JP2010000743A - Gas barrier laminate - Google Patents

Abstract

An object of the present invention is to provide a gas barrier laminate excellent in water resistance and hot water resistance that does not cause deterioration of physical properties such as adhesion deterioration even after being stored for a certain period of time in a hot and humid environment. I will provide a.
A gas barrier film in which at least an anchor coat layer and an inorganic vapor deposition layer are laminated on one side or both sides of a base film made of a plastic material, and the inorganic film after the hydrothermal treatment of the gas barrier film at 120 ° C. for 30 minutes. adhesion strength measured in water of the deposition layer and the substrate film is at 1N / 15 mm or more, to 3000cm ^-1 ~3500cm ^-1 to peeling boundary gas barrier laminate, characterized in that there is IR absorption based on OH stretching vibration Provide the body.
[Selection] Figure 1

Description

  It relates to a gas barrier laminate, and is a high barrier film particularly excellent in water resistance and hot water resistance.

  In recent years, food and pharmaceutical packaging has been required to prevent the influence of oxygen, water vapor, and other gases that alter the contents in order to suppress the alteration of the contents and maintain their functions and properties. Gas barrier films that block (gas) have been used. In recent years, this gas barrier film has been used in non-food packaging such as electronic materials, liquid crystal display elements, solar cells, electromagnetic wave shields, touch panels, EL substrates, color filters, etc. The use for materials is being considered. Since the range of use and the period are greatly expanded for this industrial material application, physical property guarantees after storage for a certain period in a high temperature and high humidity environment are required as an accelerated test.

  Conventional gas barrier films mainly include metal foils made of metals such as aluminum, resin films such as polyvinyl alcohol and ethylene vinyl alcohol copolymers, polyvinylidene chloride and polyacrylonitrile, or plastic films coated with these resins. Has been used. However, metal foil and metal vapor-deposited film have excellent gas barrier properties, but the contents cannot be confirmed through the packaging material, metal detectors cannot be used for inspection, and they must be treated as non-combustible materials when discarded after use. There are problems such as unavoidable. Gas barrier resin films and films coated with them are highly temperature and humidity dependent and cannot maintain high gas barrier properties. Furthermore, vinylidene chloride, polyacrylonitrile, etc. may be a source of harmful substances when discarded or incinerated. There are some problems. In other words, it can be said that the gas barrier wrapping materials that are currently used mainly have various problems.

  As a method for solving these problems, a laminated structure in which a metal oxide sol is coated on a metal oxide vapor-deposited plastic film (see Patent Document 1) has been disclosed. Water resistance and hot water resistance are required, and improvements are desired.

The patent literature is as follows.
Japanese Patent Laid-Open No. 7-164591 JP 11-129384 A JP-A-11-147276

  The object of the present invention is excellent in water resistance and hot water resistance, which can maintain high barrier properties without causing deterioration of physical properties such as adhesion reduction even after hydrothermal treatment or storage in a high temperature and high humidity environment for a certain period of time. The object is to provide a gas barrier laminate.

The present invention has been made to solve such problems, and the object of the present invention is, in claim 1, to provide at least an anchor coat layer and an inorganic vapor deposition layer on one or both sides of a base film made of a plastic material. The adhesion strength measured in water between the inorganic vapor-deposited layer and the substrate film after hydrothermal treatment at 120 ° C. for 30 minutes of the gas barrier film is 1 N / 15 mm or more, and 3000 cm at the peeling interface. is solved by a gas barrier laminate, characterized in that the ^{-1 ~3500cm -1} is IR absorption based on OH stretching vibration.

According to claim 2, is solved by the gas barrier laminate according to claim 1, wherein the said anchor coat layer is IR absorption based on OH stretching vibration 3000cm ^-1 ~3500cm ^-1.

In claim 3, the anchor coat layer having IR absorption based on the OH stretching vibration is Si (OR) ₄ (wherein R represents CH ₃ , C ₂ H ₅ , or C ₂ H ₄ OCH ₃ ) and its hydrolysis. One of the decomposition products, (R′Si (OR ″) ₃ ) _n (where R ′ represents an organic functional group, R ″ represents CH ₃ , C ₂ H ₅ , or C ₂ H ₄ OCH _3. And a hydrolyzate thereof. This is solved by the gas barrier laminate according to claim 1 or 2.

In claim 4, the anchor coat layer having IR absorption based on the OH stretching vibration is Si (OR) ₄ (wherein R represents CH ₃ , C ₂ H ₅ , or C ₂ H ₄ OCH ₃ ) and its hydrate. One of the decomposition products, (R′Si (OR ″) ₃ ) _n (where R ′ represents an organic functional group, R ″ represents CH ₃ , C ₂ H ₅ , or C ₂ H ₄ OCH _3. And a hydrolyzate thereof, and a water-soluble polymer, and is solved by the gas barrier laminate according to claim 1 or 2.

According to claim 5, wherein the anchor coat layer comprises at least two or more layers, characterized in that a layer to layer and 3000cm ^-1 ~3500cm ^-1 consisting of a non-aqueous resin is IR absorption based on OH stretching vibration sequentially stacked This is solved by the gas barrier laminate according to any one of claims 1 to 4.

  In Claim 6, the anchor coat layer made of the non-aqueous resin is made of an acrylic polyol and an isocyanate resin, which is solved by the gas barrier laminate according to claim 5.

  The seventh aspect of the present invention is solved by the gas barrier laminate according to any one of the first to sixth aspects, wherein the inorganic vapor deposition layer is made of silicon oxide.

  An eighth aspect of the present invention is solved by the gas barrier laminate according to any one of the first to seventh aspects, wherein an overcoat layer is laminated on the vapor deposition layer.

The overcoat layer according to claim 9 is one of Si (OR) ₄ (wherein R represents CH ₃ , C ₂ H ₅ , or C ₂ H ₄ OCH ₃ ) and a hydrolyzate thereof, (R 'Si (OR ″) ₃ ) _n (where R ′ represents an organic functional group, R ″ represents CH ₃ , C ₂ H ₅ , or C ₂ H ₄ OCH ₃ ) and its hydrolyzate The gas barrier laminate according to any one of claims 1 to 8, wherein the gas barrier laminate is one of them and a water-soluble polymer.

  A tenth aspect of the present invention is solved by the gas barrier laminate according to any one of the first to ninth aspects, wherein a film is laminated on the gas barrier laminate and / or on the opposite surface.

  In Claim 11, it uses the gas barrier laminated body for the solar cell back surface protection sheet which is one member which comprises a solar cell module, It is solved by the gas barrier laminated body in any one of the Claims 1 thru | or 10 characterized by the above-mentioned.

According to the present invention, a gas barrier excellent in water resistance and hot water resistance that can maintain high barrier properties without causing deterioration of physical properties such as adhesion reduction even after storage for a certain period of time in a hot and humid environment. A laminate is provided.

  The present invention will be described in more detail with reference to the drawings. 1 and 2 are cross-sectional views illustrating a gas barrier film laminate of the present invention.

  FIG. 1 is a side sectional view of a packaging material according to an embodiment of the present invention, in which a base film 1, an anchor coat layer I2, an anchor coat layer II3, an inorganic vapor deposition layer 4, an adhesive layer 5, and a sealant film 6 are sequentially laminated. It has a laminated structure.

  FIG. 2 is a side sectional view of a packaging material according to an embodiment of the present invention, in which a base film 1, an anchor coat layer I2, an anchor coat layer II3, an inorganic vapor deposition layer 4, an overcoat layer 7, an adhesive layer 5, and a sealant. It has a laminated structure in which the films 6 are sequentially laminated.

  The base film described above is a transparent plastic material, and a transparent film is preferable in order to make use of the transparency of the deposited thin film layer. For example, polyester films such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), polyolefin films such as polyethylene and polypropylene, polystyrene films, polyamide films such as nylon-6, nylon 66, polyvinyl alcohol, polyvinyl chloride film, polycarbonate A film, a polyacrylonitrile film, a polyimide film, or the like is used, which may be either stretched or unstretched, and preferably has mechanical strength and dimensional stability. These are processed into a film and used. In particular, polyethylene terephthalate arbitrarily stretched in the biaxial direction is preferably used. In addition, various known additives and stabilizers such as an antistatic agent, an ultraviolet ray preventing agent, a plasticizer, a lubricant, and the like may be used on the surface of the base material. In order to improve the adhesion to the thin film, As pretreatment, corona treatment, low-temperature plasma treatment, ion bombardment treatment may be performed, chemical treatment, solvent treatment, or the like may be performed.

  The thickness of the base film is not particularly limited. However, considering the suitability as a packaging material and the workability in the case of laminating other layers, it is practically in the range of 3 to 200 μm, depending on the application. It is preferable to be set to ˜100 μm.

  The anchor coat layer of the present invention is provided on a base film made of a transparent plastic material, enhances the adhesion between the base material and the inorganic vapor-deposited thin film layer, and performs high-temperature hot water treatment such as boil and retort sterilization and high-temperature and high-humidity. Next, by preventing the occurrence of exfoliation after the accelerated storage test in the environment, and by reducing the strength even when filled with contents that require strong adhesion, and by smoothing the surface The purpose of the present invention is to obtain the two effects of forming the deposited thin film layer of the process uniformly without defects and further assisting the minute barrier defects of the deposited film to express high barrier performance.

In order to obtain these effects, the anchor coat layer has an adhesion strength measured in water between the inorganic vapor-deposited layer and the substrate film after hydrothermal treatment at 120 ° C. for 30 minutes of 1 N / 15 mm or more, and 3000 at the peeling interface. There must be IR absorption based on OH stretching vibration at ˜3500 cm ⁻¹ .

For this reason, it is preferable that an anchor coat layer is two or more layers. As an anchor coat layer in which the adhesion strength measured in water between the inorganic vapor-deposited layer and the substrate film after hydrothermal treatment at 120 ° C. for 30 minutes is maintained at 1 N / 15 mm or more, the anchor coat layer on the substrate film is non-coated. As an anchor coat layer that uses a material made of an aqueous resin and supports a uniform vapor deposition film and barrier defects to develop a high barrier performance, IR absorption based on OH stretching vibration is applied at 3000 to 3500 cm ^-1 below the inorganic vapor deposition layer. It is desirable that an anchor coat layer having the same be laminated.

  Examples of the anchor coating layer of the non-aqueous resin include a silane coupling agent, organic titanate, polyacryl, polyester, polyurethane, polycarbonate, polyurea, polyamide, polyolefin emulsion, polyimide, melamine, and phenol. In view of the hot water resistance of the anchor coat layer, it is more preferable that an organic polymer having at least one urethane bond and urea bond is included.

  Even if the urethane bond and urea bond are used in the polymer introduced in the polymerization stage in advance, polyols such as acrylic and methacrylic polyols and isocyanate compounds having isocyanate groups, or amine resins having amino groups and epoxy groups and glycidyl groups are used. A compound in which a urethane bond is formed by reacting an epoxy compound or the like having a urea bond by a reaction between an isocyanate compound and a solvent such as water or ethyl acetate or an amine resin having an amino group may be used.

  As a result of intensive studies, the anchor coat layer of the non-aqueous resin is more preferably a composite of acrylic polyol, polyester polyol, isocyanate compound, silane coupling agent and the like.

  An acrylic polyol is a polymer compound obtained by polymerizing an acrylic acid derivative monomer or a polymer compound obtained by copolymerizing an acrylic acid derivative monomer and other monomers and having a hydroxyl group at the terminal. These are reacted with an isocyanate group of an isocyanate compound added later. 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 such as hexahydrophthalic acid and reactive derivatives thereof, ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-hexanediol, diethylene glycol, dipropylene glycol, 1,4-cyclohexanedimethanol, Polyester resin inner powder obtained by a known production method from alcohol raw materials such as neopentyl glycol, bishydroxyethyl terephthalate, trimethylol methane, trimethylol propane, glycerin, pentaerythritol Those having 2 or more hydroxyl groups in one in which the reaction with the isocyanate groups of the isocyanate compound added later.

  The isocyanate compound is added in order to increase the adhesion to the base material and the inorganic oxide by a urethane bond formed by reacting with the acrylic polyol and the polyester polyol, and mainly acts as a crosslinking agent or a curing agent. To achieve this, as isocyanate compounds, monomers such as aromatic tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), aliphatic xylene diisocyanate (XDI), and hexadiisocyanate (HMDI), These polymers and derivatives are used, and these are used alone or as a mixture.

  As the silane coupling agent, a silane coupling agent containing any organic functional group can be used. For example, ethyltrimethoxysilane, vinyltrimethoxysilane, γ-chloropropylmethyldimethoxysilane, γ-chloropropyltrimethylsilane. Use one or more of silane coupling agents such as methoxysilane, glycidoxypropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane or hydrolysates thereof. Can do.

An anchor coat layer having IR absorption based on OH stretching vibration at 3000 to 3500 cm ⁻¹ is Si (OR) ₄ (where R represents CH ₃ , C ₂ H ₅ , or C ₂ H ₄ OCH ₃ ) and its hydrate. One of the decomposition products, (R′Si (OR ″) ₃ ) _n (where R ′ represents an organic functional group, R ′
'Represents CH ₃ , C ₂ H ₅ , or C ₂ H ₄ OCH ₃ ) and a hydrolyzate thereof.

One of Si (OR) ₄ (wherein R represents CH ₃ , C ₂ H ₅ , or C ₂ H ₄ OCH ₃ ) and its hydrolyzate, (R′Si (OR ″) ₃ ) _n (Where R ′ represents an organic functional group, R ″ represents CH ₃ , C ₂ H ₅ , or C ₂ H ₄ OCH ₃ ) and an anchor coat layer made of one of the hydrolysates thereof, The anchor coat layer made of a non-aqueous resin and the inorganic vapor deposition layer are brought into close contact with each other, and the smoothness of the film and high barrier performance are expressed by assisting defects in the inorganic vapor deposition film due to hydrogen bonding of OH groups.

  The material having an OH group assists the defect of the deposited film and improves the barrier property. However, since OH groups have hydrogen bonds, water resistance and hot water resistance are low, and when used for anchor coats, the coating swells after hot water treatment or storage in a high temperature and humidity environment for a certain period of time, resulting in adhesion and barrier properties. It will decline. However, by using the silicon compound of the present invention or a hydrolyzate thereof, water resistance can be improved while maintaining physical properties that improve barrier properties.

  The hot water evaluation at 120 ° C. for 30 minutes is a condition for general retort sterilization treatment, and was used as a water resistance evaluation of the gas barrier laminate. When the gas barrier laminate is deteriorated by hot water evaluation, the adhesion strength between the inorganic vapor-deposited layer and the base film is lowered. The adhesion strength measured in water is a method for evaluating the water resistance of a coating deteriorated by hot water. If the adhesion strength is 1 N / 15 mm or more, there is no deterioration and the barrier performance does not deteriorate. In addition, when there is IR absorption based on OH stretching vibration from the peeling interface, the anchor coat layer assists the defect of the deposited film, and the gas barrier laminate has high barrier performance.

Si (OR) ₄ (wherein R represents CH ₃ , C ₂ H ₅ , or C ₂ H ₄ OCH ₃ ) is specifically tetramethoxysilane [Si (OC ₃ ) ₄ ], tetraethoxysilane [ Si (OC ₂ H ₅ ) ₄ ], tetraisopropoxysilane and the like. Among them, tetraethoxysilane is preferable because it is inexpensive. Si (OR) ₄ becomes a material having an OH group by hydrolyzing a part or all of the OR groups with an acid or alkali catalyst.

(R′Si (OR ″) ₃ ) _n (where R ′ represents an organic functional group, R ″ represents CH ₃ , C ₂ H ₅ , or C ₂ H ₄ OCH ₃ ), and its water One of the decomposition products is generally commercially available as a silane coupling agent, and examples of the functional group include a vinyl group, an amino group, an epoxy group, an isocyanate group, and the like. It can be used in a mixture. Whichever is used, the effect of improving water resistance can be obtained. These silane coupling agents may be mixed directly with Si (OR) ₄ (where R represents CH ₃ , C ₂ H ₅ , or C ₂ H ₄ OCH ₃ ), or hydrolyzed with an acid or alkali catalyst. Then you may mix. (R′Si (OR ″) ₃ ) _n (where R ′ represents an organic functional group, R ″ represents CH ₃ , C ₂ H ₅ , or C ₂ H ₄ OCH ₃ ) is also an acid or an alkali It becomes a material having an OH group by being hydrolyzed with a catalyst. (R′Si (OR ″) ₃ ) _n (where R ′ represents an organic functional group and R ″ represents CH ₃ , C ₂ H ₅ , or C ₂ H ₄ OCH ₃ ) The blending ratio is not particularly limited, and is determined by barrier performance, adhesion performance, and water resistance performance.

  Furthermore, by mixing a water-soluble resin with the above-mentioned silicon compound or a hydrolyzate thereof, the wettability to the anchor coat layer made of a non-aqueous resin can be improved, and the barrier performance by assisting defects in the deposited film can be improved. it can.

The water-soluble polymer is preferably polyvinyl alcohol, starch, cellulose, polyacrylic acid, ethylene vinyl alcohol resin, or oxazoline group-containing resin. Si (OR) ₄ (where R represents CH ₃ , C ₂ H ₅ , or C ₂ H ₄ OCH ₃ ) and (R′Si (OR ′
') ₃ ) _n (where R' represents an organic functional group and R '' represents CH ₃ , C ₂ H ₅ , or C ₂ H ₄ OCH ₃ ) or a hydrolyzate thereof with a water-soluble polymer. By mixing, wettability, film-forming property, and uniformity of the coating can be improved.

  The compounding ratio of the above-mentioned silicon compound or a hydrolyzate thereof and the water-soluble polymer to be mixed as appropriate is determined by the barrier performance, adhesion performance, and water resistance performance depending on the application. The water-soluble polymer has a weight ratio of 1000/1 to 1/1, and more preferably 100/1 to 3/1 is a blending ratio that exhibits physical properties while maintaining good water resistance.

  In consideration of wettability and prevention of cracking due to shrinkage, the anchor coat layer is made of a known additive such as an isocyanate compound, clay minerals such as colloidal silica and smectite, stabilizers, colorants, viscosity modifiers, etc. Can be added within a range that does not impair the properties and water resistance.

  The thickness after drying is not particularly limited, but if the thickness exceeds 50 μm or more, cracks are likely to occur, so 0.01 to 50 μm is desirable.

  As the anchor coat layer forming method, a normal coating method can be used. For example, dipping method, roll coating, gravure coating, reverse coating, air knife coating, comma coating, die coating, screen printing method, spray coating, gravure offset method and the like can be used. Two or more anchor coat layers may be applied simultaneously inline using these coating methods, or may be laminated off-line. As the drying method, any of these may be used as long as heat is applied such as hot air drying, hot roll drying, high-frequency irradiation, infrared irradiation, UV irradiation, etc., and solvent molecules may be skipped, or two or more of these may be combined. In addition to the usual coating method, the base film may be melted by an extruder, and an anchor coat layer may be applied to an unstretched film to stretch the film.

  The inorganic vapor deposition layer is composed of oxides such as silicon, aluminum, titanium, zirconium, tin, and magnesium, nitrogen, fluoride units, or a composite thereof, and vacuum such as vacuum vapor deposition, sputtering, plasma vapor deposition, etc. Formed by the process. In particular, aluminum oxide is colorless and transparent and excellent in boiling sterilization and heat / pressure sterilization, and can be used for a wide range of applications. Considering water resistance under severe high temperature and high humidity conditions, a vapor deposition layer made of silicon oxide is most preferable.

  The thickness of the deposited layer varies depending on the application, but it is preferably in the range of several tens to 5,000 mm. However, if it is less than 50 mm, there is a problem in the continuity of the thin film, and if it exceeds 3000 mm, cracks are likely to occur and the flexibility is high. Since it falls, it is preferably 50 to 3000 mm.

  By providing the overcoat layer on the vapor deposition film, the hard and brittle vapor deposition film can be protected and cracks due to rubbing and bending can be prevented.

  Non-aqueous silane coupling agents, organic titanates, polyacrylates, polyesters, polyurethanes, polycarbonates, polyureas, polyamides, polyolefin emulsions, polyimides, melamines, phenols, etc. can be used for the overcoat layer. Further, a resin layer may be formed by combining known curing agents. As the aqueous overcoat layer, polyethyleneimine or a derivative thereof, polyvinyl alcohol, starch, cellulose, polyacrylic acid, ethylene vinyl alcohol resin, oxazoline group-containing resin, and the like can be used, and these can be used in appropriate combinations. it can.

As a result of intensive studies, the overcoat layer has one of Si (OR) ₄ (where R represents CH ₃ , C ₂ H ₅ , or C ₂ H ₄ OCH ₃ ) and a hydrolyzate thereof (R 'Si (OR ″) ₃ ) _n (where R ′ represents an organic functional group, R ″ represents CH ₃ , C ₂ H ₅ , or C ₂ H ₄ OCH ₃ ), and a hydrolyzate thereof It is preferable to consist of one of these and a water-soluble polymer.

  By using an anchor coat layer having IR absorption based on OH stretching vibration for the overcoat layer, it can be used as an overcoat agent having excellent adhesion, water resistance, and defect assisting ability of the deposited film. The formulation of the overcoat layer may be exactly the same as that of the anchor coat layer, and depending on the product application such as adhesion to the material laminated on the overcoat layer, barrier performance, water resistance, etc. Etc. may be appropriately changed.

  The thickness after drying is not particularly limited, but if the thickness exceeds 50 μm or more, cracks are likely to occur, so 0.01 to 50 μm is desirable.

  As a method for forming a film of the overcoat layer, a normal coating method can be used. For example, dipping method, roll coating, gravure coating, reverse coating, air knife coating, comma coating, die coating, screen printing method, spray coating, gravure offset method and the like can be used. It apply | coats on a vapor deposition layer using these coating systems.

  The overcoat layer may be dried by hot air drying, hot roll drying, high frequency irradiation, infrared irradiation, UV irradiation, etc., or a combination of two or more thereof.

  By providing a film on the gas barrier laminate of the present invention or / and on the opposite side, a more practical laminate film can be provided. The film is used as an adhesive part when a bag-like package or the like is formed by laminating a sealant film having heat sealability. 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 metals A resin such as a cross-linked product is used. The thickness is determined according to the purpose, but is generally in the range of 15 to 200 μm. Moreover, even if a heat seal layer is provided on the reverse surface (base material side) depending on the shape of the package, it may be in one direction. Moreover, by laminating a polyethylene terephthalate film or a polyethylene naphthalate film on the laminate of the present invention or / and on the reverse side, sealing of liquid crystal display elements, transparent conductive sheets used in solar cells, electromagnetic wave shields, touch panels, etc. It can be used as a stop material.

  The film can be formed by dry lamination using a two-component curable urethane adhesive, non-solvent dry lamination using a non-solvent adhesive, and extruding the above resin into a curtain. Any of the lamination methods such as the extrusion laminating method can be formed by a known laminating method.

  A printing layer can be laminated on the gas barrier laminate as necessary, and a plurality of resins can be laminated via an adhesive. On the opposite surface of the base film, a plurality of resins can be laminated via a printing layer, a heat seal layer, and an adhesive.

  Moreover, the gas barrier laminated body of this invention can be used for the solar cell back surface protection sheet which is one member which comprises a solar cell module.

Solar cells used for photovoltaic power generation do not use a single solar cell element as it is. Generally, several to several tens of solar cell elements are wired in series and in parallel for a long time ( About 20
In order to protect the device over a period of years, various packaging has been performed and unitized. A unit built in this package is called a solar cell module. Generally, the surface that is exposed to sunlight is covered with glass, the gap is filled with a filler made of thermoplastic, and the back is made of a heat- and weather-resistant plastic material. The structure is protected by a white sheet. Since these solar cell modules are used outdoors, the white back surface protection sheet having weather resistance is required to have a low water vapor transmission rate.

  Since the gas barrier laminate of the present invention is excellent in water resistance in addition to high barrier performance, it can be used in the above-described back protective sheet for solar cells.

  FIG. 3 is a side cross-sectional view of an example in which the gas barrier laminate of the present invention is used for the construction of a solar cell back surface protective sheet.

  The back protective sheet for solar cell is formed by sequentially laminating a base film (1) anchor coat layer I (2) anchor coat layer II (3) inorganic vapor deposition layer (4) overcoat layer (7), and an adhesive on the overcoat layer surface. The white multilayer polyester film (8) is laminated through the layers, and the white multilayer polyester film of the same construction is laminated on the reverse side of the base film via an adhesive. .

  The gas barrier laminate of the present invention will be further described with specific examples, but the present invention is not limited to these examples as long as it does not exceed the gist thereof.

<Measurement method>
1. Gas barrier property Oxygen permeability was measured by an oxygen permeability measuring device (manufactured by OXTRAN 2/20 Modern Control) in an atmosphere of 30 ° C. and 70% RH. The water vapor permeability was measured with a water vapor permeability measuring device (PERMATRAN 3/31 manufactured by Modern Control) in an atmosphere of 40 ° C. and 90% RH.

2. Adhesive strength The strength at the time when the substrate film and the inorganic vapor-deposited layer are peeled by 90 degrees in water, simply, by dropping water at the peeling interface and measuring the peel strength, the same evaluation can be obtained. The film was cut at a width of 15 mm, and the peel strength was determined using Tensilon (a tensile tester, manufactured by Orientec Corp.). The peeling rate was 300 mm / min, 23 ° C., and relative humidity 65%. To identify the release interface, first, both sides of the release surface are colored with a neocarmine indicator that colors the NCO reaction product of the adhesive, and it is confirmed that there is no adhesive at the release interface. I confirmed that it was not.

  Next, the element strength of the inorganic vapor deposition layer was measured using the fluorescent X-rays manufactured by Rigaku Industry Co., Ltd. on the peel interface on the sealant film side of the laminated laminate structure of FIGS. 1 to 3, and it was confirmed that there was an inorganic vapor deposition layer on the sealant film side. .

  At that time, when the inorganic vapor deposition layer is made of silicon oxide, in order to avoid confusion between the strength of the overcoat layer and the anchor coat layer, there is no anchor coat layer as a reference. An inorganic vapor deposition layer / overcoat layer sample was prepared, and the strength of the reference and silica elements were compared to confirm that the inorganic vapor deposition layer was present on the sealant side.

3. IR measurement The IR measurement of the peeling interface was performed on the peeled surface with a Fourier transform infrared spectrophotometer equipped with ATR (multiple reflection) device measurement (manufactured by Perkinelmer). The infrared absorption spectrum was measured using a germanium crystal as a prism at an entrance angle of 45 °. The presence or absence of a broad peak characteristic of absorption of OH stretching vibration was confirmed at 3000 to 3500 cm ⁻¹ .

<Adjustment of anchor coat solution and overcoat solution>
(A) A solution in which tolylene diisocyanate is diluted with ethyl acetate so that the total solid content is 5 w%. (B) Acrylic polyol is added so that the NCO group is equivalent to the OH group of the acrylic polyol. 5% (by weight) of polyvinyl alcohol, diluted with ethyl acetate so as to be 5% by weight, further mixed with 5% by weight of 3-isocyanatopropylalkoxysilane to the total solid content, water / Methanol alcohol = 95/5 (weight ratio) aqueous solution (D) Tetraethoxysilane (Si (OC ₂ H ₅ ) ₄ ; hereinafter referred to as TEOS) 17.9 g and methanol 10 g 72.1 g hydrochloric acid (0.1N) In addition, hydrolyzed solution (E) γ-glycidoxypropyltrimethoxysilane having a solid content of 5% (weight ratio in terms of SiO ₂ ) that was stirred and hydrolyzed for 30 minutes Hydrochloric acid (1N) was gradually added to the isopropyl alcohol solution, and the mixture was stirred for 30 minutes for hydrolysis, followed by hydrolysis with a water / isopropyl alcohol = 1/1 solution to obtain a solid content of 5% (weight ratio R′Si ( OH) ₃ (where R ′ represents an organic functional group) converted to a hydrolyzed solution (F) 1,3,5-tris (3-trialkoxysilylalkyl) isocyanurate, water / isopropyl alcohol = 1 / 1 solution with a solid content adjusted to 5% (weight ratio R′Si (OH) ₃ (where R ′ represents an organic functional group))

<Example 1>
A biaxially stretched PET film (Toray Film Processing Co., Ltd., P60) with a thickness of 12 μm with one side corona-treated is used as the base film, and the anchor coat liquid A is applied to the corona-treated surface using a gravure coater. An anchor coat layer made of a dry film having a dry thickness of 0.1 μm was laminated. Next, an anchor coat layer 2 made of a dry film having a dry thickness of 0.1 μm was applied by applying a solution prepared by mixing the anchor coat liquids D and E in a weight ratio of 1: 1 with the same machine. Next, the vapor deposition layer which consists of a 60-nm-thick silicon oxide was laminated | stacked with the vacuum evaporation system, and the gas barrier laminated body of this invention was obtained.

<Example 2>
A gas barrier laminate of the present invention was obtained in the same manner as in Example 1 except that B was applied instead of the anchor coating liquid A.

<Example 3>
In Example 2, instead of the solution in which the anchor coating liquids D and E were mixed at a weight ratio of 1: 1, a liquid in which the anchor coating liquids C, D, and E were mixed at a weight ratio of 10/45/45 was applied. In the same manner, a gas barrier laminate of the present invention was obtained.

<Example 4>
In Example 3, the overcoat liquid A was applied on the vapor deposition layer using a gravure coater, and an overcoat layer composed of a dry film having a dry thickness of 0.3 μm was provided in the same manner. A gas barrier laminate was obtained.

<Example 5>
In Example 4, the overcoat liquid A was applied on the vapor deposition layer using a gravure coater, and an overcoat layer comprising a dry film having a dry thickness of 0.3 μm was provided in the same manner. A gas barrier laminate was obtained.

<Example 6>
A gas barrier laminate of the present invention was obtained in the same manner as in Example 5 except that aluminum oxide having a thickness of 20 nm was laminated instead of the deposited layer made of silicon oxide having a thickness of 60 nm.

<Comparative Example 1>
A gas barrier laminate of the present invention was obtained in the same manner as in Example 1 except that a solution prepared by mixing the anchor coat liquids D and E in a weight ratio of 1: 1 was not applied.

<Comparative example 2>
A gas barrier laminate of the present invention was obtained in the same manner as in Example 1 except that the anchor coat liquid A was not applied.

<Comparative Example 3>
A gas barrier laminate of the present invention was obtained in the same manner as in Example 1, except that the anchor coat liquid C was applied instead of the solution in which the anchor coat liquids D and E were mixed at a weight ratio of 1: 1.

<Experiment 1>
Using a dry laminator, the obtained gas barrier laminate was laminated with a 70 μm-thick unstretched polyolefin film (RXC18 manufactured by Tosero) on the gas barrier coating layer surface via a polyurethane adhesive, and laminated. A film was obtained. The obtained film was immersed in hot water at 121 ° C. for 30 minutes under pressure. The oxygen permeability and water vapor permeability before and after immersion were measured, and the laminate strength of the adhesion strength between the base film and the inorganic vapor deposition layer and the IR measurement of the peeling interface at that time were performed.

From Table 1, the Examples had high barrier properties, good adhesion, and good adhesion between the base material and the inorganic vapor deposition layer even after the hot water test for 120 minutes and 30 minutes. Since the OH stretching vibration was observed in the IR measurement result of the peeling interface, the barrier property was high, and since the adhesion strength was not deteriorated, the barrier property was maintained even after the hot water test. On the other hand, in Comparative Examples 2 and 3, since the adhesion decreased after the hot water test, the barrier property was also deteriorated. In Comparative Example 1, the barrier property before the test is poor because there is no OH group absorption at the peeling interface, and the barrier is deteriorated after the test.

<Experiment 2>
The gas barrier laminate obtained in Example 5 and Comparative Examples 1 to 3 was laminated with a white multilayer polyester film having a thickness of 50 μm on the gas barrier coating layer surface via a polyurethane adhesive using a dry laminating machine. Using the same machine on the reverse side, a white multilayer polyester film having a thickness of 50 μm was laminated through an adhesive to obtain a laminated film having a solar cell back surface protective sheet configuration. The obtained film was held for 3000 hours in an atmosphere of 85 ° C. and 85%, and the appearance and barrier properties after the test were confirmed.

From Table 2, since the examples have good hot water resistance, the back surface protection sheet configuration of the solar cell does not deteriorate even in the accelerated storage test under the high temperature and humidity resistance environment, the barrier property before and after the test is high, and the appearance is good. After the test, the coating deteriorated, peeled off, floated visually, and the barrier performance was also significantly deteriorated.

It is a sectional side view which shows the Example of the layer structure of the gas barrier laminated body concerning this invention. It is a sectional side view which shows the Example different from FIG. 1 of the layer structure of the gas barrier laminated body concerning this invention. It is a sectional side view which shows the Example different from FIG.1 and FIG.2 of the layer structure of the gas barrier laminated body concerning this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Base material 2 ... Anchor coat layer I
3. Anchor coat layer II
DESCRIPTION OF SYMBOLS 4 ... Inorganic vapor deposition layer 5 ... Adhesive layer 6 ... Sealant film layer 7 ... Overcoat layer 8 ... White multilayer polyester film layer

Claims (11)

A gas barrier film in which at least an anchor coat layer and an inorganic vapor deposition layer are laminated on one side or both sides of a base material film made of a plastic material, and the inorganic vapor deposition layer and the substrate after hydrothermal treatment of the gas barrier film at 120 ° C. for 30 minutes wood adhesion strength measured in water of the film is at 1N / 15 mm or more, the gas barrier laminate, characterized in that there is IR absorption based on OH stretching vibration 3000cm ^-1 ~3500cm ^-1 to peeling boundary. The gas barrier laminate according to claim 1, wherein a is the IR absorption based on OH stretching vibration 3000cm ^-1 ~3500cm ^-1 on the anchor coat layer. The anchor coat layer having IR absorption based on the OH stretching vibration is Si (OR) ₄ (where R represents CH ₃ , C ₂ H ₅ , or C ₂ H ₄ OCH ₃ ) and a hydrolyzate thereof. (R′Si (OR ″) ₃ ) _n (where R ′ represents an organic functional group, R ″ represents CH ₃ , C ₂ H ₅ , or C ₂ H ₄ OCH ₃ ) and its The gas barrier laminate according to claim 1 or 2, comprising one of the hydrolysates. The anchor coat layer having IR absorption based on the OH stretching vibration is Si (OR) ₄ (where R represents CH ₃ , C ₂ H ₅ , or C ₂ H ₄ OCH ₃ ) and a hydrolyzate thereof. (R′Si (OR ″) ₃ ) _n (where R ′ represents an organic functional group, R ″ represents CH ₃ , C ₂ H ₅ , or C ₂ H ₄ OCH ₃ ) and its The gas barrier laminate according to claim 1 or 2, comprising one of the hydrolysates and a water-soluble polymer. Claim 1, wherein the anchor coat layer comprises at least two or more layers, stacking the layers in the layer and 3000cm ^-1 ~3500cm ^-1 consisting of a non-aqueous resin is IR absorption based on OH stretching vibration sequentially 4. The gas barrier laminate according to any one of 4 to 4.   The gas barrier laminate according to claim 5, wherein the anchor coat layer made of the non-aqueous resin is made of an acrylic polyol and an isocyanate resin.   The gas barrier laminate according to any one of claims 1 to 6, wherein the inorganic vapor deposition layer is made of silicon oxide.   The gas barrier laminate according to any one of claims 1 to 7, wherein an overcoat layer is laminated on the vapor deposition layer. The overcoat layer is Si (OR) ₄ (wherein R represents CH ₃ , C ₂ H ₅ , or C ₂ H ₄ OCH ₃ ) and one of its hydrolysates (R′Si (OR ′) ') ₃ ) _n (where R' represents an organic functional group, R '' represents CH ₃ , C ₂ H ₅ , or C ₂ H ₄ OCH ₃ ) and one of its hydrolysates, and The gas barrier laminate according to any one of claims 1 to 8, comprising a water-soluble polymer.   The gas barrier laminate according to any one of claims 1 to 9, wherein a film is laminated on the gas barrier laminate or / and on the opposite surface.   The gas barrier laminate according to any one of claims 1 to 10, wherein the gas barrier laminate is used for a solar cell back surface protective sheet which is a member constituting a solar cell module.