The packaging laminated film according to claim 1, wherein the base film is made of a polypropylene resin. 3. The laminated film for packaging according to claim 1, wherein the anchor coating agent is mainly composed of a polyester urethane resin dispersed or dissolved in water and / or an alcohol solution. 4. A laminated film comprising an ethylene-vinyl alcohol copolymer resin or an inorganic layered compound which is dispersed or dissolved in water and / or an alcohol solution as main components. 2. The laminated film for packaging according to 1. 5. The polypropylene resin of the base film,
The laminated film for packaging according to claim 2, wherein the film is a highly crystalline polypropylene resin having a mesopentad fraction of 98% or more. 6. An inorganic thin film is deposited on the base film of the packaging laminated film according to claim 1 or on the laminated coating surface of an ethylene-vinyl alcohol copolymer resin dispersed or dissolved in a water and / or alcohol solution. A laminated film for vapor deposition packaging characterized by the above-mentioned. 7. The laminated film for vapor-deposition packaging according to claim 6, wherein the inorganic thin film is a metal oxide thin film, and the light transmittance of the vapor-deposited film is 70% or more. 8. The laminated film for vapor-deposition packaging according to claim 7, wherein the metal oxide thin film is a thin film mainly composed of aluminum oxide.