JP2008087162A - Gas barrier laminated film and image display element using it - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a gas barrier laminated film having high gas barrier properties and adaptable to a flexible organic EL. <P>SOLUTION: The gas barrier laminated film is constituted by providing at least one inorganic layer, and at least one organic layer which is based on a polymer of an acrylic monomer, on a base material film. The organic layer includes a polymer product of a polymerizable monomer having at least one kind of a sulfonyl group or a sulfo group. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a gas barrier laminate film having excellent gas barrier performance. More particularly, the present invention relates to a gas barrier laminate film that can be suitably used for various image display elements, and particularly useful as a substrate for flexible organic electroluminescence elements (hereinafter referred to as “organic EL elements”). The present invention relates to a laminated film, a manufacturing method thereof, and an organic EL element.

  Conventionally, a gas barrier laminate film in which a metal oxide thin film such as aluminum oxide, magnesium oxide, silicon oxide or the like is formed on the surface of a plastic substrate or film is used for packaging articles that require blocking of various gases such as water vapor and oxygen, It is widely used in packaging applications to prevent the deterioration of food, industrial goods and pharmaceuticals. Recently, gas barrier films are being used in liquid crystal display elements, solar cells, organic EL elements, and the like in addition to packaging applications.

  In the process of developing image display elements such as liquid crystal display elements and organic EL elements in recent years, long-term reliability and freedom of shape are required for transparent substrates forming these elements in addition to the requirements for weight reduction and size increase. Advanced conditions such as high degree of accuracy and curved surface display are also required. As a transparent substrate that satisfies such advanced conditions, a plastic substrate is beginning to be adopted. Plastic base material is useful as a new base material that replaces the conventional glass substrate that is heavy, fragile, and difficult to increase in area, and is also more productive than glass substrate because of its roll-to-roll method. This is also advantageous in terms of cost reduction.

However, film substrates such as transparent plastics have the disadvantage that the gas barrier performance is inferior to that of glass substrates. If a base material with inferior gas barrier properties is used, water vapor or air will permeate, causing deterioration of the liquid crystal in the liquid crystal cell, for example, resulting in display defects and deterioration of display quality. In order to solve such a problem, a gas barrier laminate film in which a metal oxide thin film is formed on a base film has been developed so far. For example, as gas barrier laminated films used for packaging materials and liquid crystal display elements, there are known those in which silicon oxide is vapor-deposited on a plastic film (see Patent Document 1) and those in which aluminum oxide is vapor-deposited (see Patent Document 2). All have a water vapor barrier property of about 1 g / m ² / day.

In large-sized liquid crystal displays and high-definition displays that have been developed in recent years, a plastic film substrate having a water vapor transmission rate of 0.1 g / m ² / day or less is required. Furthermore, recently, the development of organic EL displays, high-definition color liquid crystal displays, etc. has progressed, and while maintaining the transparency that can be used in these, even higher barrier performance (especially the water vapor transmission rate is 0.01 g / m ² / day or less) ) Is required. In order to meet these demands, recently, as a means for expecting higher barrier performance, film formation by sputtering method or CVD method in which a thin film is formed using plasma generated by glow discharge under low pressure conditions has been studied. ing. In addition, an organic light emitting device in which a barrier film having an alternately laminated structure of organic layers / inorganic layers is produced by a vacuum deposition method has been proposed (see Patent Document 3). Furthermore, in order to provide the bending resistance necessary for application to a flexible display device, a technique using an acrylic monomer having a volume shrinkage of less than 10% in an organic layer has also been proposed (see Patent Document 4).

However, in order to use these plastic films as a flexible organic EL substrate, since the adhesion between the organic layer and the inorganic layer is not sufficient, further improvement has been desired. Therefore, attempts have been made to improve the adhesion with the inorganic layer to be laminated by introducing a polar group into the organic layer (see Patent Document 5), but the gas barrier performance required for the organic EL element is insufficient. .
Japanese Patent Publication No.53-12953 JP 58-217344 A US Pat. No. 6,268,695 (page 4 [2-5] to page 5 [4-49]) JP 2003-53881 A (Page 3 [0006] to Page 4 [0008]) JP 2004-9395 A (page 3 [0005] to page 4 [0006])

  This invention is made | formed in view of the said subject, The 1st objective of this invention is provided with the water vapor | steam barrier property required for an organic EL element, and is a gas barrier property laminated film applicable also to a flexible organic EL element. It is to provide. A second object of the present invention is to provide an image display element having excellent durability using the gas barrier laminate film.

  A first object of the present invention is a gas barrier laminate film having, on a base film, an organic layer mainly composed of at least one inorganic layer and at least one acrylic monomer polymer, This is achieved by a gas barrier laminate film characterized in that the organic layer contains a polymerization product of a monomer having at least one sulfonyl group or sulfo group.

  In the gas barrier laminate film of the present invention, the inorganic layer that exhibits gas barrier properties preferably contains a metal oxide or metal nitride as a main component as an inorganic compound. In particular, it is preferable to contain a metal oxide such as silicon, aluminum, titanium, zirconium and tin, a nitride, or a composite thereof as a main component.

  Furthermore, the gas barrier laminate film of the present invention is preferably such that the inorganic layer and the organic layer are alternately laminated on the base film. In order to further improve the adhesion between the organic layer and the inorganic layer, the surface of the organic layer in contact with the inorganic layer may be subjected to plasma treatment.

Furthermore, the gas barrier laminate film of the present invention has an oxygen permeability of less than 0.01 ml / m ² / day · atm at 38 ° C. and 90% relative humidity, and a water vapor permeability at 38 ° C. and 90% relative humidity. It is preferably less than 0.01 g / m ² / day.

  The second object of the present invention is achieved by an image display device using the gas barrier laminate film. The gas barrier laminate film is useful as a substrate for an image display element, and particularly useful as a substrate for an organic EL element.

  The gas barrier laminate film of the present invention is excellent in moisture permeability resistance. Moreover, since the image display element of the present invention has the gas barrier laminate film of the present invention, it has high definition and high durability.

  Hereinafter, the gas barrier laminate film of the present invention and its use will be described in detail. The description of the constituent elements described below may be made based on typical embodiments of the present invention, but the present invention is not limited to such embodiments. In the present specification, a numerical range represented by using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.

<Gas barrier laminate film>
[Layer structure of gas barrier laminate film]
The gas barrier laminate film of the present invention has at least one inorganic layer and at least one organic layer mainly composed of a polymer of an acrylic monomer on a base film. An inorganic layer and an organic layer may be laminated | stacked only on the single side | surface of a base film, respectively, and may be laminated | stacked on both surfaces of a base film. When laminating on both sides, the number of inorganic layers and organic layers laminated on both sides may be the same or different. Moreover, after forming an inorganic layer on a base film, an organic layer may be formed on it, and an inorganic layer may be formed after forming an organic layer. Preferred is an embodiment in which an inorganic layer is formed on an organic layer formed on a base film for the purpose of imparting smoothness to the surface on which the inorganic layer is formed. Moreover, when forming multiple layers of an organic layer and an inorganic layer on a base film, it is preferable to form an organic layer and an inorganic layer alternately. A plurality of composite layers in which an inorganic layer and an organic layer are stacked may be formed. Moreover, you may further provide the organic layer which does not satisfy | fill the conditions of this invention, and the functional layer mentioned later in the gas barrier laminated film of this invention. Details of the functional layer will be described later.
Below, each layer which comprises the gas barrier laminated film of this invention is demonstrated in detail.

[Organic layer]
(Characteristics of organic layer)
The organic layer formed in the gas barrier laminate film of the present invention is a layer mainly composed of a polymer of acrylic monomers. The organic layer formed in the gas barrier laminate film of the present invention contains a polymerization product of a polymerizable monomer having a sulfonyl group or a sulfo group.

(Polymerizable monomer having a sulfonyl group or a sulfo group)
The polymerizable monomer having a sulfonyl group or a sulfo group used for the organic layer in the present invention will be described.
Examples of the monomer having a sulfonyl group used in the present invention include compounds represented by the following general formula (1). Examples of the monomer having a sulfo group used in the present invention include compounds in which R ¹ or R ² is a hydroxyl group in the following general formula (1).

R ¹ and R ² in the general formula (1) are each independently a hydrogen atom, a hydroxyl group, a saturated hydrocarbon group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, or an araalkyl having 7 to 20 carbon atoms. Group, aryl group having 6 to 20 carbon atoms, saturated hydrocarbon oxy group having 1 to 20 carbon atoms, alkenyloxy group having 2 to 20 carbon atoms, araalkyloxy group having 7 to 20 carbon atoms, and 6 to 20 carbon atoms Represents an aryloxy group, and at least one of R ^{1 and} R ² has a group capable of undergoing a polymerization reaction (polymerizable group); When either R ¹ or R ² is a saturated hydrocarbon oxy group, alkenyloxy group, araalkyloxy group or aryloxy group, the monomer represented by the general formula (1) is a sulfonic acid ester monomer. Note that the saturated hydrocarbon group, alkenyl group, araalkyl group, and aryl group may each be substituted.

  Examples of the saturated hydrocarbon group having 1 to 20 carbon atoms include methyl group, ethyl group, n-propyl group, i-propyl group, butyl group (n-butyl group, i-butyl group, t-butyl group, sec -Butyl group), pentyl group (n-pentyl group, i-pentyl group, neopentyl group, cyclopentyl group, etc.), hexyl group (n-hexyl group, i-hexyl group, cyclohexyl group etc.), heptyl group (n-heptyl). Group, i-heptyl group, etc.), octyl group (n-octyl group, i-octyl group, t-octyl group etc.), nonyl group (n-nonyl group, i-nonyl group etc.), decyl group (n-decyl) Group, i-decyl group, etc.), undecyl group (n-undecyl group, i-undecyl group, etc.), dodecyl group (n-dodecyl group, i-dodecyl group, etc.) and the like. Considering the balance of operability at the time of molding, it is preferably a saturated hydrocarbon having 1 to 16 carbon atoms, particularly preferably a saturated hydrocarbon having 1 to 12 carbon atoms.

  Examples of the alkenyl group having 2 to 20 carbon atoms include acyclic alkenyl groups and cyclic alkenyl groups. Examples thereof include vinyl group, propenyl group, butenyl group, pentenyl group, hexenyl group, cyclohexenyl group, cyclohexenylethyl group, norbornenylethyl group, heptenyl group, octenyl group, nonenyl group, decenyl group, undecenyl group, A dodecenyl group etc. are mentioned. Considering the balance of operability during molding, an alkenyl group having 2 to 16 carbon atoms is preferable, and an alkenyl group having 2 to 12 carbon atoms is particularly preferable.

  Examples of the aralkyl group having 7 to 20 carbon atoms include benzyl group and phenethyl group. Moreover, the benzyl group, the phenethyl group, etc. by which C1-C13, Preferably the C1-C8 alkyl group was substituted by 1 or multiples are mentioned.

  Examples of the aryl group having 6 to 20 carbon atoms include a phenyl group and a tolyl group. Moreover, the phenyl group, tolyl group, xylyl group etc. which were substituted by the C1-C14, preferably C1-C8 alkyl group are mentioned.

  Examples of the saturated hydrocarbon oxy group having 1 to 20 carbon atoms, the alkenyloxy group having 2 to 20 carbon atoms, the araalkyloxy group having 7 to 20 carbon atoms, and the aryloxy group having 6 to 20 carbon atoms include the above saturated Specific examples of the oxy form of a hydrocarbon group, an alkenyloxy group, an araalkyloxy group, and an aryloxy group can be given.

  The above saturated hydrocarbon group, alkenyl group, araalkyl group, and aryl group may each be substituted. Examples of the substituent include an alkyl group, an alkyloxy group, a hydroxyl group, and a halogen atom.

Preferred examples of the polymerizable group that can be taken by at least one of R ^{1 and} R ² include acrylic groups such as acryloyl group, methacryloyl group, and acrylamide group. Usually, a compound in which either one of R ¹ or R ² contains a polymerizable group is used, but a compound in which both R ¹ and R ² contain a polymerizable group may be used. In this case, R ¹ and R ² may be the same or different. Preferred is an embodiment using a compound in which any one of R ^{1 and} R ² contains a polymerizable group.

Among the compounds represented by the general formula (1), R ¹ is preferably a functional group containing a polymerizable group among acryloyl group, methacryloyl group, acrylamide group and methacrylamide group, and R ² is a hydroxyl group. A compound which is a substituted or unsubstituted aryl group, alkyl group, or alkyloxy group. Of the compounds represented by the general formula (1), R ¹ is a functional group containing an acryloyl group or an acrylamide group, and R ² is a hydroxyl group, a substituted or unsubstituted aryl group, an alkyl group, an alkyloxy group. It is a compound that is a group. Of the compounds represented by the general formula (1), a compound in which R ¹ is a functional group containing an acryloyl group or an acrylamide group and R ² is a hydroxyl group is more preferable.

  Specific examples of the compound represented by the general formula (1) include compounds exemplified below. The substituent R in each chemical structural formula is hydrogen or a methyl group, and each is classified into an acryloyl (acrylamide) group and a methacryl (methacrylamide) group, but an acryloyl (acrylamide) group is preferable in consideration of curability. In addition, the polymerizable monomer which has a sulfonyl group or a sulfo group which can be used for an organic layer by this invention is not limitedly interpreted by the compound illustrated below.

  A particularly preferred polymerizable monomer is 2-acrylamido-2-methyl-1-propanesulfonic acid represented by the following formula. Although this polymerizable monomer is commercially available, in the present invention, a commercially available product may be used as it is, or a synthesized product may be used.

(binder)
The polymerizable monomer having a sulfonyl group or a sulfo group is preferably used by mixing with a binder capable of reacting with the polymerizable group for the purpose of maintaining or improving the film strength of the organic layer. Examples of the binder that can react with the polymerizable group include a thermosetting resin and a radiation curable resin.

  Examples of the thermosetting resin include epoxy resins and radiation curable resins. Examples of the epoxy resin include polyphenol type, bisphenol type, halogenated bisphenol type, and novolac type resins. A known curing agent can be used as the curing agent for curing the epoxy resin. Examples thereof include curing agents such as amines, polyaminoamides, acids and acid anhydrides, imidazoles, mercaptans, and phenol resins. Among these, from the viewpoint of solvent resistance, optical properties, thermal properties, etc., polymers containing acid anhydrides and acid anhydride structures or aliphatic amines are preferably used, and polymers containing acid anhydrides and acid anhydride structures are particularly preferred. Used. In the present invention, as the thermosetting resin, one kind of resin may be used or several kinds of resins may be mixed and used. Further, it is preferable to add an appropriate amount of a curing catalyst such as known tertiary amines and imidazoles to the thermosetting resin.

  A radiation curable resin is a resin that cures when irradiated with radiation such as ultraviolet rays and electron beams. Specifically, an unsaturated double molecule such as an acryloyl group, a methacryloyl group, or a vinyl group in a molecule or a single structure. A resin containing a bond. Among these, an acrylic resin containing an acryloyl group and the like is particularly preferable. In the present invention, as the radiation curable resin, one kind of resin or a mixture of several kinds of resins may be used, but an acrylic resin having two or more acryloyl groups or the like in the molecule or unit structure. It is preferable to use a resin. Examples of such polyfunctional acrylate resins include, but are not limited to, tripropylene glycol diacrylate, dipentaerythritol hexaacrylate, pentaerythritol tetraacrylate, urethane acrylate, ester acrylate, and epoxy acrylate. In particular, tripropylene glycol diacrylate, urethane acrylate, and the like are preferable in that the organic layer has flexibility and the film strength against bending can be improved.

  When these radiation curable resins are cured by irradiating them with ultraviolet rays, an appropriate amount of a known photoreaction initiator is added to the radiation curable resin.

  The organic layer constituting the gas barrier laminate film of the present invention is preferably a layer containing a copolymer of the above polymerizable monomer having a sulfonyl group or sulfo group and another type of acrylic polymerizable compound. Especially, the aspect whose polymerizable group of the polymerizable monomer which has a sulfonyl group or a sulfo group is an acryloyl group, and the binder which can react is a polyfunctional acrylate is preferable.

(Composition and thickness in the organic layer)
The use ratio of the polymerizable monomer having a sulfonyl group or a sulfo group in the organic layer is preferably 1 to 80% by mass, more preferably 5 to 70% by mass, and more preferably 10 to 60% by mass based on all monomers. More preferably. If the use ratio of the monomer is 5% by mass or more, when an inorganic layer is formed adjacently, sufficient adhesion with the inorganic layer is easily obtained, and sufficient gas barrier properties are easily obtained. Moreover, if the use ratio of the monomer is 70% by mass or less, sufficient film strength is easily obtained.

  An additive may be contained in the organic layer. Examples of the additive that can be added to the organic layer include a reactive binder capable of reacting with a polymerizable group. The content of the additive is preferably 30% by mass or less, more preferably 20% by mass or less, and further preferably 10% by mass or less.

  The thickness of the organic layer in the present invention is not particularly limited, but is preferably in the range of 10 nm to 5 μm, more preferably in the range of 50 nm to 2 μm, and further preferably in the range of 100 nm to 1 μm.

(Formation method of organic layer)
Examples of the method for forming the organic layer of the present invention include a coating method and a vacuum film forming method. The vacuum film formation method is not particularly limited, but a film formation method such as vapor deposition or plasma CVD is preferable, and a resistance heating vapor deposition method that easily controls the film formation rate when a polymerizable monomer-containing composition is used is more preferable. .

  When the organic layer is formed by a coating method, various conventionally used coating methods such as roll coating, gravure coating, knife coating, dip coating, curtain flow coating, spray coating, and bar coating may be used. it can.

  The crosslinking method of the polymerizable monomer used in the present invention is not limited at all. However, crosslinking by electron beam or ultraviolet ray by irradiation with active energy rays is easy to attach in a vacuum chamber, and high molecular weight by crosslinking reaction is rapid. Desirable in terms. The said active energy ray means the radiation which can propagate energy by irradiation of an ultraviolet-ray, X-ray | X_line, an electron beam, infrared rays, a microwave, etc., The kind and energy can be selected arbitrarily according to a use.

  In the present invention, the organic layer is preferably subjected to surface treatment such as plasma treatment. In particular, when a polymerizable monomer having a sulfonyl group is used, or when an inorganic layer is formed on the organic layer, it is preferable to perform plasma treatment. The plasma treatment in the present invention uses oxygen gas, nitrogen gas, argon gas, helium gas or the like as plasma gas, and performs surface modification of a resin base material or an organic layer. In the present invention, when the plasma treatment is performed on the surface of the organic layer, it is more preferable to use oxygen gas or a mixed gas of oxygen gas and inert gas such as nitrogen gas, argon gas, and helium gas. The plasma treatment can be performed, for example, by introducing oxygen gas or a mixed gas containing oxygen gas into the chamber using a normal plasma CVD apparatus or the like.

[Inorganic layer]
(Constituent material of inorganic layer)
The inorganic layer formed in the gas barrier laminate film of the present invention is a layer made of an inorganic material. The inorganic layer is preferably a layer made of a metal oxide such as silicon, aluminum, titanium, zirconium or tin, a nitride or an oxynitride, and may be formed of a composite thereof.

(Inorganic layer thickness)
The thickness of the inorganic layer is preferably 30 nm to 1 μm, and more preferably 50 nm to 200 nm. When the thickness of the inorganic layer is in the range of 50 nm to 1 μm, it is difficult to be affected by defective portions and portions having low density between crystals, and high gas barrier properties are obtained. Further, even when it is deformed, the destruction of the inorganic layer can be reduced, which is preferable in practice.

(Formation method of inorganic layer)
The inorganic layer can be formed by vapor deposition, physical vapor deposition (PVD) such as sputtering or ion plating, various chemical vapor deposition (CVD), or liquid phase such as plating or sol-gel. There is a growth method. Among these, chemical vapor deposition (CVD) and physical vapor deposition are effective in avoiding the effects of heat on the base film during inorganic layer formation, high production speed, and easy to obtain a uniform thin film layer. The method (PVD) is preferred. Moreover, it is also preferable to form an inorganic layer by a sol-gel method from the viewpoint that a thick film can be easily obtained. Here, the thick film refers to a film in the range of 100 nm to 1 μm.

[Base film]
(Properties of base film)
The base film used in the gas barrier laminate film of the present invention is preferably made of a heat-resistant material so that it can be used as an image display element described later. Preferably, a transparent plastic film having a glass transition temperature (Tg) of 100 ° C. or higher and / or a linear thermal expansion coefficient of 40 ppm / ° C. or lower and high heat resistance is used as the base film. Tg and the linear expansion coefficient can be changed by an additive or the like.

(polymer)
The polymer used for the base film may be either a thermoplastic polymer or a thermosetting polymer. The thermoplastic polymer is preferably a polymer having a Tg of 120 to 300 ° C, more preferably 160 to 250 ° C. As such a thermoplastic resin, polyethylene naphthalate (PEN: 120 ° C.), polycarbonate (PC: 140 ° C.), alicyclic polyolefin (for example, ZEONOR 1600: 160 ° C. manufactured by Nippon Zeon Co., Ltd.), polyarylate (PAr: 210 ° C.), polyethersulfone (PES: 220 ° C.), polysulfone (PSF: 190 ° C.), cycloolefin copolymer (COC: compound of JP 2001-150584 A, 162 ° C.), fluorene ring-modified polycarbonate (BCF-PC) : Compound disclosed in JP 2000-227603 A: 225 ° C., alicyclic modified polycarbonate (IP-PC: Compound disclosed in JP 2000-227603 A: 205 ° C.), acryloyl compound (compound disclosed in JP 2002-80616 A) : 300 ° C or higher) (In parentheses are the Tg). In particular, when transparency is required, it is preferable to use an alicyclic polyolefin or the like.

  Examples of the thermosetting polymer include epoxy resins and radiation curable resins. Examples of the epoxy resin include polyphenol type, bisphenol type, halogenated bisphenol type, and novolac type resins. A known curing agent can be used as the curing agent for curing the epoxy resin. Examples thereof include curing agents such as amines, polyaminoamides, acids and acid anhydrides, imidazoles, mercaptans, and phenol resins. Among them, from the viewpoint of solvent resistance, optical properties, thermal properties, etc., polymers containing acid anhydrides and acid anhydride structures or aliphatic amines are preferably used, and among them, polymers containing acid anhydrides and acid anhydride structures. Is particularly preferably used. In the present invention, as the thermosetting resin, one kind of resin may be used or several kinds of resins may be mixed and used. Furthermore, it is preferable to add a suitable amount of a curing catalyst such as a known tertiary amine or imidazole to the thermosetting polymer.

  A radiation curable resin is a resin that cures when irradiated with radiation such as ultraviolet rays and electron beams. Specifically, an unsaturated double molecule such as an acryloyl group, a methacryloyl group, or a vinyl group in a molecule or a single structure. A resin containing a bond. In the present invention, among these, it is preferable to use an acrylic resin containing an acryloyl group. The radiation curable resin may be one kind of resin or a mixture of several kinds of resins, but an acrylic resin having two or more acryloyl groups in a molecule or unit structure may be used. preferable. Examples of such polyfunctional acrylate resins include urethane acrylates, ester acrylates, and epoxy acrylates, but resins that can be used in the present invention are not limited to these.

  When these radiation curable resins are cured by irradiating them with ultraviolet rays, an appropriate amount of a known photoreaction initiator is added to the radiation curable resin.

(Additive)
In order to further strengthen the interaction with the polymer molecule, an alkoxysilane hydrolyzate or a silane coupling agent may be mixed with the epoxy resin and the radiation curable resin. As the silane coupling agent, one having a hydrolyzable reactive group such as a methoxy group, an ethoxy group, or an acetoxy group and the other having an epoxy group, a vinyl group, an amino group, a halogen group, or a mercapto group. Preferably, in this case, those having a vinyl group having the same reactive group are particularly preferably used for fixing to the main component resin. For example, KBM-503, KBM-803 of Shin-Etsu Chemical Co., Ltd., Nippon Unicar Co., Ltd. A-187, etc., manufactured by These addition amounts are preferably 0.2 to 3% by mass.

(transparency)
The gas barrier laminate film of the present invention is preferably used for an image display element such as a display. When used for an image display element, the base film used for the gas barrier laminate film of the present invention is preferably transparent, specifically, the light transmittance is preferably 80% or more, and 85% or more. More preferably, it is more preferably 90% or more. If the light transmittance of the base film is 80% or more, it can be suitably used as a base film of an organic EL element described later.

  Even when it is used for a display application, transparency is not necessarily required when it is not installed on the observation side or when an opaque packaging material is used. When used in such applications, an opaque material can be used as the base film. Examples thereof include polyimide, polyacrylonitrile, and known liquid crystal polymers.

  The light transmittance used as a scale of transparency in this specification is determined by measuring the total light transmittance and the amount of scattered light using the method described in JIS-K7105, that is, using an integrating sphere light transmittance measuring device. It can be calculated by subtracting the diffuse transmittance from the light transmittance.

[Other layers]
(Functional layer)
Furthermore, the gas barrier laminate film of the present invention may be provided with various functional layers in addition to the inorganic layer and the organic layer containing a sulfonyl group or a sulfo group. Examples of the functional layer include an optical functional layer such as an antireflection layer, a polarizing layer, a color filter, and a light extraction efficiency improving layer; a mechanical functional layer such as a hard coat layer and a stress relaxation layer; an antistatic layer and a conductive layer. An electric functional layer such as: an antifogging layer; an antifouling layer; a printing layer, and the like. In addition, an organic layer that does not satisfy the condition that a polymerization product of a polymerizable monomer having a sulfonyl group or a sulfo group as a main component and containing a polymerization product of an acrylic monomer is included (hereinafter, the conditions of the present invention are not satisfied). An organic layer) may be provided. These layers may be formed between the base film and the inorganic layer, between the base film and the organic layer, between the inorganic layer and the organic layer, or may be formed as the outermost layer. Moreover, you may form on the base film of the side in which the inorganic layer and / or the organic layer are not installed. Further, different types of functional layers may be formed adjacent to each other.

(Gas barrier laminate layer)
Furthermore, the gas barrier laminate film of the present invention may be provided with a gas barrier laminate layer in which an inorganic layer, an organic layer that does not satisfy the conditions of the present invention, and an inorganic layer are laminated in this order. The inorganic layer here is preferably an inorganic layer exhibiting a gas barrier property comparable to that of the above-described inorganic layer. The gas barrier laminate layer has a function of preventing intrusion and permeation of water molecules and the like, and has an effect of further improving the gas barrier property of the gas barrier laminate film of the present invention. Such a gas barrier laminate layer is preferably provided on the base film (opposite side) opposite to the side (surface) on which the inorganic layer and the organic layer satisfying the conditions of the present invention are formed. By providing it on the opposite surface, water molecules can be prevented from entering from the opposite surface of the film, and by suppressing the dimensional change of the gas barrier laminate film, stress concentration and destruction on the surface layer can be prevented. As a result, the durability when applied to an image display device or the like can be further improved.

<Image display device>
The gas barrier laminate film of the present invention can be used for various applications. In particular, it can be preferably incorporated into an image display device. The image display element in the present invention refers to, for example, a circularly polarizing plate / liquid crystal display element, electronic paper, or an organic EL element. Although the use of the gas barrier laminate film of the present invention is not particularly limited, it can be suitably used as a substrate or a sealing film of the display element. In the following, an application example to main image display devices will be specifically described.

[Circularly polarizing plate]
The circularly polarizing plate can be produced by laminating a λ / 4 plate and a polarizing plate on the gas barrier laminate film of the present invention. In this case, the lamination is performed so that the slow axis of λ / 4 and the absorption axis of the polarizing plate are 45 °. As such a polarizing plate, it is preferable to use what is extended | stretched in the 45 degree direction with respect to the longitudinal direction (MD), For example, what is described in Unexamined-Japanese-Patent No. 2002-865554 can be used suitably.

[Liquid crystal display element]
Liquid crystal display devices can be broadly classified into reflective liquid crystal display devices and transmissive liquid crystal display devices.

  The reflective liquid crystal display device has a configuration including a lower substrate, a reflective electrode, a lower alignment film, a liquid crystal layer, an upper alignment film, a transparent electrode, an upper substrate, a λ / 4 plate, and a polarizing film in order from the bottom. The gas barrier laminate film of the present invention can be used as a transparent electrode and an upper substrate. When the reflective liquid crystal display device has a color display function, it is preferable to further provide a color filter layer between the reflective electrode and the lower alignment film, or between the upper alignment film and the transparent electrode.

  The transmissive liquid crystal display device includes a backlight, a polarizing plate, a λ / 4 plate, a lower transparent electrode, a lower alignment film, a liquid crystal layer, an upper alignment film, an upper transparent electrode, an upper substrate, and a λ / 4 plate in order from the bottom. And a polarizing film. Among these, the gas barrier laminate film of the present invention can be used as an upper transparent electrode and an upper substrate. Further, when the transmissive liquid crystal display device is provided with a color display function, it is preferable to further provide a color filter layer between the lower transparent electrode and the lower alignment film, or between the upper alignment film and the transparent electrode.

  The structure of the liquid crystal layer is not particularly limited. An OCB (Optically Compensatory Bend) type or a CPA (Continuous Pinwheel Alignment) type is preferable.

[Organic EL device]
An organic EL element has a cathode and an anode on a substrate, and an organic compound layer including an organic light emitting layer (hereinafter sometimes simply referred to as “light emitting layer”) between both electrodes. In view of the properties of the light emitting element, at least one of the anode and the cathode is preferably transparent.

  When the gas barrier laminate film of the present invention is used for organic EL or the like, JP-A-11-335661, JP-A-11-335368, JP-A-2001-192651, JP-A-2001-192652, JP-A-2001-192653. JP, JP 2001-335776, JP 2001-247859, JP 2001-181616, JP 2001-181617, JP 2002-181816, JP 2002-181617, JP 2002-056776. It is preferable to use the contents described in the above publications and the techniques described in JP 2001-148291, JP 2001-221916, and JP 2001-231443. That is, the gas barrier laminate film of the present invention can be used as a base film and / or a protective film when forming an organic EL element.

  Hereinafter, the features of the present invention will be described more specifically with reference to Examples and Comparative Examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be construed as being limited by the specific examples shown below.

<< Manufacture and evaluation of laminated films >>
(Example 1)
1 g of 2-acrylamido-2-methyl-1-propanesulfonic acid (manufactured by Aldrich) as an acrylic monomer having a sulfo group, 9 g of tripropylene glycol diacrylate (manufactured by Daicel Cytec) as a photopolymerizable acrylate to be mixed, and light 0.1 g of a polymerization initiator (manufactured by Ciba Specialty Chemicals, Irgacure 907) was prepared and dissolved in 190 g of a mixture of methyl ethyl ketone and methanol (mixing mass ratio 4: 1) to obtain a coating solution. This coating solution is applied to a 100 μm-thick polyethylene naphthalate resin substrate (Teonex Q65, manufactured by Teijin DuPont) using a wire bar, and an air-cooled metal halide lamp of 160 W / cm under a nitrogen purge with an oxygen concentration of 0.1% or less. An organic layer having a film thickness of 500 nm was formed by irradiating ultraviolet rays having an illuminance of 350 mW / cm ² and an irradiation amount of 500 mJ / cm ² using (made by IGraphics Co., Ltd.). Furthermore, a 100 nm-thick silicon oxide film was formed on the organic layer by sputtering to produce a laminated film.

(Example 2)
Instead of 2-acrylamido-2-methyl-1-propanesulfonic acid used in Example 1, 4-methacryloyl-4′-isopropoxydiphenyl sulfone having a sulfonyl group was used in the same manner as in Example 1. A laminated film was produced.

(Example 3)
After forming a silicon oxide film having a thickness of 100 nm on the resin base material by sputtering, an organic layer and an inorganic layer are formed in the same manner as in Example 1, and the resin base material / inorganic layer / organic layer / inorganic layer is formed. A laminated film was produced.

Example 4
Resin substrate / inorganic layer / organic in the same manner as in Example 3 except that the coating solution used in Example 2 was used instead of the coating solution in Example 1 used for forming the organic layer in Example 3. A layer / inorganic layer laminate film was produced.

(Comparative Example 1)
A silicon oxide film having a thickness of 100 nm was formed on the above resin base material by sputtering to produce a resin base material / inorganic layer laminated film.

(Comparative Example 2)
A laminated film was produced in the same manner as in Example 1 except that only 2-propyleneglycol diacrylate was used without using 2-acrylamido-2-methyl-1-propanesulfonic acid used in Example 1.

(Comparative Example 3)
A laminated film was prepared in the same manner as in Example 1 except that neopentyl glycol-modified trimethylolpropane diacrylate (KAYARAD R-604, manufactured by Nippon Kayaku) was used instead of the tripropylene glycol diacrylate used in Comparative Example 2. Manufactured.

(Comparative Example 4)
A laminated film was produced in the same manner as in Example 1 except that acrylic acid (manufactured by Tokyo Chemical Industry) was used instead of 2-acrylamido-2-methyl-1-propanesulfonic acid used in Example 1.

(Comparative Example 5)
A laminated film was produced in the same manner as in Example 1 except that methyl methacrylate (manufactured by Tokyo Chemical Industry) was used instead of 2-acrylamido-2-methyl-1-propanesulfonic acid used in Example 1.

(Comparative Example 6)
A silicon oxide film having a thickness of 100 nm is formed on a resin substrate by sputtering, and then an organic layer and an inorganic layer are formed in the same manner as in Comparative Example 2, and a laminated film of resin substrate / inorganic layer / organic layer / inorganic layer is formed. Manufactured.

(Comparative Example 7)
After forming a silicon oxide film having a thickness of 100 nm on the resin substrate by sputtering, an organic layer and an inorganic layer are formed in the same manner as in Comparative Example 3, and a laminated film of resin substrate / inorganic layer / organic layer / inorganic layer is formed. Manufactured.

(Comparative Example 8)
After forming a silicon oxide film having a thickness of 100 nm on the resin substrate by sputtering, an organic layer and an inorganic layer are formed in the same manner as in Comparative Example 4, and a laminated film of resin substrate / inorganic layer / organic layer / inorganic layer is formed. Manufactured.

(Comparative Example 9)
A silicon oxide film having a thickness of 100 nm is formed on a resin substrate by sputtering, and then an organic layer and an inorganic layer are formed in the same manner as in Comparative Example 5, and a laminated film of resin substrate / inorganic layer / organic layer / inorganic layer is formed. Manufactured.

(Comparative Example 10)
3.3 g of isocyanuric acid triacrylate (Aronix M-315, manufactured by Toagosei Co., Ltd.), 6.5 g of diethylene glycol, 0.1 g of 3-acryloxypropyltrimethoxysilane (manufactured by Tokyo Chemical Industry), and a photopolymerization initiator (Ciba Specialty) 0.1 g of Irgacure 907 manufactured by Chemicals was prepared and dissolved in 40 g of methyl ethyl ketone to prepare a coating solution. This coating solution was applied to a polyethylene naphthalate substrate in the same manner as in Example 1 to form an approximately 2 μm organic layer, and a 30 nm silicon oxide film was formed thereon. Further, 10 g of neopentyl glycol-modified trimethylolpropane diacrylate (manufactured by Nippon Kayaku Co., Ltd., KAYARAD R-604), 0.1 g of photopolymerization initiator (manufactured by Ciba Specialty Chemicals, Irgacure 907), and 190 g of methyl ethyl ketone are mixed. The applied coating solution is applied onto the above silicon oxide film to form an organic layer of 500 nm, and a silicon oxide film of 30 nm is formed thereon, so that the resin substrate / organic layer / inorganic layer / organic layer / inorganic A laminated film of layers was produced.

(Evaluation)
The oxygen transmission rate and water vapor transmission rate of each laminated film obtained were measured at 38 ° C. and a relative humidity of 10% or 90% using the MOCON method (oxygen: MOCON OX-TRAN 2/20 L, water vapor: MOCON PERMATRAN-W3) / 31). The results are shown in the table below.

  From Table 1, the laminated film (Examples 1-4) which laminated | stacked the organic layer and inorganic layer containing a sulfonyl group or a sulfonic acid are laminated films (Comparative Example 1), a sulfonyl group, or a sulfonic acid which does not laminate | stack an organic layer. It can be seen that the oxygen transmission rate and the water vapor transmission rate are superior to those of a laminated film (Comparative Examples 2 to 8) obtained by laminating an organic layer and an inorganic layer that do not contain. In particular, when the laminated films composed of resin base material / inorganic layer / organic layer / inorganic layer (Examples 3 to 4 and Comparative Examples 6 to 9) were compared, the difference in oxygen permeability and water vapor permeability was more prominent. . From these results, it can be seen that the gas barrier laminate film of the present invention can obtain good gas barrier performance by laminating an organic layer containing a polyacrylate containing a sulfonyl group or a sulfonic acid and an inorganic layer.

<< Production of Substrate and Organic EL Element >>
The gas barrier laminate film produced in Example 3 was introduced into a vacuum chamber, and a transparent conductive layer (transparent electrode) composed of an ITO thin film having a thickness of 200 nm was formed by DC magnetron sputtering using an ITO target. Furthermore, the lead wire of aluminum was connected from the formed transparent electrode (ITO), and the laminated structure was formed. The surface of the transparent electrode was spin-coated with an aqueous dispersion of polyethylene dioxythiophene / polystyrene sulfonic acid (BAYER, Baytron P: solid content: 1.3% by mass), and then vacuum-dried at 150 ° C. for 2 hours to obtain a thick layer. A hole-transporting organic thin film layer having a thickness of 100 nm was formed. This was designated as substrate X.

On the other hand, using a spin coater, a coating solution for a light-emitting organic thin film layer having the following composition is formed on one surface of a temporary support made of polyethersulfone having a thickness of 188 μm (Sumilite FS-1300, manufactured by Sumitomo Bakelite Co., Ltd.). By coating and drying at room temperature, a light-emitting organic thin film layer having a thickness of 13 nm was formed on the temporary support. This was designated as transfer material Y.
Polyvinylcarbazole 40 parts by mass (Mw = 63000, manufactured by Aldrich)
Tris (2-phenylpyridine) iridium complex 1 part by mass (orthometalated complex)
1,200 parts by mass of 1,2-dichloroethane

  The upper surface of the organic thin film layer of the substrate X is overlapped with the light emitting organic thin film layer side of the transfer material Y, and heated and pressurized at 160 ° C., 0.3 MPa, 0.05 m / min using a pair of heat rollers, and temporarily supported. By peeling off the body, a light-emitting organic thin film layer was formed on the upper surface of the substrate X. This was designated as substrate XY.

A patterned mask (a mask with a light emitting area of 5 mm × 5 mm) is placed on one side of a polyimide film (UPILEX-50S, manufactured by Ube Industries, Ltd.) having a thickness of 50 μm cut into 25 mm square, and Al is deposited to a thickness of 250 nm by vapor deposition. Then, LiF was formed to a thickness of 3 nm by a vapor deposition method. A coating solution for an electron transporting organic thin film layer having the following composition is applied onto the obtained laminated structure using a spin coater coating machine, and vacuum dried at 80 ° C. for 2 hours, whereby an electron having a thickness of 15 nm is obtained. A transportable organic thin film layer was formed on LiF. Furthermore, an aluminum lead wire was connected from the Al electrode, and this was used as a substrate Z.
Polyvinyl butyral 2000L 10 parts by mass (Mw = 2000, manufactured by Denki Kagaku Kogyo Co., Ltd.)
1-butanol 3500 parts by mass An electron transporting compound having the following structure 20 parts by mass

  Using the substrate XY and the substrate Z, the electrodes are stacked so that the electrodes face each other with the light-emitting organic thin film layer interposed therebetween, and heated and pressed at 160 ° C., 0.3 MPa, 0.05 m / min using a pair of heat rollers. Were bonded to produce an organic EL element.

  A direct measure voltage was applied to the obtained organic EL device using a source measure unit 2400 type (manufactured by Toyo Technica Co., Ltd.) to emit light. The organic EL device of the present invention emitted light well. After the organic EL device was fabricated, it was allowed to stand at 25 ° C. and 10% relative humidity and 90% for 12 hours for 10 days, and the light was emitted in the same manner. However, the device was not deteriorated.

  The gas barrier film of the present invention has high gas barrier properties. For this reason, it can be effectively applied to a wide variety of articles that need to block water vapor, oxygen, and the like, and flexible articles. Further, if the gas barrier film of the present invention is used, a high-definition image display element having high durability can be provided, and a flexible high-definition display can be preferably provided. Therefore, the present invention has high industrial applicability.

Claims (11)

  A gas barrier laminate film having, on a substrate film, at least one inorganic layer and at least one organic layer mainly composed of a polymer of an acrylic monomer, wherein the organic layer has at least one sulfonyl group A gas barrier laminate film comprising a polymerization product of a polymerizable monomer having a sulfo group.   The gas barrier laminate film according to claim 1, wherein the polymerizable monomer is a monofunctional acrylic monomer.   3. The gas barrier laminate film according to claim 1, wherein 1 to 80% by mass of the polymerizable monomer having a sulfonyl group or a sulfo group is included among all monomers forming the polymerization product. .   The gas barrier laminate film according to any one of claims 1 to 3, wherein the organic layer is subjected to plasma treatment, and the inorganic layer is formed on the organic layer.   The gas barrier laminate film according to any one of claims 1 to 4, wherein the inorganic layer and the organic layer are laminated in this order on the base film.   The gas barrier laminate film according to any one of claims 1 to 4, wherein the organic layer and the inorganic layer are laminated in this order on the base film.   The gas barrier laminate film according to claim 1, comprising a plurality of composite layers in which the inorganic layer and the organic layer are laminated. The oxygen transmission rate at 38 ° C. and 90% relative humidity is less than 0.01 ml / m ² / day · atm, and the water vapor transmission rate at 38 ° C. and 90% relative humidity is less than 0.01 g / m ² / day. The gas barrier laminate film according to any one of claims 1 to 7, wherein   The board | substrate for image display elements using the gas-barrier laminated | multilayer film as described in any one of Claims 1-8.   The image display element using the gas-barrier laminated film as described in any one of Claims 1-8.   The organic electroluminescent element using the gas-barrier laminated film as described in any one of Claims 1-8.