JP2016175223A - Gas barrier laminate, and solar battery module and image display element using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a gas barrier laminate which has sufficient barrier performance as applications for a packaging material, a solar battery and an image display element, is strong against an external impact and does not impair barrier performance even under high-temperature and high-humidity environment and to provide a solar battery module and an image display element using the same.SOLUTION: There is provided a gas barrier laminate which comprises a substrate, a barrier layer formed on a first surface of the substrate, and an urethane layer and a hard coat layer having a hydroxyl group which are sequentially formed on a second surface of the substrate, wherein the ratio α/β between the isocyanate group weight α contained in the urethane layer and the hydroxyl group weight β is 1.5 or more and 2.0 or less.SELECTED DRAWING: Figure 2

Description

  The present invention relates to a gas barrier laminate, a solar cell module using the same, and an image display element.

  Solar cells constitute the heart of a photovoltaic power generation system that directly converts sunlight energy into electricity, and semiconductors such as silicon, cadmium-tellurium, and germanium-arsenic are used. Currently, single crystal, polycrystalline silicon, and amorphous silicon are frequently used.

  A solar cell does not use a single element as it is, and generally several to several tens of solar cell elements are wired in series and in parallel to protect the element over a long period (about 20 years). Therefore, various packaging is performed and unitized.

  The unit incorporated in the package as described above is called a solar cell module, and the surface to which sunlight is applied is generally covered with glass, and the thermoplastic cell is used for fixing and protecting the solar cell module in the solar cell and for electric insulation. The gap is filled with a filler consisting of the above, and the back surface of the solar cell module is further protected with a back surface protection sheet.

  Since these solar cell modules are used outdoors, their construction, material structure, etc. can withstand harsh natural environments over a long period of time, durability such as heat resistance, weather resistance, hydrolysis resistance, moisture resistance, In addition to UV resistance, gas barrier properties are required to block the entry of water vapor (moisture) and oxygen from the outside.

  This is because the permeation of water vapor may cause the filler to peel off, change color, corrode the wiring, and affect the output. Amorphous silicon and chalcopyrite thin film polycrystalline solar cells require a particularly high barrier property because the solar cell element is easily altered by water.

  Conventionally, a structure in which a solar cell element is sandwiched with a fluorine-based resin film such as polyvinyl fluoride is used for a front plate of a solar cell module and a back protective sheet (Patent Documents 1 and 2).

  However, it is necessary to design a solar cell module of a type installed in a private house so that it can be easily installed. In order to install manually without using heavy machinery, it is important to reduce the weight of the solar cell module, and even if considering earthquake resistance, it is necessary to reduce the weight to install on the roof of a private house. For this reason, weight reduction is achieved by switching the glass used for the front plate of the solar cell module to a plastic material.

  Further, when an aluminum foil is used as the back surface protection sheet of the solar cell, there is a drawback that when the deterioration progresses and penetrates, the aluminum foil and the electrode are short-circuited to adversely affect the battery performance.

Therefore, in order to solve the above problems, for example, a back surface protection sheet or a front surface protection using a gas barrier plastic substrate in which a vapor deposition film of an inorganic oxide is provided on one surface of a film substrate such as polyethylene terephthalate (PET). A sheet has been proposed. (Patent Literature 3, Patent Literature 4).

  However, the back surface protection sheet and the front surface protection sheet proposed above do not have sufficient barrier performance for amorphous silicon or chalcopyrite thin film polycrystalline solar cells with low moisture resistance of the solar cell elements, resulting in deterioration of the solar cell elements. However, it is difficult to maintain long-term durability.

  In addition, in an image display element such as a liquid crystal display panel, an organic EL display panel, an electrochromic panel, and electronic paper, an element using a glass substrate has been conventionally used. In recent years, since light weight, flexibility, impact resistance, and the like are excellent and an area can be easily increased, demand is changing from an element using a glass substrate to an element using a plastic film substrate.

  However, the plastic film substrate has a problem that the gas barrier property against water vapor and oxygen is inferior to that of the glass substrate, and the display performance of an image display device using the same is likely to be hindered.

  The organic EL display of the self-luminous type thin display device has a structure in which a hole injection layer, a hole transport layer, a light emitting layer, an electron injection layer, and an electron transport layer are laminated between a pair of electrodes. Yes. However, the organic material constituting these layers stacked in the organic EL element is generally weak against water vapor and oxygen, and further, the metal material used for the electrode has a disadvantage that it is very weak against water vapor and oxygen. Yes.

  Therefore, a protective film called a passivation layer made of a material such as silicon oxide, silicon nitride, or metal insulating film is provided on the outermost layer of the organic EL element or the like in order to protect it from oxygen or water vapor. There are many.

  Patent Document 5 proposes an element configuration in which a protective film is formed in a region constituting a light emitting element, and a coating layer is formed on the protective film. However, in order to achieve high barrier performance in order to maintain the display characteristics of the light emitting element, it is necessary to form a plurality of protective films, which is extremely problematic in consideration of cost and productivity.

  Patent Document 6 reports that a sufficient performance can be obtained without a protective film by providing a low hardness layer and a high hardness layer on the opposite side of the barrier layer. However, in the light-emitting element or the display element, when it is intended to realize a high water vapor barrier property, it is necessary to provide a plurality of protective films, which increases the process cost.

  Furthermore, Patent Document 7 reports that sufficient performance can be obtained even if the passivation layer is eliminated by providing a low hardness layer and a high hardness layer on the side opposite to the barrier layer. However, with this method, it has been difficult to ensure adhesion between the low hardness layer and the high hardness layer under high temperature and high humidity.

JP-T 8-500214 Japanese translation of PCT publication No. 2002-520820 JP 2001-111077 A JP 2006-120972 A JP 2003-282242 A JP 2004-127606 A JP 2009-90632 A

  The present invention provides a gas barrier laminate that has sufficient barrier performance as a packaging material, solar cell, display device application, is resistant to external impact, and does not impair barrier performance even in a high-temperature and high-humidity environment, and a solar cell using the same An object is to provide a battery module and an image display element.

  The invention according to claim 1 of the present invention includes a base material, a barrier layer formed on the first surface of the base material, a urethane layer sequentially formed on the second surface of the base material, and a hydroxyl group. A gas barrier laminate having a ratio α / β of an isocyanate group amount α and a hydroxyl group amount β contained in the urethane layer of 1.5 or more and 2.0 or less. It is a thing.

  The invention according to claim 2 of the present invention is characterized in that an overcoat layer is formed on the barrier layer formed on the first surface of the base material. It is a body.

The invention according to claim 3 of the present invention is characterized in that the overcoat layer contains at least one selected from the group consisting of an organosilicon compound represented by the following chemical formula (a) and a hydrolyzate thereof. The gas barrier laminate according to claim 2.
(RO) ₃ Si— (CH ₂ ) _n —Si (OR) ₃ (a)
[However, R is an alkyl group, and n is an integer of 1-8. ]

  The invention according to claim 4 of the present invention is the gas barrier laminate according to any one of claims 1 to 3, wherein an anchor coat layer is provided between the base material and the barrier layer. It is.

  The invention according to claim 5 of the present invention is the gas barrier laminate according to any one of claims 1 to 4, wherein the barrier layer contains metal silicon and silicon dioxide.

  The invention according to claim 6 of the present invention is a solar cell module using the gas barrier laminate according to any one of claims 1 to 5.

  The invention according to claim 7 of the present invention is an image display device characterized by using the gas barrier laminate according to any one of claims 1 to 5.

  The present invention can provide a gas barrier laminate that has high barrier performance, is resistant to external impact, and does not deteriorate barrier performance even in a high-temperature and high-humidity environment, and a solar cell module and an image display element using the same. .

1 is a schematic cross-sectional view of a gas barrier laminate 10 according to a first embodiment of the present invention. It is a schematic sectional drawing of the gas-barrier laminated body 20 which concerns on 2nd embodiment of this invention. It is the schematic sectional drawing which showed an example of the back surface protection sheet used for the solar cell module which concerns on embodiment of this invention. It is the schematic sectional drawing which showed an example of the front surface protection sheet used for the solar cell module which concerns on embodiment of this invention. It is the schematic sectional drawing which showed an example of the solar cell module which concerns on embodiment of this invention. It is the schematic sectional drawing which showed an example of the organic EL element as an example of the image display element which concerns on embodiment of this invention.

[First embodiment of gas barrier laminate]
In FIG. 1, the schematic sectional drawing of the gas-barrier laminated body 10 of 1st embodiment is shown. In the gas barrier laminate 10, the barrier layer 12 and the overcoat layer 13 are sequentially laminated on the first surface of the resin substrate 11, and the urethane layer 14 and the hard coat layer 15 are laminated on the second surface of the resin substrate 11. It is the laminated body of the structure laminated | stacked one by one. The overcoat layer 13 may be omitted depending on the use conditions of the gas barrier laminate. The barrier layer 12 and the overcoat layer 13 can enhance the barrier property by a structure in which two or more layers are alternately laminated.

[Second Embodiment of Gas Barrier Laminate]
In FIG. 2, the schematic sectional drawing of the gas-barrier laminated body 20 of 2nd embodiment is shown.
In the gas barrier laminate 20, the anchor coat layer 24, the barrier layer 12, and the overcoat layer 13 are sequentially laminated on the first surface of the resin substrate 11, and the urethane layer 14 and the second surface of the resin substrate 11 are laminated. It is a laminate having a configuration in which hard coat layers 15 are sequentially laminated. The overcoat layer 13 may be omitted depending on the use conditions of the gas barrier laminate. Also in the second embodiment, the barrier layer 12 and the overcoat layer 13 can enhance the barrier property by adopting a structure in which two or more layers are alternately laminated.

The gas barrier laminate 20 has the same configuration as the gas barrier laminate 10 of the first embodiment except that an anchor coat layer 24 is provided between the resin base material 11 and the barrier layer 12. Accordingly, in FIG. 1 and FIG. 2, the same or corresponding parts are denoted by the same reference numerals.
Hereinafter, the base material which comprises the gas-barrier laminated bodies 10 and 20, and each layer are demonstrated in detail.

(Resin substrate 11)
It does not specifically limit as the resin base material 11, It can select suitably from a sheet-like base material (a film-like thing is included). Examples thereof include polyethylene terephthalate (PET) and polyethylene naphthalate (PEN). Although the thickness of the resin base material 11 does not have a restriction | limiting in particular, 50 micrometers-200 micrometers are suitable. In order to improve the adhesion of the barrier layer 12, a pretreatment such as a corona treatment or a plasma treatment may be performed.

(Barrier layer 12)
The barrier layer 12 made of an inorganic material is provided for imparting gas barrier properties. Examples of the inorganic material include metals such as Si, Al, Zn, and Sn, metal oxides including at least one of these metals, and metal nitrides.

As a method for forming the barrier layer, a known method such as vacuum deposition may be used. In order to increase the transparency of the barrier layer 12, reactive vapor deposition may be performed in which vapor deposition is performed by reacting evaporated particles with oxygen gas introduced into the atmosphere. By performing reactive vapor deposition with oxygen gas or the like, the metal component in the vapor deposition material is oxidized, and the transparency of the barrier layer 12 can be improved. When introducing the gas, it is desirable that the pressure in the film forming chamber be 2 × 10 ⁻¹ Pa or less. If the pressure in the film formation chamber is higher than 2 × 10 ⁻¹ Pa, the barrier layer 12 may not be uniformly laminated, and the barrier property may be lowered.

  Since the barrier layer 12 is particularly excellent in transparency and barrier properties against oxygen gas and water vapor, it is preferable that a vapor deposition material containing metal silicon and silicon dioxide is vacuum-deposited. The ratio of the content of metal silicon and silicon dioxide is not particularly limited, but it is preferably contained at a ratio of 1.0 to 1.8 in terms of the atomic ratio O / Si between silicon and oxygen. When O / Si is 1.0 or more, the transparency is good, and when it is 1.8 or less, the barrier property is good.

  Although vacuum deposition has been described as a method for forming the barrier layer, a similar inorganic film formed by sputtering may be used.

  The film thickness of the barrier layer 12 is preferably 5 nm or more and 300 nm or less. When the thickness is 5 nm or more, sufficient barrier properties are exhibited, and when the thickness is 300 nm or more, cracks are likely to occur in the post-process and the barrier properties are likely to be lowered.

(Overcoat layer 13)
The overcoat layer 13 barriers a coating solution containing at least one (A) (hereinafter referred to as component (A)) selected from the group consisting of an organosilicon compound represented by the following chemical formula (a) and a hydrolyzate thereof. It can be applied to the layer 12 and heat dried.
(RO) ₃ Si— (CH ₂ ) _n —Si (OR) ₃ (a)
[However, R is an alkyl group, and n is an integer of 1-8. ]

  Moreover, a fluorine-type leveling agent can be added to the overcoat layer 13 used as the outermost layer, and a contact angle with a pure water can be 100 degrees or more. By adding a fluorine-based leveling agent and setting the contact angle with pure water to 100 ° or more, there is no generation of scratches due to friction when forming a roll, and gas barrier properties are not impaired.

  By laminating the overcoat layer 13 on the barrier layer 12, it is possible to obtain excellent gas barrier properties that cannot be expressed by a single layer of the barrier layer 12. The overcoat layer 13 also has a function of protecting the dense and fragile barrier layer 12, and can suppress generation of cracks due to rubbing or bending.

In addition, in an organosilicon compound having a Si-OR structure, an OR group bonded to a silicon atom becomes an OH group (hydroxyl group) by a hydrolysis reaction, and a siloxane bond is formed by dehydration condensation of the OH group. For this reason, a dense and strong network polymerization film can be formed by using the organosilicon compound of the formula (a). Moreover, by having (CH ₂ ) _n in the molecule, an organic-inorganic composite film having both toughness and flexibility is formed. Therefore, even if the organic silicon compound and a water-soluble polymer such as polyvinyl alcohol are not combined, the function as an overcoat layer is sufficiently exerted, and the heat resistance, water resistance, moisture resistance, etc. are excellent. High gas barrier properties can be maintained.

  In formula (a), the alkyl group of R is preferably an alkyl group having 1 to 3 carbon atoms, and examples of the organosilicon compound include bistrimethoxysilylethane. Examples of the hydrolyzate of the organosilicon compound represented by the formula (a) include those in which at least one of the six ORs in the formula (a) is OH.

In addition to the component (A), the coating liquid for forming the overcoat layer includes an organosilicon compound represented by the following chemical formula (b1), an organosilicon compound represented by the following chemical formula (b2), and a hydrolyzate thereof. It is preferable to contain at least 1 type (B) (henceforth (B) component) chosen from the group which consists of. By containing (B) component as an auxiliary component of (A) component, barrier property improves.
Si (OR1) ₄ (b1)
R3-Si (OR2) ₃ ... (b2)
[However, R1 is an alkyl group, R2 is an alkyl group, and R3 is an organic group having one of an epoxy group and an NCO group. ]

  In the formula (b1), examples of the alkyl group for R1 include the same as those for R. Examples of the organosilicon compound include tetraethoxysilane and tetramethoxysilane. Examples of the hydrolyzate of the organosilicon compound represented by the formula (b1) include those in which at least one of the four OR1s in the formula (b1) is OH.

In the formula (b2), examples of the alkyl group for R2 include the same as those for R, and examples of R3 include a group represented by the chemical formula (I).
X- (CH ₂ ) _m − (I)
(However, X is a glycidoxy group or an NCO group, and m is an integer of 1 to 8.)

  Examples of the organosilicon compound represented by the formula (b2) include those having an epoxy group such as 3-glycidoxypropyltrimethoxysilane and those having an NCO group (isocyanate group) such as 3-isocyanatopropyltriethoxysilane. Etc. Examples of the hydrolyzate of the organosilicon compound represented by the formula (b2) include those in which at least one of the three OR2s in the formula (b2) is OH.

  In addition to the component (A) or the component (A) and the component (B), the coating liquid for forming the overcoat layer further includes an acrylic polyol (C) having two or more OH groups (hereinafter referred to as (C) Component) and an isocyanate compound (D) having at least two NCO groups in the molecule (hereinafter referred to as component (D)) or both.

  In other words, in addition to the organosilicon compound (components (A) and (B)), by adding one or both of the components (C) and (D), the organic and inorganic materials are homogeneous when applied and dried. A composite membrane is formed. Therefore, compared with the case where only the organosilicon compound is used, the gas barrier property due to the interaction with the barrier layer 12 is improved, and the swelling deterioration of the overcoat layer 13 under high temperature and high humidity is suppressed. Deterioration of the protective function is suppressed, and excellent gas barrier properties can be maintained.

  For example, the component (C) has compatibility with a polymer formed by polymerization of a hydrolyzate of an organosilicon compound represented by the formula (a), (b1) or (b2), and The effect of improving gas barrier properties is exhibited by combining with coalescence.

  Moreover, (D) component reacts with the Si-OH group formed by hydrolysis of the organosilicon compound represented by the formula (a), (b1) or (b2) to form a urethane bond. Furthermore, when both the (C) component and the (D) component are used in combination, in addition to the siloxane bond, the OH group of the (C) component and the NCO group of the (D) component react to form a composite crosslinked structure of urethane bonds. It is formed and exhibits excellent gas barrier properties.

  Examples of the component (C) include polymer compounds obtained by polymerizing a (meth) acrylic acid derivative monomer having an OH group. Examples of the (meth) acrylic acid derivative monomer having an OH group include hydroxyalkyl (meth) acrylates such as hydroxyethyl (meth) acrylate.

  (C) A component may be used individually by 1 type, or may use 2 or more types together. The blending amount of the component (C) in the coating solution for forming the overcoat layer is preferably 5 to 50% by weight with respect to the total solid content. The effect which mix | blends (C) component is fully acquired as it is 5 weight% or more. If it exceeds 50% by weight, the barrier property may be lowered.

  The component (D) may be any component having at least two NCO groups in the molecule, and examples thereof include tolylene diisocyanate, diphenylmethane diisocyanate, and hexamethylene diisocyanate.

  (D) A component can be used individually by 1 type or in combination of 2 or more types. The blending amount of the component (D) in the coating solution is preferably 5 to 50% by weight with respect to the total solid content. The effect which mix | blends (D) component is fully acquired as it is 5 weight% or more. If it exceeds 50% by weight, the barrier property may be lowered.

  The solvent of the coating solution for forming the overcoat layer may be any solvent that can dissolve the compounding components, and examples thereof include water, alcohol, toluene, ethyl acetate, and acetone.

  The overcoat layer 13 can be formed by applying the coating solution on the barrier layer 12 and drying by heating. As a coating method of the coating liquid, for example, a known method such as a dipping method, a roll coating method, a gravure coating method, a reverse coating method, an air knife coating method can be used. The film thickness is preferably from 0.1 to 2 μm. When it is 0.1 μm or more, the barrier property is stably expressed, and when it is 2 μm or less, it is excellent in post-processing suitability such as lamination or bending of other films.

(Urethane layer 14)
The urethane layer 14 is a layer obtained by a reaction between a polyol compound and an isocyanate compound. Examples of the polyol compound include acrylic polyols and polycarbonate polyols. The isocyanate compound only needs to have at least two NCO groups in the molecule, and examples thereof include tolylene diisocyanate and hexamethylene diisocyanate.

  The gas barrier laminate according to claim 1 of the present invention is characterized in that the ratio α / β of the isocyanate group amount α and the hydroxyl group amount β contained in the urethane layer is 1.5 or more and 2.0 or less. Is. The reason will be specifically described in Examples.

(Hard coat layer 15)
The gas barrier laminate of the present invention preferably contains a polyfunctional acrylic monomer (I), a urethane acrylate oligomer (II), a radical photopolymerization initiator (III), and inorganic fine particles (IV) in the hard coat layer 15. .

  Examples of the polyfunctional acrylic monomer (I) include polyester acrylates and urethane acrylates, as well as those in which a reactive acrylic group is bonded to an acrylic resin skeleton.

  The radical photopolymerization initiator (III) is a compound that initiates the polymerization reaction of the polyfunctional acrylic monomer (I), and the amount used is the polyfunctional acrylic monomer (I) of the hard coat layer forming composition and the polyfunctional urethane. 0.01 to 15 weight% is suitable with respect to the sum total of acrylate oligomer (II). When the amount is less than 0.01% by weight, a sufficient curing reaction does not proceed. When the amount exceeds 15% by weight, ionizing radiation does not reach the lower portion of the hard coat layer.

  Examples of the inorganic fine particles (IV) include metal fluorine fine particles such as silica, aluminum oxide, zirconia, titania, zinc oxide, germanium oxide, indium oxide, tin oxide, indium tin oxide (ITO), and sodium.

The particle size of the inorganic fine particles (IV) of the present invention is 40 nm to 80 nm, and the amount used is preferably 10 to 30% by weight based on the total solid content of the hard coat layer forming composition. When the amount used is less than 40 nm and less than 10%, the surface unevenness is insufficient and blocking occurs. When the particle size exceeds 80 nm and the amount used exceeds 30%, the surface roughness increases, haze increases, and adhesion to the substrate decreases.

  The hard coat layer is formed by applying a coating solution in which a solvent is added to the functional acrylic monomer (I), urethane acrylate oligomer (II), radical photopolymerization initiator (III), and inorganic fine particles (IV) on the urethane layer. What is necessary is just to apply | coat and dry.

(Anchor coat layer 24)
The anchor coat layer 24 enhances the adhesion between the resin base material 11 and the barrier layer 12 on the resin base material 11, sterilization treatment such as retort sterilization, peeling of the barrier layer 12 due to long-term outdoor installation, and accompanying gas barrier. It is provided in order to prevent deterioration of the property.

  The anchor coat layer 24 includes an acrylic polyol (1) having two or more OH groups and an isocyanate having at least two NCO groups in the molecule from the viewpoint of improving the adhesion between the resin substrate 11 and the barrier layer 12. It is preferably formed using an anchor coating agent containing compound (2).

  Examples of the acrylic polyol (1) include hydroxyalkyl (meth) acrylates such as hydroxyethyl (meth) acrylate as polymer compounds obtained by polymerizing a (meth) acrylic acid derivative monomer having an OH group.

  The acrylic polyol (1) preferably has an OH group value of 50 to 250 mgKOH / g. Here, the OH group value (mgKOH / g) is an index of the amount of OH groups in the acrylic polyol, and indicates the number of mg of potassium hydroxide required to acetylate the hydroxyl group in 1 g of the acrylic polyol.

  When the OH group value is less than 50 mgKOH / g, the amount of reaction with the isocyanate compound (2) is small, and the adhesion between the resin substrate 11 and the barrier layer 12 by the anchor coat layer 24 may not be sufficiently exhibited. On the other hand, if the OH group value is larger than 250 mgKOH / g, the amount of reaction with the isocyanate compound (2) becomes too large, and the film shrinkage of the anchor coat layer 24 becomes large, and the barrier layer 12 is neatly laminated thereon. Therefore, there is a possibility that sufficient gas barrier properties are not exhibited.

  The isocyanate compound (2) may be any compound having at least two NCO groups in the molecule, and examples thereof include tolylene diisocyanate and hexamethylene diisocyanate.

  In the anchor coating agent, the equivalent ratio (NCO / OH) of the NCO group of the isocyanate compound (2) to the OH group of the acrylic polyol (1) is preferably 0.15 to 0.75. When NCO / OH is 0.15 or more, the adhesion to the substrate is improved, and when it is 0.75 or less, the adhesion after the wet heat resistance test is improved.

  The anchor coating agent can be prepared by mixing the acrylic polyol (1), the isocyanate compound (2), an optional component (such as a silane coupling agent), and a solvent. Any solvent may be used as long as it can dissolve the acrylic polyol (1) and the isocyanate compound (2). Examples thereof include methyl acetate, ethyl acetate, cyclohexanone, and acetone.

The anchor coat layer 24 can be formed by applying the anchor coat agent on the resin substrate 11 and drying it by heating. As a coating method, a known method such as a dipping method, a roll coating method, a gravure coating method, a comma coating method, or a die coating method can be used. Drying methods include hot air drying, infrared irradiation, and UV irradiation.

  The film thickness of the anchor coat layer 24 is preferably 0.02 μm or more and 1.0 μm or less. Adhesiveness of the resin base material 11 and the barrier layer 12 becomes favorable as it is 0.02 micrometer or more. If it is thicker than 1.0 μm, the influence of internal stress is increased, and the barrier layer 12 is not neatly laminated, and there is a risk that gas barrier properties will not be exhibited.

[Embodiment of Solar Cell Module]
FIG. 3 is a cross-sectional view of the back surface protection sheet 30 used in the solar cell module according to the present invention. The back surface protection sheet 30 for solar cell modules of this example is a back surface protection sheet for solar cell modules in which a weather resistant film 31 is bonded to one surface of the gas barrier laminate 10 or 20 and a colored film 32 is bonded to the other surface. It is.

  The weather resistant film 31 is a polyethylene terephthalate film or a fluororesin film excellent in hydrolysis resistance. Fluorine resin film is made of vinyl fluoride resin (PVF) film, vinylidene fluoride resin (PVDF) film, trifluoroethylene chloride (PCTFE) film, ethylene / tetrafluoroethylene copolymer (ETFE) film, polytetra Examples thereof include a fluorine-based film selected from a fluoroethylene (PTFE) film and a tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA) film. In order to increase the reflectance, a white pigment such as titanium oxide may be dispersed in the film to be whitened.

  The colored film 32 has a function of improving the light utilization efficiency of the solar cell module and improving the power generation efficiency, and white is particularly preferable because of its high reflectance. As white film, white pigment is developed by applying white pigment on polyester film or ethylene-vinyl acetate (EVA) film on the film surface, kneading at the time of film molding, and having foamed bubbles in the film resin. There are things, and you can use any of them. Moreover, you may use a black film from the point of design property.

  As a method for laminating the back surface protection sheet 30 for the solar cell module of the present invention, for example, a dry lamination method can be used. As an adhesive for dry lamination, it is necessary that the adhesive strength does not cause delamination due to deterioration when used outdoors for a long time, and that the adhesive does not turn yellow, etc., and it supports high heat resistance, moisture heat resistance, etc. Therefore, it is desirable to use a resin or the like as a main component of the vehicle constituting the adhesive which can be crosslinked or cured to form a three-dimensional network crosslinked structure.

  For example, by reaction energy consisting of heat or light in the presence of an isocyanate-based curing agent or cross-linking agent such as a two-component curable polyurethane adhesive, aliphatic or alicyclic isocyanate, or aromatic isocyanate. It is preferable that the adhesive for laminating forms a crosslinked structure.

  FIG. 4 is a cross-sectional view of the front protective sheet 40 used in the solar cell module according to the present invention. In the solar cell module front protective sheet 40 of this example, a transparent weather resistant film 41, an ultraviolet cut film 42, and a gas barrier laminate 10 or 20 are sequentially laminated to form a solar cell module front protective sheet 40.

The transparent weather-resistant film 41 is selected from the same material as the weather-resistant film 31, but the film is required to be transparent in the photovoltaic region of the solar cell. 380 nm to 800
The light transmittance of the film in the wavelength region of nm needs to be 60% or more.

  The ultraviolet protection film 42 is used for the front surface protection sheet 40 for solar cell modules in order to suppress the deterioration of the solar cell element in the below-mentioned solar cell module. The ultraviolet cut film 42 preferably contains an ultraviolet absorber.

  Preferred examples of the ultraviolet absorber include salicylic acid compounds, benzophenone compounds, benzotriazole compounds, cyanoacrylate compounds, benzoxazinone compounds, cyclic imino ester compounds, and the like. A benzoxazinone-based compound is most preferable from the viewpoints of ultraviolet cut ability at 390 nm, color tone, and the like.

  The said compound may be used by 1 type and may be used together 2 or more types. Moreover, combined use of stabilizers, such as HALS (hindered amine light stabilizer) and antioxidant, is more preferable.

  Examples of benzoxazinone-based compounds that are preferable materials include 2-p-nitrophenyl-3,1-benzoxazin-4-one and 2- (p-bezoylphenyl) -3,1-benzoxazine-4. -One, 2- (2-naphthyl) -3,1-benzoxazin-4-one, 2-2'-p-phenylenebis (3,1-benzoxazin-4-one), 2,2 '-( 2,6-naphthylene) bis (3,1-benzoxazin-4-one) and the like can be exemplified. The amount of these compounds added is preferably 0.05 to 1.0% by weight in the film.

  The method for producing the front protective sheet 40 for solar cell modules of the present invention can also be selected from the methods used for the back protective sheet 30 for solar cell modules.

  FIG. 5 is a cross-sectional view of the solar cell module 50 of the present invention using the solar cell module front protective sheet 40 and the solar cell module back protective sheet 30. The solar cell element 51 can employ various methods such as an amorphous silicon solar cell, a single crystal silicon solar cell, and a polycrystalline silicon solar cell, but is not particularly limited thereto. The solar cell element 51 is disposed between the front protective sheet 40 and the back protective sheet 30. Although not shown, other functional layers may be disposed and laminated between the layers. For example, you may arrange | position a sealing material, a wavelength conversion member, a connection wiring, etc. between the front surface protection sheet 40 and the solar cell element 51. A sealing material, a light reflection / scattering layer, a connection wiring, and the like can also be disposed between the back surface protection sheet 30 and the solar cell element 51.

[Embodiment of Organic EL Element]
FIG. 6 is a schematic cross-sectional view showing an example of an organic EL element as an example of an image display element according to an embodiment of the present invention. The organic EL element 70 according to this embodiment uses the gas barrier laminate 10 or 20 shown in FIGS. 1 and 2 as the lowermost film substrate. That is, on the lowermost film substrate using the gas barrier laminate 10 or 20, the anode 74 and the light emission auxiliary layer 75 as pixel electrodes are disposed.

  As the material of the anode 74, a metal composite oxide such as ITO (indium tin composite oxide) or IZO (indium zinc composite oxide), or a single layer or a laminate of metal materials such as gold or chromium is used. it can. This forming method is selected according to the material. As the light emission auxiliary layer 75, any of a hole transport layer, a hole injection layer, an electron transport layer, an electron injection layer, and a charge generation layer can be used, and is appropriately selected as necessary. The material used for each can be selected according to the characteristics.

A partition wall 72 is disposed so as to cover the anode 74. The partition 72 needs to have insulating properties, and a photosensitive material or the like can be used. The photosensitive material may be a positive type or a negative type, and is a photo-curing resin of a photo radical polymerization system, a photo cation polymerization system, or a copolymer containing an acrylonitrile component, polyvinyl phenol, polyvinyl Alcohol, novolac resin, polyimide resin, cyanoethyl pullulan, or the like can be used. Further, as a partition wall forming _material, it is also possible to use SiO 2, SiN, TiO ₂ or the like.

  An organic light emitting layer is disposed on the anode 74. As the organic light emitting layer, a blue light emitting layer 76, a green light emitting layer 77, and a red light emitting layer 78 are stacked. The organic EL material that constitutes the organic light emitting layer is classified into low molecular weight materials and high molecular weight materials, and the formation method is also classified into a vacuum film formation method and a wet coating method, but should be selected as appropriate. Can do.

  A cathode 73 is disposed on the organic light emitting layer. As the material of the cathode 73, a substance having a high electron injection efficiency is used. As a forming method, a dry film forming method such as a resistance heating evaporation method, an electron beam evaporation method, or a sputtering method can be used depending on the material. Further, when it is necessary to form a pattern, patterning can be performed using a mask or the like. The arrangement of the cathode 73 and the anode 74 can be changed with respect to the organic light emitting layer.

  The uppermost film substrate using the gas barrier laminate 10 or 20 is provided on the support 79 so that the support 79 is disposed on a part of the cathode 73 and a space exists between the support 73 and the cathode 73. Arranged. The support 79 is preferably excellent in mechanical strength and dimensional stability. As described above, the lowermost layer and the uppermost film substrate using the gas barrier laminate 10 or 20 are used to form the partition 72, the cathode 73, the anode 74, the light emission auxiliary layer 75, the blue light emitting layer 76, the green light emitting layer 77, and the red color. The light emitting layer 78 is sealed from the outside.

  Here, the organic EL element has been described in detail. However, in other image display elements such as a liquid crystal display panel, an electrochromic panel, and electronic paper, the gas barrier laminate of the present invention is used as a substrate instead of a normal film substrate. By using it, it is possible to obtain an image display element that has a high barrier performance as in the case of a glass substrate and does not deteriorate in a high temperature and high humidity environment.

  Hereinafter, the gas barrier laminate of the present invention will be described more specifically based on Examples and Comparative Examples. However, the present invention is not limited to the following Examples without departing from the gist of the present invention. Absent.

<Example 1>
A gas barrier laminate having the structure according to the second embodiment shown in FIG. 2 was produced by the following procedure.
First, an acrylic polyol (weight average molecular weight of about 10,000) was obtained by copolymerizing hydroxyethyl methacrylate and methyl methacrylate as monomers so that the OH group value was 178 mgKOH / g.

  Solid content in which the acrylic polyol obtained above is used as the main agent as the anchor coating agent, and hexamethylene diisocyanate as the curing agent is blended so that the equivalent ratio of NCO groups is 0.5 with respect to the amount of OH groups in the main agent. A 5 wt% methyl ethyl ketone solution was prepared.

  A first surface of a PEN film (film thickness: 100 μm) as a resin base material is subjected to corona treatment, and the solution is applied to a dry film thickness of 0.15 μm, and then placed in a thermostatic chamber at 50 ° C. for 48 hours. An anchor coat layer was formed by storage and aging treatment.

  On the anchor coat layer, using a vacuum deposition apparatus, a deposition material in which metal silicon powder and silicon dioxide powder are mixed so that the atomic ratio O / Si after film formation is 1.5 is deposited, A barrier layer having a thickness of 50 nm was formed.

  As a coating solution for forming the overcoat layer, a hydrolyzed solution of bistrimethoxysilylethane and glycidoxypropyltrimethoxysilane are used, and bistrimethoxysilylethane: glycidoxypropyltrimethoxysilane = 80: 20 (molar ratio). And mixed with IPA to prepare a solution having a solid content of 5% by weight. This coating solution was applied onto the barrier layer with a bar coater and heat-dried at 120 ° C. for 2 minutes to form an overcoat layer having a thickness of 1 μm. By repeating the above process three times, a laminate in which three barrier layers and three overcoat layers were laminated was obtained. Here, 0.02 of a fluorine-based leveling agent (DIC Megafac RS-75) is added to the outermost layer of the overcoat layer in a weight ratio with the overcoat agent, and the contact angle with pure water becomes 100 ° or more. I did it.

  Mixing so that the ratio α / β of the isocyanate group amount α of the hexamethylene diisocyanate compound (HDI) and the hydroxyl group amount β of the polycarbonate-based polyol compound Duranol 5650J is 1.5, and NV (Non Volatile Organic Compound) value in MEK. After the solution diluted so as to be 50% was applied to the second surface of the resin substrate with a bar coater, it was dried at 120 ° C. to form a urethane layer having a thickness of 20 μm.

  On the urethane layer, polyfunctional acrylic monomer: PE-3A (pentaerythritol triacrylate (PETA), Kyoeisha Chemical) 40 wt%, polyfunctional urethane acrylate oligomer: UA-306H (Kyoeisha Chemical) 60 wt%, initiator: Irgacure 184 (Ciba Specialty Chemicals) 10% by weight, inorganic fine particles: ELCOM TP1416SIV (silica fine particles) (catalyst chemical industry) particle size 80 nm, 20% by weight, solvent: ethyl acetate 100% by weight. And the hard-coat layer was formed so that the film thickness after hardening might be set to 5 micrometers, and the barriering laminated body concerning 2nd embodiment was produced.

<Example 2>
Example 1 except that the urethane layer was mixed so that the ratio of the isocyanate group amount α of the hexamethylene diisocyanate compound (HDI) and the hydroxyl group amount β of the polycarbonate polyol compound Duranol 5650J was α / β = 2.0. Under the conditions, a barrier laminate was produced.

<Comparative Example 1>
Example 1 except that the urethane layer was mixed so that the ratio of the isocyanate group amount α of the hexamethylene diisocyanate compound (HDI) and the hydroxyl group amount β of the polycarbonate polyol compound Duranol 5650J was α / β = 1.0. Under the conditions, a barrier laminate was produced.

<Comparative example 2>
The same conditions as in Example 1 except that the urethane layer was mixed so that the ratio α / β = 2.5 of the isocyanate group amount α of the hexamethylene diisocyanate compound (HDI) and the hydroxyl group amount β of the polycarbonate polyol compound Duranol 5650J was 2.5. Thus, a barrier laminate was produced.

<Comparative Example 3>
A barrier laminate was produced under the same conditions as in Example 1 except that the urethane layer and the hard coat layer were not provided.

<Evaluation method>
[Impact resistance evaluation]
After placing a pachinko ball on the hard coat surface of the gas barrier laminates of Examples 1 and 2 and Comparative Examples 1 to 3 (Comparative Example 3 is the second surface of the resin base material) and applying a load of 200 g, 105 ° C., It preserve | saved for 96 hours under 100% humidity, and the change of the water-vapor-permeation rate before a preservation | save was measured. The case where the change in the water vapor transmission rate was ± 10% or less was marked with ◯, and the case where it was more than that was marked with ×. As a method for measuring the water vapor transmission rate, the water vapor transmission rate (g / m ² · day) in a 40 ° C.-90% RH atmosphere was measured with a water vapor transmission meter (MOCON PERMATRAN-W 3/31) manufactured by Modern Control. Was measured.

[Adhesion test]
After the gas barrier laminates of Examples 1 and 2 and Comparative Examples 1 and 2 were stored at 105 ° C. and 100% humidity for 96 hours, a 10 × 10 square cross-cut peel test was performed on the hard coat layer surface. The presence or absence of peeling of the hard coat layer was confirmed. The target was not peeling in 100 squares, that is, the number of squares after peel test / the number of squares before peel test = 100/100.

  Table 1 shows the evaluation results of Examples 1 and 2 and Comparative Examples 1 to 3.

  From Examples 1 and 2 and Comparative Examples 1 and 2, when the ratio α / β of the isocyanate group amount α of the urethane layer and the hydroxyl group amount β of the polyol compound is 1.5 and 2.0, the impact resistance is ○. It was. When α / β was 1.0 or 2.5, the impact resistance was x.

  From the results of the adhesion test, when α / β is 1.0 or 2.5, the adhesion between the urethane layer and the hard coat layer is deteriorated and peeling occurs, which is considered to be a factor that deteriorates the impact resistance. . When α / β is 1.0, it is considered that the bond between the residual isocyanate group of the urethane layer and the residual hydroxyl group of the hard coat layer was not formed, and adhesion was deteriorated. When α / β is 2.5, it is considered that the film hardness of the urethane layer is increased, the cushioning property is lowered, and the adhesiveness is also lowered.

  From Comparative Example 3, when the urethane layer and the hard coat layer were not provided, the impact resistance was x.

DESCRIPTION OF SYMBOLS 10 Gas barrier laminated body 11 Resin base material 12 Barrier layer 13 Overcoat layer 14 Urethane layer 15 Hard coat layer 20 Gas barrier laminated body 24 Anchor coat layer 30 Back surface protection sheet 31 for solar cell modules Weatherproof film 32 Colored film 40 Solar cell Front protective sheet 41 for module Transparent weather resistant film 42 UV cut film 50 Solar cell module 51 Solar cell element 70 Organic EL element 72 Partition 73 Cathode 74 Anode 75 Light emission auxiliary layer 76 Blue light emission layer 77 Green light emission layer 78 Red light emission layer 79 Support body

Claims (7)

A substrate;
A barrier layer formed on the first surface of the substrate;
The urethane layer sequentially formed on the second surface of the substrate, and a hard coat layer having a hydroxyl group,
The gas barrier laminate having a ratio α / β of isocyanate group amount α and hydroxyl group amount β contained in the urethane layer of 1.5 or more and 2.0 or less. The gas barrier laminate according to claim 1, wherein an overcoat layer is formed on the barrier layer formed on the first surface of the base material. The gas barrier laminate according to claim 2, wherein the overcoat layer contains at least one selected from the group consisting of an organosilicon compound represented by the following chemical formula (a) and a hydrolyzate thereof.
(RO) ₃ Si— (CH ₂ ) _n —Si (OR) ₃ (a)
[However, R is an alkyl group, and n is an integer of 1-8. ]   The gas barrier laminate according to any one of claims 1 to 3, further comprising an anchor coat layer between the base material and the barrier layer.   The gas barrier laminate according to any one of claims 1 to 4, wherein the barrier layer contains metal silicon and silicon dioxide. A solar cell module using the gas barrier laminate according to any one of claims 1 to 5. An image display element comprising the gas barrier laminate according to any one of claims 1 to 5.

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