JP2005254795A - Gas barrier film and its manufacturing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a gas barrier film which enables the exhibition of a superior gas barrier performance when it is applied to a picture image displaying element such as a liquid crystal displaying element or an organic EL element or the like, its manufacturing method and the organic EL element formed by using the gas barrier film. <P>SOLUTION: The gas barrier film has at least one inorganic layer and at least one organic layer alternatively formed on a substrate with a glass transition temperature of ≥250°C and the said organic layer is formed by applying a liquid containing a polymer with a hydrogen boding group and a metal alkoxide and then by drying at a temperature of 150-350°C. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a gas barrier film having excellent gas barrier performance, a method for producing the same, and an organic electroluminescence element (hereinafter referred to as “organic EL element”) using the film. More specifically, the present invention relates to a gas barrier film optimum as a substrate for various devices, a method for producing the same, and a flexible organic EL element using the gas barrier film.

  Conventionally, a gas barrier film in which a metal oxide thin film such as aluminum oxide or magnesium oxide silicon oxide is formed on the surface of a plastic substrate or film is used for packaging of goods, food, Widely used in packaging applications to prevent alteration of industrial products and pharmaceuticals. In addition to packaging applications, gas barrier films have recently been used in liquid crystal display elements, solar cells, electroluminescence (hereinafter referred to as “EL”), and the like.

  In the development process of image display elements such as liquid crystal display elements and EL elements in recent years, long-term reliability and flexibility of shape are required for transparent base materials forming these elements in addition to the conditions of weight reduction and size increase. Advanced conditions such as high image quality and the ability to display curved surfaces are also required. As a transparent base material satisfying such advanced conditions, a plastic base material is beginning to be adopted as a new base material that replaces a conventional glass substrate that is heavy, fragile and difficult to increase in area. In the case of a plastic substrate, not only the above conditions are satisfied, but also a roll-to-roll method is possible, so that the productivity is better than a glass substrate and it is advantageous in terms of cost reduction.

However, the plastic substrate has a problem that the gas barrier property is inferior to that of the glass substrate. 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 problems, plastic films in which a metal oxide thin film is formed on a plastic film have been developed so far. Examples of such plastic films include those obtained by vapor-depositing silicon oxide on a plastic film (Japanese Patent Publication No. 53-12953) and those obtained by vapor-depositing aluminum oxide (Japanese Patent Laid-Open No. 58-217344). Both 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, the gas barrier performance required for plastic film substrates is about 0.1 g / m ² · day for water vapor barrier properties. Furthermore, recently, the development of organic EL displays and high-definition color liquid crystal displays has progressed, and while maintaining the transparency that can be used in these, even higher barrier performance, especially less than 0.1 g / m ² · day for water vapor barriers There is a demand for transparent substrates having the following performance. 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 (for example, Patent Document 1).

  However, in these thin film formation methods, the organic matter ejected as high-temperature vapor aggregates on the film and forms a thin film, so that the film is temporarily heated and partially deformed. There was a problem that the process became non-uniform and sufficient barrier ability could not be obtained. In addition, these thin film forming methods have a problem in that the number of laminations increases and the cost increases. Furthermore, when surface treatment of a plastic substrate having a high water absorption rate is performed, the absorbed water vaporizes, so that it takes a long time to evacuate and the processing cost increases.

Further, in recent years, the heat resistance of the base film has been required to a higher level when installing TFTs for producing an active matrix image element. For example, Patent Document 2 describes a method of forming a polycrystalline silicon film at a temperature of 300 ° C. or lower by plasma decomposition of a gas containing SiH ₄ . Patent Document 3 describes a method for forming a semiconductor layer in which amorphous silicon and polycrystalline silicon are mixed on a polymer substrate at a temperature of 300 ° C. or less by irradiation with an energy beam. Patent Document 4 describes a method of providing a thermal buffer layer and irradiating a pulse laser beam to form a polycrystalline silicon semiconductor layer on a plastic substrate at a temperature of 300 ° C. or lower.

As described above, various methods for forming a polycrystalline silicon film for TFT at 300 ° C. or lower have been proposed, and it is useful to have a heat resistance of 250 ° C. or higher as a base material. On the other hand, the semiconductor layer forming method as described above has a complicated structure and apparatus and is expensive, and thus heat resistance of 300 ° C. to 350 ° C. or higher is required for the plastic substrate.
Moreover, although the method of forming the laminated body of an organic layer and an inorganic layer as a gas barrier layer on a heat resistant board | substrate is also known, heat resistance was not enough (patent document 5).
JP 2002-532850 A (Claim 1, FIG. 1) JP-A-7-81919 (Claim 3, [0016] to [0020]) JP 10-512104 A (pages 14-22, FIGS. 1 and 7) JP-A-11-102867 (Claims 1 to 10, [0036]) US Pat. No. 6,492,026 (Claim 1, Example)

  The present invention has been made in view of the above problems, and an object of the present invention is to provide a gas barrier film capable of exhibiting excellent gas barrier performance when applied to an image display element such as a liquid crystal display element or an organic EL element. It is in providing the manufacturing method. Still another object of the present invention is to provide an organic EL device using the gas barrier film.

As a result of intensive studies, the present inventors have found that the object of the present invention can be achieved by the gas barrier film shown below.
That is, the object of the present invention is achieved by a gas barrier film characterized by having at least one inorganic layer and at least one organic layer alternately on a resin substrate having a glass transition temperature of 250 ° C. or higher. Is done.

As the resin used in the gas barrier film of the present invention, a resin having a spiro structure represented by the following general formula (1) or a resin having a cardo structure represented by the following general formula (2) can be used.

However, in general formula (1), ring α represents a monocyclic or polycyclic ring, and the two rings are connected by a spiro bond.

  However, in general formula (2), ring β and ring γ represent a monocyclic or polycyclic ring, and two rings γ may be the same or different, and one ring on ring β Linked to quaternary carbon.

  The gas barrier film of the present invention is preferably formed in the order of an inorganic layer and an organic layer on a resin substrate having a Tg of 250 ° C. or higher.

  In the gas barrier film of the present invention, the organic layer preferably contains as a main component a cross-linked polymer compound obtained by polymerizing a polyfunctional monomer having an acryloyl group or a methacryloyl group.

  The organic layer is preferably obtained by applying a liquid containing a polymer having a hydrogen bonding group and a metal alkoxide and drying.

The gas barrier film of the present invention has an oxygen permeability of 0.02 ml / m ² · day · atm or less at 23 ° C. and a relative humidity of 90%, and a water vapor permeability of 0.02 g / at 23 ° C. and a relative humidity of 100%. m ² · day or less is preferable.

  In addition, the gas barrier film of the present invention includes a step of forming at least one inorganic layer on a resin substrate having a glass transition temperature of 250 ° C. or higher and a step of forming at least one organic layer. Can be manufactured.

  In the manufacturing method, as the resin base material, a base material made of a resin having a spiro structure represented by the following general formula (1) or a resin having a cardo structure represented by the following general formula (2) may be used. it can.

  In general formula (1), ring α represents a monocyclic or polycyclic ring, and the two rings are connected by a spiro bond.

  In general formula (2), ring β and ring γ represent a monocyclic or polycyclic ring, and two rings γ may be the same or different, and one quaternary ring on ring β. Linked to carbon.

  In the said manufacturing method, it is preferable that the said organic layer is formed by apply | coating the composition containing the polymer and metal alkoxide which have a hydrogen bond group, and drying at 150-350 degreeC.

  Another object of the present invention is achieved by an organic electroluminescence device using the gas barrier film.

  The gas barrier film of the present invention uses a resin having a Tg of 250 ° C. or more as a substrate, and alternately has at least one inorganic layer and at least one organic layer on the substrate. For this reason, the gas barrier film of this invention is excellent in heat resistance and gas barrier property. Moreover, according to the method for producing a gas barrier film of the present invention, a gas barrier film having both excellent heat resistance and a gas barrier function can be obtained.

  Moreover, the organic EL element of this invention uses the gas barrier film of this invention as a board | substrate or a protective film. Thus, the organic EL element of the present invention is an organic EL element having a flexible substrate and excellent in high definition and durability.

  The gas barrier film of the present invention, the method for producing the film, and the organic EL device using the film will be described in detail below.

  In the present specification, “to” is used as a meaning including numerical values described before and after the lower limit value and the upper limit value.

[Gas barrier film]
<Base material>
The resin substrate used in the gas barrier film of the present invention is not particularly limited as long as the glass transition temperature (Tg) is 250 ° C. or higher, and may be a thermoplastic resin or a curable resin. Preferably it is 250-600 degreeC, More preferably, it is 300-550 degreeC, More preferably, it is 350-500 degreeC. Resins in which the glass transition temperature is not substantially observed (for example, in a measurement range of 400 ° C. or lower) can also be preferably used in the present invention.

  Examples of the resin having a Tg of 250 ° C. or higher include polyimide resins (for example, Kapton (trade name: manufactured by DuPont: 400 ° C. or higher), Upilex-R (trade name: manufactured by Ube Industries: 285 ° C.), Upilex-S (trade name: Ube Industries, Ltd .: 400 ° C. or higher)), fluorinated polyimide resin (for example, Flupi-01 (trade name: manufactured by NTT: 335 ° C.)), acryloyl resin (compound of Example-1 of JP-A-2002-80616): (The temperature in parentheses represents Tg).

  The resin preferably has a high Tg or is substantially colorless and transparent. Specifically, polyimide resin (for example, Kapton (trade name: manufactured by DuPont: 400 ° C. or higher), Upilex-R (trade name: manufactured by Ube Industries: 285 ° C.), Upilex-S (trade name: manufactured by Ube Industries: 400) Fluorinated polyimide resin (for example, Flupi-01 (trade name: manufactured by NTT: 335 ° C.)), acryloyl resin (compound of Example-1 of JP-A-2002-80616: 300 ° C. or higher), etc. It can be preferably used (the temperature in parentheses represents Tg).

  In addition, as a particularly preferable example of a resin having a Tg of 250 ° C. or higher used for the substrate, a resin having a spiro structure represented by the general formula (1) or a resin having a cardo structure represented by the general formula (2) is used. Can be mentioned. These polymers are compounds having high heat resistance, high elastic modulus, and high tensile fracture stress, and are excellent in optical transparency and optical isotropy, requiring various heating operations in the manufacturing process, and bending. It is suitable as a substrate material for a display such as an organic EL element that is required to have a performance that is difficult to be destroyed.

In general formula (1), ring α represents a monocyclic or polycyclic ring, and the two rings are connected by a spiro bond.

  In general formula (2), ring β and ring γ represent a monocyclic or polycyclic ring, and two rings γ may be the same or different, and one quaternary ring on ring β. Linked to carbon.

  Preferred examples of the resin having a spiro structure represented by the general formula (1) include a polymer having a spirobiindane structure represented by the following general formula (3) in a repeating unit, and a spiro represented by the following general formula (4). Examples thereof include a polymer containing a bichroman structure in the repeating unit and a polymer containing a spirobibenzofuran structure represented by the following general formula (5) in the repeating unit.

In the general formula (3), R ³¹ , R ³² and R ³³ each independently represent a hydrogen atom or a substituent. In addition, each may be linked to form a ring. m and n represent an integer of 1 to 3. Examples of preferred substituents are a halogen atom, an alkyl group or an aryl group. More preferred examples of R ³¹ and R ³² are hydrogen atom, methyl group, and phenyl group, and more preferred examples of R ³³ are hydrogen atom, chlorine atom, bromine atom, methyl group, isopropyl group, t-butyl group, and phenyl group. It is.

In the general formula (4), R ⁴¹ and R ⁴² each independently represents a hydrogen atom or a substituent. In addition, each may be linked to form a ring. m and n represent an integer of 1 to 3. Examples of preferred substituents are a halogen atom, an alkyl group or an aryl group. More preferred examples of R ⁴¹ are hydrogen atom, methyl group or phenyl group, and more preferred examples of R ⁴² are hydrogen atom, chlorine atom, bromine atom, methyl group, isopropyl group, t-butyl group or phenyl group. is there.

In the general formula (5), R ⁵¹ and R ⁵² each independently represents a hydrogen atom or a substituent. In addition, each may be linked to form a ring. m and n represent an integer of 1 to 3. Examples of preferred substituents are a halogen atom, an alkyl group or an aryl group. More preferred examples of R ⁵¹ are hydrogen atom, methyl group or phenyl group, and more preferred examples of R ⁵² are hydrogen atom, chlorine atom, bromine atom, methyl group, isopropyl group, t-butyl group or phenyl group. is there.

  Moreover, the polymer which contains the fluorene structure represented by following General formula (6) in a repeating unit as a preferable example of resin which has a cardo structure represented by General formula (2) is mentioned.

In General Formula (6), R ⁶¹ and R ⁶² each independently represent a hydrogen atom or a substituent. In addition, each may be linked to form a ring. j and k represent an integer of 1 to 4. Examples of preferred substituents are a halogen atom, an alkyl group or an aryl group. More preferred examples of R ⁶¹ and R ⁶² are a hydrogen atom, a chlorine atom, a bromine atom, a methyl group, an isopropyl group, a t-butyl group, or a phenyl group.

  The polymer containing the structure represented by the general formulas (3) to (6) in the repeating unit may be a polymer linked by various bonding methods such as polycarbonate, polyester, polyamide, polyimide, polyurethane, etc. Polycarbonates, polyesters, and polyurethanes derived from bisphenol compounds having structures represented by formulas (3) to (6) are preferred from the viewpoint of optical transparency. Among these, aromatic polyesters are particularly preferable from the viewpoint of heat resistance.

  Preferred specific examples of the polymer having a structure represented by the general formula (1) and the general formula (2) are given below, but the present invention is not limited thereto.

  The polymer having the structure represented by the general formula (1) and the general formula (2) used in the present invention may be used singly or as a mixture of plural kinds. Moreover, a homopolymer may be sufficient and the copolymer which combined multiple types of structure may be sufficient. When the copolymer is used, a known repeating unit that does not contain the structure represented by the general formula (1) or (2) in the repeating unit may be copolymerized within a range that does not impair the effects of the present invention. In addition, the copolymer is more improved than the homopolymer in terms of solubility and transparency, and can be preferably used.

  The preferred molecular weight of the polymer having the structure represented by the general formula (1) and the general formula (2) used in the present invention is 1 to 500,000, more preferably 2 to 300,000, particularly preferably in terms of weight average molecular weight. 3 to 200,000. When the molecular weight is 10,000 or more, film formation becomes easy, and when the molecular weight is 500,000 or less, the molecular weight can be easily controlled in terms of synthesis, and the solution has a low viscosity and is easy to handle. The molecular weight can be based on the corresponding viscosity.

  In the present invention, as the resin used for the base material, a curable resin (crosslinked resin) excellent in solvent resistance, heat resistance, etc. can be used in addition to the thermoplastic resin as long as Tg is 250 ° C. or higher. As the curable resin, both a thermosetting resin and a radiation curable resin can be used, and those known in the art can be used without particular limitation. Examples of the thermosetting resin include phenol resin, urea resin, melamine resin, unsaturated polyester resin, epoxy resin, silicon resin, diallyl phthalate resin, furan resin, bismaleimide resin, cyanate resin and the like.

  In addition, the crosslinking method of the curable resin can be used without particular limitation as long as it is a reaction that forms a covalent bond. The reaction is performed at room temperature that forms a urethane bond using a polyalcohol compound and a polyisocyanate compound. A system in which the process proceeds can also be used without particular limitation. However, such a system often has a problem of pot life before film formation, and is usually used as a two-component mixed type in which a polyisocyanate compound is added immediately before film formation. On the other hand, when used as a one-component type, it is effective to protect the functional group involved in the crosslinking reaction, and it is also commercially available as a block type curing agent.

  As commercially available block type curing agents, B-882N manufactured by Mitsui Takeda Chemical Co., Ltd., Coronate 2513 manufactured by Nippon Polyurethane Industry Co., Ltd. (above block polyisocyanate), Cymel 303 manufactured by Mitsui Cytec Co., Ltd. (methylated melamine resin) ) Etc. are known. Further, a blocked carboxylic acid such as the following B-1 that protects a polycarboxylic acid that can be used as a curing agent for an epoxy resin is also known.

  Radiation curable resins are roughly classified into radical curable resins and cationic curable resins. As the curable component of the radical curable resin, a compound having a plurality of radical polymerizable groups in the molecule is used. As a typical example, a polyfunctional acrylate monomer having 2 to 6 acrylate groups in the molecule Or a compound having a plurality of acrylate groups in the molecule called urethane acrylate, polyester arylate, or epoxy acrylate.

  As a typical curing method of the radical curable resin, there are a method of irradiating an electron beam and a method of irradiating ultraviolet rays. Usually, in the method of irradiating with ultraviolet rays, a polymerization initiator that generates radicals upon irradiation with ultraviolet rays is added. In addition, if the polymerization initiator which generate | occur | produces a radical by heating is added, it can also be used as a thermosetting resin.

  As the curable component of the cationic curable resin, a compound having a plurality of cationic polymerizable groups in the molecule is used, and as a typical curing method, a photoacid generator that generates an acid by irradiation with ultraviolet rays is added, A method of curing by irradiating with ultraviolet rays is mentioned. Examples of the cationically polymerizable compound include a compound containing a ring-opening polymerizable group such as an epoxy group and a compound containing a vinyl ether group.

  In the resin base material used in the present invention, different types of resins may be selected and mixed from each of the above-described thermosetting resins or radiation curable resins, and a thermosetting resin and a radiation curable resin may be used. May be used in combination. Moreover, you may mix and use curable resin (crosslinkable resin) and the polymer which does not have a crosslinkable group.

  In the base material used in the present invention, it is preferable to mix the curable resin (crosslinkable resin) because the solvent resistance, heat resistance, optical properties and toughness of the base material are obtained. Moreover, it is also possible to introduce a crosslinkable group into the resin used in the base material, and it may have a crosslinkable group at any position in the polymer main chain terminal, the polymer side chain, or the polymer main chain. . In this case, you may produce a base material, without using said general purpose crosslinkable resin together.

  When the gas barrier film of the present invention is used for liquid crystal display or the like, the resin used is preferably an amorphous polymer in order to achieve optical uniformity. Furthermore, for the purpose of controlling the retardation (Re) and its wavelength dispersion, it is possible to combine resins having different signs of intrinsic birefringence of the resins, or to combine resins having large (or small) wavelength dispersion.

  In the present invention, the resin base material can be suitably used for the purpose of controlling retardation (Re) or improving gas permeability and mechanical properties, etc. A preferred combination of different resins is not particularly limited, and any of the above-described resins can be used in combination.

  The resin base material used in the present invention may be stretched. By stretching, mechanical strength such as folding strength is improved, and there is an advantage that handling property is improved. In particular, those having an orientation release stress in the stretching direction (ASTM D1504, hereinafter abbreviated as “ORS”) of 0.3 to 3 GPa are preferable because the mechanical strength is improved. ORS is an internal stress generated by stretching inherent in a stretched film or stretched sheet.

  As the stretching method, a known method can be used. For example, a roll uniaxial stretching method, a tenter uniaxial stretching method, a simultaneous biaxial stretching method, at a temperature between 10 ° C. and 50 ° C. higher than the Tg of the resin, The film can be stretched by a sequential biaxial stretching method or an inflation method. The draw ratio is preferably 1.1 to 3.5 times.

  Although the thickness of the resin base material used by this invention is not specifically limited, It is preferable that it is 30-700 micrometers, It is more preferable that it is 40-200 micrometers, It is further more preferable that it is 50-150 micrometers. The haze is preferably 3% or less, more preferably 2% or less, and further preferably 1% or less. Further, the total light transmittance is preferably 70% or more, more preferably 80% or more, and further preferably 90% or more.

  The resin substrate used in the present invention is a plasticizer, a dye / pigment, an antistatic agent, an ultraviolet absorber, an antioxidant, an inorganic fine particle, a peeling accelerator, a leveling agent, as long as the effect of the present invention is not impaired as necessary. Resin modifiers such as inorganic layered silicate compounds and lubricants may be added.

<Inorganic layer>
In the present invention, the type and film forming method of the inorganic layer are not particularly limited, and a known inorganic layer and film forming method can be applied. The inorganic layer includes an inorganic oxide layer and a transparent conductive layer. The inorganic layer may be formed by any method as long as the target thin film can be formed. Sputtering, vacuum deposition, ion plating, plasma CVD, and the like are suitable. Films can be formed by the methods described in Japanese Patent No. 3400324, Japanese Patent Application Laid-Open No. 2002-322561, and Japanese Patent Application Laid-Open No. 2002-361774.

  There are no particular limitations on the constituent components of the inorganic layer, but for example, an oxide or nitride or oxynitride containing one or more of Si, Al, In, Sn, Zn, Ti, Cu, Ce, Ta, and the like may be used. it can. The thickness of the inorganic layer is not particularly limited, but the thickness per layer of the inorganic layer is preferably in the range of 5 to 1000 nm, more preferably 10 to 1000 nm, and most preferably 10 to 200 nm. . When the thickness is within this range, cracks due to bending stress do not occur, the film does not form islands, and is uniformly distributed, and the water vapor barrier property is improved.

Moreover, when it has two or more inorganic layers, each may be the same composition or another composition, and there is no restriction | limiting in particular. In order to achieve both water vapor barrier properties and high transparency, it is preferable to use silicon oxide or silicon oxynitride as the composition of the inorganic layer. Silicon oxide is expressed as SiO _x . For example, when SiO _x is used as the inorganic layer, 1.6 <x <1.9 in order to achieve both good water vapor barrier properties and high light transmittance. Is desirable. Although silicon oxynitride is expressed as SiO _x N _y , the ratio of x and y is an oxygen-rich film when importance is placed on improving adhesion, and 1 <x <2, 0 <y <1. Preferably, when importance is placed on improving the water vapor barrier property, a nitrogen-rich film is preferable, and 0 <x <0.8 and 0.8 <y <1.3.

<Organic layer>
The gas barrier film of the present invention is provided with an organic layer adjacent to the inorganic layer in order to improve the barrier performance of the inorganic layer.
The “organic layer” in this specification means a layer having a function of compensating for defects in the inorganic layer (defect compensation layer), and includes an inorganic oxide layer and an organic-inorganic hybrid layer formed by a sol-gel method. It is.

  In the present invention, a method for forming an organic layer is not particularly limited as long as it can function as a defect compensation layer. (1) A method using an inorganic oxide layer produced by a sol-gel method, and (2) an organic substance A method of forming a layer by applying or vapor-depositing and then curing with ultraviolet rays or an electron beam can be suitably used. Moreover, in the formation of the organic layer, the methods (1) and (2) may be used in combination. For example, after the organic layer is formed on the base film by the method (1), an inorganic layer is formed. Then, the organic layer may be formed by the method (2).

(1) Method using an inorganic oxide layer prepared by using a sol-gel method In the sol-gel method of the present invention, a metal alkoxide is preferably hydrolyzed and polycondensed in a solution or in a coating film to obtain a dense solution. A thin film. At this time, an organic-inorganic hybrid material may be used in combination with a resin.
As used herein, “organic-inorganic hybrid” refers to a state in which an inorganic material and an organic material are mixed at the molecular level and nano-order, for example, Adv. Polym. Sci., 100, 11 (1992). , Poly.Mater.Encyclopedia, 6,4793 (1996), Current Opinion in Solid State & Materials Science, 1,806 (1996), showing a composite material of an organic material and an inorganic material obtained by a sol-gel method .

  As the metal alkoxide used in the sol-gel method, alkoxysilane and / or metal alkoxide other than alkoxysilane can be used. The metal alkoxide other than alkoxysilane is preferably zirconium alkoxide, titanium alkoxide, aluminum alkoxide or the like.

The alkoxysilanes preferably used in the present invention will be further described.
Examples of the tetrafunctional type include tetramethoxysilane, tetraethoxysilane, tetra n-propoxysilane, tetra-i-propoxysilane, tetra-n-butoxysilane, and tetra-acetoxysilane.

  Examples of the trifunctional type include methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, i-propyltrimethoxysilane, i -Propyltriethoxysilane, γ-chloropropyltrimethoxysilane, γ-chloropropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-methacryloyloxypropyltrimethoxysilane Γ-mercaptopropyltriethoxysilane, phenyltrimethoxysilane, vinyltriethoxysilane, 3,4-epoxycyclohexylethyltrimethoxysilane, 3,4-epoxycyclohexylethyltriethoxy Silane, and the like.

  Examples of the bifunctional type include dimethyldimethoxysilane, dimethyldiethoxysilane, methylphenyldimethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, di-n-propyldimethoxysilane, di-n-propyldiethoxysilane, di- Examples include i-propyldimethoxysilane, di-i-propyldiethoxysilane, diphenyldimethoxysilane, and divinyldiethoxysilane.

  The polymer used in combination during the sol-gel reaction preferably has a hydrogen bonding group. Examples of the resin having a hydrogen bonding group include a polymer having a hydroxyl group and a derivative thereof (polyvinyl alcohol, polyvinyl acetal, ethylene-vinyl alcohol copolymer, phenol resin, methylol melamine and the like and derivatives thereof); a carboxyl group Polymers and derivatives thereof (single or copolymer containing units of polymerizable unsaturated acid such as poly (meth) acrylic acid, maleic anhydride, itaconic acid, and esterified products of these polymers (vinyl esters such as vinyl acetate, Homo- or copolymers containing units such as (meth) acrylic acid esters such as methyl methacrylate)); polymers having an ether bond (polyalkylene oxide, polyoxyalkylene glycol, polyvinyl ether, silicon resin, etc.); amide bond (> N (CO ) -Bond (wherein R represents a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent) N-acyl of polyoxazoline or polyalkyleneimine And polyvinylpyrrolidone and derivatives thereof having> NC (O) -bond; polyurethane having urethane bond; polymer having urea bond, and the like. A silyl group-containing polymer may also be used. Particularly preferred as the silyl group-containing polymer is a silyl group-containing vinyl polymer whose main chain is a vinyl polymer.

  The content of the silyl group-containing polymer in the sol-gel reaction composition (sol-gel solution) is 1 to 200% by mass, preferably 3 to 100% by mass, more preferably 5 to 50% by mass, based on the total alkoxysilane used. . In addition, an organic-inorganic hybrid material can be produced by using a monomer in combination during the sol-gel reaction and polymerizing during or after the sol-gel reaction.

  During the sol-gel reaction, the metal alkoxide is hydrolyzed and polycondensed in water and an organic solvent. At this time, it is preferable to use a catalyst. As a catalyst for hydrolysis, an acid is generally used. As the acid, an inorganic acid or an organic acid is used. Inorganic acids include hydrochloric acid, hydrogen bromide, hydrogen iodide, sulfuric acid, sulfurous acid, nitric acid, nitrous acid, phosphoric acid, phosphorous acid, etc., and organic acid compounds include carboxylic acids (formic acid, acetic acid, propionic acid, butyric acid, succinic acid, Cyclohexanecarboxylic acid, octanoic acid, maleic acid, 2-chloropropionic acid, cyanoacetic acid, trifluoroacetic acid, perfluorooctanoic acid, benzoic acid, pentafluorobenzoic acid, phthalic acid, etc.), sulfonic acids (methanesulfonic acid, ethanesulfone) Acid, trifluoromethanesulfonic acid), p-toluenesulfonic acid, pentafluorobenzenesulfonic acid, etc.), phosphoric acid / phosphonic acids (phosphoric acid dimethyl ester, phenylphosphonic acid, etc.), Lewis acids (boron trifluoride etherate, scandium triflate, Alkyl titanic acid, aluminate, etc.), hetero It can be mentioned Li acid (phosphomolybdic acid, phosphotungstic acid).

  The amount of the acid used is 0.0001 to 0.05 mol per 1 mol of metal alkoxide (alkoxysilane and other metal alkoxide in the case of containing alkoxysilane and other metal alkoxide). 001-0.01 mol.

  After hydrolysis, a basic compound such as an inorganic base or an amine may be added to bring the pH of the solution to near neutrality to promote condensation polymerization. Examples of inorganic bases include sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, and ammonia. Examples of organic base compounds include amines (ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, triethylamine, Dibutylamine, N, N-dimethylbenzylamine, tetramethylethylenediamine, piperidine, piperazine, morpholine, ethanolamine, diazabicycloundecene, quinuclidine, aniline, pyridine, etc.), phosphines (triphenylphosphine, trimethylphosphine, etc.) Can be used.

  Moreover, it is also preferable to use the amine described in Japanese Patent Application No. 2002-110061 after hydrolysis with an acid. In this case, the amount of amine added is suitably equimolar to 100-fold mol, preferably equimolar to 20-fold mol with respect to the acid.

  In addition, other sol-gel catalysts such as metal chelate compounds having Al, Ti, and Zr as a central metal, organometallic compounds such as tin compounds, and metal salts such as alkali metal salts of organic acids can be used in combination.

  The content of the sol-gel catalyst compound in the sol-gel reaction composition is 0.01 to 50% by mass, preferably 0.1 to 50% by mass, and more preferably 0. 0% by mass with respect to the mass of the alkoxysilane that is the raw material of the sol liquid. 5 to 10% by mass.

  Next, the solvent used for the sol-gel reaction will be described. The solvent uniformly mixes each component in the sol solution, and at the same time prepares the solid content of the composition of the present invention, so that it can be applied to various coating methods to improve the dispersion stability and storage stability of the composition. Is. These solvents are not particularly limited as long as they can fulfill the above purpose. Preferable examples of these solvents include water and organic solvents that are highly miscible with water.

  Examples include tetrahydrofuran, dimethoxyethane, formic acid, acetic acid, methyl acetate, alcohols (methanol, ethanol, n-propyl alcohol, i-propyl alcohol, t-butyl alcohol), ethylene glycol, diethylene glycol, triethylene glycol, ethylene. Examples include glycol monobutyl ether, ethylene glycol monoethyl ether acetate, acetone, N, N-dimethylformamide, N, N-dimethylacetamide, and dimethyl sulfoxide.

For the purpose of adjusting the speed of the sol-gel reaction, an organic compound capable of multidentate coordination may be added to stabilize the metal alkoxide. Examples thereof include β-diketones and / or β-ketoesters, and alkanolamines. Specific examples of the β-diketone and / or β-ketoester include acetylacetone, methyl acetoacetate, ethyl acetoacetate, acetoacetate-n-propyl, acetoacetate-i-propyl, acetoacetate-n-butyl, acetoacetate Acetic acid-sec-butyl, acetoacetic acid-t-butyl, 2,4-hexane-dione, 2,4-heptane-dione, 3,5-heptane-dione, 2,4-octane-dione, 2,4-nonane -Dione, 5-methylhexane-dione, etc. can be mentioned. Of these, ethyl acetoacetate and acetylacetone are preferred, and acetylacetone is particularly preferred. These β-diketones and / or β-ketoesters may be used alone or in combination of two or more.
These compounds capable of multidentate coordination can also be used for the purpose of adjusting the reaction rate when the metal chelate compound is used as a sol-gel catalyst.

  Next, a method for coating the sol-gel reaction composition will be described. The sol solution can form a thin film on the transparent film by coating methods such as curtain flow coating, dip coating, spin coating, and roll coating. In this case, the hydrolysis may be performed at any time during the production process. For example, a solution of a required composition is hydrolyzed and partially condensed to prepare a desired sol solution, which is applied and dried, and a solution of the required composition is prepared and dried while hydrolyzing and partially condensing simultaneously. Method, application-After primary drying, a method of applying a water-containing liquid necessary for hydrolysis repeatedly and applying hydrolysis can be suitably employed. In addition, the coating method can take various forms. However, when productivity is important, each of the lower layer coating solution and the upper layer coating solution is required on a slide Geyser having a multistage discharge port. A method (simultaneous multi-layer method) is preferably used in which the discharge flow rate is adjusted so that the coating amount is obtained, and the formed multilayer flow is continuously placed on a support and dried.

  The drying temperature after applying the sol-gel reaction composition is 150 to 350 ° C, preferably 150 to 250 ° C, and more preferably 150 to 200 ° C. If the drying temperature after coating is 150 to 350 ° C., a denser film can be produced, and the interaction with the inorganic oxide interface can be promoted to improve the gas barrier ability.

In order to further refine the film after coating and drying, the organic layer may be irradiated with energy rays. Although there is no restriction | limiting in particular in the kind of irradiation beam, In consideration of the influence with respect to a deformation | transformation and modification | denaturation of a base material, it is preferable to use irradiation of an ultraviolet-ray, an electron beam, or a microwave. The irradiation intensity is 30 to 500 mJ / cm ² , preferably 50 to 400 mJ / cm ² . As the irradiation temperature, a temperature from room temperature to the deformation temperature of the substrate can be adopted without limitation, and is preferably 30 to 150 ° C, more preferably 50 to 130 ° C.

(2) Method of applying or vapor-depositing organic substance to form a layer and then curing with ultraviolet rays or electron beam Next, the case of using an organic layer formed mainly of a polymer obtained by crosslinking a monomer will be described. .
The monomer is not particularly limited as long as it contains a group that can be cross-linked by ultraviolet rays or an electron beam, but it is preferable to use a monomer having an acryloyl group, a methacryloyl group, or an oxetane group. Examples of such monomers include epoxy (meth) acrylate, urethane (meth) acrylate, isocyanuric acid (meth) acrylate, pentaerythritol (meth) acrylate, trimethylolpropane (meth) acrylate, ethylene glycol (meth) acrylate, Among polyester (meth) acrylates and the like, it is preferable that the main component is a polymer obtained by crosslinking a monomer having a bifunctional or higher functional acryloyl group or methacryloyl group. These monomers having a bifunctional or higher acryloyl group or methacryloyl group may be used as a mixture of two or more kinds, or as a mixture of monofunctional (meth) acrylates. Moreover, as a thing which has an oxetane group, it is preferable to use the thing which has a structure described in Unexamined-Japanese-Patent No. 2002-356607 General formula (3)-(6). In this case, you may mix these arbitrarily.

  Further, from the viewpoints of heat resistance and solvent resistance required for display applications, it is more preferable that the main component is isocyanuric acid acrylate, epoxy acrylate, urethane acrylate having a particularly high degree of crosslinking and a Tg of 250 ° C. or higher. .

  In the present invention, the thickness of the organic layer per layer is not particularly limited, but is preferably 10 nm to 5 μm, more preferably 10 nm to 2 μm, and particularly preferably 200 nm to 2 μm. Within this thickness range, structural defects in the inorganic layer can be efficiently filled with the organic layer, so that the uniformity is improved and the occurrence of cracks in the organic layer can be suppressed by an external force such as bending.

  As a method for forming the organic layer of the present invention, a coating method, a vacuum film forming method, or the like can be used. Although there is no restriction | limiting in particular as a vacuum film-forming method, Film-forming methods, such as vapor deposition and plasma CVD, are preferable, and the resistance heating vapor deposition method which is easy to control the film-forming rate of an organic substance monomer is more preferable. The method for crosslinking the organic substance monomer of the present invention is not limited at all. However, crosslinking with an electron beam or ultraviolet rays is desirable in that it can be easily mounted in a vacuum chamber and a high molecular weight can be obtained by a crosslinking reaction. When the coating method is used, various conventionally used coating methods such as spray coating, spin coating, and bar coating can be used.

<Functional layer>
The gas barrier film of the present invention can further have the following various functional layers in addition to the inorganic layer and the organic layer.

(Transparent conductive layer)
A known metal film or metal oxide film can be applied as the transparent conductive layer. Among these, a metal oxide film is preferable from the viewpoint of transparency, conductivity, and mechanical properties. For example, a metal oxide film such as indium oxide, cadmium oxide and tin oxide to which tin, tellurium, cadmium, molybdenum, tungsten, fluorine or the like is added as an impurity, and zinc oxide or titanium oxide to which aluminum is added as an impurity can be given. In particular, a thin film of indium oxide (ITO) containing 2 to 15% by mass of tin oxide is excellent in terms of transparency and conductivity, and is preferably used. Examples of the method for forming the transparent conductive layer include methods such as vacuum deposition, sputtering, and ion beam sputtering.

  The thickness of the transparent conductive layer is preferably in the range of 15 to 300 nm. If the film thickness of the transparent conductive layer is 15 to 300 nm, the film becomes a continuous film, sufficient conductivity is obtained, and sufficient transparency and bending resistance are obtained.

  The transparent conductive layer may be disposed on the base material side or the gas barrier coat layer side as long as it is the outermost layer, but it is preferably disposed on the gas barrier coat layer side in order to prevent entry of a trace amount of moisture contained in the base material.

(Primer layer)
The gas barrier film of this invention can install a well-known primer layer or an inorganic thin film layer between a base material, an inorganic layer, and an organic layer (gas barrier layer). As the primer layer, for example, an acrylic resin, an epoxy resin, a urethane resin, a silicon resin, or the like can be used. In the present invention, an organic / inorganic hybrid layer is used as the primer layer, and an inorganic vapor deposition layer or an inorganic thin film layer is used. It is preferable to use a dense inorganic coating thin film by a sol-gel method. As an inorganic vapor deposition layer, vapor deposition layers, such as a silica, a zirconia, an alumina, are preferable. The inorganic vapor deposition layer can be formed by a vacuum vapor deposition method, a sputtering method, or the like.

(Other functional layers)
Various known functional layers may be provided on the organic layer and the inorganic layer (gas barrier coat layer) or on the outermost layer as necessary. Examples of such functional layers include optical functional layers such as antireflection layers, polarizing layers, color filters, ultraviolet absorbing layers, light extraction efficiency improving layers, mechanical functional layers such as hard coat layers and stress relaxation layers, and antistatic Examples thereof include an electrical functional layer such as a layer / conductive layer, an antifogging layer, an antifouling layer, and a printing layer.

In the gas barrier film of the present invention, any of the above-described lamination order of the inorganic layer and the organic layer may be formed first. From the viewpoint of adhesion to the substrate, it is preferable to laminate the inorganic layer and the organic layer in this order on the substrate. Moreover, it is preferable to repeatedly laminate the inorganic layer or the organic layer once or more alternately on the inorganic layer or the organic layer, because the gas barrier performance can be improved.
In the present specification, “having at least one inorganic layer and at least one organic layer alternately” includes a two-layer structure including one inorganic layer and one organic layer. included.

The gas barrier film of the invention, 23 ° C., an oxygen permeability at 90% relative humidity is suitably to be ^{0~0.02ml / m 2 · day · atm} , 0~0.01ml / m 2 · day · It is preferably atm, more preferably 0 to 0.005 ml / m ² · day · atm. If the oxygen transmission rate at 23 ° C. and 90% relative humidity is 0.02 ml / m ² · day · atm or less, for example, when used in an organic EL or LCD, the deterioration of the EL element due to oxygen can be substantially eliminated. This is preferable because it is possible.

Further, the gas barrier film of the present invention suitably has a water vapor transmission rate of 0 to 0.02 g / m ² · day at 23 ° C. and 100% relative humidity, and 0 to 0.01 g / m ² · day. It is preferable that it is 0 to 0.005 g / m ² · day.

[Image display element]
Although the use of the gas barrier film of the present invention is not particularly limited, it can be suitably used as a transparent electrode substrate of an image display element because of its excellent gas barrier performance. The term “image display element” as used herein means a circularly polarizing plate / liquid crystal display element, a touch panel, an organic EL element, or the like. In particular, it is preferably used as a substrate for an organic EL element.

<Circularly polarizing plate>
A circular polarizing plate can be prepared by laminating a λ / 4 plate and a polarizing plate on the gas barrier film of the present invention. In this case, the lamination is performed so that the slow axis of the λ / 4 plate 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>
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 substrate of the present invention can be used as the transparent electrode and the upper substrate. In the case of color display, 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, a λ / 4 plate, and a polarization in order from the bottom. It has a structure consisting of a film. Of these, the substrate of the present invention can be used as the upper transparent electrode and the upper substrate. In the case of color display, 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 liquid crystal cell is not particularly limited, but more preferably TN (Twisted Nematic) type, STN (Supper Twisted Nematic) type or HAN (Hybrid Aligned Nematic) type, VA (Vertically Alignment) type, ECB type (Electrically Controlled Birefringence), OCB A type (Optically Compensatory Bend) and a CPA type (Continuous Pinwheel Alignment) are preferable.

<Touch panel>
The touch panel can be applied to those described in JP-A-5-127822, JP-A-2002-48913, and the like.

<Organic EL>
The gas barrier film of the present invention can be particularly suitably used as a transparent electrode substrate for organic EL.
When the gas barrier film of the present invention is used as a substrate film and / or protective film for organic EL or the like, JP-A-11-335661, JP-A-11-335368, JP-A-2001-192651, JP-A-2001-192652 JP, JP-A-2001-192653, JP-A-2001-335776, JP-A-2001-247859, JP-A-2001-181616, JP-A-2001-181617, JP-A-2002-181816, It is preferable to use together with the contents described in JP-A-2001-181617 and JP-A-2002-056776 and JP-A-2001-148291, 2001-221916, and 231443.

  Hereinafter, although the gas barrier film and organic EL element of this invention are demonstrated in detail based on an Example, this invention is not limited to these Examples.

<Example 1>
In Example 1, a 100 μm-thick polyimide resin (manufactured by Ube Industries, trade name Upilex-R, Tg: 285 ° C.) was used as the plastic substrate for the present invention. Moreover, in the comparative example, the polyether sulfone (PES) film (Tg: 220 degreeC) and the zeonore film (Tg: 160 degreeC) were used.

1. Production of Inorganic Oxide Layer As shown in FIG. 1, an inorganic layer was produced using a roll-to-roll type sputtering apparatus 1. This apparatus 1 has a vacuum chamber 2, and a drum 3 for cooling a plastic film (base material) 6 in contact with the surface is disposed at the center thereof. The vacuum chamber 2 is provided with a feed roll 4 and a take-up roll 5 for winding the plastic film 6. The plastic film 6 wound around the delivery roll 4 is wound around the drum 3 via the guide roll 7, and the plastic film 6 is further wound around the roll 5 via the guide roll 8. As a vacuum exhaust system, the vacuum chamber 2 is always exhausted from the exhaust port 9 by the vacuum pump 10. As a film forming system, a target (not shown) is mounted on a cathode 12 connected to a DC-type discharge power supply 11 to which pulse power can be applied. The discharge power source 11 is connected to a controller 13, and the controller 13 is further connected to a gas flow rate adjustment unit 14 that supplies the vacuum chamber 2 while adjusting a reaction gas introduction amount via a pipe 15. The vacuum chamber 2 is configured to be supplied with a discharge gas at a constant flow rate (not shown). Specific conditions are shown below.

Si was set as a target, and a pulse application type DC power source was prepared as the discharge power source 11. As the plastic film 6, the polyimide film having a thickness of 100 μm described above was used, and this was put on the feed roll 4 and passed to the take-up roll 5. After completing the preparation of the base material in the sputtering apparatus 1, the door of the vacuum chamber 2 was closed, the vacuum pump 10 was started, and vacuuming and cooling of the drum were started. When the ultimate pressure reached 4 × 10 ⁻⁴ Pa and the drum temperature reached 5 ° C., the plastic film 6 started to run. Argon was introduced as a discharge gas, the discharge power supply 11 was turned on, plasma was generated on the Si target at a discharge power of 5 kW and a film formation pressure of 0.3 Pa, and pre-sputtering was performed for 3 minutes. Thereafter, oxygen was introduced as a reaction gas. After the discharge was stabilized, the amounts of argon and oxygen gas were gradually reduced to lower the film forming pressure to 0.1 Pa. After confirming the stability of the discharge at 0.1 Pa, a silicon oxide film was formed for a certain period of time. After film formation was completed, the vacuum chamber 2 was returned to atmospheric pressure, and the film on which silicon oxide was formed was taken out.

2. Preparation of Sol-Gel Layer 8 g of Soarnol D2908 (manufactured by Nippon Synthetic Chemical Industry Co., Ltd., ethylene-vinyl alcohol copolymer) was dissolved in a mixed solvent of 18.8 g of 1-propanol and 73.2 g of water at 80 ° C. 2.4 ml of 2M / l (2N) hydrochloric acid was added to 10.72 g of this solution and mixed. While stirring this solution, 1 g of tetraethoxysilane was added dropwise and stirring was continued for 30 minutes. Next, dimethylbenzylamine was added to the obtained coating solution as a pH control immediately before coating, and the resulting coating solution was coated on the inorganic oxide sputtered film with a wire bar.
Then, the sol-gel layer with a film thickness of about 1 micrometer was formed on the said inorganic oxide vapor deposition base by drying at 140 degreeC. This was designated as film 1A.
Next, films 1B and 1C were produced in the same manner as described above except that the drying temperature was changed as shown in Table 1.

Films 1D to 1F and 1G to 1I were prepared in the same manner as 1A to 1C, respectively, except that polyethersulfone and zeonore films were used instead of the polyimide films of 1A to 1C.
Moreover, except not forming an inorganic vapor deposition layer in 1A-1C, the film 1J was produced by the method similar to 1A-1C. Furthermore, a film 1K was produced in the same manner as in 1A to 1C, except that no organic layer was formed in 1A to 1C.

3. Measurement of oxygen transmission rate and water vapor transmission rate The oxygen transmission rates of the obtained films 1A to 1K were measured by the MOCON method at 23 ° C. and a relative humidity of 90%, and the water vapor transmission rate at 23 ° C. and a relative humidity of 10%. . The results are shown in Table 1.

From Table 1, when polyimide having a Tg of 250 ° C. or higher is used as the resin for the film substrate (films 1A to 1C), the oxygen permeability is less than 0.15 ml / m ² · atm and the water vapor permeability is It was less than 0.30 g / m ² · day. On the other hand, when polyethersulfone or zeonore having a Tg of 250 ° C. or lower is used (1D to 1I), the oxygen transmission rate is 0.20 ml / m ² · atm or more and the water vapor transmission rate is also 0.1. It became larger than 48g / m ² · day. Further, when a polyimide having a Tg of 250 ° C. or higher is used and the drying temperature of the organic layer is 150 ° C. or higher (films 1B and 1C), the drying temperature is lower than 150 ° C. (film 1A). Compared to the above, the oxygen permeability and the water vapor permeability were drastically improved. Further, when only one of the organic layer and the inorganic layer was provided on the film substrate (films 1J and 1K), only high oxygen permeability and water vapor permeability were obtained.
From this, it can be seen that the gas barrier film of the present invention has excellent gas barrier performance by using a film substrate having a Tg of 250 ° C. or higher and further combining an inorganic layer and an organic layer. Furthermore, it turns out that the gas barrier film of this invention has the further outstanding gas barrier performance by making the drying process temperature of the organic layer formed by the sol-gel method into 150 degreeC or more.

<Example 2>
1. Production of Plastic Substrate Resin C-3 (Tg: 270 ° C.) represented by the general formula (1) synthesized as follows is dissolved in a dichloromethane solution so as to be 15% by mass, and then on a stainless steel band by a die coating method. It was cast into. Next, the first film was peeled off from the band and dried until the residual solvent concentration became 0.08% by mass, then both ends were trimmed and knurled, and then wound up to produce a film 2A having a thickness of 100 μm. .
(Synthesis example of C-3)

235.59 g (646.8 mmol) of M-100, 9.171 g (33 mmol) of tetrabutylammonium chloride, 2805 ml of dichloromethane and 2475 ml of water were put into a reaction vessel equipped with a stirrer, and 300 rpm in a water bath under a nitrogen stream. Stir with. After 30 minutes, 134.05 g (660 mmol) of terephthalic acid chloride was charged as powder and washed with 330 ml of dichloromethane. Ten minutes later, 3.966 g (26.4 mmol) of p-tert-butylphenol was dissolved in 693 ml of 2M (2N) aqueous sodium hydroxide solution, and a solution diluted with 132 ml of water was added dropwise over 1 hour using a dropping device. Thereafter, it was washed with 165 ml of water. Then, after continuing stirring for 3 hours, 1 L of dichloromethane was added, and the organic phase was separated. Further, a solution obtained by diluting 6.6 ml of 12M (12N) hydrochloric acid water with 2.5 L of water was added, and the organic phase was washed. After further washing with 2.5 L of water twice, 1 L of dichloromethane was added to the separated organic phase, diluted, and then poured into 25 L of methanol that was vigorously stirred over 1 hour. The resulting white precipitate in methanol was collected by filtration, heated and dried at 40 ° C. for 12 hours, and then dried at 70 ° C. under reduced pressure for 3 hours to obtain 307.2 g of the desired compound C-3.
As a result of measuring the molecular weight of the obtained C-3 by GPC (THF solvent), the weight average molecular weight was 61000.

  Further, the film 2B was prepared in the same manner as the film 2A except that the resins F-3, FL-1 and FL-7 represented by the general formulas (1) and (2) synthesized as follows were used. 2C and 2D were prepared.

(Synthesis example of F-3)

To a liquid in which 7.69 g of M-101 was suspended in 98 ml of methylene chloride, 113 ml of water in which 0.09 g of hydrosulfite sodium and 0.42 g of tetrabutylammonium bromide were dissolved was added and stirred vigorously. Then, 31.5 ml of 2M NaOH aqueous solution, 1.52 g of terephthalic acid chloride, and 20 ml of methylene chloride solution of 1.52 g of isophthalic acid chloride were added simultaneously at room temperature over 1 hour. After the addition, the reaction was further performed for 6 hours, and then the organic layer was separated by a liquid separation operation. Further, it was washed twice with 300 ml of diluted hydrochloric acid, and methylene chloride was distilled off under reduced pressure. 20 ml of methylene chloride was added to the residue for dissolution, and after removing dust and filtering, it was slowly put into 200 ml of methanol. The precipitated resin was collected by filtration, washed with methanol, and dried to obtain 10.5 g of the target compound F-3 as a white solid.
The obtained resin had a weight average molecular weight of 50500 and Tg of 262 ° C. Moreover, NMR of the obtained resin was as follows.
¹ H-NMR (δin CDCl ₃ ): 4.60 (dd) 6.87 (dd) 6.96 (d) 7.04 (dd) 7.59 (m) 8.21 (d) 8.34 (br.d) 8.86 (br.s)

(Synthesis example of FL-1)
Polyarylate (FL-1) derived from fluorene bisphenol-isophthalic acid / terephthalic acid was synthesized by the following method.
BPFL (trade name) manufactured by JFE Chemical Co., Ltd. was recrystallized twice with acetonitrile, followed by heating and vacuum drying at 70 ° C. for 3 hours to obtain a fluorene compound A-1 having an HPLC purity of 99.9% or more. (However, 8.6 mass% of acetonitrile is contained).
253.03 g (660 mmol) of the obtained A-1, 9.171 g (33 mmol) of tetrabutylammonium chloride, 2227 ml of dichloromethane and 2475 ml of water were put into a reaction vessel equipped with a stirrer. Stirring was performed at 300 rpm in a water bath. After 30 minutes, a solution prepared by dissolving 67.0 g (330 mmol) of isophthalic acid chloride and 67.0 g (330 mmol) of terephthalic acid chloride in 743 ml of dichloromethane, a solution obtained by diluting 693 ml of 2M (2N) sodium hydroxide aqueous solution with 132 ml of water, Were dropped simultaneously over 1 hour using separate dropping devices, and after completion, each was washed with 165 ml of water and 165 ml of dichloromethane. Subsequently, after stirring was continued for 3 hours, 1 L of dichloromethane was added and the organic phase was separated. Further, a solution obtained by diluting 6.6 ml of 12M (12N) hydrochloric acid water with 2.5 L of water was added, and the organic phase was washed. After further washing with 2.5 L of water twice, 1 L of dichloromethane was added to the separated organic phase, diluted, and then poured into 25 L of methanol that was vigorously stirred over 1 hour. The resulting white precipitate was collected by filtration, dried by heating at 40 ° C. for 12 hours, and then dried at 70 ° C. under reduced pressure for 3 hours to obtain 286 g of the desired compound FL-1.
As a result of measuring the molecular weight of the obtained FL-1 by GPC (THF solvent), the weight average molecular weight was 258,000. The Tg measured by DSC was 324 ° C.

(Synthesis example of FL-7)
BPFL (trade name) manufactured by JFE Chemical Co., Ltd. was recrystallized twice with acetonitrile, followed by heating and vacuum drying at 70 ° C. for 3 hours to obtain a fluorene compound A-1 having an HPLC purity of 99.9% or more. (However, 8.6 mass% of acetonitrile is contained).
253.03 g (660 mmol) of the obtained A-1, 9.171 g (33 mmol) of tetrabutylammonium chloride, 2805 ml of dichloromethane and 2475 ml of water were put into a reaction vessel equipped with a stirrer. Stirring was performed in a water bath at a stirring speed of 300 rpm. Thirty minutes later, 167.03 g (660 mmol) of 2,6-naphthalenedicarboxylic acid chloride was added as a powder and washed with 330 ml of dichloromethane. Ten minutes later, a solution obtained by diluting 693 ml of a 2M (2N) aqueous sodium hydroxide solution with 132 ml of water was added dropwise over 1 hour using a dropping device, and then washed with 165 ml of water. Subsequently, after stirring was continued for 3 hours, 1 L of dichloromethane was added to separate the organic phase. Further, a solution obtained by diluting 6.6 ml of 12M (12N) hydrochloric acid water with 2.5 L of water was added to wash the organic phase. After further washing twice with 2.5 L of water, 1 L of dichloromethane was added to the separated organic phase for dilution, and then the mixture was poured into 25 L of methanol that was vigorously stirred for 1 hour.
The resulting white precipitate was collected by filtration, dried by heating at 40 ° C. for 12 hours, and then dried at 70 ° C. under reduced pressure for 3 hours to obtain 302 g of the desired compound FL-7.
As a result of measuring the molecular weight of the obtained compound FL-7 by GPC (THF solvent), the weight average molecular weight was 170,000. The Tg measured by DSC was 369 ° C.

2. Preparation of Inorganic Layer and Organic Layer An inorganic oxide layer was formed on the films 2A to 2D in the same manner as in Example 1. Next, a radical initiator (a) was mixed with a solution in which (a) tetraethylene glycol diacrylate, (b) caprolactone acrylate, and (c) tripropylene glycol monoacrylate were mixed at a mass ratio of 7: 1.2: 1.4. Irgacure 651 (manufactured by Ciba Geigy) is added in an amount of 1% by mass, dissolved in a solvent, applied onto the films 2A to 2D on which the inorganic oxide layer is formed, dried, cured by UV irradiation, and inorganic oxidized. An organic layer having a thickness of about 2 μm was formed on the physical layer.
The above operation was repeated to produce a film having a six-layer structure, and the oxygen transmission rate and water vapor transmission rate were measured and evaluated in the same manner as in Example 1. The results are shown in Table 2.

  Instead of 2A resin compound C-3, a commercially available polycarbonate film (Mitsubishi Gas Chemical Iupilon, Tg: 140 ° C.), polyethersulfone, polyimide resin (trade name Upilex-R, Tg: 285 ° C., manufactured by Ube Industries) is used. A laminated film 2E, 2F, 2G was prepared in the same manner as 2A except that the oxygen permeability and water vapor permeability were measured and evaluated in the same manner as in Example 1. The results are shown in Table 2.

  Table 2 shows that when the resin represented by the general formula (1) or (2) of the present invention is used (films 2A to 2D, 2G), the oxygen transmission rate and water vapor are lower than those of the comparative examples (films 2E, 2F). The transmittance was shown. Moreover, it turns out that the direction using the films 2A-2C of Example 2 shows higher barrier performance than the case where the film of Example 1 is used. This is because the resin represented by the general formula (1) or (2) of the present invention has a high Tg, so that the smoothness of the substrate during vapor deposition can be maintained, and the adhesion to the inorganic layer is further improved. .

<Example 3>
Films 3A to 3G in which an inorganic layer made of an inorganic oxide and an organic layer made of an acrylate resin are laminated on the films 2A to 2G produced in Example 2 by the method described in JP-T-2002-532850. 3G was produced. Subsequently, the water vapor transmission rate was measured and evaluated at 45 ° C. and a relative humidity of 100%. Table 3 shows the results of the measured water vapor transmission rate.

  A gas barrier film described in JP-T-2002-532850 was prepared, and the water vapor transmission rate was measured by the same method as in 3A to 3G. Table 3 shows the results of the measured water vapor transmission rate.

  From Table 3, it can be seen that the gas barrier film of the present invention has a much lower water vapor transmission rate than the gas barrier film of JP-T-2002-532850. From this, it can be seen that the gas barrier film of the present invention is far superior in gas barrier performance to the gas barrier film disclosed in JP-T-2002-532850.

<Example 4>
In order to investigate the effect of having an organic layer (sol-gel layer) obtained by the sol-gel method on the film, the following evaluation was performed.
On the film 1A produced in Example 1, an organic layer was formed in the same manner as in Example 2 to produce a film 4A. Furthermore, according to the method of Example 2, after depositing an inorganic oxide thin film layer on a base film (PES), an organic layer was formed to produce a film 4B.
The obtained films 4A and 4B were measured for oxygen permeability and water vapor permeability and evaluated. Table 4 shows the measured oxygen transmission rate and water vapor transmission rate.

From Table 4, it can be seen that in the present invention, after providing the sol-gel layer as in the film 4A, the vapor deposition of the inorganic oxide layer is superior to the film 4B in which the sol-gel layer is not provided.
In addition, although the same gas permeability was measured with the gas barrier film which formed the organic layer formed by the method of Example 2 on the film substrate instead of the sol-gel layer of film 4A, in the case of film 4A which has a sol-gel layer Such a remarkable improvement effect was not obtained.

<Example 5>
1. A film 3A for producing an organic EL element was introduced into a vacuum chamber, and a transparent electrode made of an IXO thin film having a thickness of 0.2 μm was formed by DC magnetron sputtering using an IXO target. An aluminum lead wire was connected from the transparent electrode (IXO) to form a laminated structure. 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 mass%), and then vacuum-dried at 150 ° C. for 2 hours to obtain a thick 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, a coating solution for a light-emitting organic thin film layer having the following composition was applied on one surface of a temporary support made of polyethersulfone (Sumitomo Bakelite Co., Ltd. Sumilite FS-1300) having a thickness of 188 μm using a spin coater. Then, a light-emitting organic thin film layer having a thickness of 13 nm was formed on the temporary support by drying at room temperature. This was designated as transfer material Y.

Polyvinylcarbazole (Mw = 63000, manufactured by Aldrich) 40 parts by mass Tris (2-phenylpyridine) iridium complex (orthometalated complex):
1 part by mass Dichloroethane: 3200 parts by mass

The luminescent organic thin film layer side of the transfer material Y is superimposed on the upper surface of the organic thin film layer of the substrate X, heated and pressurized at 160 ° C., 0.3 MPa, 0.05 m / min using a pair of heat rollers, and the temporary support is attached. By peeling off, a light-emitting organic thin film layer was formed on the upper surface of the substrate X. This was designated as substrate XY.
Further, a patterned evaporation mask (a mask having a light emission area of 5 mm × 5 mm) is placed on one side of a polyimide film (UPILEX-50S, manufactured by Ube Industries) having a thickness of 50 μm cut into a 25 mm square. Al was evaporated in a reduced pressure atmosphere of 1 mPa to form an electrode having a film thickness of 0.3 μm. Using an Al ₂ O ₃ target by DC magnetron sputtering, the Al ₂ O ₃ was deposited in the same pattern as the Al layer and the thickness of 3 nm. Aluminum lead wires were connected from the Al electrode to form a laminated structure. A coating solution for an electron transporting organic thin film layer having the following composition is coated on the obtained laminated structure using a spin coater coating machine, and vacuum dried at 80 ° C. for 2 hours, thereby transporting an electron having a thickness of 15 nm. An organic thin film layer was formed. This was designated as substrate Z.

Polyvinyl butyral 2000L (Mw = 2000, manufactured by Denki Kagaku Kogyo Co., Ltd.): 10 parts by mass 1-butanol: 3500 parts by mass Electron transporting compound having the following structure: 20 parts by mass

Using the substrates XY and 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 pressurized at 160 ° C., 0.3 MPa, 0.05 m / min using a pair of heat rollers, The organic EL element 1 was produced by bonding.
Moreover, in the production of the substrate X as a comparative organic EL element, an organic EL element 2 was produced using the sample 3E as a support.

2. A direct measure voltage was applied to the organic EL elements 1 and 2 obtained by the evaluation using a source measure unit 2400 type (manufactured by Toyo Technica Co., Ltd.) to emit light. Both organic EL elements 1 and 2 emitted light well.
When the organic EL elements 1 and 2 were left to stand at 25 ° C. and a relative humidity of 75% for one month after the element was made to emit light in the same manner, the organic EL element 1 showed good light emission in the same manner. In the EL element 2, defects increased.

<Example 6>
1. Preparation of organic EL element assuming TFT installation By forming a transparent electrode on film 3A and then performing a heat treatment at 230 ° C. for 30 minutes assuming TFT installation, the same method as in Example 5 Organic EL element 3A (resin base material Tg: 270 ° C.) was produced.
Moreover, it changed into what formed the inorganic oxide layer and the sol-gel layer on the conditions similar to the film 1F of Example 1 on the film using the polyimide 1 (Tg: 285 degreeC) which has the following structure. Except for the above, an organic EL element 3W was produced in the same manner as the organic EL element 3A.

Moreover, organic EL element 3D was produced by the method similar to organic EL element 3A except having changed the base material into film 3D and having changed heat processing into 300 degreeC and 1 hour.
On the other hand, the organic EL element was produced in the same manner as the organic EL element 3A except that the film 1F (Tg of resin base material: 160 ° C.) was used as a comparative organic EL element. After the treatment, the film 1F was severely deformed and an organic EL device could not be produced.

2. When the organic EL elements 3A, 3D, and 3W obtained by evaluation were applied to the organic EL element using a source measure unit 2400 type (manufactured by Toyo Technica Co., Ltd.), all emitted light.
Thus, it can be seen that the gas barrier film of the present invention functions as a substrate film for an organic EL element even when a heat treatment assuming a TFT process is performed.

  Since the gas barrier film of the present invention has excellent gas barrier performance, it can be widely used as a substrate for image display elements such as liquid crystal display devices and organic EL devices.

1 is a schematic explanatory diagram of a roll-to-roll type sputtering apparatus in Example 1. FIG.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Sputtering apparatus 2 Vacuum tank 3 Drum 4 Delivery roll 5 Take-up roll 6 Plastic film 7 Guide roll 8 Guide roll 9 Exhaust port 10 Vacuum pump 11 Discharge power source 12 Cathode 13 Controller 14 Gas flow rate adjustment unit 15 Reactive gas piping

Claims (9)

A gas barrier film having alternately at least one inorganic layer and at least one organic layer on a resin substrate having a glass transition temperature of 250 ° C. or higher. The gas barrier film according to claim 1, wherein the resin is a resin having a spiro structure represented by the following general formula (1) or a resin having a cardo structure represented by the following general formula (2).

[In general formula (1), ring α represents a monocyclic or polycyclic ring, and the two rings are connected by a spiro bond. ]

[In general formula (2), ring β and ring γ represent a monocyclic or polycyclic ring, and two rings γ may be the same or different from each other. Linked to quaternary carbon. ] The gas barrier film according to claim 1 or 2, wherein the organic layer contains as a main component a crosslinked polymer compound obtained by polymerizing a polyfunctional monomer having an acryloyl group or a methacryloyl group. The gas barrier film according to any one of claims 1 to 3, wherein the organic layer is obtained by applying and drying a liquid containing a polymer having a hydrogen bonding group and a metal alkoxide. The oxygen permeability at 23 ° C. and 90% relative humidity is 0.02 ml / m ² · day · atm or less, and the water vapor permeability at 23 ° C. and 100% relative humidity is 0.02 g / m ² · day or less. The gas barrier film as described in any one of Claims 1-4. A method for producing a gas barrier film, comprising: a step of forming at least one inorganic layer on a resin substrate having a glass transition temperature of 250 ° C. or higher; and a step of forming at least one organic layer. The gas barrier film according to claim 6, wherein the resin base material is a base material made of a resin having a spiro structure represented by the following general formula (1) or a resin having a cardo structure represented by the following general formula (2). Manufacturing method.

[In general formula (1), ring α represents a monocyclic or polycyclic ring, and the two rings are linked by a spiro bond. ]

[In general formula (2), ring β and ring γ represent a monocyclic or polycyclic ring, and two rings γ may be the same or different, and one ring 4 on ring β Linked to grade carbon. ] The gas barrier film according to claim 6 or 7, wherein the organic layer is formed by applying a composition containing a polymer having a hydrogen bonding group and a metal alkoxide and then drying at 150 to 350 ° C. Method. An organic electroluminescence device using the gas barrier film according to any one of claims 1 to 5.

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