JP2011093195A - Barrier film laminate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a barrier film laminate having high a barrier property to water vapor and hardly causing delamination even in an environment of a high temperature and high humidity to maintain the high barrier property. <P>SOLUTION: The barrier film laminate is formed by sticking barrier films through an adhesive layer. The barrier film includes, on at least an outermost layer at one side, an inorganic oxide layer or a coating layer comprising a composite film formed by the reaction of resin with a hydrophilic group, a hydrolysate of alkoxide and/or its condensate. At least one surface of the adhesive layer abuts on the surface of the inorganic oxide layer or the surface of the coating layer, and the adhesive layer contains a silane coupling agent. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a barrier film laminate having a high barrier property against water vapor and hardly causing delamination even in a high temperature and high humidity environment.

  In the field of packaging foods, pharmaceuticals, etc., barrier films are used to prevent the contents from being altered by the ingress of oxygen or water vapor. In recent years, higher quality barrier films have been demanded and developed as packaging materials for electronic members and optical members.

  As a method for forming the barrier film, there are a method of depositing an inorganic compound on the surface of the base film, or coating a resin having a barrier property on the base film. For example, Patent Document 1 discloses a packaging film with improved barrier properties by depositing aluminum oxide on the surface of a base film. Patent Document 2 discloses a gas barrier film in which a polyvinyl alcohol resin layer having high barrier properties but poor adhesion to a base film is laminated on the base film via an easy-adhesion layer. Yes.

  However, although these barrier films have a high barrier property against oxygen, it is difficult to say that the barrier property against water vapor is sufficient, and further development is required for use as a packaging material for electronic and optical members that are susceptible to moisture. There was room for.

Japanese Patent Laid-Open No. 62-179935 JP-A-10-296929

  By the way, in order to further improve the barrier property of the barrier film, it is considered that it is preferable that the barrier films having high barrier properties are bonded together to form a multilayer barrier structure. However, in the barrier film laminate using an adhesive for bonding the barrier films together, bubbles remain between the adhesive layer and the adherend layer, so that the haze increases and the transparency decreases. On the other hand, in the barrier film laminate using an adhesive for laminating the barrier films, since it is difficult for air bubbles to remain between the adhesive layer and the adherend layer, a decrease in transparency does not occur. When used in a high-temperature and high-humidity environment, the laminate strength decreases with time due to moisture entering from the end face of the pressure-sensitive adhesive layer, resulting in poor durability.

  The present invention has been made in view of the above circumstances, and the object thereof is to have a high barrier property against water vapor, and it is difficult to cause delamination even in a high temperature and high humidity environment. It is providing the barrier film laminated body which can maintain barrier property.

  The present inventor has made extensive studies in order to solve the above-mentioned problems.As a result, the barrier films having high water vapor barrier properties are bonded to each other via an adhesive layer containing a silane coupling agent. The inventors have found that this can be solved, and have completed the present invention. Specifically, the following are provided.

  (1) A barrier film laminate in which barrier films are bonded to each other via an adhesive layer, and the barrier film includes an inorganic oxide layer or a resin having a hydrophilic group in at least one outermost layer. A coating layer comprising a composite film formed by a reaction with a hydrolyzate of alkoxide and / or a condensate thereof, wherein at least one surface of the pressure-sensitive adhesive layer is the surface of the inorganic oxide layer or the coating layer. A barrier film laminate, wherein the pressure-sensitive adhesive layer contains a silane coupling agent in contact with the surface.

  (2) The barrier film laminate according to (1), wherein at least one surface of the pressure-sensitive adhesive layer is in contact with the surface of the coat layer.

  According to the present invention, the barrier films having a high barrier property against water vapor are bonded together via an adhesive layer containing a silane coupling agent, thereby having a very excellent water vapor barrier property, and It is possible to provide a barrier film laminate in which delamination hardly occurs even in a high temperature and high humidity environment.

It is sectional drawing which showed typically the barrier film laminated body which concerns on the 1st Embodiment of this invention. It is sectional drawing which showed typically the barrier film laminated body which concerns on the 2nd Embodiment of this invention. It is sectional drawing which showed typically the barrier film laminated body which concerns on the 3rd Embodiment of this invention. It is sectional drawing which showed typically the barrier film laminated body which concerns on the 4th Embodiment of this invention.

  Hereinafter, specific embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments, and may be implemented with appropriate modifications within the scope of the object of the present invention. can do.

[Barrier film laminate]
The barrier film laminate of the present invention is a barrier film laminate in which barrier films are bonded together via an adhesive layer. The barrier film is a coating layer formed of a composite film formed by a reaction of an inorganic oxide layer or a hydrolyzate of alkoxide and / or a condensate thereof with an inorganic oxide layer or at least one outermost layer. Wherein at least one surface of the pressure-sensitive adhesive layer is in contact with the surface of the inorganic oxide layer or the surface of the coat layer, and the pressure-sensitive adhesive layer contains a silane coupling agent.

  In the barrier film laminate of the present invention, in order to improve barrier properties, a composite film formed by a reaction of an inorganic oxide layer or a resin having a hydrophilic group with a hydrolyzate of alkoxide and / or a condensate thereof is used. Barrier films having a high barrier property provided with a coating layer to be bonded together were bonded via an adhesive layer. When used in a high-temperature, high-humidity environment, a laminate of barrier films that are bonded together via an adhesive layer reduces the laminate strength and delamination due to moisture entering from the end face of the adhesive layer. It becomes easy. This phenomenon is remarkable in a barrier film having an inorganic oxide layer having a high barrier property and the coating layer. Therefore, in the present invention, in order to obtain a barrier film laminate having a very excellent water vapor barrier property and hardly causing delamination even in a high-temperature and high-humidity environment, the barrier films provided with an inorganic oxide layer and the above-described coating layer For the bonding, a pressure-sensitive adhesive layer containing a silane coupling agent was used. As a result, the group present on the surface of the layer in contact with the pressure-sensitive adhesive layer and the group possessed by the silane coupling agent contained in the pressure-sensitive adhesive layer react and chemically bond, not only improving the adhesiveness, Even if it is an environment where moisture easily enters from the end face of the pressure-sensitive adhesive layer, the group that reacts with water molecules (hydrophilic group) is chemically bonded to the group that the silane coupling agent has, so water molecules It is considered that delamination does not easily occur.

  The barrier film laminate of the present invention is a composite film formed by reacting at least one outermost layer with an inorganic oxide layer or a hydrolyzate of alkoxide and / or a condensate thereof with a hydrophilic group-containing resin. A barrier film comprising a coating layer made of is bonded via an adhesive layer, and at least one surface of the adhesive layer is in contact with the surface of the inorganic oxide layer or the surface of the coating layer. It has the composition which is. In addition, if it has such a structure, the number of bonding of a barrier film will not be specifically limited, It can select suitably considering a desired barrier property, transparency, a softness | flexibility, etc. . Moreover, if it has such a structure, the barrier film may be provided with layers other than a base material, an inorganic oxide layer, and a coating layer, and may be a multilayer structure of more multilayers.

  First, the structure of the barrier film laminated body of this invention is demonstrated using drawing. FIG. 1 is a cross-sectional view schematically showing a barrier film laminate 1 according to the first embodiment of the present invention. In FIG. 1, a barrier film laminate 1 includes an inorganic oxide layer 3 on one outermost layer, and barrier films 11 each having a substrate 2 on the other outermost layer are surfaces of the inorganic oxide layer 3. And one side of the pressure-sensitive adhesive layer 4 are bonded to each other.

  Moreover, FIG. 2 is sectional drawing which showed typically the barrier film laminated body 1 which concerns on the 2nd Embodiment of this invention. In FIG. 2, the barrier film laminate 1 includes a coat layer 5 formed of a composite film formed by a reaction between a resin having a hydrophilic group and a hydrolyzate of alkoxide and / or a condensate thereof in one outermost layer. And barrier film 11 provided with the base material 2 in the other outermost layer is bonded together so that the surface of the said coat layer 5 and one surface of the adhesive layer 4 may contact | connect.

  FIG. 3 is a cross-sectional view schematically showing the barrier film laminate 1 according to the third embodiment of the present invention. In FIG. 3, the barrier film laminate 1 includes the inorganic oxide layer 3 on one outermost layer, and the barrier films 11 including the substrate 2 on the other outermost layer are the surfaces of the inorganic oxide layer 3. And the both sides of the pressure-sensitive adhesive layer 4 are bonded together.

  FIG. 4 is a cross-sectional view schematically showing a barrier film laminate 1 according to the fourth embodiment of the present invention. In FIG. 4, the barrier film laminate 1 includes a coat layer 5 made of a composite film formed by a reaction between a resin having a hydrophilic group and a hydrolyzate of alkoxide and / or a condensate thereof in one outermost layer. And barrier film 11 provided with the base material 2 in the other outermost layer is bonded together so that the surface of the said coat layer 5 and both surfaces of the adhesive layer 4 may contact | connect.

  Although not shown in the figure, a barrier film 11 having an inorganic oxide layer 3 in at least one outermost layer, a hydrolyzate of a resin and an alkoxide having a hydrophilic group in at least one outermost layer, and / or its The barrier film laminate 1 in which the barrier film 11 including the coating layer 5 made of the composite film formed by the reaction with the condensate is bonded via the pressure-sensitive adhesive layer 4 is also included in the scope of the present invention.

  In the barrier film laminate 1 of the present invention, one outermost layer is preferably a layer other than the inorganic oxide layer 3 or the coat layer 5, and both outermost layers are the inorganic oxide layer 3 or the coat layer. A layer other than 5 is more preferable. This is because, when the outermost layer is the inorganic oxide layer 3 or the coat layer 5, human hands or objects come into contact with each other, so that the outer layer is easily damaged and the barrier property is likely to be lowered.

  Below, each structure of the barrier film laminated body 1 of this invention is demonstrated in detail.

[Base material]
If the base material 2 has required intensity | strength and a softness | flexibility, it will not specifically limit, According to a use, it can select suitably. Generally, a synthetic resin film is used. Synthetic resin film materials include polyester resins, polypropylene resins, polyvinyl chloride resins, fluorine resins, polystyrene resins, poly (meth) acrylic resins, cellulose resins, polycarbonate resins, polyamide resins, Known resins such as polyolefin resins, polyester resins, polyvinyl alcohol resins, polyimide resins, phenol resins, polyurethane resins and the like can be mentioned. These can be used alone or in combination of two or more. Moreover, a single layer may be sufficient and the laminated body of two or more layers may be sufficient. A uniaxially stretched or biaxially stretched film is preferred in terms of mechanical strength. In the present invention, among the synthetic resins, it is particularly preferable to use a polyester-based resin from the viewpoints of transparency, heat resistance, dimensional stability, rigidity, flexibility, suitability for stacking, price, and the like.

  Examples of the polyester-based resin include polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, polybutylene naphthalate, polyarylate, polytetramethylene terephthalate, etc. Among them, from the viewpoint of ease of handling, low cost, etc. Polyethylene terephthalate is particularly preferred.

  The thickness of the base material 2 is not particularly limited, and can be appropriately selected depending on the application. Usually, it is about 9-150 micrometers, Preferably it is 12-125 micrometers, More preferably, it is 12-100 micrometers. If it is the said range, mechanical strength is sufficient, it is hard to produce a curvature, a slack, a fracture | rupture, etc., workability | operativity is favorable, and it is also possible to supply and process in a continuous belt shape. If the thickness exceeds the above-mentioned thickness, excessive performance may increase the cost.

  The substrate 2 preferably has high transparency. For example, the light transmittance in the visible range (380 to 780 nm) is preferably 85% or more. It is not always necessary to be colorless and transparent, and it may be colored and transparent. The light transmittance can be measured (based on JIS-Z8701) using a commercially available spectrophotometer, for example, UV-3100PC manufactured by Shimadzu Corporation.

  The formation method of the base material 2 is not specifically limited, For example, conventionally well-known film forming methods, such as a solution casting method, a melt extrusion method, and a calendar method, can be used. Moreover, you may use the commercially available base material previously formed into a film form by the said method.

  The base material 2 may be subjected to a known easy adhesion treatment such as corona treatment, plasma treatment, or ozone treatment.

[Inorganic oxide layer]
The barrier film 11 which comprises the barrier film laminated body 1 which concerns on 1st, 3rd embodiment of this invention is equipped with the inorganic oxide layer 3 in one outermost layer, as shown in FIG. By sticking the barrier film 11 provided with the inorganic oxide layer 3, a higher water vapor barrier property can be obtained as compared with the case of the barrier film 11 provided with the inorganic oxide layer 3 alone.

  The inorganic compound forming the inorganic oxide layer 3 is not particularly limited as long as it exhibits a barrier property against water vapor. For example, aluminum oxide, magnesium oxide, silicon oxide, titanium oxide, tin oxide, indium oxide, Examples include calcium oxide, potassium oxide, sodium oxide, lead oxide, boron oxide, and zirconium oxide. Among these, aluminum oxide and silicon oxide are preferable in that they have transparency, excellent water resistance, and are inexpensive.

  In the barrier film (FIGS. 1 and 3) constituting the barrier film laminate 1 according to the embodiment of the present invention, the inorganic oxide layer 3 is formed on the substrate 2. In addition, in this invention, although the inorganic oxide layer 3 may be formed through another layer between the base materials 2, here, the inorganic oxide layer 3 is formed on the said base material 2. The case of forming will be described. Examples of the method for forming the inorganic oxide layer 3 on the substrate 2 include vapor deposition and coating. Among these, vapor deposition is preferable in that it has suitability for mass production, is excellent in barrier stability, and can provide high barrier performance. In addition, as a vapor deposition method, a chemical vapor deposition method (CVD method) and a physical vapor deposition method (PVD method) are mentioned, Any can be used suitably. Examples of chemical vapor deposition include plasma chemical vapor deposition, thermal chemical vapor deposition, and photochemical vapor deposition. Examples of the physical vapor deposition method include a vacuum deposition method, a sputtering method, and an ion plating method. Among these, the vacuum vapor deposition method is preferable in terms of easy film thickness adjustment and easy thin film molding.

  In addition, it is preferable that the film thickness of the inorganic oxide layer 3 formed by vapor deposition is 50-4000cm, and it is more preferable that it is 100-1000cm. If it is the said range, sufficient barrier property with respect to water vapor | steam will be exhibited, and it will be hard to generate | occur | produce a crack.

[Coat layer]
As shown in FIGS. 2 and 4, the barrier film 11 constituting the barrier film laminate 1 according to the second and fourth embodiments of the present invention includes a resin having a hydrophilic group in one outermost layer and an alkoxide. The coating layer 5 which consists of a composite film formed by reaction with a hydrolyzate and / or its condensate is provided. By sticking the barrier film 11 provided with the coat layer 5, a higher water vapor barrier property can be obtained as compared with the case of the barrier film 11 provided with the coat layer 5 alone.

  The composite membrane in the present invention is formed by a resin having a hydrophilic group being condensed and crystallized with a hydrolyzate of alkoxide and / or a condensate thereof. The composite film formed in this manner is firmly adhered to the inorganic oxide layer 3 by a chemical bond such as a hydrogen bond, so that it is considered that the water vapor barrier property is further improved.

  In general, alkoxides are condensed after hydrolysis to form a film, which is hard and prone to cracking. Therefore, in the coating layer 5 in the present invention, a resin having a hydrophilic group is added to impart flexibility to the film and prevent the occurrence of damage such as cracks in the molding process. Thereby, the barrier film laminated body 1 which maintains a high water vapor | steam barrier property after a shaping | molding process can be obtained. The resin having a hydrophilic group is not particularly limited, and examples thereof include polyvinyl alcohol, methyl cellulose, and ethylene / vinyl alcohol copolymer. These can be used alone or in combination of two or more. Examples of the hydrophilic group include, but are not limited to, a hydroxyl group, a sulfone group, a carboxyl group, and an amide group. Among the above resins, polyvinyl alcohol having a large number of hydroxyl groups and forming a very strong hydrogen bond with the hydroxyl group of the hydrolyzate of alkoxide or its condensate is preferable because of its high gas barrier properties. The saponification degree and molecular weight of polyvinyl alcohol are not particularly limited, but those having a high molecular weight with a high saponification degree and a high polymerization degree are preferred because of excellent water resistance. A combination of polyvinyl alcohol and an ethylene / vinyl alcohol copolymer is more preferable in terms of excellent gas barrier properties, water resistance, and weather resistance.

The alkoxide is not particularly limited. For example, the general formula: R1 _n M (OR2) _m (wherein M is a metal element, R1 and R2 are organic groups having 1 to 8 carbon atoms, n is 0 or more, and m is 1) Those represented by the above integer, n + m represents the valence of M) can be suitably used. In addition, the hydrolyzate of alkoxide does not need to be a thing in which all the alkoxy groups are hydrolyzed, What is necessary is just one or more hydrolyzed.

  In the above general formula, examples of the metal element represented by M include silicon, zirconium, titanium, and aluminum. Among these, silicon and aluminum are preferable. Examples of the organic group represented by R1 include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, t-butyl group, Examples thereof include alkyl groups such as n-hexyl group and n-octyl group, and examples of the organic group represented by R2 include methyl group, ethyl group, n-propyl group, i-propyl group, and n-butyl group. And alkyl groups such as sec-butyl group. Note that the organic group represented by R1 and the organic group represented by R2 may be the same or different.

Examples of the alkoxysilane in which the metal element represented by M is silicon include tetramethoxysilane: Si (OCH ₃ ) ₄ , tetraethoxysilane: Si (OC ₂ H ₅ ) ₄ , tetrapropoxysilane: Si (OC ₃ H ₇ ) ₄ , tetrabutoxysilane: Si (OC ₄ H ₉ ) _{4 and the} like can be suitably used. Further, _{methyltrimethoxysilane: CH 3 Si (OCH 3)} 3, methyl _{triethoxysilane: CH 3 Si (OC 2 H} 5) 3, _{dimethyldimethoxysilane: (CH 3) 2 Si (} OCH 3) 2, dimethyldi Alkoxyalkoxysilanes such as ethoxysilane: (CH ₃ ) ₂ Si (OC ₂ H ₅ ) ₂ can also be suitably used. These alkoxysilanes and alkylalkoxysilanes can be used alone or in combination of two or more. Furthermore, polycondensation products of alkoxysilanes such as polytetramethoxysilane and polytetraemethoxysilane can also be suitably used. Among the alkoxysilanes, tetraethoxysilane is preferable because it is relatively stable in an aqueous solvent after hydrolysis.

Examples of the zirconium alkoxide in which the metal element represented by M is zirconium include tetramethoxyzirconium: Zr (O—CH ₃ ) ₄ , tetraethoxyzirconium: Zr (O—C ₂ H ₅ ) ₄ , tetraisopropoxyzirconium. : Zr (O—Iso—C ₃ H ₇ ) ₄ , tetra-n-butoxyzirconium Zr (O—C ₄ H ₉ ) _{4 and the} like can be suitably used.

Examples of the titanium alkoxide in which the metal element represented by M is titanium include tetramethoxy titanium: Ti (O—CH ₃ ) ₄ , tetraethoxy titanium: Ti (O—C ₂ H ₅ ) ₄ , and tetraisopropoxy titanium. _{: Ti (O-Iso-C} 3 H 7) 4, tetra -n- butoxy _{titanium: Ti (O-C 4 H} 9) 4 and the like can be suitably used.

Examples of the aluminum alkoxide in which the metal element represented by M is aluminum include tetramethoxyaluminum: Al (O—CH ₃ ) ₄ , tetraethoxyaluminum: Al (O—C ₂ H ₅ ) ₄ , and tetraisopropoxyaluminum. _{: Al (O-Iso-C} 3 H 7) 4, tetra -n- butoxy _{aluminum: Al (O-C 4 H} 9) 4 and the like can be suitably used.

  In the present invention, the coat layer 5 in which the resin having a hydrophilic group is polyvinyl alcohol and the alkoxide is tetraethoxysilane is preferable because it has a high water vapor barrier property.

  In the coating layer 5 of the present invention, the element ratio (M / C) of the metal element (M) derived from the alkoxide and the carbon element (C) derived from the resin having the hydrophilic group is 2.8 <M / C <4.12 is preferable, and 2.8 <M / C <3.4 is more preferable. When the ratio of the carbon element derived from the resin having a hydrophilic group is too large, the swelling of the resin having the hydrophilic group cannot be suppressed, the surface of the coat layer 5 becomes rough, and the water vapor barrier property is lowered. When the proportion of the metal element derived from the alkoxide is too large, condensation polymerization of the alkoxide hydrolyzate or the like or between the alkoxide hydrolyzate and the resin having a hydrophilic group proceeds excessively, and a large aggregate is formed. Therefore, a dense film cannot be formed. If it does so, the surface of the coating layer 5 will become rough and water vapor | steam barrier property will fall.

  In the barrier film (FIGS. 2 and 4) constituting the barrier film laminate 1 according to the embodiment of the present invention, the coat layer 5 is formed on the inorganic oxide layer 3. In the present invention, the coat layer 5 may be formed on the substrate 2, or may be formed through another layer between the inorganic oxide layer 3. In the case where the barrier film laminate 1 of the present invention includes the inorganic oxide layer 3 and the coat layer 5, it is preferable because higher water vapor barrier properties can be obtained. The coat layer 5 also functions as a protective film. For example, by forming the inorganic oxide layer 3 on the inorganic oxide layer 3, even if there is a defect site in the inorganic oxide layer 3, it is possible to ensure the barrier property by filling it.

  The method for forming the coating layer 5 is not particularly limited. For example, a conventionally known method such as a roll coating method, a spin coating method, a gravure coating method, a reverse coating method, a dipping method, a spray coating method, or a bar coating method is used. Can be used. For example, when the coat layer 5 is formed on the inorganic oxide layer 3, the resin having a hydrophilic group and the alkoxide are dissolved or dispersed in water or a mixed solvent of water and an organic solvent. Thereafter, the inorganic oxide layer 3 is coated and dried by heating. The thickness of the coat layer 5 is not particularly limited, but is usually 0.01 to 30 μm, preferably 0.1 to 10 μm. If it is the said range, it is hard to produce a crack.

[Adhesive layer]
As shown in FIGS. 1 to 4, the barrier film laminate 1 of the present invention is obtained by bonding the barrier films 11 to each other via the pressure-sensitive adhesive layer 4, and at least one surface of the pressure-sensitive adhesive layer 4 is It is in contact with the surface of the inorganic oxide layer 3 or the surface of the coating layer 5 made of a composite film formed by a reaction between a resin having a hydrophilic group and a hydrolyzate of alkoxide and / or a condensate thereof. The barrier film 11 including the coating layer 5 made of a composite film formed by a reaction of the inorganic oxide layer 3 or a resin having a hydrophilic group with a hydrolyzate of alkoxide and / or a condensate thereof has high barrier properties. However, when the barrier film laminate 1 in which these are bonded through the pressure-sensitive adhesive layer is used in a high-temperature and high-humidity environment, the laminate strength is remarkably reduced due to moisture entering from the end face of the pressure-sensitive adhesive layer 4. And delamination is likely to occur. In particular, since the coating layer has a hydrophilic group that reacts with water molecules, it tends to attract water molecules and has a strong tendency. In the present invention, a silane coupling agent is blended in the pressure-sensitive adhesive layer 4 in order to suppress a decrease in laminate strength in a high temperature and high humidity environment. As a result, the group present on the surface of the layer in contact with the pressure-sensitive adhesive layer and the group possessed by the silane coupling agent contained in the pressure-sensitive adhesive layer react and chemically bond, not only improving the adhesiveness, Even if it is an environment where moisture easily enters from the end face of the pressure-sensitive adhesive layer, the group that reacts with water molecules (hydrophilic group) is chemically bonded to the group that the silane coupling agent has, so water molecules It is considered that the decrease in the laminate strength can be suppressed. Moreover, it is thought that durability and heat resistance of adhesive layer 4 itself improve by use of a silane coupling agent.

  The pressure-sensitive adhesive used for the pressure-sensitive adhesive layer 4 of the present invention is not particularly limited as long as it has necessary adhesion, transparency, coating suitability, etc., and can be appropriately selected from known pressure-sensitive adhesives. it can. For example, acrylic, urethane, silicone, synthetic rubber, and natural rubber adhesives can be used. These can be used alone or in combination of two or more. In the present invention, it is preferable to use an acrylic adhesive or a synthetic rubber adhesive. The acrylic pressure-sensitive adhesive is preferable not only because it has favorable properties as a barrier film, which is excellent in heat resistance, transparency and coating suitability, but is also low in cost. Synthetic rubber-based pressure-sensitive adhesives are preferable in that they are inexpensive and have excellent long-term stability in performance.

  Although it does not specifically limit as an acrylic adhesive, For example, the acrylic ester copolymer which copolymerized acrylic ester and another monomer is mentioned. Examples of the acrylate ester include ethyl acrylate, acrylate-n-butyl, acrylate-2-ethylhexyl, isooctyl acrylate, isononyl acrylate, hydroxylethyl acrylate, propylene glycol acrylate, acrylamide, glycidyl acrylate, and the like. Is mentioned. These can be used alone or in combination of two or more. In the present invention, among the acrylic esters, ethyl acrylate, acrylic acid-n-butyl, and acrylic acid-2-ethylhexyl are preferable in that they have good adhesion to the adherend. Other monomers include, for example, methyl acrylate, methyl methacrylate, styrene, acrylonitrile, vinyl acetate, acrylic acid, methacrylic acid, itaconic acid, hydroxylethyl acrylate, hydroxylethyl methacrylate, propylene glycol acrylate, acrylamide Methacrylamide, glycidyl acrylate, glycidyl methacrylate, dimethylaminoethyl methacrylate, tert-butylaminoethyl methacrylate, n-ethylhexyl methacrylate, and the like. These can be used alone or in combination of two or more. In the present invention, among the other monomers, n-ethylhexyl methacrylate is preferable.

  The weight average molecular weight (Mw) of the acrylic ester copolymer used as the acrylic pressure-sensitive adhesive is not particularly limited as long as the acrylic pressure-sensitive adhesive exhibits a desired adhesive force, but 200,000 to 2 , 500,000, preferably 600,000-2,200,000. The weight average molecular weight is a value in terms of polystyrene when measured by gel permeation chromatography (GPC).

  In addition, as a commercial item of the said acrylic adhesive, SK dyne 2094 (made by Soken Chemical Co., Ltd.), SK dyne 2096 (made by Soken Chemical Co., Ltd.) etc. can be used suitably, for example.

  Although it does not specifically limit as a synthetic rubber adhesive, For example, styrene-isoprene copolymer rubber (SIS), styrene-butadiene copolymer rubber (SBR), polyisoprene rubber (IR), polyisobutylene (PIB), Examples thereof include butyl rubber (IIR). These can be used alone or in combination of two or more. In the present invention, isoprene-based rubber is preferable, and SIS is particularly preferable.

  In addition, as a commercial item of the said rubber-type adhesive, JSR SIS 5200 (made by JSR Corporation), HYBRAR 7311 (made by Kuraray Co., Ltd.) etc. can be used suitably, for example.

  Although it does not specifically limit as a silane coupling agent, It is an organosilicon compound which has at least 1 or more alkoxysilyl group in a molecule | numerator, Comprising: The thing with favorable compatibility with the said adhesive is suitable. Examples include tetraethoxysilane, trimethoxysilane, dimethylethoxysilane, methyltrimethoxysilane, aminosilane, chlorosilane, dichlorosilane, and the like, taking into account the properties of the barrier film surface in contact with the adhesive layer 4 and the type of adhesive. Can be appropriately selected. In addition, you may use these individually or in combination of 2 or more types.

  The compounding amount of the silane coupling agent is preferably 0.1 to 1.5 parts by mass and more preferably 0.3 to 1.2 parts by mass with respect to 100 parts by mass of the adhesive solid content. . If it is the said range, favorable adhesiveness, adhesiveness, heat resistance, durability, and workability | operativity can be provided to an adhesive layer.

  In addition, a cross-linking agent, a tackifier, a metal chelating agent, a surfactant, an antioxidant, an ultraviolet absorber, a pigment, a dye, a colorant, an antistatic agent, as necessary, as long as the object of the present invention is not impaired. Various additives such as preservatives, antifoaming agents, wettability adjusting agents and the like can be blended.

  In addition, the crosslinking agent which can be mix | blended with the adhesive layer of this invention will not be specifically limited if an adhesive can be bridge | crosslinked, For example, an epoxy-type crosslinking agent, an isocyanate type crosslinking agent, etc. are mentioned. Examples of the epoxy-based crosslinking agent include sorbitol polyglycidyl ether, polyglycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, diglycerol polyglycidyl ether, glycerol polyglycidyl ether, trimethylolpropane polyglycidyl ether, neopentyl glycol diglycidyl ether. 1, 6-hexanediol diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, polybutadiene diglycidyl ether, and the like. Examples of the isocyanate-based crosslinking agent include a polyisocyanate compound, a trimer of a polyisocyanate compound, a urethane prepolymer having an isocyanate group at a terminal obtained by reacting a polyisocyanate compound and a polyol compound, and the urethane prepolymer. The trimer of etc. is mentioned. Examples of the polyisocyanate compound include 2,4-tolylene diisocyanate, 2,5-tolylene diisocyanate, 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, diphenylmethane-4,4′-diisocyanate, 3 -Methyldiphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, dicyclohexylmethane-2,4'-diisocyanate, lysine isocyanate and the like. These may be used alone or in combination of two or more, and may be appropriately selected depending on the type of the pressure-sensitive adhesive.

  Further, the tackifier that can be blended in the pressure-sensitive adhesive layer of the present invention is not particularly limited, and examples thereof include rosin resins such as rosin ester, hydrogenated rosin ester, disproportionated rosin ester, and polymerized rosin ester; Coumarone indene resins such as malon indene resin, hydrogenated coumarone indene resin, phenol modified coumarone indene resin, epoxy modified coumarone indene resin; polyterpene resin, styrene modified terpene resin, phenol modified terpene resin, aliphatic petroleum resin And petroleum resins such as aromatic petroleum resins, aromatic modified aliphatic petroleum resins, and aromatic pure monomer resins. These may be used alone or in combination of two or more, and may be appropriately selected depending on the type of the pressure-sensitive adhesive. For example, when isoprene rubber is used as the adhesive, rosin resin, terpene resin, aliphatic petroleum resin, aromatic petroleum resin, alicyclic petroleum resin, and hydrogenation of these petroleum resins Resins are preferred from the standpoint of affinity.

  Although it does not specifically limit as a formation method of the adhesive layer 4, For example, the method by printing, coating, etc. is mentioned. The thickness of the pressure-sensitive adhesive layer 4 can be appropriately selected within a range that does not impair the adhesiveness and adhesion to the barrier film surface in consideration of the state and shape of the barrier film surface in contact with the pressure-sensitive adhesive layer 4. Usually, it is 5-100 micrometers, Preferably it is 10-50 micrometers. If it is the said range, adhesive physical property will be stabilized. If the thickness is 5 μm or less, sufficient adhesive strength may not be obtained. If the thickness is 100 μm or more, optical characteristics such as light transmittance may be adversely affected.

[Barrier film laminate]
The method for forming the barrier film laminate 1 is not particularly limited. For example, in the case of the barrier film laminate 1 according to the first embodiment of the present invention shown in FIG. 1, a silane coupling agent is added to an acrylic pressure-sensitive adhesive and sufficiently dispersed to form a pressure-sensitive adhesive layer forming coating solution. Prepare. Next, the entire surface of the inorganic oxide layer 3 of the barrier film 11 is coated with a coating solution for forming a pressure-sensitive adhesive layer using an applicator to form the pressure-sensitive adhesive layer 4. Then, it is dried, and it can form by bonding the barrier film 11 using a roller so that the base material 2 surface of the barrier film 11 may contact the coating surface of the adhesive layer 4 after drying.

  The barrier film laminate 1 of the present invention is obtained by laminating a barrier film having a high water vapor barrier property and further imparting performance capable of withstanding use in a high temperature and high humidity environment. Therefore, according to the barrier film laminate 1 of the present invention, since it has excellent water vapor barrier properties and can prevent deterioration and alteration of the contents due to water vapor, foods and drinks, pharmaceuticals, electronic members, chemicals, It can be suitably used as a packaging material for various articles such as daily necessities. Further, it can be suitably used as a protective material for electrophoretic ink of electronic paper that is easily affected by moisture. Furthermore, the barrier film laminate 1 of the present invention can be applied to a solar cell backsheet, a display substrate such as a liquid crystal display and an organic EL display. When the display element is exposed to water vapor, its performance deteriorates, and troubles such as not emitting light may occur. According to the barrier film laminate 1 of the present invention, for example, the display element can be protected from water vapor by applying to the outside of the glass substrate instead of the two glass substrates of the display.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention does not receive a restriction | limiting at all by these description.

<Comparative Example 1>
Cross-linking agent (trade name: E-5XM, solid content: 5%, manufactured by Soken Chemical Co., Ltd.) with respect to 100 parts by mass of the acrylic pressure-sensitive adhesive (trade name: SK Dyne 2094, solid content: 25%, manufactured by Soken Chemical Co., Ltd.) ) 0.27 parts by mass was added and sufficiently dispersed to prepare a coating solution for forming an adhesive layer. Next, barrier film A (trade name: IB-PET-PXB, constitution: base material (polyethylene terephthalate) / deposition layer (aluminum oxide) / coat layer (polyvinyl alcohol + tetraethoxysilane), thickness: 12 μm, Dai Nippon Printing The pressure-sensitive adhesive layer-forming coating solution was applied over the entire surface of the coating layer surface of the company) using an applicator so that the film thickness after drying was 10 μm. Then, it was dried, and the barrier film A was bonded using a 2 kg roller so that the coating layer surface of the barrier film A was in contact with the coated surface of the pressure-sensitive adhesive layer after drying. Obtained.

<Comparative example 2>
Cross-linking agent (trade name: E-5XM, solid content: 5%, manufactured by Soken Chemical Co., Ltd.) with respect to 100 parts by mass of the acrylic pressure-sensitive adhesive (trade name: SK Dyne 2094, solid content: 25%, manufactured by Soken Chemical Co., Ltd.) ) 0.27 parts by mass was added and sufficiently dispersed to prepare a coating solution for forming an adhesive layer. Next, the entire surface of the coating layer of the barrier film A was coated with a coating solution for forming an adhesive layer using an applicator so that the film thickness after drying was 10 μm, thereby forming an adhesive layer. Thereafter, it is dried, and on the coated surface of the pressure-sensitive adhesive layer after drying, barrier film B (trade name: Tech barrier L, constitution: base material (polyethylene terephthalate) / deposition layer (silicon oxide), thickness: 12 μm, Mitsubishi Plastics The barrier film laminate of Comparative Example 2 was obtained by bonding the barrier film B using a 2 kg roller so that the vapor-deposited layer surface of the company) was in contact.

[Measurement of laminate strength]
The barrier film laminates of Comparative Examples 1 and 2 were cut into 15 mm × 150 mm to prepare test pieces. This test piece is allowed to stand for 500 hours in a high-temperature and high-humidity atmosphere at a temperature of 60 ° C. and a humidity of 90%, and the laminate strength of the test piece after being left is measured using a tensile tester (product name: RTF-1150H, manufactured by A & D). And measured (conforms to JIS Z 0237, speed: 300 mm / min, peel distance: 150 mm, peel angle: 180 °). In addition, the laminate strength was also measured and compared for the test piece before being left and the test piece left for 500 hours in a high-temperature atmosphere at 80 ° C. The results are shown in Table 1.

  In the barrier film laminated body bonded through the pressure-sensitive adhesive layer containing no silane coupling agent, a decrease in adhesiveness was observed when left in a high-temperature and high-humidity atmosphere (Comparative Examples 1 and 2).

<Example 1>
Cross-linking agent (trade name: E-5XM, solid content: 5%, manufactured by Soken Chemical Co., Ltd.) with respect to 100 parts by mass of the acrylic pressure-sensitive adhesive (trade name: SK Dyne 2094, solid content: 25%, manufactured by Soken Chemical Co., Ltd.) ) 0.27 parts by mass and 0.16 parts by mass of a silane coupling agent (trade name: SE-50, solid content: 50%, manufactured by Soken Chemical Co., Ltd.) are added and dispersed sufficiently to form an adhesive layer. A coating solution was prepared. Next, the entire surface of the coating layer of the barrier film A was coated with a coating solution for forming an adhesive layer using an applicator so that the film thickness after drying was 10 μm, thereby forming an adhesive layer. Then, it was dried, and the barrier film A was bonded using a 3 kg roller so that the coating layer surface of the barrier film A was in contact with the coated surface of the pressure-sensitive adhesive layer after drying, and the barrier film laminate of Example 1 was obtained. Obtained.

<Example 2>
Cross-linking agent (trade name: E-5XM, solid content: 5%, manufactured by Soken Chemical Co., Ltd.) with respect to 100 parts by mass of the acrylic pressure-sensitive adhesive (trade name: SK Dyne 2094, solid content: 25%, manufactured by Soken Chemical Co., Ltd.) ) 0.27 parts by mass and 0.16 parts by mass of a silane coupling agent (trade name: SE-50, solid content: 50%, manufactured by Soken Chemical Co., Ltd.) are added and dispersed sufficiently to form an adhesive layer. A coating solution was prepared. Next, the entire surface of the barrier film A was coated with an adhesive layer forming coating solution using an applicator so that the film thickness after drying was 10 μm, thereby forming an adhesive layer. Then, it dried and bonded the barrier film B using a 3 kg roller so that the vapor deposition layer surface of the barrier film B was in contact with the coated surface of the pressure-sensitive adhesive layer after drying, and the barrier film laminate of Example 2 was obtained. Obtained.

[Measurement of laminate strength]
The barrier film laminated body of the said Example 1, 2 was cut | disconnected to 15 mm x 150 mm, and the test piece was created. This test piece is allowed to stand for 500 hours in a high-temperature and high-humidity atmosphere at a temperature of 60 ° C. and a humidity of 90%, and the laminate strength of the test piece after being left is measured using a tensile tester (product name: RTF-1150H, manufactured by A & D). And measured (conforming to JIS Z0237, speed: 300 mm / min, peel distance: 150 mm, peel angle: 180 °). In addition, the laminate strength was also measured and compared for the test piece before being left and the test piece left for 500 hours in a high-temperature atmosphere at 80 ° C. The results are shown in Table 2.

  In the barrier film laminate bonded through the acrylic pressure-sensitive adhesive layer containing the silane coupling agent, even when left in a high temperature and high humidity atmosphere for a long time, almost no decrease in adhesiveness was observed (Example 1). , 2).

<Example 3>
Synthetic rubber-based adhesive (trade name: JSR SIS 5200, solid content: 100%, manufactured by JSR), 7 parts by weight tackifier (trade name: KE-100, solid content: 100%, Arakawa Chemical Industries) 3 parts by mass) and 0.02 parts by mass of a silane coupling agent (trade name: KBM-802, solid content: 100%, manufactured by Shin-Etsu Chemical Co., Ltd.) are added and dispersed sufficiently to form an adhesive layer. A coating solution was prepared. Next, the entire surface of the barrier film A was coated with an adhesive layer forming coating solution using an applicator so that the film thickness after drying was 15 μm, thereby forming an adhesive layer. Then, it dried and bonded the barrier film A using a 2 kg roller so that the coating layer surface of the barrier film A was in contact with the coated surface of the pressure-sensitive adhesive layer after drying, and the barrier film laminate of Example 3 was obtained. Obtained.

<Example 4>
Except that 0.03 parts by mass of a silane coupling agent (trade name: KBM-802, solid content: 100%, manufactured by Shin-Etsu Chemical Co., Ltd.) was added when preparing the adhesive layer forming coating solution. In the same manner as in Example 3, the barrier film laminate of Example 4 was obtained.

<Example 5>
Except that 0.04 parts by mass of a silane coupling agent (trade name: KBM-802, solid content: 100%, manufactured by Shin-Etsu Chemical Co., Ltd.) was added when preparing the adhesive layer forming coating solution. A barrier film laminate of Example 5 was obtained in the same manner as in Example 3.

<Example 6>
Synthetic rubber-based adhesive (trade name: JSR SIS 5200, solid content: 100%, manufactured by JSR), 7 parts by weight tackifier (trade name: KE-100, solid content: 100%, Arakawa Chemical Industries) 3 parts by mass) and 0.02 parts by mass of a silane coupling agent (trade name: KBM-802, solid content: 100%, manufactured by Shin-Etsu Chemical Co., Ltd.) are added and dispersed sufficiently to form an adhesive layer. A coating solution was prepared. Next, the entire surface of the substrate surface of the barrier film B was coated with a coating solution for forming an adhesive layer using an applicator so that the film thickness after drying was 15 μm, thereby forming an adhesive layer. Then, it dried and bonded the barrier film B using a 2 kg roller so that the vapor deposition layer surface of the barrier film B was in contact with the coated surface of the pressure-sensitive adhesive layer after drying, and the barrier film laminate of Example 6 was obtained. Obtained.

<Example 7>
Except that 0.03 parts by mass of a silane coupling agent (trade name: KBM-802, solid content: 100%, manufactured by Shin-Etsu Chemical Co., Ltd.) was added when preparing the adhesive layer forming coating solution. The barrier film laminate of Example 7 was obtained in the same manner as in Example 6.

<Example 8>
Except that 0.04 parts by mass of a silane coupling agent (trade name: KBM-802, solid content: 100%, manufactured by Shin-Etsu Chemical Co., Ltd.) was added when preparing the adhesive layer forming coating solution. In the same manner as in Example 6, the barrier film laminate of Example 8 was obtained.

<Comparative Example 3>
When preparing the coating solution for forming the pressure-sensitive adhesive layer, Example 3 and Example 3 except that a silane coupling agent (trade name: KBM-802, solid content: 100%, manufactured by Shin-Etsu Chemical Co., Ltd.) was not added. By the same method, the barrier film laminated body of the comparative example 3 was obtained.

<Comparative example 4>
Example 6 with the exception that a silane coupling agent (trade name: KBM-802, solid content: 100%, manufactured by Shin-Etsu Chemical Co., Ltd.) was not added when preparing the adhesive layer forming coating solution. In the same manner, a barrier film laminate of Comparative Example 4 was obtained.

[Measurement of laminate strength]
The barrier film laminates of Examples 3 to 8 and Comparative Examples 3 and 4 were cut into 15 mm × 150 mm to prepare test pieces. This test piece was left in a high-temperature and high-humidity atmosphere at a temperature of 60 ° C. and a humidity of 90% for 500 hours and 1000 hours, and the laminate strength of the test piece after being left for each time was measured by a tensile tester (product name: RTF-1150H, A & D) (based on JIS Z0237, speed: 300 mm / min, peel distance: 150 mm, peel angle: 180 °). Also, the laminate strength was measured in the same manner for the test piece before being left, the test piece left for 500 hours in a high temperature atmosphere at 80 ° C., and the test piece left for 1000 hours in a high temperature atmosphere at 80 ° C. Compared. The results are shown in Table 3.

  In the barrier film laminate bonded through a synthetic rubber-based pressure-sensitive adhesive layer not containing a silane coupling agent, a decrease in adhesiveness was observed when left for a long time in a high-temperature and high-humidity atmosphere (Comparative Examples 3 and 4). On the other hand, in the barrier film laminate bonded through a synthetic rubber-based pressure-sensitive adhesive layer containing a silane coupling agent, even when left in a high-temperature and high-humidity atmosphere for a long time, the adhesiveness is hardly reduced. None (Examples 3-8).

[Measurement of water vapor permeability]
The barrier film laminate, barrier film A (Reference Example 1), and barrier film B (Reference Example 2) of Examples 1, 2, and 6 were cut into 100 mm × 100 mm to prepare test pieces. The water vapor permeability of these test pieces was measured under the conditions of a temperature of 40 ° C. and a humidity of 90% using a measuring machine (model name: PERMATRAN) manufactured by MOCON (USA) (JIS K7129). Compliant) and compared. The results are shown in Table 4.

  By adhering the barrier film to form a laminate, the water vapor permeability was significantly reduced (Examples 1, 2, 6, Reference Examples 1 and 2). According to the barrier film laminate of the present invention, delamination hardly occurs even in a high-temperature and high-humidity environment, and thus high water vapor barrier properties can be maintained.

DESCRIPTION OF SYMBOLS 1 Barrier film laminated body 2 Base material 3 Inorganic vapor deposition layer 4 Adhesive layer 5 Coat layer 11 Barrier film

Claims (2)

A barrier film laminate in which the barrier films are bonded together via an adhesive layer,
The barrier film is a coat layer comprising an inorganic oxide layer or a composite film formed by a reaction of a hydrolyzate of alkoxide and / or a condensate thereof with an inorganic oxide layer or at least one outermost layer. With
At least one surface of the pressure-sensitive adhesive layer is in contact with the surface of the inorganic oxide layer or the surface of the coat layer,
The said adhesive layer contains a silane coupling agent, The barrier film laminated body characterized by the above-mentioned.   The barrier film laminate according to claim 1, wherein at least one surface of the pressure-sensitive adhesive layer is in contact with the surface of the coat layer.

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