JP2005349582A - Transparent gas barrier laminated film and lid material using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a transparent gas barrier laminated film excellent in transparency and environmental correspondence, having high gas barrier properties, causing no breakage of the laminated film from a seal surface at the time of opening when used as a lid material and showing good opening properties, and also to provide the lid material using the film. <P>SOLUTION: In the transparent gas barrier laminated film constituted by successively laminating a vapor deposition thin film layer (3), an intermediate layer (5) and a sealant layer (6) on at least one side of a base material layer (1) comprising a synthetic resin material through adhesive layers (4 and 4'), a thermally crosslinkable primer coating layer (2) is provided between the base material layer (1) and the vapor deposition thin film layer (3). <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a laminated film used for a lid for a plastic container and a lid using the same, and more specifically, has a high gas barrier property and transparency, and further seals when the lid is opened. The present invention relates to a transparent gas barrier laminated film having good openability without tearing of the laminated film from the surface, and a lid material using the transparent gas barrier laminated film.

  Conventionally, a lid for a plastic container is required to have rigidity (stiffness) from the viewpoint of ease of opening at the time of opening. Generally, two layers of stretched films are bonded together, and a heat-sealable film is bonded. Laminated films are often used.

  In addition, depending on the contents of food, non-food, pharmaceuticals, etc. packaged in the container, the packaging container should be provided with a gas barrier property in order to suppress the deterioration of the contents and maintain their functions and properties. Is required.

  Therefore, a stretched film coated with a vinylidene chloride resin having an appropriate and low gas barrier property has been conventionally used for the laminated film forming the lid.

  For example, biaxially stretched polyethylene terephthalate film (KPET) coated with vinylidene chloride resin (PVDC) 12 μm // biaxially stretched polyethylene terephthalate film (PET) 12 μm // linear low density polyethylene film (L-LDPE) 60 μm (/ The / part shows lamination with an adhesive by a dry lamination method).

  However, since vinylidene chloride resin (PVDC) generates harmful dioxins during incineration, it is taken up as one of the environmental problems and is desired to be replaced.

  Therefore, as an alternative to the biaxially stretched polyethylene terephthalate film (KPET) coated with vinylidene chloride resin (PVDC), a transparent gas barrier film in which an inorganic oxide vapor-deposited thin film is formed on a plastic film has been developed and marketed.

  A transparent gas barrier film (for example, see Patent Document 1) in which a deposited thin film is formed using magnesium oxide as an inorganic oxide on a plastic film, or a transparent gas barrier film (for example, Patent Document 2) in which silicon oxide is used as an inorganic oxide. See).

Prior art documents are shown below.
JP 60-27532 A Japanese Patent Publication No.53-12953

However, a laminated film using the inorganic oxide vapor-deposited film described above, for example, an inorganic oxide vapor-deposited polyethylene terephthalate film (PET) 12 μm // biaxially stretched polyethylene terephthalate film (PET) 12 μm // linear low density polyethylene film ( (L-LDPE) 60 μm (// indicates the lamination with a laminated layer film by dry lamination method), and a lid material made of a laminated film is formed, and a ring-shaped heat seal is applied to the plastic molded container. As a result, tearing of the laminated film occurred in one part from the seal part, and the lid material remained in the container, resulting in a problem that it was difficult to take out the contents.

  That is, the ring seal, which is one of the methods for sealing the lid material to the container, may cause a decrease in the adhesive strength of the seal portion because the heat and pressure during sealing are concentrated in a narrow seal width. Ring seal suitability is required so that the problem of unsealability due to delamination of the seal portion and tearing of the laminated film at the time of opening the lid does not occur, but the above configuration is insufficient as ring seal suitability.

  The present invention is intended to solve such problems of the prior art, is excellent in transparency, environmental friendliness, and has a high gas barrier property. It aims at providing the transparent gas barrier laminated film which does not generate | occur | produce the tear of a laminated | multilayer film, and shows favorable openability, and a cover material using the same.

  The present invention has been made to solve the above-mentioned problems. The invention according to claim 1 of the present invention provides a vapor deposition thin film layer (at least on one surface of a base material layer (1) made of a synthetic resin material). 3) In the transparent gas barrier laminated film in which the intermediate layer (5) and the sealant layer (6) are sequentially laminated via the adhesive layer (4, 4 ′), the base material layer (1) and the deposited thin film layer (3 And a thermally crosslinkable primer coat layer (2).

The invention according to claim 2 of the present invention is the transparent gas barrier laminated film according to claim 1, wherein the thermally crosslinkable primer coat layer (2) has the general formula M (OR) n (wherein M: Si, Zr , Metal elements such as Ti and Al, R: alkyl groups such as CH ₃ and C ₂ H ₅ , n: oxidation number of metal elements), hydrolyzates of the metal alkoxides, or a general formula Trifunctional organosilane represented by R′Si (OR) ₃ (R ′: alkyl group, vinyl group, epoxy group, glycidoxypropyl group, R: alkyl group, etc.) or hydrolysis of the organosilane A transparent gas barrier laminated film comprising a composite of at least one of a product and a polyol compound and an isocyanate compound.

The invention according to claim 3 of the present invention is the transparent gas barrier laminated film according to claim 1, wherein the thermally crosslinkable primer coat layer (2) is represented by the general formula R′Si (OR) ₃ (where R ′ : A transparent gas barrier laminate film comprising a composite of a trifunctional organosilane represented by an amino group, isocyanate group, sulfoxide group, etc., R: alkyl group, etc., a polyol compound and an isocyanate compound. .

  The invention according to claim 4 of the present invention is the transparent gas barrier laminated film according to any one of claims 1 to 3, wherein the deposited thin film layer (3) is an inorganic oxide. It is a laminated film.

  The invention according to claim 5 of the present invention is the transparent gas barrier laminate film according to claim 4, wherein the inorganic oxide is aluminum oxide, silicon oxide, magnesium oxide or a mixture thereof. It is a film.

  The invention according to claim 6 of the present invention is the transparent gas barrier laminated film according to any one of claims 1 to 5, wherein the thickness of the vapor-deposited thin film layer (3) is 5 to 500 nm. Transparent gas barrier laminated film.

  The invention according to claim 7 of the present invention is such that a gas barrier coating layer (7) is further laminated on the vapor-deposited thin film layer (3) of the transparent gas barrier laminate film according to any one of claims 1 to 6. The gas barrier coating layer comprises a water-soluble polymer and at least one of (a) one or more metal alkoxides and hydrolysates thereof, or (b) tin chloride. It is a gas barrier laminate film.

  The invention according to claim 8 of the present invention is such that a gas barrier coating layer (7) is further laminated on the vapor-deposited thin film layer (3) of the transparent gas barrier laminate film according to any one of claims 1 to 6. The gas barrier coating layer (7) is a composite of a water-soluble polymer, (a) at least one of one or more metal alkoxides and hydrolysates thereof, or (b) tin chloride, and an inorganic layered compound. It is a transparent gas barrier laminated film characterized by consisting of a thing.

  The invention according to claim 9 of the present invention is the transparent gas barrier laminated film according to any one of claims 1 to 8, wherein the intermediate layer (5) is a biaxially stretched polyethylene terephthalate film, a biaxially stretched polyamide film, And a transparent gas barrier laminated film characterized by being a biaxially stretched polypropylene film.

  The invention according to claim 10 of the present invention is a lid member attached to the container opening by heat sealing, and is characterized by comprising the transparent gas barrier laminated film according to any one of claims 1 to 9. It is a lid material with excellent openability.

  The invention according to claim 11 of the present invention is the lid material according to claim 10, wherein the lid material is attached to the container opening by a ring seal.

  The transparent gas barrier laminated film of the present invention is the transparent gas barrier laminated film in which a vapor-deposited thin film layer, an intermediate layer, and a sealant layer are sequentially laminated via an adhesive layer on at least one surface of a base material layer made of a synthetic resin material. By having a heat-crosslinkable primer coat layer between the material layer and the vapor-deposited thin film layer, it is excellent in transparency and environmental friendliness, and has a high gas barrier property. The tear of the laminated film does not occur and good openability is exhibited.

  An embodiment of the present invention will be described in detail with reference to FIG.

  FIG. 1 is a sectional side view showing one embodiment of a layer structure of a transparent gas barrier laminated film according to the present invention.

  As shown in FIG. 1, the transparent gas barrier laminated film according to the present invention has a vapor-deposited thin film layer (3), an intermediate layer (5), and a sealant layer (6) on at least one surface of a base material layer (1) made of a synthetic resin material. ) In succession through the adhesive layer (4, 4 '), a thermally crosslinkable primer coat layer (2) between the substrate (1) and the deposited thin film layer (3). It is characterized by having.

  Further, in order to improve the gas barrier property, a gas barrier coating layer (7) can be added between the vapor-deposited thin film layer (3) and the intermediate layer (5).

  The material used for the base material layer (1) is not particularly limited, but a single film and various laminated films can be used in consideration of processability and the like.

  For example, polyesters such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polybutylene terephthalate (PBT), polyolefins such as polyethylene (PE), polypropylene (PP), polystyrene (PS), nylon-6, nylon Polyamide (PA) such as -66, polycarbonate (PC), polyacrylonitrile (PAN), polyimide (PI), polyvinyl chloride (PVC), polyvinylidene chloride (PVDC), polyvinyl alcohol (PVA), ethylene-vinyl alcohol A polymer (EVOH), polyether sulfone (PES), polymethyl methacrylate (PMMA), or a copolymer thereof is an unstretched or stretched film.

  Usually, these are used after being processed into a film shape, and it is preferable to use a polyethylene terephthalate film (PET) arbitrarily stretched in the biaxial direction from the viewpoints of heat resistance, strength, cost and the like.

  The thickness of the base material layer (1) is preferably in the range of 3 to 200 μm, more preferably 6 to 30 μm, in consideration of workability.

  Next, the heat-crosslinkable primer coat layer (2) will be described below. The heat-crosslinkable primer coat layer (2) of the present invention is provided on the substrate layer (1), and the substrate layer It is provided to improve the adhesion between (1) and the deposited thin film layer (3).

What can be used as the thermally crosslinkable primer coat layer (2) in order to achieve the above object is first of the general formula M (OR) n (wherein M: a metal such as Si, Zr, Ti, Al, etc.) Element, R: alkyl group such as CH ₃ , C ₂ H ₅ , n: oxidation number of metal element) or a hydrolyzate of the metal alkoxide, or a general formula, R′Si (OR) ₃ At least one of trifunctional organosilanes represented by (R ′: alkyl group, vinyl group, epoxy group, glycidoxypropyl group, R: alkyl group, etc.) or a hydrolyzate of the organosilane It is a composite comprising a polyol compound and an isocyanate compound.

Next, the heat-crosslinkable primer coat layer (2) is represented by a general formula, R′Si (OR) ₃ (wherein R ′: amino group, isocyanate group, sulfoxide group, R: alkyl group, etc.). A composite composed of a trifunctional organosilane, a polyol compound and an isocyanate compound can also be used.

The metal alkoxide used in the present invention has a general formula, M (OR) n (wherein M: a metal element such as Si, Zr, Ti, Al, etc., R: an alkyl group such as CH ₃ or C ₂ H _5). , N: oxidation number of metal element), for example, an alkoxysilane compound, a zirconium alkoxide compound, a titanium alkoxide compound, and the like can be used.

Specifically, tetramethoxysilane [Si (O—CH ₃ ) ₄ ], tetraethoxysilane [Si (O—C ₂ H ₅ ) ₄ ], tetraisopropoxysilane [Si (O—iso—C ₃ H _{7). 4} ], tetrabutoxysilane [Si (O—C ₄ H ₉ ) ₄ ], dimethyldimethoxysilane [(H ₃ C) ₂ Si (O—CH ₃ ) ₂ ], trimethoxymethylsilane [H ₃ CSi (O -CH _{3) 3],} dimethyldiethoxysilane _{[(H 3 C) 2 Si} (O-C 2 H 5) 2] alkoxysilane compounds such as tetramethoxysilane zirconium _{[Zr (O-CH 3)} 4], tetra Ethoxyzirconium [Zr (O—C ₂ H ₅ ) ₄ ], tetraisopropoxyzirconium [Zr (O-iso-C ₃ H ₇ ) ₄ ], tetrabutoxyzirconium [Zr (O—C ₄ H ₉ ) ₄ ] and the like Zirconi Arm alkoxide compounds, tetramethoxysilane titanium _{[Ti (O-CH 3)} 4], tetraethoxysilane titanium _{[Ti (O-C 2 H} 5) 4], tetraisopropoxy titanium [Ti (O-
and titanium alkoxide compounds such as iso-C ₃ H ₇ ) ₄ ] and tetrabutoxy titanium [Ti (O—C ₄ H ₉ ) ₄ ].

Further, the metal alkoxide used for the heat-crosslinkable primer coat layer (2) has a general formula, M (OR) n (wherein M: a metal element such as Si, Zr, Ti, Al, R: CH ₃ , It may be a hydrolyzate of a compound represented by an alkyl group such as C ₂ H ₅ , n: oxidation number of metal element).

Next, the trifunctional organosilane has a general formula R′Si (OR) ₃ (wherein R ′: alkyl group, vinyl group, epoxy group, glycidoxypropyl group, R: alkyl group, etc.) ), And examples thereof include ethyltrimethoxysilane, vinyltrimethoxysilane, glycidoxypropyltrimethoxysilane, glycidoxytrimethoxysilane, and epoxycyclohexylethyltrimethoxysilane. These compounds may be used alone or in a mixture of two or more.

The trifunctional organosilane used in the heat-crosslinkable primer coat layer (2) is the general formula R′Si (OR) ₃ (wherein R ′: an alkyl group, a vinyl group, an epoxy group). And a hydrolyzate of a compound represented by R: an alkyl group, etc.).

Further, the trifunctional organosilane used in the heat-crosslinkable primer coat layer (2) has a general formula, R′Si (OR) ₃ (wherein R ′: amino group, isocyanate group, sulfoxide group, etc. R: an alkyl group), for example, γ-amino-propyltrimethoxysilane, γ-amino-propyltriethoxysilane, γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, etc. Although these can be mentioned, these compounds may be used alone or in a mixture of two or more.

The trifunctional organosilane used in the heat-crosslinkable primer coat layer (2) is the general formula R′Si (OR) ₃ (wherein R ′: amino group, isocyanate group, sulfoxide group). Or a hydrolyzate of a compound represented by R: an alkyl group or the like.

  Next, a polyester polyol or an acrylic polyol can be used as the polyol compound constituting the thermally crosslinkable primer coat layer (2).

  First, the polyester polyol is terephthalic acid, isophthalic acid, phthalic acid, methylphthalic acid, trimellitic acid, pyromellitic acid, adipic acid, sebacic acid, succinic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid. , Acid raw materials of hexahydrophthalic acid and reactive derivatives thereof, ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-hexanediol, diethylene glycol, dipropylene glycol, 1,4-cyclohexanedimethanol, Among polyester resins obtained by known production methods from alcohol raw materials such as neopentyl glycol, bishydroxyethyl terephthalate, trimethylol methane, trimethylol propane, glycerin and pentaerythritol Those having 2 or more hydroxyl groups on the end (hydroxyl group) but to react with the isocyanate groups of the isocyanate compound added later.

  Next, the acrylic polyol has a hydroxyl group at the terminal out of a polymer compound obtained by polymerizing an acrylic acid derivative monomer or a polymer compound obtained by copolymerization with an acrylic acid derivative monomer and other monomers. It is made to react with the isocyanate group of the isocyanate compound added later.

  Among them, an acrylic polyol obtained by polymerizing an acrylic acid derivative monomer such as ethyl methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, or hydroxybutyl methacrylate alone, or an acrylic polyol copolymerized by adding other monomers such as styrene is preferably used. .

  In consideration of reactivity with an isocyanate compound, the hydroxyl value is preferably between 5 and 200 (KOHmg / g).

  Next, the blending ratio of the polyol compound and the trifunctional organosilane is preferably in the range of 1/1 to 100/1 by weight ratio, more preferably in the range of 2/1 to 50/1. It is.

  The dissolving and diluting solvent is not particularly limited as long as it can be dissolved and diluted. For example, esters such as ethyl acetate and butyl acetate, alcohols such as methanol, ethanol and isopropyl alcohol, and ketones such as methyl ethyl ketone. In addition, aromatic hydrocarbons such as toluene and xylene can be used alone or arbitrarily blended.

  However, since an aqueous solution such as hydrochloric acid or acetic acid is sometimes used to hydrolyze the trifunctional organosilane, a solvent in which isopropyl alcohol or the like and a polar solvent, ethyl acetate, are arbitrarily mixed is used as a co-solvent. More preferably.

  Further, a reaction catalyst may be added in order to accelerate the reaction when the trifunctional organosilane is blended.

The catalyst to be added is a tin compound such as tin chloride (SnCl ₂ , SnCl ₄ ), tin oxychloride (SnOHCl, Sn (OH) ₂ Cl ₂ ), tin alkoxide from the viewpoint of reactivity and polymerization stability. Is preferred.

  These catalysts may be added directly at the time of compounding, or may be added after being dissolved in a solvent such as methanol.

  If the addition amount is too small or too large, the catalytic effect cannot be obtained, and therefore the molar ratio is preferably within a range of 1/10 to 1/10000 with respect to the trifunctional organosilane, more preferably 1 More preferably within the range of / 100 to 1/2000.

  Next, the isocyanate compound is added in order to improve the adhesion with the base material layer (1) or the vapor-deposited thin film layer (3) by a urethane bond formed by reacting with polyester polyol or acrylic polyol. Acts as a crosslinking agent or curing agent.

  As such an isocyanate compound, monomers such as aromatic tolylene diisocyanate, diphenylmethane diisocyanate, aliphatic xylylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, and polymers and derivatives thereof are used. Are used alone or as a mixture.

  The blending ratio of the polyol compound and the isocyanate compound is not particularly limited, but if the isocyanate compound is too small, curing may be poor, and if it is too much, blocking or the like occurs and there is a problem in processing.

  Therefore, the mixing ratio of the polyol compound and the isocyanate compound is preferably 50 times or less of the isocyanate group derived from the isocyanate compound than the hydroxyl group derived from the polyol compound.

  Particularly preferred is a case where an isocyanate group and a hydroxyl group are mixed in an equal amount, and a known method can be used as the mixing method.

  Next, as a method for preparing a primer solution for forming the primer coat layer (2), a composite mixed solution in which an organosilane having a trifunctional group, a polyol compound and an isocyanate compound are mixed at an arbitrary mixing ratio is prepared. It is formed by coating the base material layer (1).

  As a method of making the composite mixed solution, a method of mixing a trifunctional organosilane and a polyol compound, adding a solvent and a diluent, diluting to an arbitrary concentration, and then mixing with an isocyanate compound to make a composite mixed solution, Alternatively, a method in which a trifunctional organosilane is mixed in a solvent in advance and then a polyol compound is mixed and then diluted to an arbitrary concentration by adding a solvent and a diluent, and then an isocyanate compound is added to make a composite mixed solution. and so on.

  Various additives such as tertiary amines, imidazole derivatives, carboxylic acid metal chlorides, quaternary ammonium salts, quaternary phosphonium salts, and other accelerators, phenols, sulfurs, and phosphites It is also possible to add antioxidants, leveling agents, flow preparation agents, catalysts, crosslinking reaction accelerators, fillers and the like as necessary.

  Next, the thickness of the heat-crosslinkable primer coat layer (2) is not particularly limited as long as a uniform coating film can be formed, but the dry film thickness is preferably in the range of 5 to 300 nm.

  If the thickness is 5 nm or less, a uniform coating cannot be formed, and stable adhesion cannot be obtained. If the thickness is 300 nm or more, physical properties are reached, which is not economical.

  Next, as a method of forming the heat-crosslinkable primer coat layer (2), for example, a known gravure roll coating method, reverse roll coating method, bar coating method, dropping method or the like can be used.

  In order to further improve the adhesion to the heat-crosslinkable primer coat layer (2), the surface of the base material layer (1) is subjected to corona discharge treatment, glow discharge treatment, low temperature plasma treatment, flame treatment, chemicals. Pretreatment may be performed by a known method such as treatment or solvent treatment.

  Moreover, it is also possible to use well-known various additives and stabilizers, for example, an antistatic agent, a ultraviolet absorber, a plasticizer, a lubricant, etc. on the front and back surfaces of the base material layer (1).

  As mentioned above, the heat-crosslinkable primer coat layer (2) described above imparts resistance to high heat and pressure by the ring seal when the lid material is put on the plastic container body and ring-sealed. 1) and the deposited thin film layer (3) are prevented from deteriorating before and after the ring seal of the adhesion force, and the function as a lid material is sufficiently exhibited.

  Further, the heat-crosslinkable primer coat layer (2) is preferably provided with an aging step after being applied to the base material layer (1) in order to obtain its performance more sufficiently. It is better to leave in an atmosphere of 40 to 60 ° C. for about 1 to 5 days.

Next, as the vapor-deposited thin film layer (3) of the inorganic oxide, it is basically possible to use a metal oxide such as aluminum, silicon, magnesium, calcium, potassium, tin, sodium, boron. , Oxides of titanium, lead, zirconium, yttrium, or a mixture thereof.

  In general, aluminum oxide, silicon oxide, and magnesium oxide are preferably used from the viewpoint of transparency, physical properties, and productivity.

  As a method of forming such a vapor deposition layer, a vacuum vapor deposition method, a sputtering method, or the like can be used. However, in consideration of productivity, the vacuum vapor deposition method is preferable.

  There are three types of vacuum deposition methods, depending on the form of the body to be vapor-deposited. 1) Batch method: vapor deposition method of molded products, 2) take-up semi-continuous method: vacuum for roll-shaped film (web) After unwinding, vapor deposition, and winding in the system, return to the atmospheric system again and take out the vapor deposition product. 3) Unwinder (unwinding device) for roll type film (web) ) And a rewinder (winding device) are arranged in the atmospheric system, and a vapor deposition drum and an evaporation source are arranged in a vacuum system to vaporize the evaporated substance on a roll film (web). This is a completely continuous method called a to-air method and has a feature of high productivity.

  When evaporating a vaporized material on a roll-shaped film (web), a take-up semi-continuous method is particularly widespread. Describes the internal structure.

  First, the constituent elements are a roll film (web), an evaporation source, an evaporation substance, a vapor deposition drum, a vacuum system, an unwinder (unwinding device), a rewinder (winding device), a guide roll, and the like.

  Next, the outline of the work process will be described. First, as a preparatory step, the door of the vacuum evaporation apparatus is opened, a roll-shaped film (web) is set in the unwinder (unwinding apparatus), and it is arranged between the unwinder and the evaporation drum. The web is caused to travel to the vapor deposition drum through a guide roll that is wound around the rewinder (winding device) via a guide roll disposed between the web and the rewinder (winding device). Preparation of vapor deposition of the evaporating substance on is completed.

  Next, the door of the vacuum deposition apparatus is closed, and the vacuum suction chamber in the vacuum deposition apparatus and the vacuum deposition chamber divided by the partition walls are set to a predetermined vacuum environment by a vacuum pump, and the web is unwound from the unwinder. The evaporating substance is evaporated on the web by evaporating the evaporating substance from the evaporation source disposed at the lower part of the evaporating drum on the web that has been run through the guide roll.

  Since the vapor deposition drum is cooled, the vaporized substance is recrystallized and fixed on the web, and the vapor deposited on the rewinder side guide roll is wound around the rewinder.

  The internal structure of the vacuum deposition apparatus is divided into a vacuum suction constant pressure chamber and a vacuum deposition chamber by partition walls. The vacuum suction constant pressure chamber is composed of an unwinder, guide roll, tension control device, speed control device, position control device, and vapor deposition drum. Some rewinders are arranged.

In the vacuum deposition chamber, a part of the deposition drum, the evaporation source, its heating device, and the like are arranged, and the vacuum suction constant pressure chamber has a degree of vacuum of 1 by a vacuum pump attached to the periphery of the vacuum deposition apparatus main body. × 10 ⁰ MPa about, the vacuum deposition chamber provided via the partition wall is set to a degree 1 × 10 ^-2 MPa (SI units).

  Since the two chambers are divided by the partition walls, impurities (dust) such as gas generated from the web in the vacuum suction constant pressure chamber are unlikely to adversely affect the deposition in the vacuum deposition chamber.

  On the contrary, the radiant heat from the evaporation source arranged in the vacuum deposition chamber has little influence on the vacuum suction constant pressure chamber, so that the influence of the heat on the web is small.

  The vacuum deposition method is also a heating method: 1) Indirect resistance method, 2) Direct resistance heating method (wire feed method), 3) High frequency induction heating method, 4) Electron beam method (Electoron Beam, EB method for short) 4 There are two methods, but when the evaporated substance uses an insulating metal oxide such as silicon oxide or aluminum oxide, the electron beam method with high energy conversion efficiency is optimal.

  The wound-up electron beam vacuum deposition method is a method in which the evaporative material is directly irradiated with an electron beam and scanned on the surface of the evaporative material, and the surface of the evaporative material is heated. And evaporating the evaporated substance.

  Although the thickness of this vapor deposition thin film layer (3) is suitably selected by the end use of a vapor deposition film (A), it is preferable to exist in the range of 5-400 nm.

  If the film thickness is less than 5 nm, a uniform film cannot be provided, so that a sufficient gas barrier property cannot be obtained. If the film thickness exceeds 400 nm, flexibility is lost, and due to external factors such as bending and pulling, the deposited film is not formed. It is not preferable because cracks and peeling easily occur.

  On the vapor-deposited thin film layer (3) of the vapor-deposited film (A) comprising the base material layer (1) / thermally crosslinkable primer coat layer (2) / vapor-deposited thin film layer (3) prepared as described above. The intermediate layer (5) is provided via the adhesive layer (4).

  The intermediate layer (5) is provided between the vapor-deposited film (A) and the sealant layer (6) to prevent tearing of the transparent gas barrier laminated film from the sealing surface when opened when used as a lid. For example, polyesters such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polybutylene terephthalate (PBT), polyethylene (PE), polypropylene (PP), polystyrene (PS), etc. Polyamide (PA) such as polyolefin, nylon-6, nylon-66, polycarbonate (PC), polyacrylonitrile (PAN), polyimide (PI), polyvinyl chloride (PVC), polyvinylidene chloride (PVDC), polyvinyl alcohol (PVA) ), Ethylene-vinyl alcohol Polymer (EVOH), polyether sulfone (PES), a non-stretched or stretched film of polymethylmethacrylate (PMMA), etc., and copolymers thereof.

  Usually, these are processed into a film and used, particularly from the viewpoint of mechanical strength and thermal stability, either a biaxially stretched polyethylene terephthalate film, a biaxially stretched polyamide film, or a biaxially stretched polypropylene film. Preferably there is.

  The thickness of the intermediate layer (5) is preferably in the range of 3 to 200 μm, more preferably in the range of 6 to 30 μm, considering the strength and workability.

  Next, as the adhesive layer (4), it is possible to use adhesives for laminates such as polyurethane, polyester, epoxy, polyacryl, polyvinyl acetate, cellulose, and the like.

  The lamination method may be a known method such as a dry lamination method, a non-solvent dry lamination method, a hot melt lamination method, or an extrusion lamination method.

  For example, the dry lamination method includes three sections: a coating unit that applies an adhesive on a film, a drying device, and a nip roller unit, and an unwinding, winding, and tension control system.

  The coating portion generally employs a gravure coating method or a reverse coating method.

  As the lamination adhesive, a solvent type adhesive or a solventless type adhesive is used. However, when a solventless type adhesive is used, a drying apparatus is not necessary, and this is called a non-solvent dry lamination method. Yes.

  The hot melt lamination method is a method in which a hot melt adhesive such as a heat-melted ethylene-vinyl acetate copolymer (EVA) is applied onto a film, and another film is immediately laminated.

  The extrusion lamination method involves heating a thermoplastic resin such as polyethylene or polypropylene, melting it in a cylinder called a cylinder, extruding it by applying pressure with a screw, and forming a narrow slit called a T die at the tip of the cylinder. The resin melted in the form of a curtain is extruded and laminated into a film.

  As described above, as a method of laminating the deposited film (A) and the intermediate layer (5), a dry lamination method, a non-solvent dry lamination method, a hot melt lamination method, an extrusion lamination method, and the like can be used. In view of heat resistance and cost, a dry lamination method is preferable.

  As another lamination method, a sandwich lamination method can also be used.

  Further, in order to provide a function as a lid, a sealant layer (6) that can be sealed with the plastic container body is provided on the intermediate layer (5) via an adhesive layer (4 ').

  Examples of the sealant layer (6) include polyolefin resins such as low density polyethylene (LDPE), medium density polyethylene (MDPE), high density polyethylene (HDPE), linear low density polyethylene (L-LDPE), and unstretched polypropylene. (CPP), ethylene-vinyl acetate copolymer (EVA), ionomer, cyclic polyolefin and the like can be used.

  The thickness of the sealant layer (6) is preferably in the range of 15 to 200 μm, more preferably in the range of 30 to 60 μm, considering the strength and workability.

  The adhesive layer (4 ') uses the same material and lamination method as the adhesive layer (4).

  The transparent gas barrier laminate film of the present invention may further include a printed layer (not shown), an anchor coating layer (not shown), and the like.

  When the printing layer is provided on the base material layer (1), the printing surface of the base material layer (1) can be printed on either the front surface or the back surface. In consideration of weather resistance and the like, it is preferable to provide a printing layer on the back surface of the base material layer (1).

  As the printing ink for forming the printing layer, a color material composed of a pigment or a dye that gives color to the ink, a resin that adheres to the printing medium while dispersing and holding the color material in fine particles, and the resin are used. A vehicle composed of a solvent that can stably dissolve, disperse the pigments and dyes, maintain the fluidity of the ink, and transfer an appropriate amount of ink from the printing plate, and further disperse the coloring material. The pigment is formed from an auxiliary agent such as a surfactant for the purpose of improving color development, preventing precipitation, and improving fluidity. In particular, the colorant is preferably a pigment having good weather resistance.

  As a printing method for providing the printing layer, for example, a known printing method such as a gravure printing method, a silk screen printing method, a flexographic printing method, and an offset printing method can be used, but copper plating is performed on the surface of an iron cylinder (cylinder). Forming a base, providing a release layer on the copper-plated surface, further copper-plating, and creating a recess (cell) by engraving or corrosion method on the polished copper surface of the surface, A gravure printing method in which the printing ink in the cell is transferred to the base material layer (1), can be printed in a colorful manner, and has a high appealing effect is preferable.

  In addition, when printing on the base material layer (1), if necessary to improve the adhesion between the base material layer (1) and the ink, ozone treatment is performed on the printing surface side of the base material layer (1). Pretreatment such as corona treatment is preferably performed, and an anchor coating agent or the like may be further coated.

  Examples of the anchor coat agent include isocyanate-based (urethane-based), polyethyleneimine-based, polybutadiene-based, and organic titanium-based anchor coat agents, or polyurethane-based, polyacrylic-based, polyester-based, epoxy-based, and polyvinyl acetate-based. , Cellulosic, and other lamination adhesives can be used.

  As a method of coating the anchor coating agent, a known gravure roll coating method, reverse roll coating method, bar coating method, dropping method, or the like can be used.

  Next, by adding the gas barrier coating layer (7) between the vapor-deposited thin film layer (3) and the intermediate layer (5) of the transparent gas barrier laminated film of the present invention described above, the gas barrier property is further improved. It can be further enhanced.

  As shown in FIG. 1, a base material layer (1), a heat crosslinkable primer coat layer (2), a vapor deposition thin film layer (3), a gas barrier coating layer (7), an adhesive layer (4), an intermediate layer (5 ), An adhesive layer (4 ′), and a sealant layer (6), a transparent gas barrier laminated film having a layer structure.

  The gas barrier coating layer (7) prevents various secondary damages in the post-process of the vapor deposition thin film layer (3) and provides a higher gas barrier property on the vapor deposition thin film layer (3). An aqueous solution or a water / alcohol mixed solution containing at least one of a water-soluble polymer and (a) one or more metal alkoxides and hydrolysates thereof, or (b) tin chloride. A coating agent containing as a main component is applied onto the deposited thin film layer (3) to form a gas barrier coating layer (7).

For example, a solution in which a water-soluble polymer and tin chloride are dissolved in an aqueous (aqueous solution or water / alcohol mixed solution) solvent, or a solution in which a metal alkoxide is directly or previously hydrolyzed and mixed. Is deposited on the vapor-deposited thin film layer (3) and dried by heating.

  Alternatively, the gas barrier coating layer (7) may be an aqueous solution containing at least one of a water-soluble polymer and (a) one or more metal alkoxides and hydrolysates thereof, or (b) tin chloride. You may form by apply | coating the coating agent which added the inorganic layered compound to the alcohol mixed solution.

  Examples of the water-soluble polymer include polyvinyl alcohol (PVA), polyvinyl pyrrolidone, starch, methyl cellulose, carboxymethyl cellulose, and sodium alginate.

  In particular, polyvinyl alcohol (PVA) is preferable because of its excellent gas barrier properties. The polyvinyl alcohol (PVA) here is generally obtained by saponifying polyvinyl acetate.

  Examples of the polyvinyl alcohol (PVA) include fully saponified polyvinyl alcohol (PVA) in which only several percent of acetic acid groups remain from so-called partially saponified polyvinyl alcohol (PVA) in which several tens of percent of acetic acid groups remain. There is no particular limitation.

  The tin chloride is stannous chloride, stannic chloride, or a mixture thereof, and anhydrides and hydrates of these tin chlorides can also be used.

  Next, as the metal alkoxide, tetraethoxysilane, triisopropoxyaluminum and the like that are relatively stable in an aqueous solvent after hydrolysis are preferable.

  Furthermore, known additives such as isocyanate compounds, silane coupling agents, or dispersants, stabilizers, viscosity modifiers, colorants and the like are added to the coating agent as necessary, as long as the gas barrier properties are not impaired. Can be added.

  As the isocyanate compound added to the coating agent, those having two or more isocyanate groups in the molecule are preferable.

  Examples of such isocyanate compounds include monomers such as tolylene diisocyanate, triphenylmethane triisocyanate, and tetramethylxylene diisocyanate, and polymers and derivatives thereof.

  The gas barrier coating layer (7) is formed on the deposited thin film layer (3) by applying a known method such as a gravure coating method, reverse roll coating method, air knife coating method, etc., followed by heating and drying. Is done.

  In this case, the thickness of the gas barrier coating layer (7) is preferably in the range of 0.01 to 50 μm after drying.

  When the thickness after drying is 0.01 μm or less, sufficient gas barrier properties cannot be obtained, and when it is 50 μm or more, the coating film is liable to crack and adversely affects the gas barrier.

The inorganic layered compound refers to a crystalline inorganic compound having a layered structure, such as kaolinite, hyrosite, curdstone, smectite, vermiculite, pyrophyllite, mica, and the like. Examples include chemicals such as clay minerals, synthetic smectites, and synthetic mica.

  As long as it is an inorganic layered compound, its type, particle size, aspect ratio, and the like can be appropriately selected depending on the desired required quality and the like, and are not particularly limited, but are highly swellable and have a layered structure. Specific examples of the smectite group include montmorillonite and saponite because water-soluble polymers can easily form a nanocomposite structure due to the inclusion of a water-soluble polymer in the correlation. Among them, swelling, dispersibility, price, and processability are examples. From the viewpoint, montmorillonite is more preferable.

  As described above, it has excellent transparency and environmental friendliness, and has a high gas barrier property, and when used as a lid material, the tear of the laminated film from the sealing surface does not occur at the time of opening, and it shows a good opening property. A transparent gas barrier laminated film can be provided.

  In addition, the lid material using the transparent gas barrier laminated film can be attached to the container opening by heat sealing, by the ring seal method, without reducing the adhesive strength of the sealing portion, and at the time of opening delamination or lid material It is possible to provide a lid material excellent in ring seal suitability without tearing.

  In the following, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these and is applied to a wider range.

<Example 1>
As shown in FIG. 1, the transparent gas barrier laminated film according to the present invention uses a biaxially stretched polyethylene terephthalate film (PET) having a thickness of 12 μm and a corona discharge treatment on one side as the base material layer (1). did.

  A thermally crosslinkable primer coat liquid having the following composition was applied and dried on the corona discharge treated surface by a gravure roll coating method, and a thermally crosslinkable primer coat (2) having a dried thickness of 0.1 μm was laminated.

  Thereafter, aging was performed at 40 ° C. for 4 days in order to promote crosslinking of the thermally crosslinkable primer coat layer (2).

  Next, the deposited thin film layer (3) made of an inorganic oxide made of aluminum oxide having a thickness of 20 nm is laminated on the thermally crosslinkable primer coat layer (2) by an electron beam heating type vacuum vapor deposition apparatus. The vapor deposition film (A) which consists of was obtained.

  Further, a gas barrier coating liquid having the following composition is applied and dried on the vapor deposition thin film layer (3) of the vapor deposition film (A) by a gravure roll coating method, and the dried gas barrier coating layer having a thickness of 0.5 μm. (7) was laminated.

Subsequently, through the adhesive layer (4) obtained by applying 3.5 g / m ² (solid content) of a polyurethane-based adhesive (A525 / A52 manufactured by Mitsui Takeda Chemical Co., Ltd.) on the gas barrier coating layer (7), An intermediate layer (5) made of a biaxially stretched polyethylene terephthalate film (PET) having a thickness of 12 μm (E5202 manufactured by Toyobo Co., Ltd.) subjected to double-sided corona discharge treatment was laminated by a dry lamination method.

Further, the thickness of the intermediate layer (5) is 50 by dry lamination method through an adhesive layer (4 ′) in which 3.5 g / m ² (solid content) of polyurethane adhesive is applied as described above.
A sealant layer (6) made of a linear low-density polyethylene film (L-LDPE) of μm (LX-711C manufactured by Idemitsu Unitech Co., Ltd.) is laminated and aged at 40 ° C. for 4 days to obtain a transparent cover material. A gas barrier laminated film was obtained.

  Preparation of the thermally crosslinkable primer coating solution was performed by mixing 0.6 g of isocyanatepropyltrimethoxysilane with 6 g of acrylic polyol (solid content 50%), stirring and adjusting the solution with a diluting solvent (solid content 20%) 7 g On the other hand, 1.5 g of an isocyanate resin (solid content 50%) and a diluting solvent were added and stirred for 30 minutes to adjust the solid content to 2% to obtain a thermally crosslinkable primer coating solution.

The gas barrier coating solution was prepared by adding 89.6 g of 0.1N-hydrochloric acid to 10.4 g of tetraethoxysilane, stirring for 30 minutes, and then hydrolyzing 3 wt% (in terms of SiO ₂ ) solid content and polyvinyl alcohol. (PVA) solution was mixed to obtain a gas barrier coating solution.

<Example 2>
In Example 1, the transparent gas barrier laminated film for lid | cover materials was obtained similarly except having changed the vapor deposition thin film layer (3) which consists of inorganic oxides into 40-nm-thick silicon oxide.

  Below, the comparative example of this invention is demonstrated.

<Comparative Example 1>
A transparent gas barrier laminated film for a lid material was obtained in the same manner as in Example 1 except that the thermally crosslinkable primer coat layer (2) was not laminated.

<Comparative example 2>
In Example 1, instead of the heat-crosslinkable primer coat layer (2), a polyurethane-based primer coat solution composed of a polyester polyol and an isocyanate compound is applied and dried to form a polyurethane-based primer coat having a thickness of 0.1 μm. A transparent gas barrier laminated film for a lid material was obtained in the same manner except that the layers were laminated.

  About the transparent gas barrier laminated films for Examples 1 and 2 and Comparative Examples 1 and 2, the respective oxygen gas barrier properties and the transparent gas barrier laminated films were cut into predetermined shapes to produce lids, and sealing conditions The openability of 30 pieces each sealed with a ring seal (seal width 7 mm) against an easy-peelable molded container (magic top SEM) was evaluated, and the results are shown in Table 1.

表１は、蓋材用の透明ガスバリア積層フィルムの開封性を評価した表である。

Table 1 is a table in which the openability of the transparent gas barrier laminated film for the lid material was evaluated.

  In addition, the evaluation method of oxygen gas barrier property is based on JIS K-7126 B method (measurement conditions 30 ° C. and 70% RH), and the evaluation of openability is evaluated by the number of unsuccessful unsealings among 30 unsealed items.

  In addition, the number of unsuccessful opening means that the lid material was torn when it was opened by hand and could not be opened over the entire opening.

  Below, the comparison result of an Example and a comparative example is demonstrated.

<Comparison result>
The products of the present invention according to Examples 1 and 2 are not only excellent in gas barrier properties, but also have extremely excellent openability regardless of ring seal conditions, as a cover material. It turns out that the performance of is fully satisfied.

  On the other hand, Comparative Examples 1 and 2 are excellent in oxygen gas barrier properties, but there are defects at the time of opening, especially when the ring seal conditions become severe (when the temperature and pressure increase), the number of defects is small. From the increase, it can be seen that the practical properties as a lid material are insufficient.

It is a sectional side view which shows one Example of the layer structure of the transparent gas barrier laminated film which concerns on this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Base material layer 2 ... Thermal crosslinkable primer coat layer 3 ... Deposition thin film layer 4 ... Adhesive layer 4 '... Adhesive layer 5 ... Intermediate layer 6 ... Sealant Layer 7 ... Gas barrier coating layer A ... Deposition film

Claims (11)

  In a transparent gas barrier laminated film in which a vapor-deposited thin film layer, an intermediate layer, and a sealant layer are sequentially laminated via an adhesive layer on at least one surface of a base layer made of a synthetic resin material, the substrate layer and the vapor-deposited thin film layer A transparent gas barrier laminated film comprising a thermally crosslinkable primer coat layer. The thermally crosslinkable primer coat layer has a general formula M (OR) n (wherein M: a metal element such as Si, Zr, Ti and Al, R: an alkyl group such as CH ₃ and C ₂ H ₅ , n: A metal alkoxide represented by the oxidation number of a metal element) or a hydrolyzate of the metal alkoxide, or a general formula, R′Si (OR) ₃ (R ′: alkyl group, vinyl group, epoxy group, glycidoxypropyl group) Or the like, wherein R is an alkyl group or the like, or a hydrolyzate of at least one of a trifunctional organosilane represented by R and an alkyl group, and a composite of a polyol compound and an isocyanate compound. The transparent gas barrier laminated film according to 1. The thermally crosslinkable primer coat layer has a trifunctional group represented by the general formula, R′Si (OR) ₃ (wherein R ′: amino group, isocyanate group, sulfoxide group, etc., R: alkyl group, etc.). 2. The transparent gas barrier laminate film according to claim 1, comprising a composite of an organosilane, a polyol compound and an isocyanate compound.   The transparent gas barrier laminated film according to any one of claims 1 to 3, wherein the deposited thin film layer is an inorganic oxide.   The transparent gas barrier laminated film according to claim 4, wherein the inorganic oxide is aluminum oxide, silicon oxide, magnesium oxide or a mixture thereof.   The transparent gas barrier laminated film according to any one of claims 1 to 5, wherein a thickness of the vapor-deposited thin film layer is 5 to 500 nm.   A structure in which a gas barrier coating layer is further laminated on the vapor-deposited thin film layer of the transparent gas barrier laminate film according to any one of claims 1 to 6, wherein the gas barrier coating layer comprises a water-soluble polymer, and (a) A transparent gas barrier laminated film comprising at least one of one or more metal alkoxides and hydrolysates thereof or (b) tin chloride.   A structure in which a gas barrier coating layer is further laminated on the vapor-deposited thin film layer of the transparent gas barrier laminate film according to any one of claims 1 to 6, wherein the gas barrier coating layer comprises a water-soluble polymer, and (a) A transparent gas barrier laminated film comprising a composite of at least one of at least one metal alkoxide and a hydrolyzate thereof or (b) tin chloride and an inorganic layered mineral.   The transparent gas barrier laminate film according to any one of claims 1 to 8, wherein the intermediate layer is any one of a biaxially stretched polyethylene terephthalate film, a biaxially stretched polyamide film, and a biaxially stretched polypropylene film. .   A lid material that is attached to a container opening by heat sealing, and comprising the transparent gas barrier laminated film according to any one of claims 1 to 9, wherein the lid material has excellent openability. The lid member according to claim 10, wherein the lid member is attached to the container opening by a ring seal.

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