JP2016101694A - Gas barrier film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a gas barrier film which has high crack resistance, when bent, and excellent adhesiveness and excellent gas barrier properties even after stored for a long period of time under a high-temperature and high-humidity environment.SOLUTION: The gas barrier film is obtained by stacking a clear hard coat layer 3 and a gas barrier layer 6 in this order on a resin base material 2 so that the clear hard coat layer is constituted of two or more kinds of resin compositions 4, 5 different in hardness so that the maximum of hardness differences between the resin compositions 4, 5 is 0.2 GPa or larger and the clear hard coat has such a pattern that the resin compositions 4, 5 constitute respective zones different from each other in the facial direction of the clear hard coat layer. At least one of the resin compositions 4, 5, for constituting the pattern of the clear hard coat layer 3 is formed into a cylinder structure independently separated on the facial direction. The pattern is a discontinuous polygonal pattern.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a gas barrier film provided with a clear hard coat layer having a pattern separated by two or more kinds of resin compositions having different hardnesses.

  An organic electroluminescence element (hereinafter also referred to as an organic EL element) using an organic material electroluminescence (hereinafter abbreviated as EL) can emit light at a low voltage of several V to several tens V. It is a thin film type complete solid-state device and has many excellent features such as high brightness, high luminous efficiency, thinness, and light weight. For this reason, in recent years, it has attracted attention as a backlight for various displays, a display plate such as a signboard or emergency light, and a surface light emitter such as an illumination light source.

  For the purpose of making the device thin and light and flexible, an organic EL device using a resin substrate as a substrate has been studied. In some cases, a gas barrier film that blocks intrusion of various gases such as water vapor and oxygen may be provided. By providing the organic EL element with the gas barrier film, the influence of harmful gas from the external environment is blocked, and the deterioration of the function of the organic EL element is suppressed.

  In the method for producing a gas barrier film used in such a field, the gas barrier layer is produced while continuously transporting a long flexible resin substrate for the purpose of increasing production efficiency and obtaining a large area gas barrier film. A roll-to-roll system capable of forming a film is actively used.

  In such a gas barrier film in which a gas barrier layer is provided on a flexible resin substrate, a high-quality gas barrier film having high gas barrier properties and no film surface failure (for example, cracks or film peeling) is obtained. In order to obtain it, it has become a big subject to improve the adhesiveness between the resin base material and the gas barrier layer, and various methods have been studied as a countermeasure.

  Specifically, the surface of the resin substrate is subjected to surface modification treatment such as corona discharge treatment, flame treatment, oxidation treatment, plasma treatment, etc. to improve adhesion, or between the resin substrate and the gas barrier layer. A method for providing a clear hard coat layer between them has been studied.

  In the method of providing the clear hard coat layer, it is known that the adhesion is improved by increasing the layer thickness. However, when a thick clear hard coat layer is incorporated in the gas barrier film, when the gas barrier film is bent, a bending crack occurs in the clear hard coat layer, and the gas barrier provided on the upper side is linked to this. Layers can also be destroyed. For the above problem, crack resistance is improved by using a thin clear hard coat layer, but the stress relaxation effect due to the difference in expansion and contraction caused by bending between the resin substrate and the gas barrier layer becomes insufficient. The film peels off. In particular, when the gas barrier film is used over a long period of time in a high-temperature and high-humidity environment, the film is likely to be peeled off. For example, when the gas barrier film is applied to an organic electroluminescence element, the film Water vapor and oxygen due to peeling and the like are likely to occur, and the organic material constituting the organic electroluminescence element that is weak against heat and moisture is deactivated, causing the occurrence of dark spots or the like that are failures during light emission.

  With respect to the above problem, in Patent Document 1, a physical vapor deposition method (PVD method) or a low temperature plasma vapor deposition method, a chemical deposition method (CVD method) is formed on a polyethylene terephthalate (hereinafter abbreviated as PET) substrate. And an inorganic / organic hybrid polymer layer (ORMOCER layer) formed by applying a metal-based metal alkoxide or a derivative thereof, an aluminum compound and, if necessary, a compound containing another metal element. A barriering laminated film that can improve bending resistance is disclosed.

  However, the barrier laminated film described in Patent Document 1 has good bending resistance, but when stored in a high-temperature and high-humidity environment, the substrate and the inorganic / organic hybrid polymer layer (ORMOCER layer) ) Is not sufficiently close, and there is a problem that the gas barrier property is lowered.

  In Patent Document 2, a gas barrier formed by subjecting a polysilazane film formed by applying a polysilazane-containing liquid to at least one surface side of a resin base material, for example, a PET film, is subjected to a modification treatment by plasma irradiation. A gas barrier film having a layer is disclosed.

  According to the method disclosed in Patent Document 2, it is said that a gas barrier film excellent in resin substrate selectivity can be provided. Similarly to the above, a resin substrate, a gas barrier layer, The adhesion between them is not sufficient, and the gas barrier property against moisture and the like is not sufficient.

  For such problems, by providing an undercoat layer, for example, a smooth layer, as a buffer layer (also referred to as a buffer layer) between the flexible resin substrate and the gas barrier layer, A method for suppressing damage to the gas barrier layer (film peeling, cracking, etc.) has been studied.

  For example, in Patent Document 3, an anchor coat layer containing an acrylate polymer, a clear hard coat layer containing a (meth) acrylic resin, and a gas barrier layer made of an inorganic compound are laminated on a plastic substrate. A laminate is disclosed.

  According to the method disclosed in Patent Document 3, it is said that a laminate having excellent adhesion, smoothness, and gas barrier properties can be provided.

  However, with a structure in which a smooth layer or a clear hard coat layer composed of a uniform composition is simply provided between the base material and the gully barrier layer, a certain degree of adhesion to the base material can be obtained. Adhesiveness with the gas barrier layer comprised of the provided inorganic oxide or the like is impure.

  Therefore, it is desired to develop a gas barrier film that has high resistance to cracking at the time of bending and is excellent in adhesion and gas barrier properties in a high temperature and high humidity environment.

Japanese Patent Laid-Open No. 2002-046208 JP 2007-237588 A Japanese Patent No. 5381017

  The present invention has been made in view of the above problems, and the problem to be solved is a gas having high resistance to cracking at the time of bending and excellent adhesion and gas barrier properties even after being stored for a long time in a high temperature and high humidity environment. It is to provide a barrier film.

  As a result of intensive studies in view of the above problems, the present inventors have laminated a clear hard coat layer and a gas barrier layer in this order on a resin base material, and the clear hard coat layer is configured with a specific hardness difference. The gas barrier film is characterized in that a plurality of resin compositions are used, and a pattern is formed in a separate and independent region by each of the plurality of resin compositions. In addition, the present inventors have found that a gas barrier film having excellent adhesion and gas barrier properties can be provided even after being stored for a long period of time, resulting in the present invention.

  That is, the said subject of this invention is solved by the following means.

1. A gas barrier film in which a clear hard coat layer and a gas barrier layer are laminated in this order on a resin substrate,
The clear hard coat layer is composed of two or more resin compositions having different hardnesses measured by a nanoindentation method,
The maximum hardness difference between two or more resin compositions having different hardnesses is 0.2 GPa or more,
The gas barrier film is characterized in that the two or more kinds of resin compositions having different hardnesses have patterns constituting different regions in the plane direction.

  2. Of the two or more resin compositions having different hardnesses, the resin composition having the lowest hardness has a hardness in the range of 0.1 to 0.6 GPa, and the resin composition having the highest hardness has a hardness of 0. The gas barrier film as described in item 1, wherein the gas barrier film is in a range of 8 to 1.5 GPa.

  3. 3. The gas barrier film according to item 1 or 2, wherein a maximum hardness difference between two or more kinds of resin compositions constituting the clear hard coat layer is 0.5 GPa or more.

  4). At least one of two or more resin compositions having different hardness constituting the pattern of the clear hard coat layer forms a cylinder structure that is independently separated in the plane direction. The gas barrier film according to any one of items 1 to 3.

  5. The gas barrier film according to any one of Items 1 to 4, wherein the pattern of the clear hard coat layer has a discontinuous polygon pattern.

  6). Two or more types of resin compositions having different hardness constituting the clear hard coat layer are each composed of different ultraviolet curable resin materials, any one of items 1 to 5 The gas barrier film as described in 2.

  7). The gas barrier film according to any one of items 1 to 6, wherein at least one of the resin compositions constituting the pattern of the clear hard coat layer contains inorganic fine particles. .

  8). The gas barrier film according to any one of items 1 to 7, wherein the gas barrier layer has a metal oxide formed by a chemical vapor deposition method or a physical vapor deposition method.

  9. The gas barrier film according to any one of items 1 to 8, further comprising a second gas barrier layer containing a modified perhydropolysilazane on the gas barrier layer.

  By the above means of the present invention, it is possible to provide a gas barrier film having high resistance to cracking at the time of bending and excellent adhesion and gas barrier properties even after being stored for a long time in a high temperature and high humidity environment.

  The expression mechanism or action mechanism of the effect of the present invention is not clear, but is presumed as follows.

  In the gas barrier film of the present invention, a clear hard coat layer and a gas barrier layer are laminated in this order on a resin substrate, and the clear hard coat layer has two or more kinds of resins having different hardnesses measured by the nanoindentation method. Consists of a composition, the resin composition is composed of a combination in which the maximum hardness difference between the resin compositions is 0.2 GPa or more, and the two or more kinds of resin compositions having different hardness constitute different regions in the plane direction. It is characterized by having a discontinuous pattern.

  As described above, in the conventional gas barrier film, wrinkles and creases occur due to differences in hardness and expansion / contraction ratio between the flexible resin base material and the gas barrier layer, or when bent or in a high temperature and high humidity environment for a long time. When stored for a long time, the film peeled off at the interface between them, or the gas barrier layer was damaged or cracked due to excessive stress, which caused deterioration of the gas barrier properties.

  In the present invention, based on the above problems, the flexible resin base material and the gas barrier layer are composed of two or more kinds of resin compositions having different hardness, and the two or more kinds of resin compositions are different in the plane direction. By forming a clear hard coat layer with a discontinuous pattern that constitutes the region, it absorbs the strain of stress generated between the flexible resin base material and the gas barrier layer during bending and prevents concentration of the stress in a certain direction. Stress and strain can be diffused in the plane direction, cracking of the gas barrier layer under high temperature environment and destruction of the gas barrier layer can be prevented, and a gas barrier film with excellent gas barrier properties can be realized. It was.

Schematic sectional view showing an example of the configuration of the gas barrier film of the present invention The top view which shows an example of the pattern (stripe form) in the clear hard-coat layer based on this invention The top view and sectional drawing which show an example of the polygon (hexagonal) pattern in the clear hard-coat layer based on this invention The top view which shows another example (a triangle and a quadrangle) of the polygonal pattern in the clear hard-coat layer which concerns on this invention Schematic diagram showing an example of a pattern formation method of a clear hard coat layer using an inkjet method Schematic diagram showing another example of pattern formation method of clear hard coat layer using inkjet method The schematic diagram which shows an example of a structure of the discharge plasma processing apparatus suitable for formation of the gas barrier layer based on this invention The schematic diagram which shows an example of a structure of the surface modification processing apparatus provided with the excimer lamp suitable for formation of the 2nd gas barrier layer based on this invention The schematic block diagram which shows an example of a structure of the organic electroluminescent element which comprised the gas barrier film of this invention

  The gas barrier film of the present invention comprises a structure in which at least a clear hard coat layer (hereinafter also simply referred to as a hard coat layer) and a gas barrier layer are laminated in this order on a resin substrate. The coat layer is composed of two or more resin compositions having different hardnesses measured by the nanoindentation method, and the maximum hardness difference between the two or more resin compositions having different hardnesses is 0.2 GPa or more, and The two or more types of resin compositions having different hardnesses have patterns that form different regions in the plane direction. This feature is a technical feature common to the inventions according to claims 1 to 9.

  As an embodiment of the present invention, from the viewpoint of more manifesting the intended effect of the present invention, the resin composition having the lowest hardness among at least two resin compositions having different hardnesses has a hardness of 0.1. It is possible to select a resin composition having a hardness of 0.8 to 1.5 GPa and a resin composition having a hardness of 0.8 to 1.5 GPa as a resin composition having the highest hardness. A clear hard coat layer having an excellent relaxation effect can be obtained, and it is preferable in that it can exhibit more excellent effects with respect to crack resistance during bending, adhesion in a high-temperature and high-humidity environment, and gas barrier properties.

  In addition, as a combination of two or more kinds of resin compositions, it is possible to form a pattern with a combination having a maximum hardness difference of 0.5 GPa or more. Similarly, it is more excellent in crack resistance during bending and in a high temperature and high humidity environment. It is preferable at the point which can obtain high adhesiveness and gas-barrier property.

  Further, in the clear hard coat layer according to the present invention, when forming a pattern in which each resin composition independently forms a different region in the surface direction, at least one of the resin compositions is a surface. Forming a cylinder structure that is independently separated in the direction, and further forming the cylinder structure with a discontinuous polygon pattern is preferable in that a higher stress relaxation effect can be exhibited as a clear hard coat layer.

  Further, at least two types of resin compositions having different hardness constituting the clear hard coat layer are constituted by different ultraviolet curable resin materials, or at least the resin composition constituting the pattern of the clear hard coat layer. It is preferable that one type of the above contains inorganic fine particles because it can be easily adjusted to a desired hardness balance.

  Further, when the gas barrier layer is a metal oxide-containing layer formed by a chemical vapor deposition method or a physical vapor deposition method, a high gas barrier property can be obtained with a dense film composition having high homogeneity. This is a preferable aspect.

  Furthermore, after applying and drying a polysilazane layer-forming coating solution containing polysilazane to form a precursor layer, the precursor layer is subjected to a modification treatment with vacuum ultraviolet light to provide a second gas barrier layer. However, this is a preferred embodiment in that more excellent gas barrier properties can be obtained.

  Hereinafter, the present invention, its components, and modes and modes for carrying out the present invention will be described in detail. In addition, "-" shown in the following description is used with the meaning which includes the numerical value described before and behind that as a lower limit and an upper limit. In the following description, the numbers shown in parentheses after each component represent the symbols described in each figure.

《Basic structure of gas barrier film》
In the gas barrier film of the present invention, the resin base material is composed of two or more different resin compositions having a hardness difference of at least 0.2 GPa, and the two or more resin compositions are in the plane direction. It is characterized in that it has a clear hard coat layer having a pattern constituting each different region, and a gas barrier layer is further laminated thereon, and as a more preferable correspondence, on the gas barrier layer The hybrid gas barrier layer structure having the second gas barrier layer is a preferred embodiment.

  The resin composition referred to in the present invention is a component for forming a clear hard coat layer pattern, for example, for forming a clear hard coat layer composed of an ultraviolet curable resin, a polymerization initiator, an organic solvent, and the like. A pattern formed using a coating solution and then cured by irradiating ultraviolet rays or the like, and a pattern formed by the resin composition (reference numerals 4, 5, etc. in the drawings described later) is called a resin structure. .

  FIG. 1 is a schematic cross-sectional view showing the configuration of the gas barrier film of the present invention.

  FIG. 1A is a schematic diagram showing an example of one gas barrier layer, and FIG. 1B is a schematic diagram showing an example of a hybrid gas barrier layer having two gas barrier layers.

  The gas barrier film (1) shown in FIG. 1 (a) has two or more kinds of different hardness on the resin base material (2) so that the hardness difference which is a feature of the present invention is at least 0.2 GPa or more. Using a resin composition, for example, a clear hard coat layer in which a pattern having different regions in the plane direction of the layer is formed by the first resin structure (4) and the second resin structure (5) ( 3), and a gas barrier layer (6), for example, a gas barrier layer having a metal oxide formed by chemical vapor deposition or physical vapor deposition is formed on the outermost layer. It is shown.

  In FIG. 1 (b), in addition to the configuration shown in FIG. 1 (a), for example, a coating liquid for forming a polysilazane layer containing polysilazane is used on the gas barrier layer (6), and vacuum ultraviolet light irradiation is performed. A second embodiment is shown in which a hybrid gas barrier layer is provided with a second gas barrier layer (7) formed by performing a modification treatment by the above method.

  Details of each component and each forming method will be described later.

<< Clear hard coat layer pattern >>
The clear hard coat layer according to the present invention is composed of two or more kinds of resin compositions having a hardness difference of at least 0.2 GPa, and the two or more kinds of resin compositions have different regions in the plane direction. It has the pattern which comprises. Furthermore, the hardness of the resin composition having the lowest hardness is in the range of 0.1 to 0.6 GPa, and the hardness of the resin composition having the highest hardness is in the range of 0.8 to 1.5 GPa. Is a preferred embodiment. More preferably, the hardness of the resin composition having the lowest hardness is in the range of 0.2 to 0.5 GPa, and the hardness of the resin composition having the highest hardness is in the range of 1.0 to 1.3 GPa. is there.

  The hardness referred to in the present invention refers to the hardness (GPa) determined by the nanoindentation method.

  The nanoindentation method can be used to measure indentation hardness at the nano level by adding an indentation hardness measurement module (configured with a transducer and an indentation tip) to an atomic force microscope (AFM). This is the latest measurement method.

  More specifically, it is a method of calculating the plastic deformation hardness from the measured value by measuring the relationship between the load and the indentation depth (displacement amount) while indenting into the clear hard coat layer on which a minute diamond indenter is formed.

  The specific measurement of hardness (GPa) by the nanoindentation method is performed by attaching a sample to a Triscope from Hysitron and a sample from Nanoscope III from Digital Instruments. In the measurement, a triangular pyramid diamond indenter called a Belkovic indenter (90 ° Cube Corm Tripr) is used as an indenter. The load was gradually applied to the surface of the clear hard coat layer on which the triangular pyramidal diamond indenter was formed, and a load was gradually applied. After reaching the maximum load, the load was gradually returned to zero. A value P / A obtained by dividing the maximum load P at this time by the projected area A of the indenter contact portion was calculated as hardness (GPa). The maximum load condition at this time is 50 μN.

  A sample for measurement was prepared by coating and drying each resin structure (4) or resin structure (5) on a polyethylene terephthalate film having a thickness of 120 μm under the condition that the film thickness during drying was 2 μm. It is produced by irradiating with ultraviolet rays under the following conditions.

  The prepared sample was dropped on the slide glass with a drop of adhesive Aron Alpha manufactured by Toagosei Co., Ltd., and then placed on a film with a clear hard coat layer cut to about 1 cm square and allowed to stand for 24 hours to cure. A measurement sample. The number of measurements was n = 3, and the average value was obtained. In measurement, the attached fused silica is used as a standard sample in advance, and the apparatus is calibrated and measured so that the hardness obtained by the indentation is 9.5 ± 1.5 GPa.

  The details of the principle of surface hardness measurement by the nanoindentation method are described in, for example, Handbook of Micro / Nano Tribology (CRC edited by Bharat Bhushan), and can be referred to.

  In the present invention, at least two kinds of resin compositions having different hardnesses are characterized by a combination in which the hardness difference is at least 0.2 GPa or more, further 0.5 GPa or more and 1.3 GPa or less. It is preferable that it is 0.5 GPa or more and 1.0 GPa or less.

  In the present invention, the pattern constituting the different regions formed in the clear hard coat layer is constituted by two or more kinds of resin compositions having a hardness difference of at least 0.2 GPa or more. , Preferably about 2 to 5 types, more preferably about 2 to 3 types, and most preferably, as shown in FIG. 1, two resin compositions (4) having a hardness difference of 0.2 GPa or more. ) And the resin composition (5) are preferable.

  In the clear hard coat layer according to the present invention, two or more kinds of resin compositions having different hardness constituting the clear hard coat layer are constituted by different ultraviolet curable resin materials, which is a preferable embodiment. The different ultraviolet curable resin materials referred to in the present invention include, in addition to different components constituting the resin, those having the same basic skeleton, different functional group numbers, different types of substituents, and the like. .

  Hereinafter, an example of a pattern formed by the two resin compositions (4) and the resin composition (5) having a hardness difference of at least 0.2 GPa will be described. However, the present invention is not limited to the shape of the pattern exemplified here.

(Pattern A)
FIG. 2 is a top view showing an example of a pattern A constituting the clear hard coat layer according to the present invention.

  In the clear hard coat layer (3) shown in FIG. 2, a stripe pattern is formed by the resin structure (4) and the resin structure (5) having different hardnesses and a hardness difference of 0.2 GPa or more. . In the pattern shown in FIG. 2, the resin compositions are alternately arranged in the plane direction, and one of the resin compositions has no separated island structure.

(Pattern B)
In the clear hard coat layer according to the present invention, it is a preferable aspect that at least one of two or more resin compositions having different hardnesses constitutes a discontinuous polygonal pattern resin structure.

FIG. 3 is a schematic diagram showing a pattern B which is an example of a more preferable embodiment constituting the clear hard coat layer according to the present invention. FIG. 3A is a clear hard coat having a hexagonal independently separated pattern. FIG.

  In the clear hard coat layer (3) shown in FIG. 3 (a), the resin structure (4) forms a hexagonal cylinder structure that is independently separated in the plane direction, and the resin structure is composed of the hexagon. The peripheral part of (4) is a configuration in which a continuous partition wall structure is formed by the resin structure (5).

  In the gas barrier film formed by arranging the clear hard coat layer (3) having such a configuration between the resin base material (2) and the gas barrier layer (6), the displacement of stress generated at the time of film folding is efficiently performed. Can be relaxed.

  In the clear hard coat layer (3) shown in FIG. 3A, the resin structure (4) is formed from the resin composition having the lowest hardness, and the resin structure (4) is formed from the resin composition having the highest hardness. Although the structure which forms 5) may be sufficient, or the reverse structure may be sufficient, the former structure is a more preferable aspect.

  FIG. 3B is a cross-sectional view of the gas barrier layer 3 cut along the cutting line AA in the top view of the gas barrier layer 3 shown in FIG.

  In the cross-sectional view shown in FIG. 3 (b), a plurality of resin structures (4) constitutes a cylinder structure that is independently separated, and the resin structure (4) is separated to form the resin structure (5). A continuous barrier rib structure is formed.

In such a configuration, as the size of the hexagonal cylinder structure constituted by an independent separate configuration of the resin structure (4) is not particularly limited, as is its width L _2, in the range of 100~1000μm More preferably, it is in the range of 150 to 700 μm, more preferably in the range of 200 to 500 μm, and particularly preferably in the range of 250 to 350 μm.

As the width _{L 1} of the partition wall structure formed by the resin structure (5) is not particularly limited, and more it is preferably in the range of 10 to 300 [mu] m, in the range of 50~200μm A range of 80 to 150 μm is particularly preferable.

(Pattern C and Pattern D)
FIG. 4 is a top view showing a pattern C and a pattern D which are an example of a preferred embodiment formed in the clear hard coat layer according to the present invention.

  4A is an example in which the separated and independent form constituted by the resin structure (4) is a triangle, and FIG. 4B is the separated and independent form constituted by the resin structure (4). Is an example of a square.

  As shown in FIG. 3 or FIG. 4, by forming a polygonal pattern such as a triangle, a quadrangle, or a hexagon as a separate and independent form, stress relaxation can be more effectively expressed when the gas barrier film is folded. This is a preferable mode, and among them, it is particularly preferable to apply a hexagon as illustrated in FIG.

(Pattern formation method)
In the clear hard coat layer according to the present invention, there is no particular limitation on the method for forming the pattern as exemplified in FIGS. 2 to 4, but there are two or more kinds of resin compositions having different hardnesses. Using the liquid, for example, gravure coater, spinner coater, wire bar coater, roll coater, reverse coater, extrusion coater, air doctor coater, spray coating, spray coating, inkjet method, etc. A pattern to be formed can be formed. Among these, an inkjet method or a gravure printing method is preferable from the viewpoint of stably forming a high-precision and fine pattern.

<< Constituent elements of gas barrier film and manufacturing method thereof >>
Next, the details of the resin base material, the clear hard coat layer, the gas barrier layer and other components constituting the gas barrier film of the present invention and the production method thereof will be described.

[Resin substrate]
As the resin base material applied to the gas barrier film of the present invention, it is preferable to use a film-like resin film. The resin film that can be used is not particularly limited in material, thickness, and the like as long as it can hold the clear hard coat layer and the gas barrier layer, and can be appropriately selected according to the purpose of use.

  In consideration of application to various uses, the resin base material is preferably a flexible resin base material. The flexible resin base material as used in the present invention refers to a resin base material that is wound around a φ (diameter) 50 mm roll and is not cracked before and after winding with a constant tension, and more preferably can be wound around a φ 30 mm roll. This refers to the resin base material.

  Specific examples of the resin material constituting the resin film include polyester resin, methacrylic resin, methacrylic acid-maleic acid copolymer, polystyrene resin, transparent fluororesin, polyimide, fluorinated polyimide resin, polyamide resin, and polyamideimide resin. , Polyetherimide resin, cellulose acylate resin, polyurethane resin, polyether ether ketone resin, polycarbonate resin, alicyclic polyolefin resin, polyarylate resin, polyether sulfone resin, polysulfone resin, cycloolefin copolymer, fluorene ring modified polycarbonate Examples thereof include thermoplastic resins such as resins, alicyclic modified polycarbonate resins, fluorene ring modified polyester resins, and acryloyl compounds.

When the gas barrier film is used as a support base material for an electronic device such as an organic EL element, the resin base material is preferably made of a heat-resistant material. Specifically, a resin base material having a linear expansion coefficient in the range of 15 to 100 × 10 ⁻⁶ / ° C. and a glass transition temperature Tg in the range of 100 to 300 ° C. is used. The resin base material satisfies the necessary conditions as a laminated film for electronic parts and displays.

That is, when using a gas barrier film for these uses, the gas barrier film may be exposed to a process of 150 ° C. or higher. In this case, when the linear expansion coefficient of the base material in the gas barrier film is in the range of 15 to 100 × 10 ⁻⁶ / ° C., the heat resistance is high and the flexibility is good. The linear expansion coefficient and Tg of the base material can be adjusted by an additive or the like.

  More preferable specific examples of the thermoplastic resin that can be used as the resin substrate include, for example, polyethylene terephthalate (PET: 70 ° C.), polyethylene naphthalate (PEN: 120 ° C.), polycarbonate (PC: 140 ° C.), and alicyclic ring. Polyolefin (for example, ZEONOR (registered trademark) 1600: 160 ° C., manufactured by Nippon Zeon Co., Ltd.), polyarylate (PAr: 210 ° C.), polyether sulfone (PES: 220 ° C.), polysulfone (PSF: 190 ° C.), cyclo Olefin copolymer (COC: compound described in JP-A No. 2001-150584: 162 ° C.), polyimide (for example, Neoprim (registered trademark): 260 ° C., manufactured by Mitsubishi Gas Chemical Company, Inc.), fluorene ring-modified polycarbonate (BCF-PC) : JP 2000-227603 Compound described in the publication: 225 ° C., alicyclic modified polycarbonate (IP-PC: compound described in JP 2000-227603 A: 205 ° C.), acryloyl compound (compound described in JP 2002-80616 A: (The numerical value in parentheses indicates Tg.).

  Since a gas barrier film is utilized for electronic devices, such as an organic EL element, it is preferable that a resin base material is transparent. That is, the light transmittance is usually 80% or more, preferably 85% or more, and more preferably 90% or more.

  The light transmittance is determined by measuring the total light transmittance and the amount of scattered light using the method described in JIS K 7105: 1981, that is, using an integrating sphere light transmittance measuring device, and subtracting the diffuse transmittance from the total light transmittance. Can be calculated.

  However, even when the gas barrier film is used for display, transparency is not necessarily required when it is not installed on the observation side. Therefore, in such a case, an opaque material can be used as the resin base material. Examples of the opaque material include polyimide, polyacrylonitrile, and known liquid crystal polymers.

  The thickness of the resin substrate used for the gas barrier film is not particularly limited because it is appropriately selected depending on the application, but is typically in the range of 1 to 800 μm, preferably in the range of 10 to 200 μm. . These resin films may have a functional layer such as a known transparent conductive layer used in conventional gas barrier films. The gas barrier film of the present invention is preferably produced by roll-to-roll. In such a case, it is preferable to use a resin film laminated in a long roll shape. The film length varies depending on the application, but is generally in the range of 100 to 10000 m, preferably in the range of 500 to 5000 m, and more preferably in the range of 800 to 3000 m.

  In addition, the base material using the above-described resins or the like may be an unstretched film or a stretched film.

  The resin base material can be manufactured by a conventionally known general method. For example, an unstretched resin base material that is substantially amorphous and not oriented can be produced by melting a resin as a material with an extruder, extruding it with an annular die or a T-die, and quenching. In addition, an unstretched resin base material is uniaxially stretched, a tenter-type sequential biaxial stretch, a tenter-type simultaneous biaxial stretch, a tubular-type simultaneous biaxial stretch, and the like in a flow direction (vertical axis) direction of the resin base material. Alternatively, a stretched substrate can be produced by stretching in the direction perpendicular to the flow direction of the resin substrate (horizontal axis). The draw ratio in this case can be appropriately selected according to the resin as the raw material of the base material, but is preferably in the range of 2 to 10 times in the vertical axis direction and the horizontal axis direction.

  Various treatments for improving adhesion, corona discharge treatment, flame treatment, oxidation treatment, plasma treatment, etc., are performed in combination as necessary on both surfaces of the resin substrate, at least on the side where the gas barrier layer is provided. be able to.

[Clear hard coat layer]
In the gas barrier film of the present invention, the clear hard coat layer is composed of two or more kinds of resin compositions having a hardness difference of at least 0.2 GPa, and the 2 described with reference to FIGS. The resin structure composed of at least one kind of resin composition has a pattern that forms different regions in the plane direction.

  Furthermore, the hardness of the resin composition having the highest hardness is in the range of 0.1 to 0.6 GPa among the resin compositions having the lowest hardness among the at least two resin compositions having different hardnesses. Is within a range of 0.8 to 1.5 GPa, or the hardness difference between at least two resin compositions having different hardnesses is 0.5 GPa or more.

  In the clear hard coat layer according to the present invention, the method for controlling the hardness of each resin composition constituting different regions in the plane direction to a desired condition is not particularly limited as long as the above condition is satisfied. For this, it is preferable to appropriately select and prepare the following constituent elements to obtain a desired combination of hardnesses.

  Although details will be described later, the hardness control means are mainly 1) selection of the type and characteristics (for example, the number of functional groups) of the resin material, in particular, an ultraviolet curable resin, and 2) control of the polymerization degree of the resin material. 3) Ratio of resin monomer to polymerization initiator, 4) Addition of filler such as inorganic fine particles, 5) Adjustment of UV irradiation amount to unreacted clear hard coat layer formed by resin monomer and polymerization initiator, etc. Is mentioned.

(Resin composition)
The resin material constituting the resin composition applicable to the clear hard coat layer according to the present invention is not particularly limited as long as a desired hardness can be obtained. For example, a thermoplastic resin group, thermosetting It is preferable to select a resin having a desired hardness from the group of curable resins and actinic ray (especially UV) curable resins, and among these, it is particularly preferable to select from transparent UV curable resins. The term “transparent” as used in the present invention means that the average light transmittance in the visible light region is 70% or more, preferably 80% or more, and more preferably 90% or more. The hardness referred to in the present invention is not the hardness after curing of the resin alone constituting the resin composition, but is formed by a resin component, a polymerization initiator for curing the resin, other additives such as inorganic fine particles, and the like. The hardness measured by the indentation method of the resin composition.

  Next, an ultraviolet curable resin that can be suitably used for the clear hard coat layer according to the present invention will be described.

  The UV curable resin is (A) monomer type: 1) radical polymerization type monofunctional acrylate, bifunctional acrylate, trifunctional acrylate, 4-6 functional acrylate, etc. 2) cationic polymerization type alicyclic epoxy resin , Glycidyl ether epoxy resin, urethane vinyl ether, polyester vinyl ether and the like.

  The (B) oligomer includes 1) radical polymerization type epoxy acrylate, urethane acrylate, polyester acrylate, copolymerization type acrylate, polybutadiene acrylate, silicone acrylate, amino acid acrylate, etc. 2) cationic polymerization type cationic polymerization type fat Examples thereof include cyclic epoxy resins, glycidyl ether epoxy resins, urethane vinyl ethers, and polyester vinyl ethers.

  In the present invention, among the ultraviolet curable resins, it is preferable to apply radical polymerization resins, and acrylate resins, urethane acrylate resins, epoxy acrylate resins, and the like are more preferable.

(Acrylate resin)
The acrylate compound applicable to the clear hard coat layer according to the present invention is preferably an ultraviolet curable (meth) acrylate resin, and more preferably an ultraviolet curable polyfunctional acrylate resin.

  The polyfunctional acrylate resin is preferably a resin selected from the group consisting of pentaerythritol polyfunctional acrylate, dipentaerythritol polyfunctional acrylate, pentaerythritol polyfunctional methacrylate, and dipentaerythritol polyfunctional methacrylate. Here, the polyfunctional acrylate is a compound having two or more acryloyloxy groups or methacryloyloxy groups in the molecule. Examples of the polyfunctional acrylate monomers include ethylene glycol diacrylate, diethylene glycol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylolethane triacrylate, and tetramethylolmethanetriacrylate. Acrylate, tetramethylol methane tetraacrylate, pentaglycerol triacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, glycerin triacrylate, dipentaerythritol triacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, Dipentae Thritol hexaacrylate, tris (acryloyloxyethyl) isocyanurate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, Tetramethylol methane trimethacrylate, tetramethylol methane tetramethacrylate, pentaglycerol trimethacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, glycerol trimethacrylate, dipentaerythritol trimethacrylate, dipentaerythritol tetra Methacrylate, dipentaerythritol penta methacrylate, dipentaerythritol hexa methacrylate, isobornyl acrylate and the like preferably. These compounds are used alone or in combination of two or more. Moreover, oligomers, such as a dimer and a trimer of the said monomer, may be sufficient.

  The resin composition according to the present invention may further contain a monofunctional acrylate. Monofunctional acrylates include isobornyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, isostearyl acrylate, benzyl acrylate, ethyl carbitol acrylate, phenoxyethyl acrylate, lauryl acrylate, isooctyl acrylate, tetrahydrofurfuryl acrylate, behenyl Examples include acrylate, 4-hydroxybutyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, and cyclohexyl acrylate. Such monofunctional acrylates can be obtained from Nippon Kasei Kogyo Co., Ltd., Shin-Nakamura Chemical Co., Ltd., Osaka Organic Chemical Co., Ltd., etc.

  Moreover, the ultraviolet curable acrylate resin can be obtained as a commercial product. In addition, the indication described in parentheses represents the pencil hardness of the resin alone measured according to JIS K 5600-5-4.

Hitachi Chemical's Hitaroid 7975 (H-2H), Hitaroid 7988 (H-2H), Hitaroid 7975D (H-2H), etc.
Neomer PA-305 manufactured by Sanyo Chemical Co., Ltd .: polypropylene glycol diacrylate, functional group number = 2 (H to 2H), neomer NA-305: neopentyl glycol (PO) n diacrylate (2H), functional group number = 2, neomer BA -641: Bisphenol A (EO) n diacrylate (2H), number of functional groups = 2, neomer TA-401: trimethylolpropane (EO) n triacrylate (3H), number of functional groups = 3, neomer TA-505: trimethylol Propane (PO) n triacrylate (3H), functional group number = 3, neomer DA-600: dipentaerythritol pentaacrylate (4H), functional group number = 5, etc. [NK ester] manufactured by Shin-Nakamura Chemical Co., Ltd. Functional acrylate (Product name: A-LEN-10, AM-90G, AM-1 30G, AMP-20GY, A-SA, S-1800A, etc.), bifunctional acrylate (product names: 701A, A-200, A-400, A-600.A-1000, A-B1206PE, ABE-300, A -BPE-10, A-BPE-4, A-BPEF, A-BPP-3, A-DCP, A-DOD-N, A-HD-N, APG-100, APG-200, etc.), polyfunctional acrylate (A-9300, A-9300-1CL, A-GLY-9E, A-TMM-3, A-TMPT, AD-TMP, A-9550, etc.), monofunctional methacrylate (CB-1, M-90G, PHE-1G, S, SA, etc.) Bifunctional methacrylate (1G, 2G, 3G, 4G, 9G, BPE-80N, BPE-500, DCP, DOD-N, HD-N, NPG, 701, 9 G, etc.), polyfunctional methacrylate (TMPT, etc.) and the like.

  As other commercial products, Adekaoptomer (registered trademark) KR / BY series: KR-400, KR-410, KR-550, KR-566, KR-567, BY-320B (above, manufactured by ADEKA Corporation) , Koei hard A-101-KK, A-101-WS, C-302, C-401-N, C-501, M-101, M-102, T-102, D-102, NS-101, FT -102Q8, MAG-1-P20, AG-106, M-101-C (manufactured by Guangei Chemical Co., Ltd.), Seika Beam (registered trademark) PHC2210 (S), PHCX-9 (K-3), PHC2213, DP -10, DP-20, DP-30, P1000, P1100, P1200, P1300, P1400, P1500, P1600, SCR900 (above, Dainichi Chemical Industry Co., Ltd.), KRM7033, KRM7039, KRM7130, KRM7131, UVECRYL29201, UVECRYL29202 (above, manufactured by Daicel UC Corporation), RC-5015, RC-5016, RC-5020, RC-5031, RC-5100, RC-5102, RC-5120, RC-5122, RC-5152, RC-5171, RC-5180, RC-5181 (manufactured by DIC Corporation), Aulex No. 340 clear (above, China Paint Co., Ltd.), SP-1509, SP-1507 (above, Showa Polymer Co., Ltd.), RCC-15C (above, Grace Japan Co., Ltd.), Aronix (registered trademark) M -6100, M-8030, M-8060 (manufactured by Toagosei Co., Ltd.) and the like can be appropriately selected and used.

  Examples of other ultraviolet curable (meth) acrylate compounds include the following compounds.

  The UV curable polyester acrylate resin can be easily obtained by reacting a monomer such as 2-hydroxyethyl acrylate, glycidyl acrylate or acrylic acid with a hydroxyl group (hydroxy group) or a carboxyl group at the end of the polyester. For example, it describes in Unexamined-Japanese-Patent No. 59-151112.).

  The ultraviolet curable epoxy acrylate resin is obtained by reacting a terminal hydroxyl group (hydroxy group) of an epoxy resin with a monomer such as acrylic acid, acrylic acid chloride, or glycidyl acrylate.

  Examples of the ultraviolet curable polyol acrylate resin include ethylene glycol (meth) acrylate, polyethylene glycol di (meth) acrylate, glycerin tri (meth) acrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, Examples include dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and alkyl-modified dipentaerythritol pentaacrylate.

<Polymerization initiator>
Examples of the polymerization initiator used for the polymerization of the acrylate resin monomer include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylazobisvaleronyl), 2,2 ′. -Azo compounds such as azobis (2-methylbutyronitrile), benzoyl peroxide (BPO), di-tert-butyl hydroperoxide, tert-butyl hydroperoxide, chlorobenzoyl peroxide, dichlorobenzoyl peroxide, bromomethyl peroxide And thermal polymerization initiators such as peroxides such as benzoyl and lauroyl peroxide.

  Examples of the photopolymerization initiator include diethoxyacetophenone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1 (Irgacure 369: manufactured by BASF Japan Ltd.), 2-hydroxy-2-methyl- Such as 1-phenylpropan-1-one, 2-methyl-2-morpholino (4-methylthiophenyl) propan-1-one and 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime Acetophenone or ketal photoinitiator, benzoin, benzoin methyl ether, benzene Benzoin ether photopolymerization initiators such as inethyl ether, benzoin isobutyl ether and benzoin isopropyl ether, benzophenone, 4-hydroxybenzophenone, methyl o-benzoylbenzoate, 2-benzoylnaphthalene, 4-benzoylbiphenyl, 4-benzoylphenyl ether Benzophenone photopolymerization initiators such as acrylated benzophenone and 1,4-benzoylbenzene, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone and 2,4-dichlorothioxanthone And thioxanthone-based photopolymerization initiators.

  Other photopolymerization initiators include ethyl anthraquinone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoylphenylethoxyphosphine oxide, bis (2,4,6-trimethylbenzoyl) phenylphosphine Oxide (Irgacure 819: manufactured by BASF Japan), bis (2,4-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, methylphenylglyoxyester, 9,10-phenanthrene, acridine compound, triazine And compounds and imidazole compounds. Moreover, what has a photopolymerization acceleration effect can also be used individually or in combination with the said photoinitiator. Examples include triethanolamine, methyldiethanolamine, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, ethyl (2-dimethylamino) benzoate, and 4,4′-dimethylaminobenzophenone.

(Urethane acrylate resin)
Next, the urethane acrylate resin suitably used for pattern formation of the clear hard coat layer according to the present invention will be described.

  The urethane acrylate resin can be basically produced by reacting a polyol, a polyisocyanate, and a hydroxy group-containing (meth) acrylate.

<Polyol>
Examples of the polyol include compounds represented by the following general formula (1).

General formula (1)
_{HO (OCH 2 CH 2) n} -CH 2 - _{[(OCH 2 CH 2) p -} (OCH 2) q ] _{-O-CH 2 - (CH 2} CH 2) n OH
In the said general formula (I), n is 0-10, Preferably it is 1-7. p represents an integer of 1 to 40, and q represents an integer of 1 to 70.

<Polyisocyanate>
Examples of the polyisocyanate include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, 1,5-naphthalene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, 3,3'-dimethyl-4,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, 3,3'-dimethylphenylene diisocyanate, 4,4'-biphenylene diisocyanate, 1,6-hexane Diisocyanate, isophorone diisocyanate, methylene bis (4-cyclohexyl isocyanate), 2,2,4-trimethylhexamethylene diisocyanate, bis (2-isocyanate ethyl) Fumarate, 6-isopropyl-1,3-phenyl diisocyanate, 4-diphenylpropane diisocyanate, lysine diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, tetramethylxylylene diisocyanate, 2,5-bis (isocyanatomethyl) -bicyclo [2.2.1] heptane, 2,6-bis (isocyanatomethyl) -bicyclo [2.2.1] heptane, and the like.

<Hydroxy group-containing (meth) acrylate>
Examples of the hydroxy group-containing (meth) acrylate include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenyloxypropyl (meth) ) Acrylate, 1,4-butanediol mono (meth) acrylate, 2-hydroxyalkyl (meth) acryloyl phosphate, 4-hydroxycyclohexyl (meth) acrylate, 1,6-hexanediol mono (meth) acrylate, neopentyl glycol Mono (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolethane di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta ( Data) acrylate, and the like.

  Further, the ultraviolet curable urethane acrylate can be obtained as a commercial product. In addition, the indication containing the alphabet described in the parenthesis represents the pencil hardness of the resin alone measured according to JIS K 5600-5-4.

  Hitachi Chemical 7900-1 (3H), Hitaloid 7909-1 (4H), TA24-195H (3H), Hitaloid 7903-1 (H), Hitaloid 7903-3 (2H), Hitaloid 7903-B (3H) ), HITALOID 7903-4 (H), HITALOID 7906D-3E (4H), HITAROID 7975 (H), HITAROID 7988 (2H), HITAROID 7975D (2H) and the like.

  Further, UV-1700B (4H, number of oligomer functional groups: 10), UV-6300B (2H-3H, number of oligomer functional groups: 7), UV-7550B (F, number of oligomer functional groups: 3), UV manufactured by Nippon Synthetic Chemical Co., Ltd. -7600B (3H, number of oligomer functional groups: 6), UV-7605B (3H-4H, number of oligomer functional groups: 6), UV-7610B (3H, number of oligomer functional groups: 9), UV-7620EA (3H, number of oligomer functional groups: 9), UV-7630B (3H, number of oligomer functional groups: 6), UV-7640B (3H-4H, number of oligomer functional groups: 6-7), UV-7650B (2H, number of oligomer functional groups: 4-5), UV- 6630B (3B-2B, number of oligomer functional groups: 2), UV-7000B (2B, number of oligomer functional groups: 2-3), UV 7510B (B, oligomeric functional groups: 3), UV-7461TE (4H~3B, oligomeric functional groups: 2 to 3), and the like.

  Other commercially available products of urethane acrylate include DIC's V-4000BA, V-4001EA, V-4005, V-4018, V-4025, V-4026, V-4200-70, V-4205, V- 4221, V-4260, V-4263, 15-829, 17-813, S2-371, RS24-241, 17-806, 17-824-9, and the like.

(Organic modified fine particles: Organic / inorganic hybrid materials)
In the present invention, in addition to the acrylate compound and the urethane acrylate compound, an ultraviolet curable organic / inorganic hybrid material (organic modified fine particles) in which an inorganic material and an organic component are combined can be used.

  As the organically modified fine particles, it is particularly preferable to use silica fine particles whose surface is modified with an organic compound having a polymerizable unsaturated group.

  Silica fine particles whose surface is modified with an organic compound having a polymerizable unsaturated group are, for example, usually silanol groups on the surface of silica fine particles having an average particle size of about 0.5 to 500 nm, preferably an average particle size of 1 to 100 nm. It can be obtained by reacting a polymerizable unsaturated group-containing organic compound having a (meth) acryloyl group which is a functional group capable of reacting with the silanol group.

  Examples of such a compound include acrylic acid, acrylic acid chloride, 2-isocyanatoethyl acrylate, glycidyl acrylate, 2,3-iminopropyl acrylate, 2-hydroxyethyl acrylate, and acryloyloxypropyltrimethoxysilane. Etc. and methacrylic acid derivatives corresponding to these acrylic acid derivatives can be used. These acrylic acid derivatives and methacrylic acid derivatives may be used alone or in combination of two or more.

  Examples of such organically modified fine particles include OPSTAR (registered trademark) Z7540, Z7521, Z7527 (pencil hardness: 4H), Z7541 (pencil hardness: 3H), KZ6445A (pencil hardness: 4H), and KZ6412 (pencil) manufactured by JSR. Hardness: 3H) or the like can be preferably used.

[Inorganic fine particles]
In the formation of the clear hard coat layer according to the present invention, by allowing the inorganic fine particles to coexist with the resin component described above, the hardness of each resin composition can be increased and adjusted to a desired hardness.

Examples of inorganic fine particles applicable to the present invention include SiO ₂ , Al ₂ O ₃ , TiO ₂ , ZrO ₂ , ZnO, SnO ₂ , In ₂ O ₃ , BaO, SrO, CaO, MgO, VO ₂ , V _{2. O 5, CrO 2, MoO 2} , MoO 3, MnO 2, Mn 2 O 3, WO 3, LiMn 2 O 4, Cd 2 SnO4, CdIn 2 O 4, Zn 2 SnO 4, ZnSnO 3, Zn 2 In 2 O ₅ , Cd ₂ SnO ₄ , CdIn ₂ O ₄ , Zn ₂ SnO ₄ , ZnSnO ₃ , Zn ₂ In ₂ O _{5 and the} like. Further, as inorganic fine particles, mica groups such as natural mica and synthetic mica, tabular particles such as talc, teniolite, montmorillonite, saponite, hectorite, synthetic smectite, zirconium phosphate represented by MgO.4SiO.H ₂ O are used. It may be used. Examples of the natural mica include muscovite, soda mica, phlogopite, biotite, sericite, and the like. Further, as the synthetic mica, non-swelling mica such as fluor-phlogopite mica KMg ₃ (AlSi ₃ O ₁₀ ) F ₂ , potash tetrasilicon mica KMg _2.5 (Si ₄ O ₁₀ ) F ₂ ; and Na tetrasilic mica NaMg _2.5 (Si ₄ O ₁₀ ) F ₂ , Na or Li Teniolite (Na, Li) Mg ₂ Li (Si ₄ O ₁₀ ) F ₂ , Montmorillonite Na or Li Hectorite (Na, Li) _1/8 Examples thereof include swellable mica such as Mg _2/5 Li _1/8 (Si ₄ O ₁₀ ) F ₂ . These inorganic particles may be used alone or in combination of two or more. Among these, silicon dioxide (SiO ₂ ) is particularly preferable.

  The number average particle size (primary particle size) of the inorganic fine particles is preferably in the range of 1 to 200 nm, and more preferably in the range of 3 to 100 nm.

  As content of the inorganic fine particle in a resin composition, it is preferable to exist in the range of 1.0-30 mass%, More preferably, it exists in the range of 5.0-20 mass%.

  Since the hardness in the resin composition according to the present invention decreases with the addition of inorganic fine particles, two or more types of resin compositions can be controlled by controlling the combination of the resin having various hardness and the addition amount of the inorganic fine particles. Thus, a desired hardness combination can be achieved.

〔solvent〕
In the clear hard coat layer according to the present invention, it is preferable that the above-described resin composition is dissolved in a solvent to prepare a coating liquid for forming a hard coat layer, and a pattern having different regions is formed by a wet coating method. is there.

  The solvent for dissolving the acrylate resin composition and the urethane acrylate resin composition is not particularly limited, but alcohols such as methanol, ethanol, propanol, isopropyl alcohol, ethylene glycol, propylene glycol, and terpenes such as α- or β-terpineol. , Ketones such as acetone, methyl ethyl ketone, cyclohexanone, N-methyl-2-pyrrolidone, diethyl ketone, 2-heptanone, 4-heptanone, aromatic hydrocarbons such as toluene, xylene, tetramethylbenzene, cellosolve, methyl cellosolve , Ethyl cellosolve, carbitol, methyl carbitol, ethyl carbitol, butyl carbitol, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene Glycol dipropyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol dipropyl ether, triethylene glycol Glycol ethers such as monomethyl ether and triethylene glycol monoethyl ether, ethyl acetate, butyl acetate, cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, carbitol acetate, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate , Propi Glycol monoethyl ether acetate, 2-methoxyethyl acetate, cyclohexyl acetate, 2-ethoxyethyl acetate, 3-methoxybutyl acetate, ethyl 3-ethoxypropionate, methyl benzoate, N, N-dimethylacetamide, Amides such as N, N-dimethylformamide may be mentioned. These solvents may be used alone or in combination of two or more.

[Other additives for clear hard coat layer]
In addition to the above description, various additives such as a surfactant, an ultraviolet absorber, and a stabilizer can be added to the clear hard coat layer according to the present invention.

[Method of forming clear hard coat layer]
(Application and pattern formation method)
As a method for forming a clear hard coat layer having patterns constituting different regions in the plane direction according to the present invention as exemplified in FIGS. 2 to 4, a resin component, a polymerization initiator or polyisocyanate, inorganic fine particles, After mixing and dissolving the components of each resin composition such as a solvent to prepare a resin composition-forming coating solution, a gravure coater, spinner coater, wire bar coater, roll coater, reverse coater, extrusion coater, air doctor A clear hard coat layer having a pattern shape is formed on a resin base material using a known wet coating method such as a coater, spray coating, or ink jet method. Furthermore, from the viewpoint of forming a denser pattern with high accuracy, an inkjet method or a method using a gravure coater is preferable, and an inkjet method is particularly preferable.

  Hereinafter, a pattern forming method using the inkjet method will be described.

  FIG. 5 is a schematic diagram illustrating an example of a method for forming a clear hard coat layer having a pattern using an inkjet method.

  FIG. 5A shows a method of forming the clear hard coat layer (3) having the hexagonal independent pattern exemplified in FIG. 3 on the resin base material (2) by the ink jet method.

  On the resin base material (2) transported in the transport direction (D) from the left to the right side of the paper, two types of coating solutions for forming resin compositions having different hardnesses from two inkjet heads (H1 and H2). A pattern having a configuration in which a continuous partition wall structure is formed by using a resin structure (5) as a peripheral portion of the resin structure (4) that is ejected as ink droplets at predetermined positions. Form. Next, ultraviolet rays are irradiated from an ultraviolet irradiation lamp (UV) installed on the downstream side, the formed pattern is cured, and a clear hard coat layer (3) is formed.

  FIG. 5B is a cross-sectional view, and two types of resin compositions are ejected as ink droplets (I) from a nozzle (N) provided on the bottom surface of the inkjet head (H1 and H2). Form a pattern.

  The ink-jet head shown in FIG. 5 is a line system fixedly installed at a position orthogonal to the transport direction of the resin base material, but even if it is a serial head system in which the head moves horizontally with respect to the transport direction Good.

  FIG. 6 is a schematic diagram illustrating another example of a method for forming a clear hard coat layer having a pattern using an inkjet method.

  In the pattern forming method shown in FIG. 6, a station 1 (S1) composed of an inkjet head (H1) and an ultraviolet irradiation lamp (UV1), and an inkjet head (H2) and an ultraviolet irradiation lamp (UV2) further downstream. Station 2 (S2) configured by arranging the respective resin compositions, the respective coating compositions for forming the resin composition are individually ejected, and patterns having different hardnesses can be formed while changing the curing conditions.

  By applying such an ink jet system as shown in FIG. 6, a resin structure (4) composed of hexagons is formed by an ink jet head (H1) using two kinds of composition forming coating liquids. A resin structure (5) having a continuous partition wall structure is formed by an inkjet head (H2), and further, irradiation conditions of the ultraviolet irradiation lamp (UV1) and the ultraviolet irradiation lamp (UV2) are controlled, and the resin structure (4 ) And the amount of ultraviolet rays received by the resin structure (5), a pattern having a hardness balance prescribed in the present invention can be formed even if the resin composition has a similar hardness as the resin component. Can do. In this method, it is an essential condition to form a resin structure with higher hardness first.

  The ink jet heads (H1 and H2) applicable in the present invention are not particularly limited. For example, the ink pressure chamber has a vibration plate provided with a piezoelectric element, and the pressure change of the ink pressure chamber by the vibration plate. It may be a shear mode type (piezo-type) ink jet head that ejects the ejected liquid with a heating element, and has a heating element, and the rapid volume due to film boiling of the coating liquid for resin composition formation by the heat energy from this heating element A thermal-type inkjet head that discharges the resin composition-forming coating liquid as an injection liquid from a nozzle may be used.

<< Method for producing gas barrier film >>
The gas barrier layer according to the present invention is preferably formed as a gas barrier layer having a metal oxide (hereinafter also referred to as a first gas barrier layer) in chemical vapor deposition or physical vapor deposition. A coating solution for forming a polysilazane layer containing polysilazane is applied and dried as a second gas barrier layer thereon to form a precursor layer, and then the precursor layer is subjected to a modification process using vacuum ultraviolet light. A method of forming the second gas barrier layer by applying the above is preferable.

(Formation of first gas barrier layer)
In the present invention, as a method for forming the first gas barrier layer, a vapor deposition method may be mentioned. More specifically, a physical vapor deposition method (PVD method) or a chemical vapor deposition method (CVD method) may be used. Can be mentioned.

  The physical vapor deposition method (PVD method) is a method of depositing a target material, for example, a thin film such as a carbon film, on the surface of the material in a gas phase by a physical method. Examples thereof include a DC sputtering method, an RF sputtering method, an ion beam sputtering method, and a magnetron sputtering method, a vacuum deposition method, and an ion plating method.

  The chemical vapor deposition (CVD) method is a method of depositing a film by a chemical reaction on the surface of the substrate or in the vapor phase by supplying a raw material gas containing a target thin film component onto the substrate. It is. In addition, for the purpose of activating the chemical reaction, there is a method of generating plasma or the like. Known CVD such as thermal CVD method, catalytic chemical vapor deposition method, photo CVD method, vacuum plasma CVD method, atmospheric pressure plasma CVD method, etc. The method etc. are mentioned. Although not particularly limited, it is preferable to apply a plasma CVD method such as a vacuum plasma CVD method or an atmospheric pressure plasma CVD method from the viewpoint of film forming speed and processing area.

  For example, if a silicon compound is used as a raw material compound and oxygen is used as the decomposition gas, silicon oxide is generated. This is because highly active charged particles and active radicals exist in the plasma space at a high density, so that multistage chemical reactions are accelerated at high speed in the plasma space, and the elements present in the plasma space are thermodynamic. This is because it is converted into an extremely stable compound in a very short time.

Examples of the chemical vapor deposition method (CVD method) applicable in the present invention include, for example, JP 2006-321127 A, JP 2007-59244 A, JP 2012-131194 A, 2013-28170, The methods described in JP 2014-141707 A, JP 2014-189891 A, and the like can be referred to, and a conventionally known sputtering method can also be applied as a sputtering method. And a method of forming SiO ₂ as a target using an L-430S-FHS sputtering apparatus manufactured by Anerva.

  Among the methods for forming the gas barrier layer, it is preferable to employ a discharge plasma chemical vapor deposition method (PE-CVD method) from the viewpoint that the composition can be precisely controlled, and further, a gas barrier layer forming component is used. A discharge plasma chemical vapor deposition method (hereinafter referred to as a plasma CVD method or a PE-CVD method) having a discharge space between rollers to which a magnetic field is applied using a raw material gas is preferable.

  Hereinafter, as a representative example of the gas barrier layer formation, the details of the gas barrier layer formation method by the plasma CVD method will be described.

  When generating plasma in the plasma CVD method, it is preferable to generate a plasma discharge in a space between a plurality of film forming rollers. A pair of film forming rollers is used, and a substrate is provided for each of the pair of film forming rollers. It is more preferable that a plasma is generated by disposing and discharging between a pair of film forming rollers. In this way, by using a pair of film forming rollers, placing a base material on the pair of film forming rollers, and discharging between the pair of film forming rollers, one film forming roller In addition to forming the surface portion of the base material present on the substrate, the surface portion of the base material existing on the other film forming roller can be simultaneously formed. The film formation rate can be doubled as compared with a method using a single roller or a plasma CVD method using a flat plate electrode without using a roller.

  Further, when discharging between the pair of film forming rollers in this way, it is preferable to reverse the polarities of the pair of film forming rollers alternately. Further, the film forming gas used in such a plasma CVD method preferably includes an organic silicon compound and oxygen, and the content of oxygen in the film forming gas is determined by the organosilicon compound in the film forming gas. It is preferable that the amount of oxygen be less than the theoretical oxygen amount necessary for complete oxidation. In the gas barrier film of the present invention, the gas barrier layer is preferably a layer formed by a continuous film forming process.

  Moreover, in the gas barrier film of this invention, from a viewpoint of productivity, the clear hard-coat layer (3) which has a pattern which comprises a respectively different area | region in the surface direction formed on the resin base material (2) by the roll to roll system A gas barrier layer (6) is formed on the substrate. An apparatus that can be used for forming the gas barrier layer (6) by such a plasma CVD method is not particularly limited, and includes at least a pair of film forming rollers and a plasma power source, and It is preferable that the apparatus has a configuration capable of discharging between a pair of film forming rollers. For example, when a CVD film forming apparatus having a discharge space between rollers to which a magnetic field shown in FIG. 7 is applied is used. It is preferable because it can be manufactured by a roll-to-roll method using a plasma CVD method.

  Hereinafter, with reference to FIG. 7, the resin base material (2) having the clear hard coat layer (3) formed by the above method is disposed on a pair of film forming rollers and discharged between the pair of film forming rollers. A method for forming the first gas barrier layer by the plasma CVD method for generating plasma will be described in more detail.

  FIG. 7 is a schematic view showing an example of a manufacturing apparatus having a discharge space between rollers to which a magnetic field that can be suitably used for forming the first gas barrier layer is formed on the clear hard coat layer. FIG.

  The CVD film forming apparatus (31) shown in FIG. 7 includes a feed roller (32), a transport roller (33, 34, 35 and 36), a film forming roller (39 and 40), and a gas supply pipe (41). And a power source for generating plasma (42), a magnetic field generator (43 and 44) installed inside the film forming rollers (39 and 40), and a winding roller (45). In such a manufacturing apparatus, at least the film forming rollers (39 and 40), the gas supply pipe (41), the plasma generation power source (42), and the magnetic field generators (43 and 44) are illustrated. It is arranged in the omitted vacuum chamber. Further, in such a manufacturing apparatus (31), the vacuum chamber (not shown) is connected to a vacuum pump (not shown), and the pressure in the vacuum chamber can be appropriately adjusted by the vacuum pump. It has become.

  In such a CVD film-forming apparatus (31), each of the film-forming roller (39) and the film-forming roller (40), which are a pair of film-forming rollers, can function as a pair of counter electrodes. The film forming rollers are each connected to a plasma generating power source (42). For this reason, in such a CVD film forming apparatus (31), electric power is supplied from the plasma generating power source (42) to discharge into the space between the film forming roller (39) and the film forming roller (40). Thus, plasma can be generated in the space between the film formation roller (39) and the film formation roller (40). In addition, when using the film-forming roller (39) and the film-forming roller (40) as electrodes as described above, the material and design may be changed as appropriate so that they can also be used as electrodes. In such a CVD film forming apparatus (31), the film forming roller (39) and the film forming roller (40), which are a pair of film forming rollers, have the same central axis as illustrated in FIG. It is preferable to arrange so as to be substantially parallel on a plane. By arranging the pair of film formation rollers (39) and film formation rollers (40) in parallel as described above, the film formation rate can be doubled and a film having the same structure can be formed. High production efficiency can be obtained.

  In such a CVD film forming apparatus, it is possible to form the gas barrier layer (6) on the clear hard coat layer (3) of the resin base material (2 + 3) by the CVD method. 39) while depositing the gas barrier layer (6) component on the surface of the clear hard coat layer (3) of the resin substrate (2), and also on the film forming roller (40) Since the component of the gas barrier layer (6) can be deposited again on the + clear hard coat layer (3) + the gas barrier layer (6), each constituent element is formed on the surface of the clear hard coat layer (3). The gas barrier layer (6) having a continuously changing structure can be efficiently formed at a double film formation rate.

  Inside the film forming rollers (39 and 40), magnetic field generators (43 and 44) fixed so as not to rotate even when the film forming rollers (39 and 40) rotate are provided, respectively.

  The magnetic field generators (43 and 44) provided on the film forming rollers (39 and 40), respectively, are the magnetic field generator (43) provided on one film forming roller (39) and the other film forming roller (40). It is preferable to arrange the magnetic poles so that the magnetic field lines do not cross between the magnetic field generators (44) provided on the magnetic field generator and the magnetic field generators (43 and 44) form a substantially closed magnetic circuit. By providing such a magnetic field generator (43 and 44), it is possible to promote the formation of a magnetic field in which magnetic lines of force swell near the opposing surface of each film forming roller (39 and 40). Since plasma is easily converged, it is excellent in that the film formation efficiency can be improved.

  The magnetic field generators (43 and 44) provided on the film forming rollers (39 and 40) are respectively provided with racetrack-shaped magnetic poles that are long in the roller axis direction, and one magnetic field generator (43) and the other magnetic field generator (43). The magnetic poles are preferably arranged so that the magnetic poles facing the magnetic field generator (44) have the same polarity. By providing such a magnetic field generator (43 and 44), the roller facing the facing space (discharge region) along the length direction of the roller shaft without straddling the roller-side magnetic field generator facing the magnetic field lines. A racetrack-like magnetic field can be easily formed in the vicinity of the surface, and plasma can be focused on the magnetic field, so that it has a wide clear hard coat layer (3) wound along the roller width direction. It is excellent in that the gas barrier layer 4 which is a vapor deposition film can be efficiently formed using the resin base material (2).

  As the film forming rollers (39 and 40), known rollers can be appropriately used. As such a film-forming roller (39 and 40), it is preferable to use a roller having the same diameter as each roller from the viewpoint of more efficiently forming a thin gas barrier layer (6). Further, the diameter of the film forming rollers (39 and 40) is preferably in the range of 300 to 1000 mmφ, particularly in the range of 300 to 700 mmφ, from the viewpoint of discharge conditions, chamber space, and the like. If the diameter of the film forming roller is 300 mmφ or more, the plasma discharge space will not be reduced, so there will be no deterioration in productivity, and the total amount of heat of plasma discharge will be reduced in a short time in the clear hard coat layer (3) or resin substrate ( Since it can avoid that it applies to 2), damage to the clear hard coat layer (3) and the resin base material (2) can be reduced, which is preferable. On the other hand, if the diameter of the film forming roller is 1000 mmφ or less, it is preferable because practicality can be maintained in terms of apparatus design including uniformity of plasma discharge space.

  In such a CVD film-forming apparatus (31), a pair of film-forming rollers (film-forming roller 39 and film-forming roller 40) are provided so that the surfaces of the resin base material (2 + 3) having the clear hard coat layer face each other. A resin base material (2 + 3) having a clear hard coat layer is disposed thereon. By disposing the resin base material (2 + 3) having the clear hard coat layer in this manner, discharge is generated in the facing space between the film formation roller (39) and the film formation roller (40) to generate plasma. At this time, it becomes possible to simultaneously form the respective surfaces of the resin base material (2 + 3) having the hard coat layer existing between the pair of film forming rollers. That is, according to such a CVD film forming apparatus, the gas barrier layer component is deposited on the surface of the resin base material (2 + 3) having the clear hard coat layer on the film forming roller (39) by the plasma CVD method. Furthermore, since the gas barrier layer component can be deposited on the film formation roller (40), the first gas barrier layer (6) is efficiently formed on the surface of the resin base material (2 + 3) having the clear hard coat layer. It becomes possible to form well.

  As the feed roller (32) and the transport rollers (33, 34, 35, and 36) used in such a CVD film forming apparatus, known rollers can be appropriately used. Further, the winding roller (45) is also capable of winding the gas barrier film (2 + 3 + 6) in which the gas barrier layer (6) is formed on the resin base material (2 + 3) having the clear hard coat layer. Well, not particularly limited, a known roller can be used as appropriate.

  Further, as the gas supply pipe (41) and the vacuum pump (not shown), those capable of supplying or discharging the raw material gas at a predetermined speed can be used as appropriate.

  In addition, the gas supply pipe (41), which is a gas supply means, is provided in one of the facing spaces (discharge region; film formation zone) formed between the film formation roller (39) and the film formation roller (40). It is preferable that a vacuum pump (not shown) as a vacuum exhaust means is provided in the other of the opposed spaces. Thus, by arranging the gas supply pipe (41) as the gas supply means and the vacuum pump (not shown) as the evacuation means, the film is provided between the film formation roller (39) and the film formation roller (40). This is a preferable aspect in that the deposition gas can be efficiently supplied to the opposing space to be formed, and the deposition efficiency can be improved.

  Furthermore, as the plasma generating power source (42), a conventionally known power source of a plasma generating apparatus can be used. Such a plasma generating power source (42) supplies power to the film forming roller (39) and the film forming roller (40) connected thereto, and uses them as a counter electrode for discharging. Is possible. Since such a plasma generating power source (42) can efficiently perform plasma CVD processing, the polarity of the pair of film forming rollers (39 and 40) can be alternately reversed. It is preferable to use a thing (AC power supply etc.). In addition, as such a plasma generation power source (42), since it is possible to perform plasma CVD processing efficiently, the applied power can be in the range of 100 W to 10 kW, and the AC frequency is What can be set within the range of 50 Hz to 500 kHz is more preferable. Moreover, as a magnetic field generator (43 and 44), a well-known magnetic field generator can be used suitably.

  Using such a CVD film forming apparatus (31) shown in FIG. 7, for example, the type of source gas, the power of the electrode drum of the plasma generator, the pressure in the vacuum chamber, the diameter of the film forming roller, and the film (base) The gas barrier layer according to the present invention can be formed by appropriately adjusting the conveying speed of the material. That is, using the CVD film forming apparatus (31) shown in FIG. 7, a film forming gas (raw material gas or the like) is supplied into the vacuum chamber while discharging between a pair of film forming rollers (film forming rollers 39 and 40). The film-forming gas (raw material gas, etc.) is decomposed by plasma, and the surface of the clear hard coat layer (3) held by the resin base material (2) on the film-forming roller (39) is formed. A gas barrier layer (6) is formed on the surface of the clear hard coat layer (3) held by the resin base material (2) on the roller (40) by a plasma CVD method. At this time, a racetrack-shaped magnetic field is formed in the vicinity of the roller surface facing the facing space (discharge region) along the length direction of the roller axis of the film forming rollers (39 and 40), and the plasma is focused on the magnetic field. . For this reason, when the resin base material (2) passes through the point A of the film forming roller (39) and the point B of the film forming roller (40) in FIG. 7, the maximum value of the carbon distribution curve in the gas barrier layer. Is formed. In contrast, the resin base material (2 + 3) having the clear hard coat layer passes through points C1 and C2 of the film forming roller (39) and points C3 and C4 of the film forming roller (40) in FIG. In doing so, a local minimum of the carbon distribution curve is formed in the gas barrier layer. For this reason, five extreme values are usually generated for the two film forming rollers.

  The film forming gas (raw material gas, etc.) used for forming the gas barrier layer (6) according to the present invention and supplied from the gas supply pipe (41) to the discharge space includes a raw material gas, a reactive gas, a carrier gas, and a discharge gas. Can be used alone or in admixture of two or more.

  The source gas in the film forming gas used for forming the gas barrier layer (6) can be appropriately selected and used depending on the material of the gas barrier layer 1b to be formed. As such a source gas, for example, an organic silicon compound containing silicon or an organic compound gas containing carbon can be used. Examples of such organosilicon compounds include hexamethyldisiloxane (HMDSO), hexamethyldisilane (HMDS), 1,1,3,3-tetramethyldisiloxane, vinyltrimethylsilane, methyltrimethylsilane, methylsilane, and dimethyl. Silane, trimethylsilane, diethylsilane, propylsilane, phenylsilane, vinyltriethoxysilane, vinyltrimethoxysilane, tetramethoxysilane (TMOS), tetraethoxysilane (TEOS), phenyltrimethoxysilane, methyltriethoxysilane, octamethyl Examples include cyclotetrasiloxane. Among these organosilicon compounds, hexamethyldisiloxane and 1,1,3,3-tetramethyldisiloxane are preferable from the viewpoint of handling properties of the compound and gas barrier properties of the resulting gas barrier layer 4. These organosilicon compounds can be used alone or in combination of two or more. Examples of the organic compound gas containing carbon include methane, ethane, ethylene, and acetylene. As these organosilicon compound gas and organic compound gas, an appropriate source gas is selected according to the type of the gas barrier layer (6) to be formed.

  Further, as the film forming gas, a reactive gas may be used together with the raw material gas. As such a reactive gas, a gas that reacts with the raw material gas to become an inorganic compound such as an oxide or a nitride can be appropriately selected and used. As a reaction gas for forming an oxide, for example, oxygen or ozone can be used. Moreover, as a reactive gas for forming nitride, nitrogen and ammonia can be used, for example. These reaction gases can be used singly or in combination of two or more. For example, when forming an oxynitride, a reaction gas for forming an oxide and a nitride are formed. It can be used in combination with a reaction gas.

  As the film forming gas, a carrier gas may be used as necessary in order to supply the source gas into the vacuum chamber. Further, as a film forming gas, a discharge gas may be used as necessary in order to generate plasma discharge. As such carrier gas and discharge gas, known ones can be used as appropriate, and for example, a rare gas such as helium, argon, neon, xenon, or hydrogen gas can be used.

  When such a film-forming gas contains a source gas and a reactive gas, the ratio of the source gas and the reactive gas is the reaction gas that is theoretically necessary for completely reacting the source gas and the reactive gas. It is preferable not to make the ratio of the reaction gas excessive rather than the ratio of the amount. By not making the ratio of the reaction gas excessive, the formed gas barrier layer (6) is excellent in that excellent barrier properties and bending resistance can be obtained.

  Moreover, when the film-forming gas contains an organosilicon compound and oxygen, it is preferable that the amount be less than the theoretical oxygen amount necessary for complete oxidation of the entire amount of the organosilicon compound in the film-forming gas.

  Moreover, although the pressure (vacuum degree) in a vacuum chamber can be suitably adjusted according to the kind etc. of source gas, it is preferable to set it as the range of 0.5-50 Pa.

  Further, in such a plasma CVD method, since an electric discharge occurs between the film forming roller (39) and the film forming roller (40), an electrode drum (in this embodiment, connected to the plasma generating power source (42)). The applied power applied to the film forming rollers 39 and 40 can be adjusted as appropriate according to the type of the source gas, the pressure in the vacuum chamber, etc. It is preferable to be within a range of -10 kW.

  Although the conveyance speed (line speed) of the resin base material (2 + 3) having the clear hard coat layer can be appropriately adjusted according to the type of raw material gas, the pressure in the vacuum chamber, and the like, 0.25 to 100 m / min. Is preferably within the range of 0.5 to 20 m / min. If the line speed is 0.25 m / min or more, generation of wrinkles due to heat in the resin substrate can be effectively suppressed. On the other hand, if it is 100 m / min or less, it is excellent in that a sufficient layer thickness can be secured as a gas barrier layer while maintaining sufficient productivity.

  As described above, as a more preferable aspect of the present embodiment, the gas barrier layer (6) according to the present invention has a long clear hard coat layer in the plasma CVD apparatus having the counter roll electrode shown in FIG. It is a preferable aspect to form a film by a roll-to-roll plasma CVD method using a resin base material (2 + 3).

  As described above, in the method of forming the gas barrier layer (6) by continuously passing the long resin substrate (2) through the plasma discharge space, The gas barrier film in which the gas barrier layer (6) is formed passes through the resin base material (2) or the resin base material (2), and is exposed to a high temperature environment, thereby affecting the effects of thermal expansion and contraction. Therefore, due to the stress difference between the resin substrate and the gas barrier layer that are continuously conveyed, creases and wrinkles are generated, which hinders stable conveyance and formation of a highly uniform gas barrier layer. In the present invention, with respect to such a problem, at the time of the CVD film forming process, two or more kinds of resin compositions having different hardnesses are used on the resin base material (2) in advance, and patterns each forming different regions in the plane direction. By providing the clear hard coat layer having, the stress due to thermal expansion and contraction can be relieved even in a discharge space at a high temperature, thereby enabling stable conveyance.

(Formation of second gas barrier layer by wet coating method)
In the gas barrier film of the present invention, a polysilazane layer-forming coating solution containing polysilazane is further applied on the first gas barrier layer and dried to form a precursor layer. The hybrid gas barrier configuration in which the second gas barrier layer is formed by performing a modification treatment with light covers fine cracks (cracks) generated on the first gas barrier layer, and higher order. It is preferable in that the gas barrier property can be obtained.

  Specifically, a gas barrier layer-forming coating solution containing polysilazane is applied and dried on the first gas barrier layer (6), and silicon oxynitride as shown in FIG. A method of forming the second gas barrier layer (7) as a component is preferable, and more preferably, a polysilazane-containing coating solution for forming a polysilazane layer is applied and dried by a wet coating method, and a wavelength of 200 nm is applied to the formed coating film. Applying a method of forming the second gas barrier layer (7) by irradiating the following vacuum ultraviolet light (VUV light, excimer light) and applying a modification treatment to the formed coating film is a vacuum apparatus. It is preferable from the viewpoint that a gas barrier layer can be easily formed without using large-scale equipment such as the above.

  The thickness of the second gas barrier layer (7) formed by the wet coating method is preferably in the range of 1 to 500 nm, more preferably in the range of 10 to 300 nm. If the thickness of the second gas barrier layer is 1 nm or more, the desired gas barrier performance can be exhibited, and if it is 500 nm or less, film quality degradation such as generation of cracks in a dense silicon oxynitride film can be achieved. Can be prevented.

<Polysilazane>
The polysilazane used for forming the second gas barrier layer (7) according to the present invention is a polymer having a silicon-nitrogen bond in the molecular structure, and is a polymer that is a precursor of silicon oxynitride. Although there is no restriction | limiting in particular, It is preferable that it is a compound which has a structure represented by the following general formula (I).

In the general formula (I), R ₁ , R ₂ and R ₃ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, aryl group, vinyl group or (trialkoxysilyl) alkyl group. . At this time, R ₁ , R ₂ and R ₃ may be the same or different. Here, as an alkyl group, a C1-C8 linear, branched or cyclic alkyl group is mentioned. More specifically, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, neopentyl group, n -Hexyl group, n-heptyl group, n-octyl group, 2-ethylhexyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group and the like. Moreover, as an aryl group, a C6-C30 aryl group is mentioned. More specifically, non-condensed hydrocarbon groups such as phenyl group, biphenyl group, terphenyl group; pentarenyl group, indenyl group, naphthyl group, azulenyl group, heptaenyl group, biphenylenyl group, fluorenyl group, acenaphthylenyl group, preadenenyl group A condensed polycyclic hydrocarbon group such as an Can be mentioned. Examples of the (trialkoxysilyl) alkyl group include an alkyl group having 1 to 8 carbon atoms having a silyl group substituted with an alkoxy group having 1 to 8 carbon atoms. More specifically, 3- (triethoxysilyl) propyl group, 3- (trimethoxysilyl) propyl group and the like can be mentioned. The substituent optionally present in R _{1 to} R ₃ is not particularly limited. For example, an alkyl group, a halogen atom, a hydroxy group (—OH), a mercapto group (—SH), a cyano group (—CN), There are a sulfo group (—SO ₃ H), a carboxy group (—COOH), a nitro group (—NO ₂ ), and the like. Incidentally, the optional substituents may not be the same as R ₁ to R ₃ to be replaced. For example, when R _{1 to} R ₃ are alkyl groups, they are not further substituted with an alkyl group. Of these, R ₁ , R ₂ and R ₃ are preferably a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a phenyl group, a vinyl group, 3 -(Triethoxysilyl) propyl group or 3- (trimethoxysilylpropyl) group.

  Moreover, in the said general formula (I), n is an integer, and it is preferable that the polysilazane which has a structure represented by general formula (I) is defined so that it may have a number average molecular weight of 150-150,000 g / mol.

In the compound having the structure represented by the general formula (I), one of preferred embodiments is perhydropolysilazane in which all of R ₁ , R ₂ and R ₃ are hydrogen atoms.

  Perhydropolysilazane is presumed to have a linear structure and a ring structure centered on a 6-membered ring and an 8-membered ring. Its molecular weight is about 600 to 2000 in terms of number average molecular weight (Mn) (gel Polystyrene conversion by permeation chromatography), which is a liquid or solid substance.

  Polysilazane is commercially available in the form of a solution dissolved in an organic solvent, and a commercially available product can be used as it is as a polysilazane-containing coating solution. Examples of commercially available polysilazane solutions include Aquamica (registered trademark) NN120-10, NN120-20, NAX120-20, NN110, NN310, NN320, NL110A, NL120A, NL120-20, and NL150A manufactured by AZ Electronic Materials Co., Ltd. NP110, NP140, SP140 and the like.

  As an organic solvent for preparing a coating liquid containing polysilazane, it is preferable to avoid using an alcohol or water-containing one that easily reacts with polysilazane. Examples of applicable organic solvents include hydrocarbon solvents such as aliphatic hydrocarbons, alicyclic hydrocarbons, and aromatic hydrocarbons, ethers such as halogenated hydrocarbon solvents, aliphatic ethers, and alicyclic ethers. Specific examples include hydrocarbons such as pentane, hexane, cyclohexane, toluene, xylene, solvesso and turben, halogen hydrocarbons such as methylene chloride and trichloroethane, and ethers such as dibutyl ether, dioxane and tetrahydrofuran. These organic solvents may be selected according to purposes such as the solubility of polysilazane and the evaporation rate of the organic solvent, and a plurality of organic solvents may be mixed.

  The concentration of polysilazane in the gas barrier layer-forming coating solution containing polysilazane varies depending on the thickness of the gas barrier layer to be formed and the pot life of the coating solution, but is preferably in the range of 0.2 to 35% by mass. is there.

  In order to promote the modification of polysilazane to silicon oxynitride, an amine catalyst, a Pt compound such as Pt acetylacetonate, a Pd compound such as propionic acid Pd, and an Rh compound such as Rh acetylacetonate are used in a coating solution for forming a gas barrier layer. A metal catalyst such as can also be added. In the present invention, it is particularly preferable to use an amine catalyst. Specific amine catalysts include N, N-diethylethanolamine, N, N-dimethylethanolamine, triethanolamine, triethylamine, 3-morpholinopropylamine, N, N, N ′, N′-tetramethyl-1 , 3-diaminopropane, N, N, N ′, N′-tetramethyl-1,6-diaminohexane and the like.

  The addition amount of these catalysts is preferably in the range of 0.1 to 10% by mass and more preferably in the range of 0.2 to 5% by mass with respect to the polysilazane contained in the gas barrier layer forming coating solution. Is more preferable, and it is still more preferable that it exists in the range of 0.5-2 mass%. By setting the addition amount of the catalyst within the range specified above, excessive silanol formation due to rapid progress of the reaction, reduction in film density, increase in film defects, and the like can be avoided.

  Moreover, in order to accelerate | stimulate modification | denaturation of polysilazane to silicon oxide, a metal alkoxide compound can also be added to the coating liquid for gas barrier layer formation.

  As the metal alkoxide compound, a commercially available product or a synthetic product may be used. Specific examples of commercially available products include, for example, AMD (aluminum diisopropylate monosec-butyrate), ASBD (aluminum secondary butyrate), ALCH (aluminum ethyl acetoacetate diisopropylate), ALCH-TR (aluminum tris). Ethyl acetoacetate), aluminum chelate M (aluminum alkyl acetoacetate / diisopropylate), aluminum chelate D (aluminum bisethylacetoacetate / monoacetylacetonate), aluminum chelate A (W) (aluminum trisacetylacetonate) , Manufactured by Kawaken Fine Chemical Co., Ltd.), Preneact (registered trademark) AL-M (acetoalkoxy aluminum diisopropylate, manufactured by Ajinomoto Fine Chemical Co., Ltd.), Moth Chicks series (manufactured by Matsumoto Fine Chemical Co., Ltd.) and the like.

  In addition, when using a metal alkoxide compound, it is preferable to mix with the solution containing polysilazane in inert gas atmosphere. This is to prevent the metal alkoxide compound from reacting with moisture and oxygen in the atmosphere and causing intense oxidation. The density | concentration of the metal alkoxide compound in a coating liquid exists in the range of 30-80 mass% with respect to polysilazane, More preferably, it is in the range of 40-70 mass%.

  As a method for applying the polysilazane layer-forming coating solution containing polysilazane, any appropriate wet coating method can be appropriately selected and employed. Specific examples include a roller coating method, a flow coating method, an ink jet method, a spray coating method, a printing method, a dip coating method, a casting film forming method, a bar coating method, and a gravure printing method.

  The thickness of the coating film can be appropriately set according to the purpose. For example, the thickness of the coating film is preferably in the range of 50 nm to 2 μm as the thickness after drying, more preferably in the range of 70 nm to 1.5 μm, and in the range of 100 nm to 1 μm. Is more preferable.

<Excimer light treatment>
The gas barrier layer formed by the wet coating method according to the present invention modifies at least a part of polysilazane into silicon oxynitride by irradiating the layer containing polysilazane with vacuum ultraviolet rays (VUV).

In vacuum ultraviolet irradiation step in the present invention, it is preferable that the illuminance of the vacuum ultraviolet rays in the coated film surface for receiving the polysilazane coating film is in the range of 30~200mW / cm ^2, within the range of 50~160mW / cm ² More preferably. If it is 30 mW / cm ² or more, there is no concern about the reduction of the reforming efficiency. If it is 200 mW / cm ² or less, the coating film does not ablate, and the resin base material or the formed clear hard coat layer can be used. This is preferable because it does not cause damage.

Irradiation energy amount of the VUV in the polysilazane coating film surface is preferably in the range of 200~10000mJ / cm ^2, and more preferably in a range of 500~5000mJ / cm ^2. If it is 200 mJ / cm ² or more, the modification can be sufficiently performed, and if it is 10000 mJ / cm ² or less, it is not excessively reformed, and cracking and thermal deformation of the resin substrate can be prevented. .

  As the vacuum ultraviolet light source, a rare gas excimer lamp is preferably used. Atoms of noble gases such as Xe, Kr, Ar, and Ne are called inert gases because they are not chemically bonded to form molecules.

  The Xe excimer lamp emits ultraviolet light having a short wavelength of 172 nm at a single wavelength, and thus has excellent luminous efficiency. Since this light has a large oxygen absorption coefficient, it can generate radical oxygen atom species and ozone at a high concentration with a very small amount of oxygen.

  Moreover, it is known that the energy of light having a short wavelength of 172 nm has a high ability to dissociate organic bonds. Due to the high energy of the active oxygen, ozone and ultraviolet radiation, the polysilazane layer can be modified in a short time.

  Therefore, compared with a low-pressure mercury lamp that emits light with wavelengths of 185 nm and 254 nm, it is possible to shorten the process time associated with high throughput, reduce the equipment area, and irradiate organic materials and plastic substrates that are easily damaged by heat.

  Since the excimer lamp has high light generation efficiency, it can be turned on with low power. In addition, light having a long wavelength that causes a temperature increase due to light is not emitted, and energy is irradiated in the ultraviolet region, that is, a short wavelength, and therefore, a rise in the surface temperature of the irradiation object is suppressed. For this reason, it is suitable for flexible film materials such as PET that are easily affected by heat.

  Oxygen is required for the reaction at the time of ultraviolet irradiation, but since vacuum ultraviolet rays are absorbed by oxygen, the efficiency in the ultraviolet irradiation process tends to decrease. It is preferable to carry out in a low state. That is, the oxygen concentration at the time of vacuum ultraviolet irradiation is preferably in the range of 10 to 10,000 ppm, more preferably in the range of 50 to 5000 ppm, and still more preferably in the range of 1000 to 4500 ppm.

  As a gas that satisfies the irradiation atmosphere used at the time of irradiation with vacuum ultraviolet rays, a dry inert gas is preferable, and a dry nitrogen gas is particularly preferable from the viewpoint of cost. The oxygen concentration can be adjusted by measuring the flow rate of oxygen gas and inert gas introduced into the irradiation chamber and changing the flow rate ratio.

  Next, a roll-to-roll type vacuum ultraviolet irradiation apparatus applicable to the present invention will be described with reference to the drawings.

  FIG. 8 is a schematic view showing an example of a roll-to-roll system applicable to the formation of the second gas barrier layer according to the present invention and a vacuum ultraviolet irradiation apparatus capable of continuous production.

  In FIG. 8, the process on the left side is performed on the resin substrate laminate 1 (314) in which the clear hard coat layer (3) and the first gas barrier layer (6) are laminated on the resin substrate (2). This is a coating / drying step (332) in which a polysilazane layer-containing coating solution containing polysilazane is applied to form a polysilazane-containing layer before modification, and the process on the right side modifies the formed polysilazane-containing layer. This is a reforming step (333) for forming a second gas barrier layer (7).

  A resin base material laminate having a polysilazane-containing layer in which a coating liquid for forming a polysilazane layer containing a polysilazane compound is applied by a die coater (329) onto a resin base material laminate 1 (314) fed from a feed roller (322). Body 2 (315) is formed. The die coater 329 is an apparatus for forming a coating film by an extrusion-type coating method. The supplied coating solution is extruded and discharged from a slit-shaped discharge port, and contains a polysilazane having a uniform thickness on a resin substrate. Layer 315 is formed.

  Subsequently, the resin base material laminated body 2 (315) which has a polysilazane content layer is conveyed with a conveyance roller (323 and 324), and dries the polysilazane content layer apply | coated within the drying zone (330).

  Next, in the reforming step (333), vacuum ultraviolet light is irradiated while continuously transporting the resin-based substrate laminate 2 (315) having a polysilazane-containing layer with a vacuum ultraviolet light lamp (excimer lamp, L1 to L30). To do. At that time, among the excimer lamps (L1 to L30), a region irradiated with the vacuum ultraviolet light by the lit excimer lamp becomes a vacuum ultraviolet light irradiation zone, and by leaving a part of the excimer lamp unlit, An area that is not lit is an irradiation suspension zone (not shown). In addition to introducing nitrogen into the casing (331) of the reforming step (333), nitrogen or air is supplied to each excimer lamp holder (not shown). On the opposite side of the excimer lamp (L1 to L30) of the resin base material laminate 2 (315) having a polysilazane-containing layer that is continuously conveyed, support rollers (T1 to T32) with a built-in temperature control device are installed. ing. The coating surface temperature in the vacuum ultraviolet light irradiation zone or the irradiation suspension zone is adjusted by a temperature control device built in the support rollers (T1 to T32). In the apparatus of FIG. 8, thirty excimer lamps are installed, but it is preferable to select the necessary number appropriately according to the thickness and type of the coating film.

  As described above, the gas barrier film in which the second gas barrier layer is formed on the resin base laminate 1 (314) having the clear hard coat layer and the first gas barrier layer by the roll-to-roll method, While being held and conveyed by the conveyance rollers (326 and 327), the film is wound into a roll shape by the winding roller (328).

[Other component layers]
In the gas barrier film of the present invention, the formation of a conventionally known smooth layer (undercoat layer, primer layer), anchor coat layer, and bleed-out prevention layer is not excluded as long as the object effects of the present invention are not impaired.

<Application field of gas barrier film>
The gas barrier film of the present invention can be suitably applied to electronic devices.

  Specifically, the gas barrier film having a high water vapor and oxygen barrier property of the present invention can be used as a sealing material and a sealing film for various electronic devices.

  The gas barrier film of this invention can be used for a display element, for example, an organic EL element, as an electronic device. When used in an organic EL device, the gas barrier film of the present invention is transparent, so that the gas barrier film can be used as a substrate to extract light from this side.

  That is, on the gas barrier film of the present invention, for example, a transparent conductive thin film such as ITO can be provided as a transparent electrode to constitute a resin substrate for an organic EL element. Then, using the ITO transparent conductive film provided on the resin substrate for organic EL elements as an anode, an organic functional layer including a light emitting layer is provided thereon, and a cathode made of a metal film is further formed to form an organic EL element. It can be formed by stacking another sealing material (which may be the same) on top of it, adhering the periphery of the gas barrier film, and encapsulating the organic EL element. It is possible to prevent the organic EL element from being affected by gases such as oxygen and oxygen.

  An organic EL device has a problem of low light extraction efficiency. Therefore, when using these gas barrier films as a film substrate, it is preferable to have a structure for improving light extraction. Therefore, when the gas barrier film of the present invention is used as a resin base material for an organic EL device, the gas barrier film has a concavo-convex shape for diffracting or diffusing light in order to improve the light extraction efficiency from the organic EL device. It is preferable.

  An organic EL panel, which is one of electronic devices using the gas barrier film of the present invention, is used as a light source for lighting, a lighting device for home lighting, interior lighting, and exposure light source in addition to a display device and a display. As one kind of lamp, it is also useful for a display device such as a backlight of a liquid crystal display device.

  As another electronic device, it can use for the film for sealing of an organic photoelectric conversion element. When the gas barrier film of the present invention is used for an organic photoelectric conversion element, the gas barrier film of the present invention is transparent. Therefore, the gas barrier film is used as a base material to receive sunlight from the arrangement side of the gas barrier film. Can be configured to do. That is, on a gas barrier film, for example, a transparent conductive thin film such as ITO can be provided as a transparent electrode to constitute a resin substrate for an organic photoelectric conversion element. Then, an ITO transparent conductive film provided on the substrate is used as an anode, a porous semiconductor layer is provided thereon, and a cathode made of a metal film is formed to form an organic photoelectric conversion element, on which another seal is formed. The organic photoelectric conversion element can be sealed by stacking the sealing material, adhering the gas barrier film substrate and the surrounding part, and encapsulating the element, thereby allowing organic photoelectric conversion by moisture such as outside air or oxygen The influence on the element can be sealed.

(Application example of gas barrier film: organic EL device)
FIG. 9 is a schematic configuration diagram illustrating an example of a configuration of an organic electroluminescence element including the gas barrier film of the present invention.

  In FIG. 9, the organic EL element (EL) is mainly a clear hard coat having a pattern in which different regions are formed by two or more kinds of resin compositions (4 and 5) on the resin substrate (2). On the gas barrier film (1) of the present invention in which the layer (3) and the gas barrier layer (6) are laminated in this order, the anode (51) as the first electrode, and then, for example, a hole injection layer , An organic functional layer group 1 (52) composed of a hole transport layer, and a light emitting layer (53), for example, an organic functional layer group 2 (54) composed of an electron transport layer, an electron injection layer, and the like are laminated. Thus, a light emitting area is configured. Further, a cathode (55) as a second electrode, a sealing adhesive layer (56), and a flexible sealing substrate (57) are provided on the upper part.

  Regarding the outline of the organic EL element applicable to the present invention, for example, JP2013-157634A, JP2013-168552A, JP2013-177361A, JP2013-187221A, JP JP 2013-191644 A, JP 2013-191804 A, JP 2013-225678 A, JP 2013-235994 A, JP 2013-243234 A, JP 2013-243236 A, JP 2013-2013 A. JP 242366, JP 2013-243371, JP 2013-245179, JP 2014-003249, JP 2014-003299, JP 2014-013910, JP 2014-014933 Gazette, JP, 2014-017494, A It can be mentioned configurations described in.

  Next, each component of the organic EL element unit will be described.

(Anode: 1st electrode)
When the first electrode (51) is provided on one surface side of the resin substrate (2), it becomes a transparent electrode functioning as an anode.

As a material constituting the first electrode (transparent electrode), a metal such as Ag, Au or the like, an alloy containing a metal as a main component, a CuI or indium-tin composite oxide (ITO), a metal such as SnO ₂ and ZnO An oxide can be mentioned, but from the viewpoint of controlling the objective effect of the present invention, in particular, the difference in refractive index from the charge injection layer to a desired condition, it is a metal or an alloy containing a metal as a main component. It is preferable that there is, and more preferable is silver or an alloy containing silver as a main component.

  The purity of silver constituting the transparent electrode as the first electrode is preferably 99% or more. Further, palladium (Pd), copper (Cu), gold (Au), or the like may be added to ensure the stability of silver.

  Moreover, when a transparent electrode is comprised from the alloy which has silver as a main component, it is preferable that the content rate of silver is 50% or more. Examples of such alloys include silver magnesium (AgMg), silver-copper (Ag-Cu), silver-palladium (Ag-Pd), silver-palladium-copper (Ag-Pd-Cu), silver-indium (Ag). -In), silver-gold (Ag-Au), silver-aluminum (Ag-Al), silver-zinc (Ag-Zn), silver-tin (Ag-Sn), silver-platinum (Ag-Pt), silver -Titanium (Ag-Ti), silver-bismuth (Ag-Bi), etc. are mentioned.

  As a method for forming such a transparent electrode, a method using a wet process such as a coating method, an inkjet method, a coating method, a dip method, a vapor deposition method (resistance heating, EB method, etc.), a sputtering method, a CVD method, etc. Examples include a method using a dry process. Of these, the vapor deposition method is preferably applied. Moreover, you may form into a film the layer containing a nitrogen atom as a base layer between a transparent electrode and a transparent base material. In addition, the transparent electrode composed of silver or an alloy containing silver as a main component is characterized by having sufficient conductivity even without an annealing treatment or the like. Etc. may be performed.

(Intermediate electrode)
The organic EL element unit has a structure in which two or more organic functional layer groups are stacked between the first electrode and the second electrode, and electrical connection is obtained between the two or more organic functional layer units. Therefore, the structure can be separated by an intermediate electrode layer unit having an independent connection terminal.

  Subsequently, the structure of the organic functional layer group containing a light emitting layer is demonstrated.

(Charge injection layer)
In the organic EL element unit according to the present invention, the charge injection layer is a layer provided between the electrode and the light emitting layer in order to lower the driving voltage and improve the light emission luminance. The details are described in Chapter 2, “Electrode Materials” (pp. 123-166) of Volume 2 of “November 30, 1998, issued by NTS Corporation”. There is.

  As a charge injection layer, generally, if it is a hole injection layer, it exists between a transparent anode and a light emitting layer or a hole transport layer, and if it is an electron injection layer, it exists between a cathode and a light emitting layer or an electron transport layer. Can be made.

  In the present invention, the hole injection layer is preferably a layer disposed adjacent to the transparent anode according to the present invention in order to lower the driving voltage and improve the light emission luminance. (Published on November 30, 1998 by NTS Corporation) "Volume 2 Chapter 2" Electrode Materials "(pp. 123-166).

  The details of the hole injection layer are also described in JP-A-9-45479, JP-A-9-260062, JP-A-8-288069, etc. Examples of the material used for the hole injection layer include: , Porphyrin derivatives, phthalocyanine derivatives, oxazole derivatives, oxadiazole derivatives, triazole derivatives, imidazole derivatives, pyrazoline derivatives, pyrazolone derivatives, phenylenediamine derivatives, hydrazone derivatives, stilbene derivatives, polyarylalkane derivatives, triarylamine derivatives, carbazole derivatives, Inrocarbazole derivatives, isoindole derivatives, acene derivatives such as anthracene and naphthalene, fluorene derivatives, fluorenone derivatives, polyvinylcarbazole, aromatic amines introduced into the main chain or side chain Material or oligomer, polysilane, a conductive polymer or oligomer (e.g., PEDOT (polyethylene dioxythiophene): PSS (polystyrene sulfonic acid), aniline copolymers, polyaniline, polythiophene, etc.) and the like can be mentioned.

  Examples of the triarylamine derivative include benzidine type represented by α-NPD (4,4′-bis [N- (1-naphthyl) -N-phenylamino] biphenyl), and MTDATA (4,4 ′, 4 ″). Examples include a starburst type represented by -tris [N- (3-methylphenyl) -N-phenylamino] triphenylamine) and a compound having fluorene or anthracene in the triarylamine-linked core.

  In addition, hexaazatriphenylene derivatives such as those described in JP-A-2003-519432 and JP-A-2006-135145 can also be used as a hole transport material.

  The electron injection layer is a layer provided between the cathode and the light emitting layer for lowering the driving voltage and improving the light emission luminance. When the cathode is composed of the transparent electrode according to the present invention, Chapter 2 “Electrode materials” (pages 123-166) of the second edition of “Organic EL elements and their forefront of industrialization” (published on November 30, 1998 by NTT) ) Is described in detail.

  The details of the electron injection layer are described in JP-A-6-325871, JP-A-9-17574, JP-A-10-74586, and the like. Specific examples of materials preferably used for the electron injection layer are as follows. Metals represented by strontium and aluminum, alkali metal compounds represented by lithium fluoride, sodium fluoride, potassium fluoride, etc., alkali metal halide layers represented by magnesium fluoride, calcium fluoride, etc. Examples thereof include an alkaline earth metal compound layer typified by magnesium, a metal oxide typified by molybdenum oxide and aluminum oxide, and a metal complex typified by lithium 8-hydroxyquinolate (Liq). Moreover, when the transparent electrode in this invention is a cathode, organic materials, such as a metal complex, are used especially suitably. The electron injection layer is desirably a very thin film, and although depending on the constituent material, the layer thickness is preferably in the range of 1 nm to 10 μm.

  In the present invention, the average value Δn of the refractive index difference (absolute value) from the transparent electrode is set in the range of 0.5 to 2.0, so that the metal or metal of the transparent electrode to be applied is a main component. A material for the charge injection layer that satisfies the above conditions is appropriately selected in relation to the refractive index of the alloy.

(Light emitting layer)
In the organic EL element unit according to the present invention, the light emitting layer constituting the organic functional layer group preferably includes a phosphorescent light emitting compound as a light emitting material.

  This light emitting layer is a layer that emits light by recombination of electrons injected from the electrode or the electron transport layer and holes injected from the hole transport layer, and the light emitting portion is in the layer of the light emitting layer. Alternatively, it may be the interface between the light emitting layer and the adjacent layer.

  As such a light emitting layer, there is no restriction | limiting in particular in the structure, if the light emitting material contained satisfy | fills the light emission requirements. Moreover, there may be a plurality of layers having the same emission spectrum and emission maximum wavelength. In this case, it is preferable to have a non-light emitting intermediate layer between the light emitting layers.

  The total thickness of the light emitting layers is preferably in the range of 1 to 100 nm, and more preferably in the range of 1 to 30 nm because a lower driving voltage can be obtained. In addition, the sum total of the thickness of a light emitting layer is the thickness also including the said intermediate | middle layer, when a nonluminous intermediate | middle layer exists between light emitting layers.

  For the light emitting layer as described above, a light emitting material and a host compound to be described later may be used by publicly known methods such as a vacuum deposition method, a spin coating method, a casting method, an LB method (Langmuir-Blodget, Langmuir Broadgett method), and an ink jet method. Can be formed.

  In the light emitting layer, a plurality of light emitting materials may be mixed, and a phosphorescent light emitting material and a fluorescent light emitting material (also referred to as a fluorescent dopant or a fluorescent compound) may be mixed and used in the same light emitting layer. The structure of the light-emitting layer preferably includes a host compound (also referred to as a light-emitting host) and a light-emitting material (also referred to as a light-emitting dopant compound), and emits light from the light-emitting material.

<Host compound>
As the host compound contained in the light emitting layer, a compound having a phosphorescence quantum yield of phosphorescence emission at room temperature (25 ° C.) of less than 0.1 is preferable. Further, the phosphorescence quantum yield is preferably less than 0.01. Moreover, it is preferable that the volume ratio in the layer is 50% or more among the compounds contained in a light emitting layer.

  As the host compound, a known host compound may be used alone, or a plurality of types of host compounds may be used. By using a plurality of types of host compounds, it is possible to adjust the movement of charges, and the efficiency of the organic electroluminescent device can be improved. In addition, by using a plurality of kinds of light emitting materials described later, it is possible to mix different light emission, thereby obtaining an arbitrary light emission color.

  The host compound used in the light emitting layer may be a conventionally known low molecular compound or a high molecular compound having a repeating unit, and a low molecular compound having a polymerizable group such as a vinyl group or an epoxy group (evaporation polymerizable light emitting host). )

  Examples of host compounds applicable to the present invention include, for example, JP-A Nos. 2001-257076, 2002-308855, 2001-313179, 2002-319491, 2001-357777, 2002-334786, 2002-8860, 2002-334787, 2002-15871, 2002-334788, 2002-43056, 2002-334789, 2002 No. -75645, No. 2002-338579, No. 2002-105445, No. 2002-343568, No. 2002-141173, No. 2002-352957, No. 2002-203683, No. 2002. 363 No. 27, No. 2002-231453, No. 2003-3165, No. 2002-234888, No. 2003-27048, No. 2002-255934, No. 2002-260861, No. 2002-280183. No. 2002, No. 2002-299060, No. 2002-302516, No. 2002-305083, No. 2002-305084, No. 2002-308837, US Patent Application Publication No. 2003/0175553, US Patent Application Publication No. 2006/0280965, US Patent Application Publication No. 2005/0112407, US Patent Application Publication No. 2009/0017330, US Patent Application Publication No. 2009/0030202, US Patent Public application No. 2005/238919, International Publication No. 2001/039234, International Publication No. 2009/021126, International Publication No. 2008/056746, International Publication No. 2004/093207, International Publication No. 2005/089025, International Publication No. 2007/063796, International Publication No. 2007/063754, International Publication No. 2004/107822, International Publication No. 2005/030900, International Publication No. 2006/114966, International Publication No. 2009/086028, International Publication No. 2009 No./003898, International Publication No. 2012/023947, Japanese Patent Application Laid-Open No. 2008-074939, Japanese Patent Application Laid-Open No. 2007-254297, EP No. 2034538, and the like.

<Light emitting material>
As the light-emitting material that can be used in the present invention, a phosphorescent compound (also referred to as a phosphorescent compound, a phosphorescent material, or a phosphorescent dopant) and a fluorescent compound (both a fluorescent compound or a fluorescent material) are used. Say).

<Phosphorescent compound>
A phosphorescent compound is a compound in which light emission from an excited triplet is observed. Specifically, it is a compound that emits phosphorescence at room temperature (25 ° C.), and the phosphorescence quantum yield is 0 at 25 ° C. A preferred phosphorescence quantum yield is 0.1 or more, although it is defined as 0.01 or more compounds.

  The phosphorescence quantum yield can be measured by the method described in Spectroscopic II, page 398 (1992 edition, Maruzen) of Experimental Chemistry Course 4 of the 4th edition. The phosphorescence quantum yield in the solution can be measured using various solvents, but when using a phosphorescent compound in the present invention, the phosphorescence quantum yield is 0.01 or more in any solvent. Should be achieved.

  The phosphorescent compound can be appropriately selected from known compounds used for the light emitting layer of a general organic EL device, but preferably contains a group 8-10 metal in the periodic table of elements. More preferred are iridium compounds, more preferred are iridium compounds, osmium compounds, platinum compounds (platinum complex compounds) or rare earth complexes, and most preferred are iridium compounds.

  In the present invention, at least one light emitting layer may contain two or more phosphorescent compounds, and the concentration ratio of the phosphorescent compound in the light emitting layer varies in the thickness direction of the light emitting layer. It may be an embodiment.

  Specific examples of known phosphorescent compounds that can be used in the present invention include compounds described in the following documents.

  Nature 395, 151 (1998), Appl. Phys. Lett. 78, 1622 (2001), Adv. Mater. 19, 739 (2007), Chem. Mater. 17, 3532 (2005), Adv. Mater. 17, 1059 (2005), International Publication No. 2009/100991, International Publication No. 2008/101842, International Publication No. 2003/040257, US Patent Application Publication No. 2006/835469, US Patent Application Publication No. 2006 /. Examples thereof include compounds described in US Patent No. 0202194, US Patent Application Publication No. 2007/0087321, US Patent Application Publication No. 2005/0244673, and the like.

  Inorg. Chem. 40, 1704 (2001), Chem. Mater. 16, 2480 (2004), Adv. Mater. 16, 2003 (2004), Angew. Chem. lnt. Ed. 2006, 45, 7800, Appl. Phys. Lett. 86, 153505 (2005), Chem. Lett. 34, 592 (2005), Chem. Commun. 2906 (2005), Inorg. Chem. 42, 1248 (2003), International Publication No. 2009/050290, International Publication No. 2002/015645, International Publication No. 2009/000673, US Patent Application Publication No. 2002/0034656, and US Pat. No. 7,332,232. US Patent Application Publication No. 2009/0108737, US Patent Application Publication No. 2009/0039776, US Patent No. 6921915, US Patent No. 6,687,266, US Patent Application Publication No. 2007/0190359, US Patent Application Publication No. 2006/0008670, US Patent Application Publication No. 2009/0165846, US Patent Application Publication No. 2008/0015355, US Pat. No. 7,250,226, US Pat. No. 7,396,598 US patent Examples include compounds described in Japanese Patent Application Publication No. 2006/0263635, US Patent Application Publication No. 2003/0138657, US Patent Application Publication No. 2003/0152802, US Pat. No. 7090928, and the like. it can.

  Also, Angew. Chem. lnt. Ed. 47, 1 (2008), Chem. Mater. 18, 5119 (2006), Inorg. Chem. 46, 4308 (2007), Organometallics 23, 3745 (2004), Appl. Phys. Lett. 74, 1361 (1999), International Publication No. 2002/002714, International Publication No. 2006/009024, International Publication No. 2006/056418, International Publication No. 2005/019373, International Publication No. 2005/123873, International Publication No. 2005/123873, International Publication No. 2007/004380, International Publication No. 2006/082742, US Patent Application Publication No. 2006/0251923, US Patent Application Publication No. 2005/0260441, US Pat. No. 7,393,599. Description, US Pat. No. 7,534,505, US Pat. No. 7,445,855, US Patent Application Publication No. 2007/0190359, US Patent Application Publication No. 2008/0297033, US Pat. No. 7,338,722 , US special Examples include compounds described in Japanese Patent Application Publication No. 2002/0134984, US Patent No. 7279704, US Patent Application Publication No. 2006/098120, US Patent Application Publication No. 2006/103874, and the like. it can.

  Furthermore, International Publication No. 2005/076380, International Publication No. 2010/032663, International Publication No. 2008/140115, International Publication No. 2007/052431, International Publication No. 2011/134013, International Publication No. 2011/157339. International Publication No. 2010/086089, International Publication No. 2009/113646, International Publication No. 2012/020327, International Publication No. 2011/051404, International Publication No. 2011/004639, International Publication No. 2011/073149, Special The compounds described in JP 2012-069737 A, JP 2009-114086 A, JP 2003-81988 A, JP 2002-302671 A, JP 2002-363552 A, and the like can also be mentioned.

  In the present invention, preferred phosphorescent compounds include organometallic complexes having Ir as a central metal. More preferably, a complex containing at least one coordination mode of a metal-carbon bond, a metal-nitrogen bond, a metal-oxygen bond, or a metal-sulfur bond is preferable.

  The phosphorescent compound described above (also referred to as a phosphorescent metal complex) is described in, for example, Organic Letter, vol. 16, 2579-2581 (2001), Inorganic Chemistry, Vol. 30, No. 8, 1685-1687 (1991), J. Am. Am. Chem. Soc. , 123, 4304 (2001), Inorganic Chemistry, Vol. 40, No. 7, 1704-1711 (2001), Inorganic Chemistry, Vol. 41, No. 12, 3055-3066 (2002) , New Journal of Chemistry. 26, 1171 (2002), European Journal of Organic Chemistry, Vol. 4, pages 695-709 (2004), and the methods described in references in these documents should be applied. Can be synthesized.

<Fluorescent compound>
Fluorescent compounds include coumarin dyes, pyran dyes, cyanine dyes, croconium dyes, squalium dyes, oxobenzanthracene dyes, fluorescein dyes, rhodamine dyes, pyrylium dyes, perylene dyes, stilbene dyes. And dyes, polythiophene dyes, and rare earth complex phosphors.

(Hole transport layer)
The hole transport layer is made of a hole transport material having a function of transporting holes. In a broad sense, the hole injection layer and the electron blocking layer also have the function of a hole transport layer. The hole transport layer can be provided as a single layer or a plurality of layers.

  The hole transport material has any of hole injection or transport and electron barrier properties, and may be either organic or inorganic. For example, triazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives, pyrazolone derivatives, phenylenediamine derivatives, arylamine derivatives, amino-substituted chalcone derivatives, oxazole derivatives, styrylanthracene derivatives, fluorenone derivatives, hydrazone derivatives, Examples include stilbene derivatives, silazane derivatives, aniline copolymers, conductive polymer oligomers, and thiophene oligomers.

  As the hole transport material, those described above can be used, but porphyrin compounds, aromatic tertiary amine compounds and styrylamine compounds can be used, and in particular, aromatic tertiary amine compounds can be used. preferable.

  Representative examples of aromatic tertiary amine compounds and styrylamine compounds include N, N, N ′, N′-tetraphenyl-4,4′-diaminophenyl, N, N′-diphenyl-N, N′— Bis (3-methylphenyl)-[1,1′-biphenyl] -4,4′-diamine (abbreviation: TPD), 2,2-bis (4-di-p-tolylaminophenyl) propane, 1,1 -Bis (4-di-p-tolylaminophenyl) cyclohexane, N, N, N ', N'-tetra-p-tolyl-4,4'-diaminobiphenyl, 1,1-bis (4-di-p -Tolylaminophenyl) -4-phenylcyclohexane, bis (4-dimethylamino-2-methylphenyl) phenylmethane, bis (4-di-p-tolylaminophenyl) phenylmethane, N, N'-diphenyl-N, '-Di (4-methoxyphenyl) -4,4'-diaminobiphenyl, N, N, N', N'-tetraphenyl-4,4'-diaminodiphenyl ether, 4,4'-bis (diphenylamino) c Audriphenyl, N, N, N-tri (p-tolyl) amine, 4- (di-p-tolylamino) -4 '-[4- (di-p-tolylamino) styryl] stilbene, 4-N, N- Examples include diphenylamino- (2-diphenylvinyl) benzene, 3-methoxy-4′-N, N-diphenylaminostilbenzene, N-phenylcarbazole and the like.

  For the hole transport layer, known methods such as vacuum deposition, spin coating, casting, printing including ink jet, and LB (Langmuir Brodget, Langmuir Broadgett) are used as the hole transport material. Thus, it can be formed by thinning. Although there is no restriction | limiting in particular about the layer thickness of a positive hole transport layer, Usually, about 5 nm-5 micrometers, Preferably it is the range of 5-200 nm. The hole transport layer may have a single layer structure composed of one or more of the above materials.

  Moreover, p property can also be made high by doping the material of a positive hole transport layer with an impurity. Examples thereof include JP-A-4-297076, JP-A-2000-196140, 2001-102175 and J.P. Appl. Phys. 95, 5773 (2004), and the like.

  Thus, it is preferable to increase the p property of the hole transport layer because an element with lower power consumption can be manufactured.

(Electron transport layer)
The electron transport layer is made of a material having a function of transporting electrons, and in a broad sense, an electron injection layer and a hole blocking layer are also included in the electron transport layer. The electron transport layer can be provided as a single layer structure or a stacked structure of a plurality of layers.

  In the electron transport layer having a single-layer structure and the electron transport layer having a multilayer structure, an electron transport material (also serving as a hole blocking material) constituting a layer portion adjacent to the light emitting layer is used as an electron transporting material. What is necessary is just to have the function to transmit. As such a material, any one of conventionally known compounds can be selected and used. Examples include nitro-substituted fluorene derivatives, diphenylquinone derivatives, thiopyran dioxide derivatives, carbodiimides, fluorenylidenemethane derivatives, anthraquinodimethane, anthrone derivatives, and oxadiazole derivatives. Furthermore, in the above oxadiazole derivative, a thiadiazole derivative in which the oxygen atom of the oxadiazole ring is substituted with a sulfur atom, and a quinoxaline derivative having a quinoxaline ring known as an electron-withdrawing group can also be used as a material for the electron transport layer. it can. Furthermore, a polymer material in which these materials are introduced into a polymer chain, or a polymer material having these materials as a polymer main chain can also be used.

In addition, metal complexes of 8-quinolinol derivatives such as tris (8-quinolinol) aluminum (abbreviation: Alq ₃ ), tris (5,7-dichloro-8-quinolinol) aluminum, tris (5,7-dibromo-8- Quinolinol) aluminum, tris (2-methyl-8-quinolinol) aluminum, tris (5-methyl-8-quinolinol) aluminum, bis (8-quinolinol) zinc (abbreviation: Znq), etc. and the central metal of these metal complexes A metal complex replaced with In, Mg, Cu, Ca, Sn, Ga, or Pb can also be used as a material for the electron transport layer.

  The electron transport layer can be formed by thinning the above material by a known method such as a vacuum deposition method, a spin coating method, a casting method, a printing method including an inkjet method, and an LB method. Although there is no restriction | limiting in particular about the layer thickness of an electron carrying layer, Usually, about 5 nm-5 micrometers, Preferably it exists in the range of 5-200 nm. The electron transport layer may have a single structure composed of one or more of the above materials.

(Blocking layer)
The blocking layer includes a hole blocking layer and an electron blocking layer, and is a layer provided as necessary in addition to the constituent layers of the organic functional layer unit 3 described above. For example, it is described in JP-A Nos. 11-204258, 11-204359, and “Organic EL elements and their forefront of industrialization” (issued by NTT, Inc. on November 30, 1998). Hole blocking (hole block) layer and the like.

  The hole blocking layer has a function of an electron transport layer in a broad sense. The hole blocking layer is made of a hole blocking material that has a function of transporting electrons but has a very small ability to transport holes, and recombines electrons and holes by blocking holes while transporting electrons. Probability can be improved. Moreover, the structure of an electron carrying layer can be used as a hole-blocking layer as needed. The hole blocking layer is preferably provided adjacent to the light emitting layer.

  On the other hand, the electron blocking layer has a function of a hole transport layer in a broad sense. The electron blocking layer is made of a material that has the ability to transport holes and has a very small ability to transport electrons. By blocking holes while transporting holes, the probability of recombination of electrons and holes is improved. Can be made. Moreover, the structure of a positive hole transport layer can be used as an electron blocking layer as needed. The layer thickness of the hole blocking layer applied to the present invention is preferably in the range of 3 to 100 nm, more preferably in the range of 5 to 30 nm.

(cathode)
The cathode is an electrode film that functions to supply holes to the organic functional layer unit, and a metal, an alloy, an organic or inorganic conductive compound, or a mixture thereof is used. Specifically, gold, aluminum, silver, magnesium, lithium, magnesium / copper mixture, magnesium / silver mixture, magnesium / aluminum mixture, magnesium / indium mixture, indium, lithium / aluminum mixture, rare earth metal, ITO, ZnO, TiO Oxide semiconductors such as ₂ and SnO ₂ .

  The cathode can be produced by using these conductive materials and forming a thin film by a method such as vapor deposition or sputtering. The sheet resistance as the cathode is preferably several hundred Ω / □ or less, and the film thickness is usually selected in the range of 5 nm to 5 μm, preferably 5 to 200 nm.

  In the case where the organic EL element is a double-sided light emitting type in which emitted light is extracted also from the cathode side, a cathode with good light transmittance may be selected and configured.

(Sealing member)
In the organic EL element, it is preferable that the cathode and the organic functional layer unit formed between the cathode and the transparent anode be shielded from the outside air by a flexible sealing plate.

  As a sealing means applicable to the present invention, as a sealing material, an organic EL element is bonded by forming a sealing structure with a sealing adhesive layer (56) and a flexible sealing plate (57). Can be mentioned.

  As a flexible sealing board, it should just be arrange | positioned so that the display area | region of an organic EL element may be covered, and concave plate shape or flat plate shape may be sufficient. Further, transparency and electrical insulation are not particularly limited.

  Moreover, in this invention, in the flexible sealing board (4), the structure which has a gas barrier layer in the surface side which contact | connects the adhesive agent layer for sealing (6) may be sufficient, The formation method of a gas barrier layer Can similarly use a gas barrier layer applied to the gas barrier film (1).

  Specifically, as a sealing material used for sealing, a flexible glass plate, a resin substrate, a thin film metal foil, or a metal composite resin film laminated with a metal foil, such as Alpet (aluminum foil / polyethylene) Terephthalate film). Specifically, each material illustrated with the said flexible substrate can be used similarly.

In this invention, since an organic EL element can be made into a thin film, a resin substrate, a thin film metal foil, and a metal composite resin film can be preferably used. Furthermore, the resin substrate has an oxygen permeability measured by a method according to JIS K 7126-1987 of 1 × 10 ⁻³ ml / (m ² · 24 h · atm) or less, and a method according to JIS K 7129-1992. It is preferable that the water vapor permeability (25 ± 0.5 ° C., relative humidity (90 ± 2)% RH) measured in (1) is 1 × 10 ⁻³ g / (m ² · 24 h) or less.

  For processing the sealing member into a concave shape, sandblasting, chemical etching, or the like is used.

  Specific examples of the adhesive for forming the sealing adhesive layer (56) include photo-curing and thermosetting adhesives having reactive vinyl groups of acrylic acid oligomers and methacrylic acid oligomers, and 2-cyanoacrylic acid. Mention may be made of moisture-curing adhesives such as esters. Moreover, heat | fever and chemical curing types (two-component mixing), such as an epoxy type, can be mentioned. Moreover, hot-melt type polyamide, polyester, and polyolefin can be mentioned. Moreover, a cationic curing type ultraviolet curing epoxy resin adhesive can be mentioned.

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto. In addition, although the display of "%" and "part" is used in an Example, unless there is particular notice, it represents "mass%" and "mass part", respectively.

<Production of gas barrier film>
[Preparation of gas barrier film 1]
(Preparation of resin base material)
A roll-shaped polyethylene terephthalate film (manufactured by Teijin DuPont: KFL12W) having a thickness of 23 μm was prepared as the resin substrate (2).

(Formation of first gas barrier layer)
Subsequently, the gas barrier film 1 was produced by forming the first gas barrier layer (6) on the resin base material (2) using the plasma CVD film forming apparatus shown in FIG.

  The roll-shaped resin base material was set on the feed roller (32) of the plasma CVD film forming apparatus (31) shown in FIG. 7, and was continuously conveyed by roll-to-roll.

  Next, a magnetic field is applied between the film formation roller (39) and the film formation roller (40), and electric power is supplied to the film formation roller (39) and the film formation roller (40), respectively. 39) and a film forming roller (40) to generate a plasma to form a discharge region. Next, a mixed gas of hexamethyldisiloxane (HMDSO), which is a raw material gas, and oxygen gas (which also functions as a discharge gas), which is a reactive gas, is used as a film forming gas in a gas supply pipe (41). The first gas barrier layer (6) having a layer thickness of 120 nm was continuously formed on the surface of the resin base material (2) by the plasma CVD method under the following conditions to produce the gas barrier film 1.

<Film formation conditions>
Feed rate of source gas (hexamethyldisiloxane, HMDSO): 50 sccm (Standard Cubic Centimeter per Minute)
Reaction gas (O ₂ ) supply amount: 500 sccm
Degree of vacuum in the vacuum chamber: 3Pa
Applied power from the power source for plasma generation: 0.8 kW
Frequency of power source for plasma generation: 70 kHz
Resin substrate transport speed: 0.8 m / min
[Preparation of gas barrier film 2]
In the production of the gas barrier film 1, a clear hard coat layer 1 having a single composition is formed between the resin base material (2) and the first gas barrier layer (6) according to the following method. Barrier film 2 was produced.

(Preparation of clear hard coat layer forming coating solution 1)
It is composed of pentaerythritol triacrylate (Shin Nakamura Chemical A-TTM-3, functional group number: 3) and hexamethylene diisocyanate. The mixture was mixed at a ratio of, and using propylene glycol monomethyl ether as an organic solvent and dissolved under the condition that the solid content was 5% by mass, to prepare clear hard coat layer forming coating solution 1 (resin composition 1). .

(Formation of clear hard coat layer 1)
A clear hard coat layer 1 having a single composition of the resin composition 1 was formed according to the following coating / drying and curing conditions.

Coater: Extruded coater Drying conditions: 90 ° C., 90 seconds Dry layer thickness: 2 μm,
Curing conditions: high pressure mercury lamp, 500 mJ / cm ²
(Measurement of hardness of resin composition 1)
A measurement sample made of the resin composition 1 was prepared using the clear hard coat layer forming coating solution 1 used for forming the clear hard coat layer 1.

  A sample for measurement was prepared by applying and drying the resin composition 1 on a polyethylene terephthalate film having a thickness of 120 μm under the condition that the film thickness upon drying was 2 μm, and then irradiating with ultraviolet rays under the above conditions.

  The prepared sample was dropped on the slide glass with a drop of adhesive Aron Alpha manufactured by Toagosei Co., Ltd., and then placed on a film with a clear hard coat layer cut to about 1 cm square and allowed to stand for 24 hours to cure. A measurement sample.

  The measurement is performed by using a Triscope from Hystron and attaching the sample to a Nanoscope III from Digital Instruments. For the measurement, a triangular pyramid diamond indenter was used as a Belkovic indenter (90 ° Cube Corm Tripr) as an indenter. A triangular pyramidal diamond indenter was applied perpendicularly to the surface of the clear hard coat layer of the sample, and a load was gradually applied. After reaching the maximum load, the load was gradually returned to zero. A value P / A obtained by dividing the maximum load P at this time by the projected area A of the indenter contact portion was calculated as hardness (GPa). The maximum load condition at this time was 50 μN.

  The number of measurements was n = 3, and the average value was obtained. In measurement, the attached fused silica was used as a standard sample in advance, and the apparatus was calibrated and measured so that the hardness obtained from the indentation was 9.5 ± 1.5 GPa.

  The hardness of the resin composition 1 constituting the clear hard coat layer 1 measured by the above method was 0.4 GPa.

[Preparation of gas barrier film 3]
In the production of the gas barrier film 2, in place of the single composition clear hard coat layer 1 (3), the resin composition 1 used for forming the clear hard coat layer (3) of the gas barrier film 2 and the following: A resin composition 2 is used to form a hexagonal resin structure (4) composed of the resin composition 2 and the resin composition 1 as shown in FIG. A gas barrier film 3 was produced in the same manner except that the clear hard coat layer 2 composed of the pattern B composed of the resin structure (5) having a partition wall structure was formed.

The width _{L 2} is 300 [mu] m, the width _{L 1} of the resin structure of the barrier rib structure (5) of the hexagonal-like resin structure as shown in FIG. 3 (4) was 60 [mu] m.

(Preparation of clear hard coat layer forming coating solution 2)
It is composed of pentaerythritol triacrylate (A-TTM-3, manufactured by Shin-Nakamura Chemical Co., triester ratio: 37%) and hexamethylene diisocyanate, and the isocyanate group of hexamethylene diisocyanate is 1. Mixed at a ratio of 0 equivalent, using pyropyrene glycol monomethyl ether as the organic solvent, dissolved under the condition that the solid content is 5% by mass, and coating liquid 2 for forming a clear hard coat layer (resin composition 2) Was prepared.

  In addition, it was 0.5 GPa as a result of measuring the hardness of the resin composition 2 produced using the coating liquid 2 for clear hard-coat layer formation according to the said method.

(Formation of clear hard coat layer 2 by inkjet method)
According to the following coating / drying and curing conditions, a clear hard coat layer 2 having a hexagonal pattern B shown in FIG. 3 was formed.

Coater: Two line head type inkjet heads (KM 512L, manufactured by Konica Minolta, standard droplet volume: 42 pl, total number of nozzles: 512) are used. Pattern formation: As shown in FIG. Two ink jet heads (H1 and H2) are arranged on the long resin base material (2) in a direction perpendicular to the transport direction (D) of the resin base material, and the first ink jet head (H1) The clear hard coat layer forming coating solution 2 (resin composition 2) is discharged from the nozzle (N) provided on the lower surface of the substrate to form a hexagonal resin structure (4), and the second inkjet head (H2 5), a clear hard coat layer forming coating solution 1 (resin composition 1) is ejected from a nozzle (N) provided on the lower surface of the substrate) to print a resin structure (5) having a partition wall structure, and FIG. Surface direction as shown by To form a pattern constituting the different areas respectively. Finally, the pattern formed by irradiating ultraviolet rays from an ultraviolet irradiation lamp (UV) was cured to form a clear hard coat layer 2.

The width L ₂ of the hexagonal resin structure (4) was 300 μm, and the width L ₁ of the partition structure resin structure (5) was 60 μm.

Drying conditions: 90 ° C., 90 seconds Drying layer thickness: 2 μm,
Ultraviolet irradiation lamp (UV): high pressure mercury lamp Curing condition: 500 mJ / cm ²
[Preparation of gas barrier film 4]
In the production of the gas barrier film 3, instead of the resin composition 2 used for forming the resin structure (4) of the clear hard coat layer 2, the following resin composition 3 was used, and the hexagon shown in FIG. A gas barrier film 4 was produced in the same manner except that the clear hard coat layer 3 having the shape pattern B was formed.

(Preparation of clear hard coat layer forming coating solution 3)
UV curable resin; UV-7650B (manufactured by Nippon Synthetic Chemical Co., Ltd., urethane acrylate resin, number of oligomer functional groups: 4, pencil hardness: 2H) 30 parts by mass radical polymerization initiator; Irgacure 184 (manufactured by BASF, 1-hydroxy-cyclohexyl) -Phenylketone) 2 parts by weight Inorganic fine particles: Silica fine particles (Aerosil R972V, manufactured by Nippon Aerosil, primary particle size: 17 nm) 0.32 parts by weight Methyl ethyl ketone 68 parts by weight After mixing the above additives, the dispersion treatment is performed to clear. A coating liquid 3 for forming a hard coat layer was prepared.

(Formation of resin structure (4))
A hexagonal pattern B shown in FIG. 3 is formed by a line head type inkjet head using the clear hard coat layer forming coating solution 3 prepared above, and a high pressure mercury lamp is used at 400 mJ / cm ² . It hardened | cured and the clear hard-coat layer 3 was formed.

  In addition, it was 0.6 GPa as a result of measuring the hardness of the resin composition 3 produced using the coating liquid 3 for clear hard-coat layer formation according to the said method.

[Preparation of gas barrier film 5]
In the production of the gas barrier film 4, instead of the resin composition 3 used for forming the resin structure (4) of the clear hard coat layer 3, the following resin composition 4 was used, and the resin structure (5) The clear hard coat layer 4 having the hexagonal pattern B shown in FIG. 3 is formed in the same manner except that the formation is performed by the resin composition 3 used for forming the resin structure (4) of the clear hard coat layer 3. A gas barrier film 5 was produced in the same manner except that was formed.

(Preparation of clear hard coat layer forming coating solution 4 (resin composition 4))
In the preparation of the coating liquid 3 for forming the clear hard coat layer (resin composition 3), the inorganic fine particles (silica fine particles) are removed, and an ultraviolet curable resin; UV-7650B (number of oligomer functional groups: 4, pencil hardness: 2H) Instead of UV-7605B (manufactured by Nippon Synthetic Chemical Co., Ltd., urethane acrylate resin, number of oligomer functional groups: 6, pencil hardness: 3H to 4H), coating solution 4 for forming a clear hard coat layer ( Resin composition 4) was prepared.

  In addition, it was 1.0 GPa as a result of measuring the hardness of the resin composition 4 produced using the coating liquid 4 for clear hard-coat layer formation according to the said method.

[Preparation of gas barrier film 6]
In the production of the gas barrier film 5, instead of the resin composition 4 used for forming the resin structure (4) of the clear hard coat layer 4, the following resin composition 5 was used, and the resin structure (5) Instead of the resin composition 3 used for formation, the clear hard coat layer 5 having the hexagonal pattern B shown in FIG. 3 was formed in the same manner except that the following resin composition 6 was used. Barrier film 6 was produced.

(Preparation of clear hard coat layer forming coating solution 5 (resin composition 5))
As an organic / inorganic hybrid material, Opstar Z7527 (pencil hardness: 4H) manufactured by JSR Corporation was used.

  The hexagonal pattern B shown in FIG. 3 was formed by a line head type ink jet head so that the dry film thickness was 2 μm. In addition, it was 1.1 GPa as a result of measuring the hardness of the resin composition 5 according to the said method.

(Preparation of clear hard coat layer forming coating solution 6 (resin composition 6))
In preparation of the coating liquid 3 for forming the clear hard coat layer (resin composition 3), inorganic fine particles (silica fine particles) are removed, and further, an ultraviolet curable resin; UV-7650B (manufactured by Nippon Synthetic Chemical Industry, urethane acrylate resin, oligomer) It is the same except that UV curable resin; UV-7600B (manufactured by Nippon Gosei Kagaku Co., Ltd., urethane acrylate resin, number of oligomer functional groups: 6, pencil hardness: 3H) is used instead of the number of functional groups: 4, pencil hardness: 2H) Thus, a clear hard coat layer forming coating solution 6 (resin composition 6) was prepared.

  In addition, it was 0.4 GPa as a result of measuring the hardness of the resin composition 6 produced using the coating liquid 6 for clear hard-coat layer formation according to the said method.

[Preparation of gas barrier film 7]
In the production of the gas barrier film 6, the clear hard coat layer 6 having the stripe pattern A shown in FIG. 2 was formed in place of the hexagonal pattern using the resin composition 5 and the resin composition 6. Except for the above, a gas barrier film 7 was produced in the same manner.

[Production of gas barrier film 8]
In the production of the gas barrier film 6, a clear hard coat layer having the triangular pattern C shown in FIG. 4A instead of the hexagonal pattern using the resin composition 5 and the resin composition 6. A gas barrier film 8 was produced in the same manner except that No. 7 was formed.

[Preparation of gas barrier film 9]
In the production of the gas barrier film 6, the resin composition 5 and the resin composition 6 are used, and the clear hard coat layer having the square pattern D shown in FIG. A gas barrier film 9 was produced in the same manner except that 8 was formed.

[Production of Gas Barrier Film 10]
In the production of the gas barrier film 6, a second gas barrier layer (7) containing a perhydropolysilazane modifier is further formed on the first gas barrier layer (6) according to the method described below. A gas barrier film 10 was produced in the same manner except that.

(Formation of second gas barrier layer)
After applying a polysilazane layer-forming coating solution containing polysilazane on the first gas barrier layer (6) and drying to form a precursor layer by the following method, the precursor layer is subjected to vacuum ultraviolet light. A reforming process was performed to form a second gas barrier layer (7).

<Preparation of coating solution for forming polysilazane layer>
A 10 mass% dibutyl ether solution of perhydropolysilazane (PHPS, Aquamica NN120-10, non-catalytic type, manufactured by AZ Electronic Materials Co., Ltd.) was used as a coating liquid for forming a polysilazane layer.

<Formation of polysilazane layer>
While continuously transporting the long (2000 m) gas barrier film 5 (314) using the surface modification treatment apparatus for forming the second gas barrier layer by the roll-to-roll method shown in FIG. 8, the die coater ( 329), the polysilazane layer-forming coating solution prepared above is applied on the first gas barrier layer so that the (average) layer thickness after drying is 300 nm, and the temperature is 85 ° C. in the drying zone (330). The polysilazane layer was formed by treating and drying for 1 minute in an atmosphere with a relative humidity of 55%.

<Formation of gas barrier layer: Silica conversion of polysilazane layer by ultraviolet light>
Next, silica conversion treatment was performed on the formed polysilazane layer in the modifying step (333). Specifically, a plurality of the following ultraviolet devices were installed in a vacuum chamber, the pressure in the device was adjusted, and silica conversion treatment was performed.

<Ultraviolet irradiation device (L1-L30)>
Apparatus: M.com Co., Ltd. excimer irradiation apparatus MODEL: MECL-M-1-200
Irradiation wavelength: 172 nm
Lamp filled gas: Xe
<Reforming treatment conditions>
The gas barrier film (315) on which the continuously containing polysilazane layer is formed is modified under the following conditions to form the second gas barrier layer (7), and the gas barrier film 11 is produced. did.

Excimer lamp light intensity: 130 mW / cm ² (172 nm)
Distance between sample and light source: 1mm
Stage heating temperature: 70 ° C
Oxygen concentration in the irradiation device: 1.0%
[Preparation of gas barrier film 11]
The production of the gas barrier film 9 was the same except that the second gas barrier layer was formed on the first gas barrier layer (6) in the same manner as used for the production of the gas barrier film 10. Thus, a gas barrier film 11 was produced.

[Preparation of gas barrier film 12]
In the preparation of the gas barrier film 6, the resin composition 5 is used as the resin laminate (4) and the resin laminate (5), and the irradiation time of the ultraviolet irradiation lamp is as follows using the following inkjet recording apparatus. A gas barrier film 12 having the clear hard coat layer 11 having the hexagonal pattern B shown in FIG. 3 was produced in the same manner except that the change was made.

  The clear hard coat layer 11 is formed by station 1 (S1) including the inkjet head (H1) and the ultraviolet irradiation lamp (UV1) shown in FIG. 6, and the inkjet head (H2) and ultraviolet irradiation on the downstream side. An ink jet recording apparatus having a configuration in which station 2 (S2) including a lamp (UV2) is arranged was used.

  In forming the hexagonal pattern B of the clear hard coat layer 11, the clear hard coat layer forming coating solution 5 (resin composition 5) is used for forming the resin structure (4) and the resin structure (5). The irradiation conditions of the ultraviolet irradiation lamp (UV) were changed as follows.

(Irradiation conditions of UV irradiation lamp (UV1))
Curing conditions: 300 mJ / cm ²
(Irradiation conditions of ultraviolet irradiation lamp (UV2))
Curing conditions: 200 mJ / cm ²
Under the above irradiation conditions, the resin structure (4) had an integrated irradiation amount of 500 mJ / cm ² and a hardness of 1.1 GPa, like the resin composition. On the other hand, the resin structure (5) had an integrated dose of 200 mJ / cm ² and a hardness of 0.5 GPa.

[Production of gas barrier film 13]
In the production of the gas barrier film 6, instead of the resin composition 5 used to form the resin structure (4) of the clear hard coat layer 5, the following hexagonal resin composition 7 is used, using the following resin composition 7. A gas barrier film 13 was produced in the same manner except that the clear hard coat layer 12 having the shape pattern B was formed.

(Preparation of clear hard coat layer forming coating solution 7 (resin composition 7))
UV curable resin; UV-1700B (manufactured by Nippon Synthetic Chemical Co., Ltd., urethane acrylate resin, number of oligomer functional groups: 10, pencil hardness: 4H) 30 parts by mass radical polymerization initiator; Irgacure 184 (manufactured by BASF, 1-hydroxy-cyclohexyl) -Phenylketone) 2 parts by mass Inorganic fine particles: silica fine particles (Aerosil R972V, manufactured by Nippon Aerosil Co., Ltd., primary particle size: 17 nm) 8 parts by mass Methyl ethyl ketone 68 parts by mass The above additives are mixed and then subjected to a dispersion treatment to form a clear hard coat A layer forming coating solution 7 was prepared.

  In addition, it was 1.3 GPa as a result of measuring the hardness of the resin composition 7 produced using the coating liquid 7 for clear hard-coat layer formation according to the said method.

[Preparation of gas barrier film 14]
In the production of the gas barrier film 6, instead of the resin composition 5 used for forming the resin structure (4) of the clear hard coat layer 5, the following hexagonal resin composition 8 is used by using the following resin composition 8. A gas barrier film 14 was produced in the same manner except that the clear hard coat layer 13 having the shape pattern B was formed.

(Preparation of clear hard coat layer forming coating solution 8 (resin composition 8))
UV curable resin: Hitaroid 7909 (manufactured by Hitachi Chemical Co., Ltd., urethane acrylate resin, pencil hardness: 4H) 30 parts by mass Radical polymerization initiator; Irgacure 184 (manufactured by BASF, 1-hydroxy-cyclohexyl-phenyl ketone) 2 parts by mass Inorganic Fine particles: Silica fine particles (Aerosil R972V, manufactured by Nippon Aerosil Co., Ltd., primary particle size: 17 nm) 8 parts by mass Methyl ethyl ketone 68 parts by mass After mixing the above additives, a dispersion treatment is performed to prepare a coating solution 8 for forming a clear hard coat layer. did.

  In addition, it was 1.3 GPa as a result of measuring the hardness of the resin composition 8 produced using the coating liquid 8 for clear hard-coat layer formation according to the said method.

[Preparation of gas barrier film 15]
In the production of the gas barrier film 6, instead of the resin composition 5 used for forming the resin structure (4) of the clear hard coat layer 5, the following resin composition 9 was used, and the resin structure (5) A gas barrier was formed in the same manner except that the clear hard coat layer 15 having the hexagonal pattern B shown in FIG. 3 was formed using the following resin composition 10 instead of the resin composition 6 used for formation. Film 15 was produced.

(Preparation of clear hard coat layer forming coating solution 9 (resin composition 9))
UV curable resin; Neomer DA-600 (manufactured by Sanyo Chemical Co., Ltd., dipentaerythritol pentaacrylate, functional group number: 5, pencil hardness: 4H) 30 parts by mass radical polymerization initiator; Irgacure 184 (manufactured by BASF, 1-hydroxy- (Cyclohexyl-phenyl ketone) 2 parts by mass Methyl ethyl ketone 68 parts by mass The above additives were mixed to prepare a clear hard coat layer forming coating solution 9.

  In addition, it was 1.1 GPa as a result of measuring the hardness of the resin composition 9 produced using the coating liquid 9 for clear hard-coat layer formation according to the said method.

(Preparation of clear hard coat layer forming coating solution 10 (resin composition 10))
UV curable resin; UV-7550B (manufactured by Nippon Synthetic Chemical Co., Ltd., urethane acrylate resin, number of oligomer functional groups: 3, pencil hardness: F) 30 parts by mass radical polymerization initiator; Irgacure 184 (manufactured by BASF, 1-hydroxy-cyclohexyl) -Phenylketone) 2 parts by mass Methyl ethyl ketone 68 parts by mass The above additives were mixed to prepare a clear hard coat layer forming coating solution 10.

  In addition, it was 0.2 GPa as a result of measuring the hardness of the resin composition 10 produced using the coating liquid 10 for clear hard-coat layer formation according to the said method.

[Preparation of gas barrier film 16]
In the production of the gas barrier film 6, instead of the resin composition 5 used for forming the resin structure (4) of the clear hard coat layer 5, the following resin composition 11 was used, and the resin structure (5) A gas barrier was formed in the same manner except that the clear hard coat layer 15 having the hexagonal pattern B shown in FIG. 3 was formed using the following resin composition 12 instead of the resin composition 6 used for formation. Film 16 was produced.

(Preparation of clear hard coat layer forming coating solution 11 (resin composition 11))
As an organic / inorganic hybrid material, Opstar KZ6445 (pencil hardness: 4H) manufactured by JSR Corporation was used.

  The hexagonal pattern B shown in FIG. 3 was formed by a line head type ink jet head so that the dry film thickness was 2 μm. In addition, as a result of measuring the hardness of the resin composition 11 according to the said method, it was 1.2 GPa.

  In addition, it was 1.2 GPa as a result of measuring the hardness of the resin composition 11 produced using the coating liquid 11 for clear hard-coat layer formation according to the said method.

(Preparation of clear hard coat layer forming coating solution 12 (resin composition 12))
UV curable resin; Neomer PA-305 (manufactured by Sanyo Chemical Co., Ltd., polypropylene glycol diacrylate, functional group number: 2, pencil hardness: H to 2H) 30 parts by mass radical polymerization initiator; Irgacure 184 (manufactured by BASF, 1-hydroxy -Cyclohexyl-phenylketone) 2 parts by mass Methyl ethyl ketone 68 parts by mass The above additives were mixed to prepare a coating solution 12 for forming a clear hard coat layer.

  In addition, it was 0.3 GPa as a result of measuring the hardness of the resin composition 12 produced using the coating liquid 12 for clear hard-coat layer formation according to the said method.

[Production of gas barrier film 17]
In the production of the gas barrier film 6, instead of the resin composition 5 used for forming the resin structure (4) of the clear hard coat layer 5, the following resin composition 13 was used, and the resin structure (5) A gas barrier was formed in the same manner except that the clear hard coat layer 16 having the hexagonal pattern B shown in FIG. 3 was formed using the following resin composition 14 instead of the resin composition 6 used for formation. Film 17 was produced.

(Preparation of clear hard coat layer forming coating solution 13 (resin composition 13))
UV curable resin; dipentaerythritol hexamethacrylate (functional group number: 6, pencil hardness: 4H) 30 parts by mass radical polymerization initiator; Irgacure 184 (BASF, 1-hydroxy-cyclohexyl-phenyl ketone) 2 parts by mass methyl ethyl ketone 68 Part by mass The above additives were mixed to prepare a clear hard coat layer forming coating solution 13.

  In addition, it was 1.1 GPa as a result of measuring the hardness of the resin composition 13 produced using the coating liquid 13 for clear hard-coat layer formation according to the said method.

(Preparation of clear hard coat layer forming coating solution 14 (resin composition 14))
UV curable resin; Neomer TA-401 (manufactured by Sanyo Kasei Co., Ltd., trimethylolpropane (EO) n triacrylate, functional group number: 3, pencil hardness: 3H) 30 parts by mass radical polymerization initiator; Irgacure 184 (manufactured by BASF, 1-hydroxy-cyclohexyl-phenyl ketone) 2 parts by mass Methyl ethyl ketone 68 parts by mass The above additives were mixed to prepare a coating solution 10 for forming a clear hard coat layer.

  In addition, it was 0.6 GPa as a result of measuring the hardness of the resin composition 14 produced using the coating liquid 14 for clear hard coat layer formation according to the said method.

[Preparation of gas barrier film 18]
In the production of the gas barrier film 16, instead of the resin composition 12 used for forming the resin structure (5) of the clear hard coat layer 5, the resin structure (5 of the clear hard coat layer 14 of the gas barrier film 15). The gas barrier film 18 was produced in the same manner except that the clear hard coat layer forming coating solution 10 (resin composition 10) used for the formation of) was used.

[Production of gas barrier film 19]
In the production of the gas barrier film 15, instead of the resin composition 5 used for forming the resin structure (4) of the clear hard coat layer 5, the following hexagonal resin composition 15 is used, using the following resin composition 15. A gas barrier film 19 was produced in the same manner except that the clear hard coat layer 18 having the shape pattern B was formed.

(Preparation of clear hard coat layer forming coating solution 15 (resin composition 15))
UV curable resin: Hitaroid 7909 (manufactured by Hitachi Chemical Co., Ltd., urethane acrylate resin, pencil hardness: 4H) 30 parts by mass Radical polymerization initiator; Irgacure 184 (manufactured by BASF, 1-hydroxy-cyclohexyl-phenyl ketone) 2 parts by mass Inorganic Fine particles: Silica fine particles (Aerosil R972V, manufactured by Nippon Aerosil Co., Ltd., primary particle size: 17 nm) 10.7 parts by mass Methyl ethyl ketone 68 parts by mass After mixing the above-mentioned additives, the dispersion treatment is carried out to form a coating solution 15 for forming a clear hard coat layer. Was prepared.

  In addition, it was 1.4 GPa as a result of measuring the hardness of the resin composition 15 produced using the coating liquid 15 for clear hard-coat layer formation according to the said method.

[Preparation of gas barrier film 20]
In the formation of the clear hard coat layer 5 of the gas barrier film 6, the formation of the hexagonal pattern B shown in FIG. 3 composed of the resin structure (4) and the resin structure (5) is performed by an inkjet method (FIG. Instead of 5), a gas barrier film 20 was produced in the same manner except that it was changed to a known gravure printing method.

[Resin component used in resin composition]
The list of the resin component which comprises the resin composition used for formation of the clear hard-coat layer of each gas barrier film below is shown below.

Resin composition 1: Pentaerythritol triacrylate (Shin-Nakamura Chemical A-TTM-3, functional group number: 3)
Resin composition 2: Pentaerythritol triacrylate (Shin-Nakamura Chemical A-TTM-3, functional group number: 3)
Resin composition 3: UV-7650B (manufactured by Nippon Synthetic Chemical Co., Ltd., urethane acrylate resin, number of oligomer functional groups: 4, pencil hardness: 2H)
Resin composition 4: UV-7605B (manufactured by Nippon Synthetic Chemical Co., Ltd., urethane acrylate resin, number of oligomer functional groups: 6, pencil hardness: 3H to 4H)
Resin composition 5: Organic / inorganic hybrid material Opstar Z7527 (pencil hardness: 4H) manufactured by JSR Corporation
Resin composition 6: UV-7600B (manufactured by Nippon Synthetic Chemical Co., Ltd., urethane acrylate resin, number of oligomer functional groups: 6, pencil hardness: 3H)
Resin composition 7: UV-1700B (manufactured by Nippon Synthetic Chemical Co., Ltd., urethane acrylate resin, number of oligomer functional groups: 10, pencil hardness: 4H)
Resin composition 8: Hitaroid 7909 (manufactured by Hitachi Chemical Co., Ltd., urethane acrylate resin, pencil hardness: 4H)
Resin composition 9: Neomer DA-600 (manufactured by Sanyo Chemical Industries, dipentaerythritol pentaacrylate, functional group number: 5, pencil hardness: 4H)
Resin composition 10: UV-7550B (manufactured by Nippon Synthetic Chemical Co., Ltd., urethane acrylate resin, number of oligomer functional groups: 3, pencil hardness: F)
Resin composition 11: Organic / inorganic hybrid material Opstar KZ6445 (pencil hardness: 4H) manufactured by JSR Corporation
Resin composition 12: Neomer PA-305 (manufactured by Sanyo Kasei Co., Ltd., polypropylene glycol diacrylate, number of functional groups: 2, pencil hardness: H to 2H)
Resin composition 13: Dipentaerythritol hexamethacrylate (functional group number: 6, pencil hardness: 4H)
Resin composition 14: Neomer TA-401 (manufactured by Sanyo Chemical Co., Ltd., trimethylolpropane (EO) n triacrylate, functional group number: 3, pencil hardness: 3H)
Resin composition 15: Hitaroid 7909 (manufactured by Hitachi Chemical Co., Ltd., urethane acrylate resin, pencil hardness: 4H)
<< Production of organic EL element >>
Using each of the gas barrier films produced above, an organic EL element having the configuration shown in FIG. 9 was produced.

(1) Formation of the first electrode (6) On the gas barrier layer (6 or 7) of each gas barrier film (1) formed as described above, it is composed of an underlayer (not shown in FIG. 9) and a thin silver electrode. The first electrode (51) was formed according to the following method.

  The gas barrier film (1) formed up to the gas barrier layer (6 or 7) is fixed to a base material holder of a commercially available vacuum deposition apparatus, and the following compound N is put in a resistance heating boat made of tungsten, and these base material holders And a heating boat were mounted in the first vacuum chamber of the vacuum deposition apparatus. Moreover, silver (Ag) was put into the resistance heating boat made from tungsten, and it attached in the 2nd vacuum chamber of a vacuum evaporation system.

Next, after depressurizing the first vacuum chamber of the vacuum deposition apparatus to 4 × 10 ⁻⁴ Pa, the heating boat containing the compound N was heated by energization, and the deposition rate was 0.1 nm / second to 0.2 nm / second. The base layer of the first electrode (51) was provided with a thickness of 10 nm.

Next, the gas barrier film formed up to the underlayer was transferred to the second vacuum chamber while being vacuumed, and the second vacuum chamber was depressurized to 4 × 10 ⁻⁴ Pa, and then the heating boat containing silver was energized and heated. . Thus, a first electrode (51) made of silver having a thickness of 8 nm was formed at a deposition rate of 0.1 nm / second to 0.2 nm / second.

(2) Organic functional layer 1 (52, hole transport layer), light emitting layer (53), organic functional layer 2 (54,
Formation of Electron Transport Layer) to Second Electrode (55) Subsequently, the gas barrier film (1) formed up to the first electrode (6) after reducing the vacuum to 1 × 10 ⁻⁴ Pa using a commercially available vacuum deposition apparatus. ), Compound HT-1 was deposited at a deposition rate of 0.1 nm / second to provide a 20 nm hole transport layer (HTL).

  Next, compound A-3 (blue light-emitting dopant), compound A-1 (green light-emitting dopant), compound A-2 (red light-emitting dopant) and compound H-1 (host compound), compound A-3 is film thickness In contrast, the vapor deposition rate was changed depending on the location so that it was linearly 35% by mass to 5% by mass, and the compound A-1 and the compound A-2 each had a concentration of 0.2% by mass without depending on the film thickness. Thus, at a deposition rate of 0.0002 nm / sec, the compound H-1 was co-deposited so that the total thickness would be 70 nm by changing the deposition rate depending on the location so that 64.6% by mass to 94.6% by mass. The light emitting layer (53) was formed.

  Thereafter, Compound ET-1 was deposited to a thickness of 30 nm to form an electron transport layer, and potassium fluoride (KF) was further formed to a thickness of 2 nm. Furthermore, aluminum 110nm was vapor-deposited and the 2nd electrode (55) was formed.

  In addition, the said compound HT-1, compound A-1 to 3, compound H-1, and compound ET-1 are the compounds shown below.

(3) Solid sealing Next, an aluminum foil having a thickness of 100 μm is used as the sealing member (57), and a thermosetting liquid adhesive (epoxy type) is used as a sealing resin layer (56) on one surface of the aluminum foil. Using a sealing member (57) bonded with a resin (thickness of 30 μm), it was superimposed on the sample formed up to the second electrode (55). At this time, the adhesive forming surface of the sealing member (57) and the organic EL element (1) are organic so that the ends of the lead electrodes of the first electrode (51) and the second electrode (55) are exposed. The functional layer unit (52 to 54) surface was continuously overlaid.

  Next, the laminated body is placed in a decompression device, and the sample and the sealing member formed between the flexible resin base material and the second electrode overlapped at 90 ° C. under a decompression condition of 0.1 MPa. Pressed and held for 5 minutes. Subsequently, the laminate was returned to the atmospheric pressure environment and further heated at 90 ° C. for 30 minutes to cure the adhesive.

  The sealing step is performed under atmospheric pressure and in a nitrogen atmosphere with a moisture content of 1 ppm or less, in accordance with JIS B 9920, with a measured cleanliness of class 100, a dew point temperature of −80 ° C. or less, and an oxygen concentration of 0.8 ppm or less. At atmospheric pressure. In addition, the description regarding formation of the lead-out wiring etc. from the 1st electrode (51) and the 2nd electrode (55) is abbreviate | omitted.

  In this way, white light emitting organic EL elements 1 to 20 were produced.

<< Evaluation of gas barrier film and organic EL element >>
[Gas barrier film: Evaluation of crack resistance]
Each of the produced gas barrier films was cut into a size of 3 cm × 10 cm and conditioned for 24 hours in an environment of 10 ° C. and 15% RH. Repeated 100 times of wrapping and releasing each conditioned sample with a clear hard coat layer side on the outside with the clear hard coat layer side in the same environment 100 times, and then the surface of the gas barrier film at a magnification of 50 times. The number of occurrences of cracks was measured for 10 visual fields, the average value thereof was determined, and crack resistance was evaluated according to the following criteria.

A: No cracks are observed. O: The average number of cracks is 1 to 2 per visual field. Δ: The average number of cracks is 3 to 5 per visual field. The average number of occurrences is 6 to 15 per field of view XX: The average number of cracks generated is 16 or more per field of view [Organic EL device: Evaluation of dark spot resistance]
Each of the produced organic EL elements is wound on a plastic roller with a curvature of 6 mmφ so that the surface on which the organic EL element is formed is outside, and stored for 100 hours in a high humidity and high temperature environment of 85 ° C. and 85% RH. did. Thereafter, a current of 1 mA / cm ² was applied to emit light. In this state, the light emitting region of the organic EL element was photographed with a 100 × optical microscope (Mortex Co., Ltd. MS-804, lens MP-ZE25-200). Next, the dark spot generation area ratio in a 1 cm × 1 cm region was measured at 10 random locations, the average value was obtained, and bending resistance was evaluated according to the following criteria.

A: The area where dark spots are generated is less than 0.1%. O: The area where dark spots are generated is 0.1% or more and less than 1.0%. Δ: The area where dark spots are generated is 1.0. %: Less than 2.5% ×: Dark spot generation area is 2.5% or more and less than 5.0% XX: Dark spot generation area is 5.0% or more The results obtained from Table 1 are shown in Table 1.

  As is clear from the results shown in Table 1, the present invention provided with a clear hard coat layer having a pattern constituting different regions in the plane direction by two kinds of resin compositions different in hardness specified in the present invention. It can be seen that the gas barrier film is less susceptible to cracking due to film breakage or the like of the gas barrier film-forming layer when it is bent than the comparative example. Furthermore, by providing the organic EL element with the gas barrier film of the present invention, the film of the gas barrier film is peeled off or broken (cracked) even after being stored for a long time in a high temperature and high humidity environment while receiving stress due to bending. It can be seen that the gas barrier ability is not deteriorated due to the above and the like, the high gas barrier property can be maintained, and the effect of excellent dark spot resistance is exhibited.

DESCRIPTION OF SYMBOLS 1 Gas barrier film 2, 314 Resin base material 3 Clear hard-coat layer 4 (1st) resin structure 5 (2nd) resin structure 6 (1st) gas barrier layer 7 2nd gas barrier layer 2 + 3 Resin substrate / organic layer 2 + 3 + 4 Resin substrate / organic layer / gas barrier layer 31 CVD film forming apparatus 32, 322 Delivery roller 33, 34, 35, 36, 323, 324, 326, 327 Transport roller 39, 40 Film formation Roller 41 Gas supply pipe 42 Power source for generating plasma 43, 44 Magnetic field generator 45, 328 Winding roller 51 Anode 52 Organic functional layer group 1
53 Light-Emitting Layer 54 Organic Functional Layer Group 2
55 Cathode 56 Sealing adhesive layer 57 Flexible sealing substrate 201 Device chamber 202 Xe excimer lamp 203 Holder 204 Sample stage 205 Sample 206 Light-shielding plate 314 Resin base material laminate 1
315 Resin substrate laminate 2
329 Die coater 330 Drying zone 331 Housing 332 Application / drying process 333 Modification process D Transport direction EL Organic EL element H1, H2 Inkjet head I Ink droplets L1 to L30 Vacuum ultraviolet lamp (excimer lamp)
N nozzle T1-T32 Support roller with built-in temperature control device S1 Station 1
S2 Station 2
Width of W ₁ resin structure (5) Width of W ₂ resin structure (4) UV, UV1, UV2 UV irradiation lamp

Claims (9)

A gas barrier film in which a clear hard coat layer and a gas barrier layer are laminated in this order on a resin substrate,
The clear hard coat layer is composed of two or more resin compositions having different hardnesses measured by a nanoindentation method,
The maximum hardness difference between two or more resin compositions having different hardnesses is 0.2 GPa or more,
The gas barrier film is characterized in that the two or more kinds of resin compositions having different hardnesses have patterns constituting different regions in the plane direction.   Of the two or more resin compositions having different hardnesses, the resin composition having the lowest hardness has a hardness in the range of 0.1 to 0.6 GPa, and the resin composition having the highest hardness has a hardness of 0. The gas barrier film according to claim 1, wherein the gas barrier film is in a range of 0.8 to 1.5 GPa.   The gas barrier film according to claim 1 or 2, wherein a maximum hardness difference between two or more kinds of resin compositions constituting the clear hard coat layer is 0.5 GPa or more.   The at least 1 sort (s) of 2 or more types of resin composition from which the hardness which comprises the pattern of the said clear hard-coat layer differs forms the cylinder structure isolate | separated independently by the surface direction. The gas barrier film according to any one of 3 to 3.   The gas barrier film according to any one of claims 1 to 4, wherein the pattern of the clear hard coat layer has a discontinuous polygon pattern.   6. The resin composition according to claim 1, wherein the two or more resin compositions having different hardnesses constituting the clear hard coat layer are made of different ultraviolet curable resin materials. The gas barrier film as described in 2.   The gas barrier film according to any one of claims 1 to 6, wherein at least one of the resin compositions constituting the pattern of the clear hard coat layer contains inorganic fine particles. .   The gas barrier film according to any one of claims 1 to 7, wherein the gas barrier layer has a metal oxide formed by a chemical vapor deposition method or a physical vapor deposition method.   The gas barrier film according to any one of claims 1 to 8, further comprising a second gas barrier layer containing a modified perhydropolysilazane on the gas barrier layer.

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