JP2005169696A - Gas barrier laminated film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a gas barrier laminated film having transparency, holding excellent gas barrier properties and not containing a cause substance exterting an adverse effect on environment at the time of disposal and incineration. <P>SOLUTION: This gas barrier laminated film comprises a laminate constituted by laminating a gas barrier film layer A comprising a cured film, which comprises a mixture of (meth)arylic acid and at least one kind of an amine compound, on one side or both sides of a base material layer comprising a transparent film or a laminate constituted by laminating a vapor deposition thin film layer of an inorganic oxide and a gas barrier film layer B comprising a cured film, which comprises a mixture of (meth)arylic acid and at least one kind of an amine compound, on one side or both sides of the base material layer comprising the transparent film. The amine compound is an alcoholamine or an amine type silane coupling agent, and the vapor deposition thin film layer and the gas barrier film layer B are continuously formed in the same vacuum film forming apparatus. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a laminated material used for packaging in the non-food field such as the food field, pharmaceuticals, and electronic parts, and in particular, it has a high gas barrier property such as oxygen and water vapor, so that the content from oxygen and water vapor in the atmosphere. The present invention relates to a laminated material having a function of blocking objects and suppressing deterioration and deterioration.

In recent years, laminated materials used for packaging in non-food fields such as food fields, pharmaceuticals, electronic parts, etc., oxygen that permeates the laminated material in order to suppress deterioration of contents and retain their functions and properties, It is necessary to prevent the influence of water vapor and other gases that alter the contents, and it is required to have gas barrier properties that block these gases. Therefore, as a gas barrier layer of a laminated material, a metal foil made of a metal such as aluminum, a metal vapor-deposited film, a resin film such as an ethylene / vinyl alcohol copolymer resin, a polyvinylidene chloride resin or a polyacrylonitrile resin, or the above resin as a base material The film etc. which were coated on have been mainly used. However, metal foil and metallized film have excellent gas barrier properties, but the contents cannot be confirmed through see-through, metal detectors cannot be used for inspection, and must be treated as non-combustible when discarded after use. There is a problem. The ethylene-vinyl alcohol copolymer resin film and the film coated with them are highly temperature and humidity dependent and cannot maintain a high gas barrier property, and those using vinylidene chloride resin or polyacrylonitrile resin should be discarded or incinerated. In some cases, there was a possibility that it could become a raw material for harmful substances. Various alternative barrier laminated films for improving these problems have been proposed (see, for example, Patent Document 1 and Patent Document 2).
Japanese Patent Laid-Open No. 10-6432 Japanese Patent Laid-Open No. 10-6433

  An object of the present invention is to provide a gas barrier laminate film that is transparent, has excellent gas burr properties, can be inspected using a metal detector, and does not contain a causative substance that adversely affects the environment during disposal or incineration. There is to do.

  The invention according to claim 1 of the present invention provides a gas barrier coating layer A comprising a cured coating of a mixture of (meth) acrylic acid and one or more amine compounds on one or both sides of a base material layer comprising a transparent film. A gas barrier laminate film comprising a laminate.

  The invention according to claim 2 of the present invention is such that a thin film layer of an inorganic oxide, a cured film of a mixture of (meth) acrylic acid and one or more amine compounds is formed on one or both sides of a base material layer made of a transparent film. A gas barrier laminate film comprising a laminate in which gas barrier coating layers B made of

The invention according to claim 3 of the present invention is a gas barrier coating layer B comprising a cured coating of a mixture of (meth) acrylic acid and one or more amine compounds on one or both sides of a base material layer comprising a transparent film, A gas barrier laminate film comprising a laminate in which vapor-deposited thin film layers of inorganic oxide are sequentially laminated.

  The invention according to claim 4 of the present invention is the gas barrier according to any one of claims 1 to 3, wherein the amine compound is an alcohol amine or an amine-based silane coupling agent. It is a conductive laminated film.

  The invention according to claim 5 of the present invention is the invention according to any one of claims 2 to 4, wherein the deposited thin film layer and the gas barrier coating layer B are continuously formed in the same vacuum film forming apparatus. A gas barrier laminate film characterized by being formed.

  In the gas barrier laminate film of the present invention, a gas barrier coating layer A made of a cured coating of a mixture of (meth) acrylic acid and one or more amine compounds is laminated on one or both sides of a base material layer made of a transparent film. Gas barrier coating layer B comprising a laminated film or a thin film layer of an inorganic oxide, or a cured coating of a mixture of (meth) acrylic acid and one or more amine compounds on one or both sides of a base material layer made of a laminate or a transparent film. A gas barrier coating layer B comprising a cured coating of a mixture of (meth) acrylic acid and one or more amine compounds on one side or both sides of a laminate obtained by sequentially laminating or a substrate layer comprising a transparent film, an inorganic oxide Since the above-described amine compound is an alcohol amine or an amine-based silane coupling agent. When it is transparent and has an excellent gas barrier property, it can be inspected using a metal detector, has no particularly bad influence when discarded and incinerated, and when the deposited thin film layer and the gas barrier coating layer B are laminated. Since the films are continuously formed in the same vacuum film forming apparatus, the efficiency is high and good quality can be maintained.

  The gas barrier laminate film of the present invention will be described below along the embodiments. FIG. 1A is a side sectional view showing an embodiment of a gas barrier laminate film of the present invention, in which a gas barrier coating layer A (2) is laminated on one side of a base material layer (1). b) is a side sectional view showing another embodiment, in which a gas barrier coating layer A (2) is laminated on both surfaces of a base material layer (1), and (c) shows still another embodiment. It is side sectional drawing, and is the structure by which the vapor deposition thin film layer (4) and the gas-barrier coating layer B (3) were laminated | stacked one by one on the one side of the base material layer (1), respectively, (d) shows other embodiment. It is side sectional drawing, and is the structure by which the vapor-deposited thin film layer (4) and the gas barrier coating layer B (3) were laminated | stacked one by one on both surfaces of the base material layer (1), respectively, (e) shows other embodiment. It is side sectional drawing, and gas barrier film layer B (3) and vapor-deposited thin film layer (4) are sequentially arranged on one side of the base material layer (1), respectively. (F) is a side sectional view showing still another embodiment, and a gas barrier coating layer B (3) and a vapor deposition thin film layer (4) are sequentially formed on both surfaces of the base material layer (1). It is a stacked configuration.

  The base material layer (1) is made of a transparent film, for example, a polyester film such as polyethylene terephthalate (PET) or polyethylene naphthalate (PEN), a polyolefin film such as polyethylene or polypropylene, a polystyrene film, 66-nylon or the like. Polyamide film, polycarbonate film, polyacrylonitrile film, polyimide film, etc. may be used, which may be either stretched or unstretched, but a film arbitrarily stretched in the biaxial direction is preferred, and has mechanical strength and dimensional stability. Things are good. Among these, a biaxially stretched polyamide film and a biaxially stretched polyester film are preferable in consideration of price, moisture resistance, filling suitability, texture, and disposal.

The substrate layer (1) may be a film to which an antistatic agent, a plasticizer, a lubricant, an antioxidant, or the like is added, and a corona treatment is performed as a pretreatment in order to improve adhesion to various layers to be laminated. Those subjected to surface treatment such as plasma treatment and ozone treatment, and those subjected to chemical treatment and solvent treatment may be used. Furthermore, you may laminate | stack the anchor coat layer for improving wettability, adhesiveness, etc. on the surface of a base material layer (1).

  The thickness of the base material layer (1) is not particularly limited, but is practically in the range of 3 to 200 μm in consideration of suitability for use and workability in the case of laminating other layers. It is more preferable.

  The gas barrier coating layer A (2) comprises a cured coating of a mixture of (meth) acrylic acid and one or more amine compounds, and the blending ratio of the mixture of (meth) acrylic acid and the amine compound is (meth). 5 to 90 parts by weight of an amine compound is preferable with respect to 10 to 95 parts by weight of acrylic acid. If the amine compound is less than 5 parts by weight, gas barrier properties are not exhibited, and if it exceeds 90 parts by weight, a film is not formed. As a forming method, a coating liquid made of a mixture is applied by a known gravure coating method or the like, and then irradiated with an electron beam or an ultraviolet ray to cross-link the mixture to form a cured film.

  The gas barrier coating layer B (3) is similarly composed of a cured coating of a mixture of (meth) acrylic acid and one or more amine compounds, and a blending ratio of (meth) acrylic acid and a mixture of amine compounds. Is preferably 5 to 90 parts by weight of an amine compound with respect to 10 to 95 parts by weight of (meth) acrylic acid. As a forming method, a coating liquid made of the mixture is applied by a method such as a spraying method in a vacuum film forming apparatus, and then irradiated with an electron beam or ultraviolet rays to crosslink the mixture to form a cured film. At this time, it is preferable to add a polymerization initiator to the mixture in order to allow the polymerization to proceed efficiently.

  The amine compound refers to a compound having nitrogen in the molecule, and may have two or more amino groups and imino groups in one molecule. Contains any primary amine such as methylamine, ethylamine or propylamine, secondary amines such as dimethylamine or diethylamine, and tertiary amines such as triethylamine or tripropylamine, which may be aliphatic or aromatic. Absent.

  In particular, an alcohol amine containing a hydroxyl group in the molecule has an ester bond between the alcohol moiety and the carboxylic acid moiety, so that in addition to the ionic bond and the amide bond, the bond is further increased and a three-dimensional cross-link is formed. improves. Alcoholamine has both hydroxyl and amino groups in the molecule, and includes ethanolamines such as monoethanolamine, diethanolamine, and triethanolamine, propanolamine, and aminoalcohols produced by the reaction of alkylamine and ethylene oxide. Is also included.

  In addition, if an amino-based silane coupling agent is used for the amine compound, the silanol moiety and the carboxylic acid moiety due to the hydrolyzed alkoxysilane moiety are bonded, and in addition to the ionic bond and amide bond, the bond is further increased and three-dimensional crosslinking is performed. Since it forms, water resistance improves further and adhesion with a base material layer and another layer also improves. The amino silane coupling agent has two or more functional groups having different reactivity such as alkoxysilyl group and amino group in one molecule. Generally N- (2-aminoethyl) 3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) 3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane Any of N-phenyl-3-aminopropyltrimethoxysilane, etc. may be used, and it is inexpensive and easy to use.

In addition, the gas barrier coating layer A (2) and the gas barrier coating layer B (3) are other acrylic monomers, silane coupling agents, organic acids, colloidal silica in consideration of adhesion, wettability, and curing acceleration. In addition, a clay mineral such as an isocyanate compound or smectite, a known additive such as a stabilizer, a colorant, or a viscosity modifier may be added to the extent that gas barrier properties and water resistance are not impaired.

  The thicknesses of the gas barrier coating layer A (2) and the gas barrier coating layer B (3) are not particularly limited. However, if the thickness is less than 0.01 μm, the performance does not appear. If the thickness exceeds 10 μm, the adhesion decreases due to poor crosslinking. In order to produce, 0.01 micrometer-10 micrometers are desirable.

  The inorganic oxide used for the vapor deposition thin film layer (4) is an oxide such as silicon, aluminum, titanium, zirconium, tin, magnesium, or a composite thereof, and is a vacuum vapor deposition method, a sputtering method, or a plasma vapor deposition method. And so on. Although the film thickness varies depending on the application, it is preferably in the range of 50 to 3000 mm, but if it is less than 50 mm, there is a problem with the continuity of the thin film, and if it exceeds 3000 mm, cracks are likely to occur and the flexibility is lowered, which is not good. .

  In addition, when laminating | stacking the said gas-barrier film layer B (3) and a vapor deposition thin film layer (4), it forms into a film simultaneously and continuously in the same vacuum film-forming apparatus. By forming the film as described above, the film can be formed efficiently and the quality is stable. The gas barrier coating layer B (3) and the deposited thin film layer (4) may be repeatedly laminated in the same order according to the required gas barrier performance.

  A printing layer can be laminated on the gas barrier coating layer A (2) and the gas barrier coating layer B (3) as needed, and a plurality of resin layers are laminated via an adhesive. Things are also possible.

  The gas barrier laminate film of the present invention is used in various packaging fields where gas barrier properties are required, and can also be used as a gas barrier protective film for various display media such as EL elements and liquid crystal display elements.

The gas barrier laminate film of the present invention will be further described with specific examples.
<Adjustment of coating liquid A for gas barrier coating layer A>
A coating solution A consisting of 70% by weight of acrylic acid and 30% by weight of triethanolamine was prepared.
<Adjustment of coating solution B for gas barrier coating layer B>
A coating solution B consisting of 70% by weight of acrylic acid and 30% by weight of N- (2-aminoethyl) 3-aminopropyltrimethoxysilane was prepared.

  As the base material layer (1), a 50 μm thick biaxially stretched polyester film (PET film) having a corona treatment on one side is used, and the adjusted coating liquid A is applied to the corona treatment surface of the PET film by a bar coater. The gas barrier coating film A (2) having a film thickness of 3.0 μm was laminated by applying and irradiating with an electron beam to obtain the gas barrier laminated film of the present invention.

  In Example 1, the gas barrier laminate film of the present invention was obtained in the same manner except that the coating liquid B was used.

As the base material layer (1), a biaxially stretched polyester film (PET film) having a thickness of 12 μm and subjected to corona treatment on one side is used, and the PET film has a thickness of 150 mm on the corona treatment surface in the same vacuum film forming apparatus. A vapor-deposited thin film layer (4) of aluminum oxide is laminated, and the gas-coating coating layer B (3) having a film thickness of 1 μm is laminated by applying electron beam irradiation after coating the prepared coating liquid A, and the present invention. The gas barrier laminate film was obtained.
<Evaluation>
The oxygen permeability of the gas barrier laminate films of Examples 1 to 3 was measured in an atmosphere at a temperature of 30 ° C. and a relative humidity of 70% using an oxygen permeability measuring device (OXTRAN-10 / 50A manufactured by Modern Control). ,evaluated. The results are shown in Table 1.

表１に示すように、実施例１〜３のガスバリア性積層フィルムは、酸素透過度が１６ｍｌ／ｍ²・２４ｈ・ＭＰａ以下であり、厚さ１２〜５０μｍのポリエステルフィルムの酸素透過度が２００ｍｌ／ｍ²・２４ｈ・ＭＰａ以上であるのに比べて、優れた酸素バリア性を有していることが判明した。

As shown in Table 1, the gas barrier laminate films of Examples 1 to 3 have an oxygen permeability of 16 ml / m ² · 24 h · MPa or less, and a polyester film having a thickness of 12 to 50 μm has an oxygen permeability of 200 ml / m ^2. It was found that the oxygen barrier property was superior to that of m ² · 24 h · MPa or more.

(A) is a sectional side view showing one embodiment of the gas barrier laminate film of the present invention, (b) is a sectional side view showing another embodiment, and (c) shows still another embodiment. It is a sectional side view, (d) is a sectional side view which shows further another embodiment, (e) is a sectional side view which shows further another embodiment, (f) is further another embodiment. It is a sectional side view shown.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Base material layer 2 ... Gas barrier film layer A
3. Gas barrier coating layer B
4 ... Vapor deposition thin film layer

Claims (5)

  It consists of the laminated body which laminated | stacked the gas-barrier film layer A which consists of a cured film of the mixture of (meth) acrylic acid and 1 or more types of amine compounds on the single side | surface or both surfaces of the base material layer which consists of a transparent film, It is characterized by the above-mentioned. Gas barrier laminate film.   A gas barrier coating layer B consisting of a vapor-deposited thin film layer of inorganic oxide and a cured coating of a mixture of (meth) acrylic acid and one or more amine compounds was sequentially laminated on one or both sides of a base material layer made of a transparent film. A gas barrier laminate film comprising a laminate.   A gas barrier coating layer B made of a cured coating of a mixture of (meth) acrylic acid and one or more amine compounds and an inorganic oxide vapor-deposited thin film layer were sequentially laminated on one side or both sides of the base material layer made of a transparent film. A gas barrier laminate film comprising a laminate.   The gas barrier laminate film according to any one of claims 1 to 3, wherein the amine compound is an alcohol amine or an amine-based silane coupling agent.   The gas barrier laminate film according to any one of claims 2 to 4, wherein the deposited thin film layer and the gas barrier coating layer B are continuously formed in the same vacuum film forming apparatus.

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