JP2014188884A - Gas barrier laminate film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To exhibit an excellent gas barrier capacity over an extended period under a severe environment.SOLUTION: The provided gas barrier laminate film is a gas barrier laminate film obtained by laminating, in proper order, an anchor coat layer 12 and a deposition layer 13 on one surface of a resin substrate 11 where the anchor coat layer 12 is formed by a composite of an acrylic polyol including hydroxyl groups (OH groups) and carboxyl groups (COOH groups) and an isocyanate compound including at least two intramolecular isocyanate groups (NCO groups), whereas a compound of any one metal selected from among Al, Zn, and Sn is included within the anchor coat layer.

Description

  The present invention relates to a gas barrier laminated film.

  Packaging materials used for packaging foods, pharmaceuticals, and the like are required to prevent deterioration of the contents. For example, for food packaging materials, it is required to suppress oxidation and alteration of proteins, fats and oils, and to maintain flavor and freshness, and for pharmaceutical packaging materials that require handling under aseptic conditions, It is required to suppress the alteration of the active ingredients in the contents and to retain the efficacy.

  Factors that cause the contents to deteriorate are often mainly caused by oxygen or water vapor that permeates the packaging material or other gases that react with the contents. Therefore, it is important that the packaging material used for packaging foods and pharmaceuticals has a property (gas barrier property) that does not allow gas such as oxygen and water vapor to permeate.

  Further, the packaging material is required to be transparent depending on the application. The reason is that the packaging material is transparent so that the shape of the contents and the color of the contents can be visually confirmed from the outside of the package, thereby preventing the contents from being mixed, whether there is damage, the contents It is mentioned that the presence or absence of alterations can be known before opening.

  In general, as a packaging material having gas barrier properties, a gas barrier laminated film in which a gas barrier material is vapor-deposited on a film substrate is known. The vapor deposited film of the gas barrier material has gas barrier properties and is formed of an extremely thin film, and therefore has excellent transparency.

  Examples of the gas barrier material include silicon oxides (SiOx) such as silicon monoxide and silicon dioxide, metal oxides such as aluminum oxide, magnesium oxide, and tin oxide, or composite oxides thereof, metal fluorides, and the like. A compound is used.

  Various methods such as vacuum vapor deposition, sputtering, ion plating, and CVD (Chemical Vapor Deposition) have been proposed as vapor deposition methods for gas barrier substances.

  Among these vapor deposition methods, from the viewpoint of productivity, a method that can be efficiently produced at a high film formation rate is desirable. In general, a method of obtaining a high film formation rate includes a vacuum deposition method, and an EB (Electron Beam) heating method is particularly suitable.

Therefore, as a gas barrier laminated film, high-speed film formation is possible, productivity is high, transparency and gas barrier properties are excellent, and silicon monoxide (SiO) or silicon / silicon dioxide is used as a film substrate. A silica-based vapor-deposited film in which a (Si / SiO ₂ ) mixed material is vapor-deposited, or a so-called alumina reactive vapor-deposited film in which metal aluminum is evaporated and reacted with oxygen to be deposited on a film substrate has attracted attention.

  However, in recent years, higher gas barrier properties have been required for gas barrier laminated films used for packaging materials.

  Gas barrier laminate films have come to be used for applications such as flat panel displays such as liquid crystal displays and organic EL displays, and back sheets and front sheets for solar cells. As a result, the functions necessary for such applications are required to have a higher level of gas barrier properties and not to lower the gas barrier properties even in a long-term severe durability test.

  However, despite the above requirements, the above-described silica-based vapor deposition film and alumina reactive vapor deposition film have insufficient gas barrier properties. Further, the gas barrier property is easily influenced by temperature and moisture, and there is a problem that the gas barrier property is remarkably lowered when a treatment such as boiling or retort sterilization is performed.

  Therefore, conventionally, in order to improve gas barrier properties, heat resistance, water resistance, moisture resistance, etc., a water-soluble polymer such as polyvinyl alcohol and tetraethoxysilane are further formed on the upper surface of the deposited film formed on the film substrate. A gas barrier laminated film in which a gas barrier film is provided by applying a coating liquid containing an alkoxysilane such as alkoxysilane or a hydrolyzate thereof and then drying by heating is proposed (for example, Patent Documents 1 and 2).

Japanese Patent Laid-Open No. 7-164591 International Publication No. 2004/048081

  Therefore, the gas barrier laminated film provided with the gas barrier coating described in Patent Documents 1 and 2 is excellent in gas barrier properties and transparency, and has a gas barrier heat resistance as compared with the case where no gas barrier coating is provided. Water resistance, moisture resistance, etc. are improved.

  However, although the gas barrier laminated films described in Patent Documents 1 and 2 can obtain the various effects as described above, there is still room for improvement. For example, in packaging material applications, the effect of suppressing deterioration of gas barrier properties when processing such as boiling or retort sterilization is not sufficient. In addition, when a durability test was performed under a severe durability test, for example, at a temperature of 85 ° C. and 85% RH (relative humidity) at a high temperature and high humidity of 1000 hours or more, deterioration in barrier properties and adhesion was observed. There's a problem. As a result, for example, there is a problem that is difficult to apply to applications that assume long-time use, such as solar cells installed outdoors.

  Therefore, as the gas barrier laminated film is used, the one having an excellent gas barrier property over a long period of time under a severe environment such as boil, retort sterilization, and the outdoors is desired as the use expands.

  This invention is made | formed in view of the said situation, Comprising: It aims at providing the gas barrier laminated | multilayer film which can exhibit the gas barrier property excellent over the long term also in the severe environment.

  In order to solve the above-mentioned problems, the invention corresponding to claim 1 is a resin base material, an anchor coat layer laminated on at least one side of the resin base material, and laminated on the surface side of the anchor coat layer. A gas barrier laminate film comprising a vapor deposition layer, wherein the anchor coat layer includes at least an isocyanate group (NCO group) in the molecule and an acrylic polyol containing a hydroxyl group (OH group) and a carboxyl group (COOH group). It is a gas barrier laminate film formed by a composite with two or more isocyanate compounds and containing any one metal compound selected from Al, Zn, and Sn in the anchor coat layer.

  The invention corresponding to claim 2 contains the hydroxyl group (OH group) and the carboxyl group (COOH group) constituting the anchor coat layer in the gas barrier laminated film according to the invention corresponding to claim 1. The acrylic polyol has a hydroxyl value of 50 mgKOH / g to 250 mgKOH / g and an acid value of 5 mgKOH / g to 50 mgKOH / g.

  The invention corresponding to claim 3 is the gas barrier laminated film according to claim 1 or claim 2, wherein the isocyanate compound for the hydroxyl group (OH group) of the acrylic polyol constituting the anchor coat layer is provided. The isocyanate group (NCO group) has an equivalent ratio (NCO / OH) of 0.15 to 0.75.

  The invention corresponding to claim 4 is the gas barrier laminate film according to any one of claims 1 to 3, wherein the vapor deposition layer is made of a vapor deposition material containing metallic silicon and silicon dioxide. It is characterized by being vacuum-deposited.

  The invention corresponding to claim 5 is the gas barrier laminate film according to claim 4, wherein the vapor deposition material is a metal selected from the group consisting of Al, Zn, Sn, Fe, and Mn, or The metal containing the oxide and selected from the group consisting of Al, Zn, Sn, Fe, and Mn is characterized by being contained in the vapor deposition layer at a ratio of 1 atm% to 20 atm%.

  The invention corresponding to claim 6 is the gas barrier laminate film according to any one of claims 1 to 5, wherein an overcoat layer is further added to the surface of the vapor deposition layer by lamination. The overcoat layer is formed of any one of a water-soluble polymer having a hydroxyl group, a water-soluble polymer having a carboxyl group, or an acrylic polyol containing a hydroxyl group and a carboxyl group. Features.

  Furthermore, the invention corresponding to claim 7 is the gas barrier laminated film according to the invention corresponding to claim 6, wherein the overcoat layer is formed of a polyacrylic compound containing a carboxyl group-containing compound containing the carboxyl group as an essential component. Any one of an acrylic polyol containing an acid or a hydroxyl group and a carboxyl group is included.

  Furthermore, the invention corresponding to claim 8 is the gas barrier laminated film according to claim 6 or claim 7, wherein the overcoat layer has an isocyanate compound having at least two isocyanate groups in the molecule. It is characterized by containing.

  ADVANTAGE OF THE INVENTION According to this invention, the gas barrier laminated | multilayer film which can exhibit the gas barrier property outstanding over the long term also in the severe environment, and can improve the heat resistance of a gas barrier property, water resistance, moisture resistance, etc. can be provided.

Sectional drawing which shows one Embodiment of the gas barrier laminated film which concerns on this invention. Sectional drawing which shows other embodiment of the gas barrier laminated film which concerns on this invention. Sectional drawing which shows other embodiment of the gas barrier laminated film which concerns on this invention.

Hereinafter, embodiments of the present invention will be described with reference to the drawings.
FIG. 1 is a sectional view showing an embodiment of a gas barrier laminate film according to the present invention.

  The gas barrier laminated film 10 includes a resin base material 11, an anchor coat layer 12, and a vapor deposition layer 13, and the anchor coat layer 12 and the vapor deposition layer 13 are sequentially laminated on one surface of the film-like resin base material 11. It is. In addition, as a gas barrier laminated film which concerns on this invention, in order to achieve higher water vapor | steam barrier property, even if it is the structure by which the anchor coat layer 12 and the vapor deposition layer 13 were laminated | stacked sequentially on both surfaces of the resin base material 11, respectively. Good.

  Examples of the resin substrate 11 include polyester films such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), polyolefin films such as polyethylene and polypropylene, polyether sulfone (PES), polystyrene film, polyamide film, and polyvinyl chloride. Examples include films, polycarbonate films, polyacrylonitrile films, polyimide films, and biodegradable plastic films such as polylactic acid.

  The resin base material 11 may contain known additives such as an antistatic agent, an ultraviolet absorber, a plasticizer, a lubricant, and a colorant. The thickness of the resin substrate 11 is not particularly limited, but is practically about 6 μm to 200 μm, preferably 12 μm to 125 μm, and more preferably 12 μm to 50 μm.

  Further, on the surface on which the other layers of the resin base material 11 (anchor coat layer 12 and vapor deposition layer 13) are laminated, physical treatment such as corona treatment, plasma treatment, flame treatment or the like is performed in order to improve adhesion. Further, chemical treatment such as chemical treatment with acid or alkali may be performed.

Next, the anchor coat layer 12 will be described in detail.
The anchor coat layer 12 is provided on the resin base material 11 to enhance the adhesion between the resin base material 11 and the vapor deposition layer 13, various sterilization treatments such as boil sterilization and retort sterilization, and long-term outdoor deposition of the vapor deposition layer. It is provided to prevent the occurrence of peeling.

  The anchor coat layer 12 is formed using a composite of an acrylic polyol containing a hydroxyl group and a carboxyl group and an isocyanate compound, and the anchor coat layer 12 includes any metal selected from Al, Zn, and Sn. By containing a compound, the adhesiveness of the resin base material 11 and the vapor deposition layer 13 can be improved.

  Acrylic polyol is a polymer compound obtained by polymerizing a (meth) acrylic acid derivative monomer, or a polymer compound obtained by copolymerizing a (meth) acrylic acid derivative monomer and another monomer, etc. It has a hydroxyl group in the side chain and reacts with an isocyanate group of an isocyanate compound.

  Examples of the (meth) acrylic acid derivative monomer having a hydroxyl group at the terminal and the side chain include hydroxyethyl (meth) acrylate and hydroxybutyl (meth) acrylate.

  Examples of other monomers copolymerizable with a (meth) acrylic acid derivative monomer having a hydroxyl group at the terminal and side chain include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, (Meth) acrylic acid derivative monomer having an alkyl group in the side chain such as t-butyl (meth) acrylate, (meth) acrylic acid derivative monomer having a carboxyl group in the side chain such as (meth) acrylic acid, benzyl (meth) There are (meth) acrylic acid derivative monomers having an aromatic ring or a cyclic structure in the side chain such as acrylate and cyclohexyl (meth) acrylate. Other than (meth) acrylic acid derivative monomers, there are styrene monomers, cyclohexylmaleimide monomers, phenylmaleimide monomers, and the like. The other monomer may have a hydroxyl group at its terminal and side chain.

  The acrylic polyol is preferably a polymer compound obtained by polymerizing a (meth) acrylic acid derivative monomer having a carboxyl group in the side chain such as (meth) acrylic acid. By forming the anchor coat layer 12 using a composite of an acrylic polyol and an isocyanate compound obtained by polymerizing a monomer having a carboxyl group, a gas barrier laminated film having higher water vapor barrier properties can be obtained.

  In the acrylic polyol having a carboxyl group, the side chain carboxyl group and the contained metal ion form an ionic bridge, so that the durability of the anchor coat layer is further enhanced and the adhesion to the vapor deposition layer 13 is increased. Therefore, it is possible to provide a gas barrier laminated film that can exhibit higher barrier properties.

  The acrylic polyol containing the hydroxyl group and carboxyl group constituting the anchor coat layer 12 has a hydroxyl (OH) group value of 50 mgKOH / g or more and 250 mgKOH / g or less, and an acid value of 5 mgKOH / g or more and 50 mgKOH / g or less. It is desirable. When the hydroxyl value is less than 50 mgKOH / g, the amount of reaction with the isocyanate curing agent is small, and the adhesion is not sufficiently developed. If it exceeds 250 mgKOH / g, the amount of reaction with the isocyanate compound increases so much that the shrinkage of the anchor coat layer 12 increases, and the vapor deposition layer 13 is not laminated neatly and does not exhibit sufficient barrier properties. When the acid value is less than 5 mgKOH / g, the reaction amount between the metal ions and the carboxyl groups in the vapor deposition layer 13 is small, and the adhesion is not sufficiently developed. If it exceeds 50 mgKOH / g, the amount of reaction between the metal ions and the carboxyl groups in the vapor deposition layer 13 increases so much that the shrinkage of the anchor coat layer 12 increases, and the vapor deposition layer 13 is not laminated neatly, so that sufficient barrier properties are obtained. Not shown.

  Here, the hydroxyl value (mgKOH / g) is an index of the amount of hydroxyl groups in the acrylic polyol, and indicates the number of mg of potassium hydroxide necessary for acetylating the hydroxyl group in 1 g of the acrylic polyol. The acid value (mgKOH / g) is an index of the amount of carboxyl groups in the acrylic polyol, and indicates the number of mg of potassium hydroxide necessary for neutralizing the carboxyl groups in 1 g of the acrylic polyol.

  The weight average molecular weight of the acrylic polyol is not particularly defined, but specifically, it is 3000 or more and 200000 or less, preferably 5000 or more and 100000 or less, and more preferably 5000 or more and 40000 or less.

  An isocyanate compound has two or more isocyanate groups in the molecule. For example, aromatic isocyanates such as tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), xylene diisocyanate (XDI), tetramethylxylylene diisocyanate (TMXDI), hexamethylene diisocyanate (HDI), bisisocyanate Examples include aliphatic isocyanates such as methylcyclohexane (H6XDI), isophorone diisocyanate (IPDI), and dicyclohexylmethane diisocyanate (H12MDI). Also, polymers or derivatives of these monomeric isocyanates can be used. For example, there are a trimeric nurate type, an adduct type reacted with 1,1,1-trimethylolpropane and the like, a biuret type reacted with biuret, and the like.

  The isocyanate compound may be arbitrarily selected from the aforementioned isocyanate compounds, polymers or derivatives thereof, and may be used alone or in combination of two or more.

  The anchor coat layer 12 is formed by applying a solution composed of a composite of the acrylic polyol and the isocyanate compound and a solvent on the resin base material 11 and reacting and curing the solution.

  As the anchor coat layer 12, the equivalent ratio (NCO / OH) of the isocyanate group (NCO group) of the isocyanate compound to the hydroxyl group (OH group) of the acrylic polyol in the anchor coat agent is in the range of 0.15 to 0.75. It is desirable that

  The reason for this is that when it is less than 0.15, sufficient adhesion cannot be obtained. On the other hand, if it is larger than 0.75, the crosslinking density becomes too high, and there is a concern that the long-term durability will be lowered.

  The solvent may be any solvent that dissolves the acrylic polyol and the isocyanate compound, and examples thereof include methyl acetate, ethyl acetate, butyl acetate, cyclohexanone, acetone, methyl ethyl ketone, dioxolane, tetrahydrofuran, and the like. One type or a combination of two or more types can be used.

The metal compound contained in the anchor coat layer 12 is not particularly limited as long as it can be an ion supply source for forming an ion cross-linked body with the COOH group in the anchor coat layer, but Al, Zn, Sn Any metal compound selected from the group consisting of oxides, hydroxides, and the like, preferably aluminum oxide (Al ₂ O ₃ ), zinc oxide (ZnO), tin oxide (SnO, SnO ₂ ), Al (OH) ₃ , hydroxides such as Zn (OH) ₂ and Sn (OH) ₃ can be exemplified.

  The particle diameter of the metal compound is preferably smaller than the film thickness of the anchor coat layer 12, and preferably has an average particle diameter of about 3 nm to 300 nm, and more preferably has an average particle diameter of 10 nm to 200 nm. From the point of view, it is good. When the particle size is 3 nm or less, the reactivity is too high and the stability as a coating agent is lowered, so that the application is difficult. When the particle size is 300 nm or more, the transparency is impaired due to the influence of light scattering, so that the application is similarly difficult.

  The addition amount is appropriately selected according to the amount of COOH groups in the anchor coat layer 12, but considering the reactivity and the like, it is generally desirably 0.5 wt% to 20 wt% in the anchor coat layer 12, 1 to 15 wt% (hereinafter, wt% means wt%) is optimal. If it is 0.5 wt% or less, the effect of ionic crosslinking cannot be expected, and if it is 20 wt% or more, application of the anchor coat layer 12 is concerned because the adhesion strength may be lowered.

  As a method for forming the anchor coat layer 12, a normal coating method is used. For example, known methods such as dipping, roll coating, gravure coating, reverse coating, air knife coating, comma coating, die coating, screen printing, spray coating, and gravure offset method can be used. As a drying method, one type of a method of applying heat such as hot air drying, hot roll drying, high frequency irradiation, infrared irradiation, UV (ultraviolet) irradiation, or a combination of two or more types can be used.

  The film thickness of the anchor coat layer 12 is desirably 0.1 μm or more and 0.5 μm or less, and preferably 0.1 μm or more and 0.3 μm or less. If the thickness is thinner than this, the adhesion between the resin base material 11 and the vapor deposition layer 13 becomes insufficient, and if it is thicker than 0.5 μm, the influence of internal stress becomes large, and the vapor deposition layer 13 is not laminated neatly, There is a problem that the expression of sex becomes insufficient.

Further, the vapor deposition layer 13 will be described in detail.
The vapor deposition layer 13 is provided on the anchor coat layer 12 and is provided for imparting gas barrier properties to the entire film.

  The vapor deposition layer 13 is not particularly limited. In the conventional gas barrier material etc., it can select suitably from the inorganic material which comprises a vapor deposition film, for example, metals, such as Si, Al, Zn, Sn, Fe, Mn, the inorganic compound containing 1 or more types of these metals, etc. Can be mentioned. Examples of the inorganic compound include metal oxides, nitrides, carbides and fluorides. Among these, at least one selected from metals and metal oxides is preferable.

  The vapor deposition layer 13 can be formed by vapor-depositing the vapor deposition material containing the above metal elements. Examples of the evaporation material include metals such as Si, Al, Zn, Sn, Fe, and Mn, oxides, nitrides, carbides, fluorides, and the like of the metals.

  As a vapor deposition method, a known method such as a physical vapor deposition (PVD) method such as a vacuum vapor deposition method or a sputtering method, or a chemical vapor deposition (PVD) method such as a plasma vapor deposition method can be appropriately used. Among these deposition methods, the vacuum deposition method is preferable in view of the fact that high-speed film formation is possible and the productivity is excellent.

  In order to increase the transparency of the vapor deposition layer 13, when vapor deposition material is vapor-deposited, reactive vapor deposition may be performed by reacting with vaporized particles and oxygen gas introduced into the atmosphere. By performing reactive vapor deposition with oxygen gas or argon gas, the metal component in the vapor deposition material is oxidized, and the transparency of the vapor deposition layer 13 can be improved. When introducing the gas, it is desirable that the pressure in the film formation chamber be 2 × 10 −1 Pa or less. If the pressure in the film forming chamber becomes higher than 2 × 10 −1 Pa, the vapor deposition layer 13 may not be neatly laminated, and the water vapor barrier property may be deteriorated.

  Since the vapor deposition layer 13 is particularly excellent in transparency and barrier properties against oxygen gas and water vapor, it is preferable that the vapor deposition material containing metal silicon and silicon dioxide is vacuum-deposited.

  In the vapor deposition material, the ratio of the content of metal silicon and silicon dioxide is not particularly limited, but the element ratio O / Si between silicon and oxygen is preferably contained at a ratio of 1.0 to 1.8. More preferably, O / Si is contained at a ratio of 1.2 to 1.7. When O / Si is 1.0 or more, transparency is good, and when O / Si is 1.8 or less, barrier properties are good.

  The vapor deposition material containing metal silicon and silicon dioxide preferably further contains a metal selected from the group consisting of Al, Zn, Sn, Fe, and Mn (hereinafter referred to as a specific metal) or an oxide thereof. . As a result, it is possible to form a vapor deposition layer having a higher film density than when a mixture of metal silicon and silicon dioxide is used as a vapor deposition material, exhibit high gas barrier properties, and an acrylic polyol containing a hydroxyl group and a carboxyl group. Due to the synergistic effect with the anchor coat layer 12 formed by a composite with an isocyanate compound having at least two isocyanate groups in the molecule, the gas barrier properties of the entire film can be further enhanced.

  In addition, the 1 type or 2 types or more of specific metal or its oxide contained in vapor deposition material may be sufficient.

  In the vapor deposition material, the content of the specific metal or its oxide is preferably 1% by mass or more and 50% by mass or less, more preferably 1% by mass or more and 40% by mass or less with respect to 100% by mass of the total of metal silicon and silicon dioxide. 5 mass% or more and 30 mass% or less are more preferable. If it is 1 mass% or more, the effect of improving the film density is sufficiently obtained. If it exceeds 50% by mass, the contents of metal silicon and silicon dioxide are relatively reduced, so that the transparency of the vapor-deposited layer, the barrier property in a moist heat resistant environment, and the like may be lowered.

  In the vapor deposition material, the remainder other than the specific metal or its oxide is preferably made of metal silicon and silicon dioxide. That is, the vapor deposition material preferably has a total of 100% by mass of the specific metal or its oxide, metal silicon, and silicon dioxide.

  As described above, when a vapor deposition material containing metal silicon and silicon dioxide is vacuum deposited, a vapor deposition layer made of an inorganic material containing silicon oxide (SiOx) is formed. Further, when a vapor deposition material containing metal silicon, silicon dioxide, and a specific metal or oxide thereof is vacuum-deposited, a vapor deposition layer made of an inorganic material containing silicon oxide and the specific metal or oxide thereof is formed. The

  The content of silicon oxide in the vapor deposition layer 13 formed on the anchor coat layer 12 is preferably 15 atm% or more, and more preferably 25 atm% or more as the abundance ratio of Si elements in all elements constituting the vapor deposition layer 13. If it is 25 atm% or more, it will be excellent in transparency, barrier properties, and the like.

  In the vapor deposition layer 13, the content of the specific metal or oxide thereof is preferably 1 atm% or more and 20 atm% or less, and preferably 3 atm% or more and 15 atm% or less as the abundance ratio of the specific metal element in all elements constituting the vapor deposition layer 13. More preferred is 3 atm% or more and 10 atm% or less. If it is 1 atm% or more, a high gas barrier property will express. If it exceeds 20 atm%, the content of silicon oxide is relatively reduced, so that the transparency of the vapor deposition layer 13 and the barrier property under a moist heat resistant environment may be deteriorated.

  The vapor deposition layer 13 in which the abundance ratio of the specific metal element is 1 atm% or more and 20 atm% or less is, for example, 1 mass% or more and 50 mass% or less of the specific metal or its oxide with respect to 100 mass% of the total of metal silicon and silicon dioxide. It can form by using the vapor deposition material mix | blended in the ratio.

  The kind and abundance ratio of the elements constituting the vapor deposition layer 13 can be measured by an X-ray photoelectron spectrometer (ESCA).

  Metallic silicon and silicon oxide desirably have an element ratio O / Si in the deposited film of 1.2 or more and 2.0 or less. When the element ratio O / Si is smaller than 1.2, the oxide component contained in the deposited film is small, and thus the transparency of the film is lowered. Theoretically, the element ratio O / Si does not exceed 2.0. As for any metal or metal oxide selected from aluminum, zinc, tin, and iron, it is desirable that any metal element is contained in the deposited film in an amount of 2 atm% to 50 atm%. If the content is less than 2 atm%, the content is too low, so the effect of improving the water vapor barrier property cannot be obtained. If it exceeds 50 atm%, the amount of the metal component contained in the deposited film increases, so the water resistance of the film Decreases.

  The film thickness of the vapor deposition layer 13 is preferably 0.005 μm or more and 0.3 μm or less, and more preferably 0.03 μm or more and 0.05 μm or less. When the thickness is less than 0.005 μm, sufficient barrier properties are not exhibited, and when the thickness exceeds 0.3 μm, it is brittle and cracks are likely to occur, and the barrier properties are not exhibited.

  Next, FIG. 2 is a sectional view showing another embodiment of the gas barrier laminate film according to the present invention.

  This gas barrier laminated film 20 is an acrylic polymer containing a hydroxyl group-containing water-soluble polymer, a carboxyl group-containing water-soluble polymer, or a hydroxyl group-carboxyl group-containing acrylic film on the vapor deposition layer 13 of the gas barrier laminated film 10 of FIG. It is the structure which gave the overcoat layer 21 which is a dry film of the thin film which consists of a coating liquid containing any one of a polyol.

  The overcoat layer 21 protects the hard and brittle vapor deposition layer 13 and prevents the occurrence of cracks due to rubbing or bending, and is provided to suppress the intrusion of oxygen, and is a water-soluble polymer having a hydroxyl group or a carboxyl group. Or a component containing any one of an acrylic polyol containing a hydroxyl group and a carboxyl group. A coating liquid containing any one of a water-soluble polymer having a hydroxyl group, a water-soluble polymer having a carboxyl group, or an acrylic polyol containing a hydroxyl group and a carboxyl group is applied onto the vapor deposition layer 13; It is formed by drying.

  As a method for forming the overcoat layer 21, a normal coating method can be used similarly to the anchor coat layer 12. For example, known methods such as dipping method, roll coating, gravure coating, reverse coating, air knife coating, comma coating, die coating, screen printing method, spray coating, and gravure offset method can be used. As a drying method, a method of applying heat such as hot air drying, hot roll drying, high frequency irradiation, infrared irradiation, UV irradiation, or the like can be used alone or in combination of two or more.

  The water-soluble polymer that forms the overcoat layer 21 includes polyvinyl alcohol resin (PVA), polyacrylic acid resin (PAA), ethylene-vinyl alcohol copolymer resin (EV hydroxyl), polyvinyl pyrrolidone resin (PVP), or An acrylic polyol having a hydroxyl group and a carboxyl group can be used, and these may be used alone or in combination.

  The overcoat layer 21 may be added with alkoxysilane in order to improve the adhesion with the vapor deposition layer 13. As the alkoxysilane, tetraethoxysilane, tetramethoxysilane, tetrapropoxysilane, methyltriethoxysilane, methyltrimethoxysilane, or the like can be used. Examples of the hydrolysis product of alkoxysilane include those prepared by dissolving alkoxysilane in an alcohol such as methanol, adding an aqueous solution of an acid such as hydrochloric acid to the solution, and causing a hydrolysis reaction.

  Moreover, in order to improve the adhesiveness with the vapor deposition layer 13, the overcoat layer 21 may add a silane coupling agent. Examples of the silane coupling agent include those having an epoxy group such as 3-glycidoxypropyltrimethoxysilane, those having an amino group such as 3-aminopropyltrimethoxysilane, and mercapto groups such as 3-mercaptopropyltrimethoxysilane. And those having an isocyanate group such as 3-isocyanatopropyltriethoxysilane. These silane coupling agents can be used alone or in combination of two or more.

  Furthermore, in order to improve the adhesion to the vapor deposition layer 13, an isocyanate compound having at least two isocyanate groups in the molecule may be added.

  FIG. 3 is a cross-sectional view showing still another embodiment of the gas barrier laminate film according to the present invention.

  This gas barrier laminate film 30 is to provide a laminate film with higher practicality by applying a laminate resin layer 32 to both surfaces of the gas barrier laminate film 20 of FIG.

  The laminate resin layer 32 is used for an adhesive portion when a bag-shaped package or the like is formed by laminating a heat sealable sealant film. For example, polyethylene, polypropylene, ethylene-vinyl acetate copolymer, ethylene-methacrylic acid copolymer, ethylene-methacrylic acid ester copolymer, ethylene-acrylic acid copolymer, ethylene-acrylic acid ester copolymer and their Resins such as metal cross-linked products are used. The thickness is determined according to the purpose, but is generally in the range of 15 μm to 200 μm. Note that the laminate resin layer 32 may be provided only on one side of the gas barrier laminated film 20 of FIG. 2 via the adhesive layer 31.

  Moreover, by laminating a polyethylene terephthalate film or a polyethylene naphthalate film on one or both sides of the gas barrier laminate film of the present invention, it can be used as a sealing material for liquid crystal display elements, solar cells, electromagnetic wave shields, transparent conductive sheets used in touch panels, etc. It can also be used.

  Hereinafter, although it demonstrates in detail using the Example and comparative example regarding a gas barrier laminated film which concern on this invention, this invention is not limited to this Example.

  The “solid content” indicating the content of the organosilicon compound or its hydrolyzate in the coating solution and anchor coating agent for forming the overcoat layer 21 is formed by polymerization of the hydrolyzed organosilicon compound. It is the amount converted into the coating film weight.

<Example 1>
In Example 1, a laminated film having the configuration shown in FIG. 2 was produced by the following procedure.

  As an anchor coat agent constituting the anchor coat layer 12, hydroxyethyl methacrylate (HEMA), methyl methacrylate (MMA) and methacrylic acid (MAA) are used together so that the hydroxyl value is 150 mgKOH / g and the acid value is 26 mgKOH / g. Acrylic polyol (weight average molecular weight of about 10,000) was obtained by polymerization.

  As the anchor coating agent, the acrylic polyol obtained as described above is used as a main agent, and a nurate type of hexamethylene diisocyanate (HDI) is used as a curing agent so that the equivalent amount of the hydroxyl group of the main agent is 0.5 equivalent. A methyl ethyl ketone (MEK) solution having a solid content of 5% by mass blended in the above was prepared, and further a methyl ethyl ketone (MEK) dispersion solution of zinc oxide fine particles having an average molecular weight of 30 nm having a solid content of 5% by mass in a ratio of 90: 10%. Mixed.

  On the corona-treated surface of a biaxially stretched PET film (Toray film processing, P60) that becomes a resin substrate 11 having a thickness of 12 μm, which is corona-treated on one side, the anchor coat agent is dried using a gravure coater. Coating was performed so that the thickness was 0.15 μm. After coating, the anchor coat layer 12 was formed by storing in a thermostatic chamber at 50 ° C. for 48 hours and performing an aging treatment.

  On the upper surface side of the anchor coat layer 12, using a vacuum deposition machine, a deposition material (A) in which metal silicon powder and silicon dioxide powder are mixed so that the element ratio O / Si is 1.5 is deposited, A vapor deposition layer (SiOx vapor deposition film) 13 having a thickness of 50 nm was formed.

  Furthermore, as a coating liquid for forming the overcoat layer 21, a coating solution prepared by the following procedure is used. The coating liquid is applied on the vapor deposition layer 13 by bar coating, followed by heating and drying at 120 ° C. for 2 minutes. An overcoat layer 21 having a thickness of 0.5 μm was formed to produce a desired laminated film.

Overcoat coating solution: Tetraethoxysilane (TEOS) hydrolyzed solution (water added with 5-fold molar equivalent of tetraethoxysilane as water using 0.01N hydrochloric acid) and an aqueous solution of polyvinyl alcohol were mixed with SiO of TEOS. A solution having a solid content of 5% by mass was prepared by mixing so that the mass ratio of ₂ equivalent amount and PVA was 50:50.

  The laminated film produced as described above was subjected to water vapor transmission immediately after production (initial stage) and after a storage test for 500 hours at 85 ° C. and 85% RH (RH means relative humidity) for the evaluation of gas barrier properties. The degree (WVTR) was measured by the following procedure.

As a result, the initial water vapor permeability (WVTR) is 0.3 [g / m ² · day], and the water vapor permeability (WVTR) after the storage test is 0.5 [g / m ² · day]. did.

[Measurement of water vapor permeability]
The water vapor permeability (WVTR) [g / m ² · day] in a 40 ° C.-90% RH atmosphere was measured with a water vapor permeability meter (MOCON PERMATRAN-W 3/31) manufactured by Modern Control.

<Example 2>
In the same manner as in Example 1, the anchor coat layer 12, the vapor deposition layer 13, and the overcoat layer 21 were laminated to produce a desired laminated film.

  However, tin oxide fine particles (average particle size 20 nm) are used for the anchor coat layer 12 instead of zinc oxide fine particles, and the metal silicon powder and silicon dioxide powder are used for the vapor deposition layer so that the element ratio O / Si is 1.5. A vapor deposition layer (SiOx-Sn composite vapor deposition film) 13 having a thickness of 50 nm was formed using a vapor deposition material (B) obtained by further mixing 20% by mass of metal tin powder with the material obtained by mixing the above.

  With respect to the laminated film thus produced, the water vapor permeability (WVTR) immediately after production (initial stage) and after a storage test of 500 hours at 85 ° C. and 85% RH was measured by the above procedure.

As a result, the initial water vapor permeability (WVTR) is 0.1 [g / m ² · day], and the water vapor permeability (WVTR) after the storage test is 0.2 [g / m ² · day]. did.

  When the element ratio in the deposited film was measured with an X-ray photoelectron spectrometer (model JPS-90MXV) manufactured by JEOL, elements of Si, Sn, and O were detected, 31.0 atm% and 5. 5 atm% and 63.1 atm% were measured.

<Comparative example 1>
A laminated film was produced in the same procedure as in Example 1 except that the acrylic polyol of the anchor coat layer 12 prepared by the following procedure was used.

  Acrylic polyol: Hydroxyethyl methacrylate (HEMA) and methyl methacrylate (MMA) are copolymerized as monomers so that the hydroxyl (OH) group value is 169 mgKOH / g, and acrylic polyol (weight average molecular weight of about 10,000) is obtained. Obtained.

  And about the laminated | multilayer film obtained by making it above, the water vapor permeability (WVTR) after a storage test for 500 hours at 85 degreeC85% RH was measured in the said procedure immediately after manufacture.

As a result, the initial water vapor permeability (WVTR) was 0.5 [g / m ² · day], and the water vapor permeability (WVTR) after the storage test was 3.2 [g / m ² · day]. did.

Then, about the laminated | multilayer film of Examples 1 and 2 and the comparative example 1 which were obtained as mentioned above, when a layer structure (use material) and an evaluation result were represented, the result as shown in Table 1 was obtained.

However, the abbreviations in Table 1 represent the following.
AC layer: anchor coat layer 12, OC layer: overcoat layer 21, HEMA: hydroxyethyl methacrylate, MMA: methyl methacrylate, MAA methacrylic acid (MAA), hydrolysis TEOS / PVA: hydrolyzate of tetraethoxysilane and polyvinyl alcohol An overcoat composition comprising:

  As apparent from Table 1 above, in Examples 1 and 2, as the anchor coating agent constituting the anchor coating layer 12, the hydroxyl value is 150 mgKOH / g, and the acid values are 26 KOH / g and 20 KOH / g, respectively. Whereas an acrylic polyol obtained by polymerizing a hydroxyl group and a carboxyl group was used, in Comparative Example 1, an acrylic polyol obtained by copolymerizing a hydroxyl group and a carboxyl group was used so that the hydroxyl value was 169 mgKOH / g, and Examples 1 and 2 and Comparative Example 1 are examples in which a metal compound is contained in the anchor coat layer 12.

  As a result, in the initial stage of production of the laminated film, Comparative Example 1 has a higher water vapor transmission rate (WVTR) than Examples 1 and 2 and the gas barrier property is somewhat lower. For example, 85 ° C. and 85% RH When the results of the storage test for 500 hours under the conditions are observed, the gas barrier property of the comparative example 1 of the acrylic polyol not considering the acid value is remarkably lowered as compared with the examples 1 and 2.

  Therefore, as is clear from a long-term severe durability test, an acrylic polyol obtained by polymerizing a hydroxyl group and a carboxyl group with a hydroxyl value of 150 mgKOH / g, an acid value of 26 KOH / g, and 20 KOH / g, respectively. The laminated film to which the anchor coat layer 12 used can exhibit excellent gas barrier properties for a long time even under harsh environments.

  Therefore, according to the embodiments and examples as described above, as the anchor coat layer 12 formed on the resin base material 11, a composite of an acrylic polyol containing a hydroxyl group and a carboxyl group and an isocyanate compound is used. The anchor coat layer 12 is formed, and by containing any metal compound selected from Al, Zn, and Sn, the adhesion between the resin base material 11 and the vapor deposition layer 13 can be improved, and thus more High barrier properties can be expressed.

  Further, by using a vapor deposition material containing metal silicon and silicon dioxide as the vapor deposition layer 13, transparency and barrier properties can be improved. Further, the vapor deposition material containing metal silicon and silicon dioxide further contains a metal selected from the group consisting of Al, Zn, Sn, Fe, and Mn or an oxide thereof, and the metal selected in the vapor deposition layer 13 Is contained at a ratio of 1 atm% or more and 20 atm% or less, the transparency of the vapor deposition layer 13 and the gas barrier property in a moist heat resistant environment can be enhanced.

  Further, as the overcoat layer 21, a coating solution containing any one of a water-soluble polymer having a hydroxyl group, a water-soluble polymer having a carboxyl group, or an acrylic polyol containing a hydroxyl group and a carboxyl group is used. Accordingly, it is possible to reliably protect the hard and fragile deposited layer 13, to prevent generation of cracks due to rubbing and bending, to suppress the intrusion of oxygen, and to realize a laminated film excellent in gas barrier properties.

  In addition, the said embodiment and Example are shown as an example and are not intending limiting the range of invention. Each of the above embodiments and examples can be implemented in various other forms, and various omissions, replacements, and changes can be made without departing from the spirit of the invention. These embodiments, examples, and modifications thereof are included in the scope and gist of the invention, and are included in the invention described in the claims and the equivalents thereof.

  The transparent gas barrier laminated film according to the present invention is expected to be particularly suitably used when high gas barrier properties are required in the fields of packaging of foods, daily necessities, pharmaceuticals, etc., and fields related to electronic equipment.

  DESCRIPTION OF SYMBOLS 10 ... Gas barrier laminated film, 11 ... Resin base material, 12 ... Anchor coat layer, 13 ... Deposition layer, 20 ... Gas barrier laminated film, 21 ... Overcoat layer, 30 ... Gas barrier laminated film, 31 ... Adhesive layer, 32 ... Laminate Resin layer.

Claims (8)

A gas barrier laminate film comprising a resin substrate, an anchor coat layer laminated on at least one side of the resin substrate, and a vapor deposition layer laminated on the surface of the anchor coat layer,
The anchor coat layer is formed by a composite of an acrylic polyol containing a hydroxyl group (OH group) and a carboxyl group (COOH group) and an isocyanate compound having at least two isocyanate groups (NCO groups) in the molecule. And the gas barrier laminated film containing any one metal compound chosen from Al, Zn, and Sn in the said anchor coat layer.   The acrylic polyol containing the hydroxyl group (OH group) and the carboxyl group (COOH group) constituting the anchor coat layer has a hydroxyl value of 50 mgKOH / g or more and 250 mgKOH / g or less, and an acid value of 5 mgKOH / g or more. It is 50 mgKOH / g or less, The gas barrier laminated film of Claim 1 characterized by the above-mentioned.   The equivalent ratio (NCO / OH) of the isocyanate group (NCO group) of the isocyanate compound to the hydroxyl group (OH group) of the acrylic polyol constituting the anchor coat layer is 0.15 to 0.75. The gas barrier laminated film according to claim 1 or 2, characterized in that   The gas barrier laminated film according to any one of claims 1 to 3, wherein the vapor deposition layer is obtained by vacuum vapor deposition of a vapor deposition material containing metal silicon and silicon dioxide. The vapor deposition material further contains a metal selected from the group consisting of Al, Zn, Sn, Fe, Mn or an oxide thereof,
5. The gas barrier laminate film according to claim 4, wherein the metal selected from the group consisting of Al, Zn, Sn, Fe, and Mn is contained in the vapor deposition layer at a ratio of 1 atm% to 20 atm%. In the gas barrier laminate film according to any one of claims 1 to 5,
An overcoat layer is further added to the surface of the vapor deposition layer by lamination,
The overcoat layer is formed of any one of a water-soluble polymer having a hydroxyl group, a water-soluble polymer having a carboxyl group, or an acrylic polyol containing a hydroxyl group and a carboxyl group. Gas barrier laminated film.   The overcoat layer is characterized in that the carboxyl group-containing compound containing the carboxyl group, which is an essential component, contains any one of polyacrylic acid or an acrylic polyol containing a hydroxyl group and a carboxyl group. The gas barrier laminate film according to claim 6.   The gas barrier laminate film according to claim 6 or 7, wherein the overcoat layer contains an isocyanate compound having at least two isocyanate groups in the molecule.

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