JPWO2016009801A1 - Gas barrier film and electronic device - Google Patents

Abstract

Provided is a gas barrier film having high gas barrier properties and excellent in-plane uniformity of gas barrier properties. In addition, an electronic device having excellent durability in a high temperature and high humidity environment is provided. A gas barrier film having, in this order, an anchor coat layer and a gas barrier layer in contact with the anchor coat layer and formed by a vacuum film forming method on a substrate, wherein the anchor coat layer is a layer containing polysilazane. It is a layer obtained by performing a modification treatment applying energy, and the thickness of the anchor coat layer is A (nm), and the atomic ratio of nitrogen atoms to silicon atoms (N / Si) of the entire anchor coat layer ) Is a gas barrier film, where A × B ≦ 60.

Description

  The present invention relates to a gas barrier film and an electronic device.

  Conventionally, a gas barrier film formed by laminating a plurality of layers including thin films of metal oxides such as aluminum oxide, magnesium oxide, and silicon oxide on the surface of a plastic substrate or film is used to block various gases such as water vapor and oxygen. For example, it is widely used for packaging of articles that require the use of, for example, packaging for preventing deterioration of foods, industrial products, pharmaceuticals, and the like.

  In addition to packaging applications, development to flexible electronic devices such as flexible solar cell elements, organic electroluminescence (EL) elements, liquid crystal display elements, etc. has been demanded, and many studies have been made. However, gas barrier films used for sealing organic EL devices are required to have high barrier properties and flexibility. In particular, a bottom emission type organic EL device using a gas barrier film as a substrate is required to have a gas barrier property with a very high glass level, and in-plane uniformity of the gas barrier property (a portion having a low barrier property in a spot shape). Is not required).

  Conventionally, a gas barrier layer included in such a gas barrier film has been formed by a plasma CVD method (see, for example, Patent Document 1). However, when the gas barrier layer was formed by plasma CVD using high plasma excitation power, it was found that the substrate surface was subject to an energy load during film formation, and the gas barrier layer was likely to be damaged. When such a gas barrier film is used as a substrate of an organic EL device, many dark spots are generated, and thus it has been demanded to improve damage to the base material and the gas barrier layer.

  In order to improve the damage to the base material and gas barrier layer of such a gas barrier film, it has recently been studied to provide an undercoat layer under the gas barrier layer formed by a vacuum film forming method. For example, Patent Document 2 discloses an undercoat layer having a high inorganic component ratio, which is formed by applying and drying a coating solution containing a silane coupling agent as a main component.

  Patent Document 3 discloses an undercoat layer mainly composed of an inorganic component formed by applying dialkoxysilane to polysilazane (PHPS) and applying and drying the mixed application liquid as an undercoat layer of the vapor deposition barrier layer. Has been.

  Furthermore, in Patent Document 4, at least a part is modified by irradiating a polysilazane film formed by applying and drying a coating liquid containing polysilazane on a lower portion of a gas barrier layer formed by a vacuum film-forming method by drying. Thus, providing an inorganic film having a gas barrier property on the surface is disclosed.

International Publication No. 2006/033233 JP 2012-232504 A JP 2012-254579 A International Publication No. 2011/007543

  However, in the technique described in Patent Document 2 or 3, an alkoxy group or Si—OH remains in the undercoat layer. For this reason, when a gas barrier layer is formed on the undercoat layer by a method such as plasma CVD, strong energy is applied to the undercoat layer, alcohol and water are generated, and defects are formed in spots in the gas barrier layer. End up. Therefore, there is a problem that the in-plane uniformity of the gas barrier property cannot be ensured.

  Furthermore, in the technique described in Patent Document 4, when a gas barrier layer is formed on the inorganic film by plasma CVD, outgas such as ammonia or hydrogen is generated from unmodified polysilazane. Thereby, the inorganic film and the gas barrier layer thereon are greatly deformed, and defects are formed in the gas barrier layer. Therefore, there has been a problem that a gas barrier film having a high level of gas barrier property used as a base of an organic EL device cannot be obtained.

  Therefore, the present invention has been made in view of the above circumstances, and an object thereof is to provide a gas barrier film having high gas barrier properties and in-plane uniformity of gas barrier properties. Another object of the present invention is to provide an electronic device excellent in durability in a high temperature and high humidity environment.

  The present inventors have intensively studied to solve the above problems. As a result, an anchor coat layer obtained by applying energy to a layer containing polysilazane and modifying the substrate, and a gas barrier layer in contact with the anchor coat layer and formed by a vacuum film formation method in this order. And the present invention finds that the above problem can be solved by a gas barrier film in which the product of the thickness of the anchor coat layer and the atomic ratio of nitrogen atoms to silicon atoms in the entire anchor coat layer is a specific value or less. It came to complete.

  That is, the above-described problem of the present invention is a gas barrier film having, in this order, an anchor coat layer and a gas barrier layer that is in contact with the anchor coat layer and is formed by a vacuum film forming method on the base material. The coat layer is a layer obtained by applying energy to the polysilazane-containing layer and performing a modification treatment. The thickness of the anchor coat layer is A (nm), and the anchor coat layer has a total thickness of silicon atoms. This is achieved by a gas barrier film where A × B ≦ 60, where B is the atomic ratio of nitrogen atoms (N / Si).

It is a schematic diagram which shows an example of the vacuum plasma CVD apparatus used for formation of the CVD layer which is a preferable form of the gas barrier layer concerning this invention. It is a schematic diagram which shows an example of the other manufacturing apparatus used for formation of the CVD layer which is a preferable form of the gas barrier layer which concerns on this invention.

  The present invention is a gas barrier film having, in this order, an anchor coat layer and a gas barrier layer that is in contact with the anchor coat layer and formed by a vacuum film formation method on a base material, wherein the anchor coat layer comprises polysilazane. The layer containing the carbon atom is obtained by applying energy to the layer, and the thickness of the anchor coat layer is A (nm), and the atomic ratio of nitrogen atoms to silicon atoms in the entire anchor coat layer A gas barrier film where A × B ≦ 60, where B is N / Si (hereinafter also referred to simply as N / Si ratio).

  The gas barrier film of the present invention has high gas barrier properties and excellent in-plane uniformity of gas barrier properties. Moreover, the electronic device having the gas barrier film of the present invention is excellent in durability in a high temperature and high humidity environment.

  The gas barrier film of the present invention is characterized in that A × B ≦ 60 when the thickness of the anchor coat layer is A (nm) and the N / Si ratio of the entire anchor coat layer is B. The gas barrier film having such a configuration has high gas barrier properties and in-plane uniformity of gas barrier properties. Here, the mechanism for exerting the above-described effects by the configuration of the present invention is presumed as follows. The present invention is not limited to the following.

  That is, the condition A × B to be satisfied by the anchor coat layer of the gas barrier film according to the present invention indirectly indicates the amount of nitrogen contained in the anchor coat layer, and the larger the value, the more included in the anchor coat layer. Indicates that the amount of nitrogen is large. By controlling this value, the amount of outgas generated can be suppressed. Therefore, it is possible to obtain a gas barrier film having high gas barrier properties and in-plane uniformity of gas barrier properties by suppressing the generation of defects during the film formation process of the gas barrier layer.

  Specifically, in order to form a high-density gas barrier layer on an anchor coat layer having a flexible and high gas barrier property, that is, a region having a composition distribution with a high carbon concentration in the film thickness direction, Unlike the conditions, it is necessary to apply high energy under vacuum. Here, the anchor coat layer is formed by applying an energy such as vacuum ultraviolet light to the layer containing polysilazane and performing a modification treatment. For this reason, an unmodified region containing more nitrogen and hydrogen tends to remain on the base material side of the anchor coat layer where the energy such as vacuum ultraviolet light is difficult to reach compared to the vicinity of the surface. When a gas barrier layer is formed by applying high energy under the above-described vacuum on the anchor coat layer where the unmodified polysilazane remains, the unmodified polysilazane contained in the anchor coat layer The reforming proceeds rapidly, and outgas consisting of ammonia, hydrogen, etc. is generated. The amount of generated outgas increases as the amount of nitrogen contained in the anchor coat layer increases.

  When the modification of the surface of the anchor coat layer has already progressed sufficiently, since it has a high gas barrier property, the exit path of the generated outgas is only on the substrate side. However, since it is under vacuum, outgas is difficult to escape, and outgas bubbles are generated between the base material and the anchor coat layer, causing defects in the gas barrier layer and the anchor coat layer. As a result, the gas barrier property of the gas barrier film is lowered, and a portion having a low gas barrier property is generated in a spot shape.

  Therefore, the amount of outgas generated between the anchor coat layer and the substrate is reduced by setting the value of A × B to a predetermined value or less, that is, by reducing the amount of nitrogen contained in the anchor coat layer. The generation of bubbles can be suppressed.

  Therefore, the gas barrier film of the present invention has high gas barrier properties and in-plane uniformity of gas barrier properties.

  Embodiments of the present invention will be described below. In addition, this invention is not limited only to the following embodiment. In addition, the dimensional ratios in the drawings are exaggerated for convenience of explanation, and may be different from the actual ratios.

  In this specification, “X to Y” indicating a range means “X or more and Y or less”. Unless otherwise specified, measurement of operation and physical properties is performed under conditions of room temperature (20 to 25 ° C.) / Relative humidity 40 to 50%.

[Base material]
Examples of the base material used in the gas barrier film of the present invention include a metal substrate such as silicon, a glass substrate, a ceramic substrate, a plastic film, and the like, and a plastic film is preferably used. The plastic film to be used is not particularly limited in material, thickness and the like as long as it can hold a barrier layer, a clear hard coat layer, and the like, and can be appropriately selected according to the purpose of use. Specific examples of the plastic film include polyester resin, methacrylic resin, methacrylic acid-maleic acid copolymer, polystyrene resin, transparent fluororesin, polyimide, fluorinated polyimide resin, polyamide resin, polyamideimide resin, and polyetherimide. Resin, cellulose acylate resin, polyurethane resin, polyetheretherketone resin, polycarbonate resin, alicyclic polyolefin resin, polyarylate resin, polyethersulfone resin, polysulfone resin, cycloolefin copolymer, fluorene ring-modified polycarbonate resin, alicyclic ring Examples thereof include thermoplastic resins such as modified polycarbonate resins, fluorene ring-modified polyester resins, and acryloyl compounds.

  In addition, as for the type of the base material and the manufacturing method of the base material, the techniques disclosed in paragraphs “0125” to “0136” of JP2013-226758A can be appropriately employed.

[Anchor coat layer]
The anchor coat layer is a layer obtained by applying a coating solution containing a polysilazane compound on a substrate and applying energy to the resulting polysilazane-containing layer for modification treatment. In the anchor coat layer according to the present invention, A × B ≦ 60, where A (nm) is the thickness of the anchor coat layer and B is the N / Si ratio of the entire anchor coat layer. The anchor coat layer may be a single layer or a laminated structure of two or more layers.

  When A × B> 60, when the gas barrier layer is formed on the anchor coat layer by a vacuum film forming method, a defect occurs in the gas barrier film due to the generation of bubbles accompanying the rapid outgas generation, and the gas barrier And in-plane uniformity of gas barrier properties are deteriorated.

  The lower limit of A × B may be 0 or more, but is preferably 3 or more, more preferably 10 or more from the viewpoint of improving gas barrier properties. Moreover, although the upper limit of AxB is 60 or less from a viewpoint of the above-mentioned outgas generation | occurrence | production, it is preferable that it is 50 or less, and it is more preferable that it is 30 or less.

  The anchor coat layer may be a single layer or a laminated structure of two or more layers. When the anchor coat layer has a laminated structure of two or more layers, the respective anchor coat layers may have the same composition or different compositions.

  As the upper limit of the thickness (A) of the anchor coat layer, when the energy is applied to the layer containing polysilazane as described later, the energy reaches the polysilazane on the substrate side for modification. From the viewpoint of sufficiently proceeding, it is preferably 1000 nm or less, more preferably 500 nm or less, still more preferably 300 nm or less, even more preferably less than 150 nm, and particularly preferably 120 nm or less. .

  Further, the lower limit value of the thickness of the anchor coat layer is preferably 5 nm or more from the viewpoint of preventing the base material from being damaged by plasma irradiation or the like during vacuum film formation or suppressing the generation of bubbles. More preferably, it is 30 nm or more, and further preferably 40 nm or more. The thickness of the anchor coat layer can be measured by observing the cross section of the layer with a transmission electron microscope (TEM).

  Further, the N / Si ratio (B) of the anchor coat layer is preferably 0.01 to 0.40, more preferably 0.05 to 0.30, and preferably 0.1 to 0.25. More preferably it is. If it is this range, the value of AxB can be made into a preferable range, having a preferable function as the above-mentioned anchor coat layer.

  In addition, when there are two or more anchor coat layers, A × B ≦ 60 is satisfied for each layer.

  The method for adjusting the N / Si ratio of the anchor coat layer is not particularly limited. For example, (1) a method for reducing the N / Si ratio during the modification treatment of the polysilazane-containing layer, and (2) polysilazane. A method of performing aging after the modification treatment of the layer containing, (3) a method of performing additional excimer modification treatment after the modification treatment of the layer containing polysilazane, and (4) modifying the layer in which the aluminum compound is added to polysilazane. And the like. By applying the above-described method in the anchor coating layer forming step, an anchor coating layer satisfying A × B ≦ 60 can be efficiently obtained, and high gas barrier properties and in-plane uniformity of gas barrier properties can be obtained. The gas barrier film which has can be obtained efficiently. Hereinafter, these methods will be briefly described.

(1) Method of reducing the N / Si ratio during the modification treatment of the layer containing polysilazane As a method of reducing the N / Si ratio during the modification treatment of the layer containing polysilazane, the film thickness of the layer containing polysilazane Is a thin layer of about 10 to 130 nm.

  When the thickness of the polysilazane-containing layer is reduced, energy such as excimer light reaches the substrate side during the modification treatment, and particularly in the range of 110 to 150 nm. The modification progresses greatly because it reaches the material surface significantly. Although this mechanism is not clear, it is known that the polysilazane layer has a high absorptivity of the excimer light when excimer light having a wavelength of 172 nm is used, for example, it absorbs about 90% at a thickness of 120 nm. In this region, the N / Si ratio can be greatly reduced from 0.8 before the modification. This is thought to be due to the fact that the excimer light reaches the substrate surface, the moisture contained in the substrate surface is released, and using this as an oxygen source, the nitrogen of the polysilazane is replaced by oxygen and the reforming proceeds.

  For this reason, the thickness of the layer containing polysilazane can be reduced, and the modification can be further promoted by changing the composition of the substrate surface. For example, a layer containing inorganic fine particles having crystal water is formed between the layer containing polysilazane and the substrate. By doing in this way, the water which contributes to modification | reformation of polysilazane in the modification | reformation process comes to be supplied more from the base material side, and modification | reformation can be accelerated | stimulated.

  The inorganic fine particles having crystal water are not particularly limited. For example, silicon oxide, titanium oxide, zinc oxide, aluminum oxide, zirconium oxide, hafnium oxide, niobium oxide, tantalum oxide, magnesium oxide, calcium oxide, strontium oxide, and oxidation. Barium, indium oxide, tin oxide, lead oxide and the like can be mentioned. Of these, silicon oxide is preferable, and colloidal silica is more preferable. Such inorganic fine particles may be contained in a clear hard coat layer coating solution that can be provided on the surface of the substrate. As such a coating solution, a commercially available product can be used. For example, an OPSTAR (registered trademark) series manufactured by JSR Corporation (a compound obtained by bonding an organic compound having a polymerizable unsaturated group to silica fine particles). Containing coating liquid).

  The film thickness of the polysilazane-containing layer in this embodiment is preferably 40 to 130 nm, from the viewpoint that oxidation proceeds to a preferable N / Si ratio with moisture supplied from the substrate side during the modification treatment. Preferably it is 60-120 nm.

(2) Method of performing aging after the modification treatment of the layer containing polysilazane By adjusting the N / Si ratio of the anchor coat layer by performing aging (heating, humidification) after the modification treatment of the layer containing polysilazane. be able to. As aging conditions, it is preferable to perform aging for 1 hour to 10 days at 40 to 90 ° C. and relative humidity of 40 to 100% RH.

  Further, by adding a catalyst to the layer containing polysilazane when aging is performed, reforming can be promoted when energy is applied, which will be described later. For example, 1-5 mass% of amine catalysts can be contained with respect to polysilazane. The thickness of the polysilazane layer in this embodiment is preferably 40 to 500 nm, more preferably 60 to 400 nm, from the viewpoint of allowing oxidation to proceed to a preferable N / Si ratio.

(3) Method of performing additional modification process after modification process of layer containing polysilazane Rather than applying the amount of irradiation energy of modification process as one modification process, the modification process is divided into multiple times Is preferable because the N / Si ratio can be greatly reduced. The number of reforming treatments is preferably 2 to 10 times. For example, when the reforming process is performed twice, the interval between the reforming processes is preferably 6 hours or more, and more preferably 12 hours or more. The upper limit of the interval when performing the twice reforming treatment is not particularly limited, but it is preferably within 7 days from the viewpoint of the process cost and the above-mentioned aging effect. The film thickness of the polysilazane-containing layer in this embodiment is preferably 40 to 500 nm, more preferably 60 to 400 nm, from the viewpoint of proceeding oxidation to a preferable N / Si ratio.

(4) Method of modifying the layer in which the aluminum compound is added to polysilazane By modifying the layer in which the aluminum compound is added to polysilazane, the modification of the polysilazane proceeds remarkably, and the N / Si ratio is almost zero. In addition, an anchor coat layer having gas barrier properties can be obtained.

  Examples of the aluminum compound include, for example, aluminum trimethoxide, aluminum triethoxide, aluminum tri n-propoxide, aluminum triisopropoxide, aluminum tri n-butoxide, aluminum tri sec-butoxide, aluminum tri tert-butoxide. , Aluminum acetylacetonate, acetoalkoxyaluminum diisopropylate, aluminum ethyl acetoacetate diisopropylate, aluminum ethyl acetoacetate di n-butyrate, aluminum diethyl acetoacetate mono n-butyrate, aluminum diisopropylate mono sec-butylate, aluminum Trisacetylacetonate, aluminum trisethylacetoacetate, bis (eth Acetoacetate) (2,4-pentanedionato) aluminum, aluminum alkyl acetoacetate diisopropylate, aluminum oxide isopropoxide trimer, aluminum oxide octylate trimer. These can be used alone or in combination of two or more.

  The content of the aluminum compound is preferably 0.01 to 0.2 as the Al / Si element ratio. Moreover, the film thickness of the layer in which aluminum is added to polysilazane in this embodiment is preferably 40 to 500 nm, more preferably 60 to 400 nm, from the viewpoint of sufficiently progressing modification of polysilazane.

  The N / Si ratio of the anchor coat layer as a whole can be obtained by measurement by the following method using XPS (photoelectron spectroscopy) analysis.

  The XPS analysis in the present invention is performed under the following conditions, but even if the apparatus and measurement conditions are changed, any measurement method that conforms to the gist of the present invention can be applied without any problem.

The measurement method according to the gist of the present invention is mainly resolution in the thickness direction, and the etching depth per measurement point (corresponding to the conditions of the following sputter ion and depth profile) is 1 to 15 nm. It is preferable that the thickness is 1 to 10 nm. Under the following conditions, the etching depth (etching rate) per measurement point corresponds to about 2.8 nm in terms of SiO ₂ .

  << XPS analysis conditions >>
  ・ Equipment: ULVAC-PHI QUANTERASXM
  ・ X-ray source: Monochromatic Al-Kα
  Measurement area: Si2p, C1s, N1s, O1s
  ・ Sputtering ion: Ar (2 keV)
  Depth profile: repeats measurement after sputtering for a certain time. One measurement is SiO ₂Adjust the sputtering time so that it becomes approximately 2.8 nm in terms of conversion.
  Quantification: The background was determined by the Shirley method, and quantified using the relative sensitivity coefficient method from the obtained peak area. For data processing, MultiPak manufactured by ULVAC-PHI was used.

  Next, a method for forming the anchor coat layer will be described.

<Coating method>
The anchor coat layer according to the present invention is formed by applying energy to a coating film formed by applying a coating liquid containing polysilazane since the defects such as film formability and cracks are few (coating film) Forming method). Hereinafter, the coating film forming method will be described.

  Examples of polysilazane include perhydropolysilazane, organopolysilazane, and the like, but perhydropolysilazane is preferred because of the small amount of residual organic matter.

Polysilazane is a polymer having a silicon-nitrogen bond, and ceramics such as SiO ₂ , Si ₃ N ₄ , and both intermediate solid solutions SiO _x N _y having bonds such as Si—N, Si—H, and N—H. It is a precursor inorganic polymer.

  Specifically, the polysilazane preferably has the following structure.

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 , Condensed polycyclic hydrocarbon groups such as acenaphthenyl group, phenalenyl group, phenanthryl group, anthryl group, fluoranthenyl group, acephenanthrenyl group, aceantrirenyl group, triphenylenyl group, pyrenyl group, chrysenyl group, naphthacenyl group, etc. 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 hydroxyl group (—OH), a mercapto group (—SH), a cyano group (—CN), There are a sulfo group (—SO ₃ H), a carboxyl group (—COOH), a nitro group (—NO ₂ ), and the like. In addition, the substituent which exists depending on the case does not become the same as R < ₁ > -R < ₃ > to substitute. 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.

  In the general formula (I), n is an integer, and the polysilazane having the structure represented by the general formula (I) is determined to have a number average molecular weight of 150 to 150,000 g / mol. preferable.

  In the compound having the structure represented by the general formula (I), one of preferable embodiments is R ₁, R₂And R₃Is perhydropolysilazane, all of which are hydrogen atoms. The anchor coat layer formed from such polysilazane has high density.

  Alternatively, polysilazane has a structure represented by the following general formula (II).

In the general formula (II), R _{1 ′} , R _{2 ′} , R _{3 ′} , R _{4 ′} , R _{5 ′} and R _{6 ′} are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, An aryl group, a vinyl group or a (trialkoxysilyl) alkyl group. In this case, R _{1 ′} , R _{2 ′} , R _{3 ′} , R _{4 ′} , R _{5 ′} and R _{6 ′} may be the same or different. The substituted or unsubstituted alkyl group, aryl group, vinyl group or (trialkoxysilyl) alkyl group in the above is the same as the definition of the general formula (I), and thus the description is omitted.

  In the general formula (II), n ′ and p are integers, and the polysilazane having the structure represented by the general formula (II) is determined to have a number average molecular weight of 150 to 150,000 g / mol. It is preferred that Note that n ′ and p may be the same or different.

Among the polysilazanes of the above general formula (II), R _{1 ′} , R _{3 ′} and R _{6 ′} each represent a hydrogen atom, and R _{2 ′} , R _{4 ′} and R _{5 ′} each represent a methyl group; R _{1 '} , R _3' and R _{6 '} each represents a hydrogen atom, R _2' , R _{4 '} each represents a methyl group, and R _5' represents a vinyl group; R _{1 '} , R _3' , R ₄ A compound in which _' and R _6' each represent a hydrogen atom and R _{2 '} and R _5' each represents a methyl group is preferred.

  Alternatively, polysilazane has a structure represented by the following general formula (III).

In the general formula (III), R _{1 ″} , R _{2 ″} , R _{3 ″} , R _{4 ″} , R _{5 ″} , R _{6 ″} , R _{7 ″} , R _{8 ″} and R _{9 ″} are each independently A hydrogen atom, a substituted or unsubstituted alkyl group, aryl group, vinyl group or (trialkoxysilyl) alkyl group, wherein R _{1 ″} , R _{2 ″} , R _{3 ″} , R _{4 ″} , R _{5 ″} , R _{6 ″} , R _{7 ″} , R _{8 ″} and R _{9 ″} may be the same or different. The substituted or unsubstituted alkyl group, aryl group, vinyl group or (trialkoxysilyl) alkyl group in the above is the same as the definition of the general formula (I), and thus the description is omitted.

  In the general formula (III), n ″, p ″ and q are integers, and the polysilazane having the structure represented by the general formula (III) has a number average molecular weight of 150 to 150,000 g / mol. It is preferable to be determined as follows. Note that n ″, p ″, and q may be the same or different.

Of the polysilazanes of the above general formula (III), R _{1 ″} , R _{3 ″} and R _{6 ″} each represent a hydrogen atom, and R _{2 ″} , R _{4 ″} , R _{5 ″} and R _{8 ″} each represent a methyl group. , R _{9 ″} represents a (triethoxysilyl) propyl group, and R _{7 ″} represents an alkyl group or a hydrogen atom.

  On the other hand, the organopolysilazane in which a part of the hydrogen atom portion bonded to Si is substituted with an alkyl group or the like has improved adhesion to the base material as a base by having an alkyl group such as a methyl group and is hard. The ceramic film made of brittle polysilazane can be toughened, and there is an advantage that the occurrence of cracks can be suppressed even when the (average) film thickness is increased. For this reason, these perhydropolysilazane and organopolysilazane may be appropriately selected according to the application, and may be used in combination.

  Perhydropolysilazane is presumed to have a linear structure and a ring structure centered on 6- and 8-membered rings. Its molecular weight is about 600 to 2000 (polystyrene conversion) in terms of number average molecular weight (Mn), and there are liquid or solid substances, and the state varies depending on the molecular weight.

  Polysilazane is commercially available in a solution state dissolved in an organic solvent, and a commercially available product may be used as it is as a coating solution for forming an anchor coat layer, or a plurality of commercially available products may be mixed and used. Moreover, you may dilute and use a commercial item with a suitable solvent. As a commercially available product of polysilazane solution, NN120-10, NN120-20, NAX120-20, NN110, NN310, NN320, NL110A, NL120A, NL120-20, NL150A, NP110, NP140, SP140, etc. manufactured by AZ Electronic Materials Co., Ltd. Is mentioned.

  When polysilazane is used, the content of polysilazane in the anchor coat layer before energy application can be 100% by mass when the total weight of the anchor coat layer is 100% by mass. When the anchor coat layer contains other than polysilazane, the content of polysilazane in the anchor coat layer is preferably 10% by mass or more and 99% by mass or less, and 40% by mass or more and 95% by mass or less. More preferably, it is 70 mass% or more and 95 mass% or less.

(Coating solution for anchor coat layer formation)
The solvent for preparing the coating solution for forming the anchor coat layer is not particularly limited as long as it can dissolve polysilazane, but water and reactive groups (for example, hydroxyl group or amine) that easily react with polysilazane. An organic solvent inert to polysilazane, and more preferably an aprotic organic solvent. Specifically, the solvent is an aprotic solvent; for example, carbon such as aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons such as pentane, hexane, cyclohexane, toluene, xylene, solvesso, terpenes, etc. Hydrogen solvents; Halogen hydrocarbon solvents such as methylene chloride and trichloroethane; Esters such as ethyl acetate and butyl acetate; Ketones such as acetone and methyl ethyl ketone; Aliphatic ethers such as dibutyl ether, dioxane and tetrahydrofuran; Alicyclic ethers and the like Ethers: Examples include tetrahydrofuran, dibutyl ether, mono- and polyalkylene glycol dialkyl ethers (diglymes), and the like. The solvent is selected according to purposes such as the solubility of the silicon compound and the evaporation rate of the solvent, and may be used alone or in the form of a mixture of two or more.

  The concentration of polysilazane in the coating liquid for forming the anchor coat layer is not particularly limited, and varies depending on the thickness of the anchor coat layer and the pot life of the coating liquid, but is preferably 1 to 80% by mass, more preferably 5 to 50% by mass. %, More preferably 10 to 40% by mass.

  The anchor coating layer forming coating solution preferably contains a catalyst in order to promote the modification. As the catalyst applicable to the present invention, a basic catalyst is preferable, and in particular, N, N-diethylethanolamine, N, N-dimethylethanolamine, triethanolamine, triethylamine, 3-morpholinopropylamine, N, N, N ", N" -tetramethyl-1,3-diaminopropane, amine catalysts such as N, N, N ", N" -tetramethyl-1,6-diaminohexane, Pt compounds such as Pt acetylacetonate, propion Examples thereof include metal catalysts such as Pd compounds such as acid Pd, Rh compounds such as Rh acetylacetonate, and N-heterocyclic compounds. Of these, it is preferable to use an amine catalyst. The concentration of the catalyst added at this time is preferably in the range of 0.1 to 10% by mass, more preferably 0.5 to 7% by mass, based on the silicon compound. By setting the addition amount of the catalyst within this range, it is possible to avoid excessive silanol formation due to rapid progress of the reaction, decrease in film density, increase in film defects, and the like.

  The following additives can be used in the anchor coating layer forming coating solution as necessary. For example, cellulose ethers, cellulose esters; for example, ethyl cellulose, nitrocellulose, cellulose acetate, cellulose acetobutyrate, etc., natural resins; for example, rubber, rosin resin, etc., synthetic resins; Aminoplasts, especially urea resins, melamine formaldehyde resins, alkyd resins, acrylic resins, polyesters or modified polyesters, epoxides, polyisocyanates or blocked polyisocyanates, polysiloxanes, and the like.

(Method for forming a layer containing polysilazane)
The layer containing polysilazane can be formed by applying the above-described coating liquid for forming an anchor coat layer on a substrate. As a coating method, a conventionally known appropriate wet coating method can be adopted. Specific examples include spin coating method, roll coating method, flow coating method, ink jet method, spray coating method, printing method, dip coating method, casting film forming method, bar coating method, die coating method, gravure printing method and the like. It is done.

  The coating thickness can be appropriately selected according to the thickness of the anchor coat layer.

  After applying the coating solution, it is preferable to dry the coating film. By drying the coating film, the organic solvent contained in the coating film can be removed. At this time, all of the organic solvent contained in the coating film may be dried or may be partially left. Even when a part of the organic solvent is left, a suitable anchor coat layer can be obtained. The remaining solvent can be removed later.

  Although the drying temperature of a coating film changes also with the base material to apply, it is preferable that it is 50-200 degreeC. For example, when a polyethylene terephthalate substrate having a glass transition temperature (Tg) of 70 ° C. is used as the substrate, the drying temperature is preferably set to 150 ° C. or less in consideration of deformation of the substrate due to heat.

<Application of energy>
Subsequently, energy is applied to the polysilazane-containing layer formed as described above to modify the polysilazane and modify the anchor coat layer.

  As a method for applying energy to the polysilazane-containing layer, a known method can be appropriately selected and applied. Specific examples of the modification treatment include plasma treatment, ultraviolet irradiation treatment, and heat treatment. However, in the case of modification by heat treatment, since a high temperature of 450 ° C. or higher is required, adaptation is difficult for flexible substrates such as plastic. For this reason, it is preferable to perform the heat treatment in combination with other reforming treatments.

  Therefore, as the modification treatment, from the viewpoint of adapting to a plastic substrate, a plasma treatment capable of a conversion reaction at a lower temperature or a conversion reaction by ultraviolet irradiation treatment is preferable.

  Hereinafter, plasma treatment and ultraviolet irradiation treatment, which are preferable modification treatment methods, will be described.

(Plasma treatment)
In the present invention, a known method can be used as the plasma treatment that can be used as the modification treatment, and an atmospheric pressure plasma treatment or the like can be preferably used. The atmospheric pressure plasma CVD method, which performs plasma CVD processing near atmospheric pressure, does not need to be reduced in pressure and is more productive than the plasma CVD method under vacuum. The film speed is high, and further, under a high pressure condition under atmospheric pressure as compared with the conditions of a normal CVD method, the gas mean free process is very short, so that a very homogeneous film can be obtained.

  In the case of atmospheric pressure plasma treatment, as the discharge gas, nitrogen gas or a gas containing Group 18 atoms of the long-period periodic table, specifically helium, neon, argon, krypton, xenon, radon, or the like is used. Among these, nitrogen, helium, and argon are preferably used, and nitrogen is particularly preferable because of low cost.

(UV irradiation treatment)
As one of the modification treatment methods, treatment by ultraviolet irradiation is preferable. Ozone and active oxygen atoms generated by ultraviolet rays (synonymous with ultraviolet light) have high oxidation ability, and can form silicon oxide films or silicon oxynitride films with high density and insulation at low temperatures It is.

  The substrate is heated by this ultraviolet irradiation, and O contributes to ceramicization (silica conversion). ₂And H₂O, an ultraviolet absorber, and polysilazane itself are excited and activated, so that the conversion of polysilazane into ceramic is promoted, and the resulting anchor coat layer becomes denser. Irradiation with ultraviolet rays is effective at any time after the formation of the coating film.

  In the ultraviolet irradiation treatment, any commonly used ultraviolet ray generator can be used.

  The ultraviolet ray referred to in the present invention generally refers to an electromagnetic wave having a wavelength of 10 to 400 nm, but in the case of an ultraviolet irradiation treatment other than the vacuum ultraviolet ray (10 to 200 nm) treatment described later, it is preferably 210 to 375 nm. Use ultraviolet light.

  In the irradiation with ultraviolet rays, it is preferable to set the irradiation intensity and the irradiation time as long as the substrate carrying the anchor coat layer to be irradiated is not damaged.

For example, when a plastic film is used as the substrate, for example, a 2 kW (80 W / cm × 25 cm) lamp is used, and the strength of the substrate surface is 20 to 300 mW / cm ² , preferably 50 to 200 mW / cm. The distance between the substrate and the ultraviolet irradiation lamp is set so as to be ^2, and irradiation can be performed for 0.1 second to 10 minutes.

  In general, when the substrate temperature during ultraviolet irradiation treatment is 150 ° C. or more, in the case of a plastic film or the like, the properties of the substrate are impaired, such as deformation of the substrate or deterioration of its strength. Become. However, in the case of a film having high heat resistance such as polyimide, a modification treatment at a higher temperature is possible. Accordingly, there is no general upper limit for the substrate temperature at the time of ultraviolet irradiation, and it can be appropriately set by those skilled in the art depending on the type of substrate. Moreover, there is no restriction | limiting in particular in ultraviolet irradiation atmosphere, What is necessary is just to implement in air.

  Examples of such ultraviolet ray generating means include metal halide lamps, high pressure mercury lamps, low pressure mercury lamps, xenon arc lamps, carbon arc lamps, and excimer lamps (single wavelengths of 172 nm, 222 nm, and 308 nm, for example, USHIO INC. Manufactured by M.D. Com Co., Ltd.), UV light laser, and the like, but are not particularly limited. In addition, when irradiating the layer containing polysilazane with the generated ultraviolet ray, from the viewpoint of achieving efficiency improvement and uniform irradiation, the layer containing polysilazane is reflected after reflecting the ultraviolet ray from the generation source with a reflector. It is preferable to apply.

  The ultraviolet irradiation can be adapted to both batch processing and continuous processing, and can be appropriately selected depending on the shape of the substrate to be used. For example, in the case of batch processing, a laminate having a polysilazane-containing layer on its surface can be processed in an ultraviolet baking furnace equipped with an ultraviolet source as described above. The ultraviolet baking furnace itself is generally known. For example, an ultraviolet baking furnace manufactured by I-Graphics Co., Ltd. can be used. Moreover, when the laminated body which has the layer containing polysilazane on the surface is a long film form, it irradiates with an ultraviolet-ray continuously in the drying zone equipped with the above ultraviolet ray generation sources, conveying this. Can be made into ceramics. The time required for ultraviolet irradiation is generally 0.1 seconds to 10 minutes, preferably 0.5 seconds to 3 minutes, although it depends on the composition and concentration of the base material used and the layer containing polysilazane.

(Vacuum ultraviolet irradiation treatment: excimer irradiation treatment)
In the present invention, the most preferable modification treatment method for the anchor coat layer is a treatment by vacuum ultraviolet irradiation (excimer irradiation treatment). The treatment by vacuum ultraviolet irradiation uses light energy of 100 to 200 nm, preferably light energy with a wavelength of 100 to 180 nm, which is larger than the interatomic bonding force in the polysilazane compound, and bonds the atoms with only photons called photon processes. This is a method of forming a silicon oxide film at a relatively low temperature (about 200 ° C. or lower) by causing an oxidation reaction with active oxygen or ozone to proceed while cutting directly by action.

  The radiation source in the present invention may be any radiation source that generates light having a wavelength of 100 to 180 nm, but preferably an excimer radiator (for example, a Xe excimer lamp) having a maximum emission at about 172 nm, and an emission line at about 185 nm. Low pressure mercury vapor lamps, and medium and high pressure mercury vapor lamps having a wavelength component of 230 nm or less, and excimer lamps having maximum emission at about 222 nm.

  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 state where the water vapor concentration is low. That is, the oxygen concentration at the time of vacuum ultraviolet irradiation is preferably 10 to 20,000 volume ppm (0.001 to 2 volume%), and preferably 50 to 10,000 volume ppm (0.005 to 1 volume%). More preferably. Also, the water vapor concentration during the conversion process is preferably in the range of 1000 to 4000 ppm by volume.

  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.

In vacuum ultraviolet irradiation step, preferably the intensity of the vacuum ultraviolet rays in the coating film surface for receiving a layer containing polysilazane is ^{1mW / cm 2 ~10W / cm 2} , it is 30mW / cm ² ~200mW / cm 2 It is more ^preferable, further preferably a ^{50mW / cm 2 ~160mW / cm 2} . If it is less than 1 mW / cm ^2, there is a concern that the reforming efficiency is greatly reduced. If it exceeds 10 W / cm ² , there is a concern that the coating film may be ablated or the substrate may be damaged.

The amount of irradiation energy (irradiation amount) of vacuum ultraviolet rays on the coating surface is preferably 100 mJ / cm ^{2 to} 50 J / cm ² , more preferably 200 mJ / cm ^{2 to 20} J / cm ² , and 500 mJ / cm 2. More preferably, it is ^{2 to} 10 J / cm ² . If it is 100 mJ / cm ² or more, it is possible to avoid insufficient modification, and if it is 50 J / cm ² or less, generation of cracks due to excessive modification and thermal deformation of the substrate can be prevented.

  Further, irradiation with vacuum ultraviolet rays may be performed in a plurality of times. In that case, it is preferable to irradiate so that the total amount of irradiation energy is within the above range.

Further, the vacuum ultraviolet light used may be generated by plasma formed of a gas containing at least one of CO, CO ₂ and CH ₄ . Further, as the gas containing at least one of CO, CO ₂ and CH ₄ (hereinafter also referred to as carbon-containing gas), the carbon-containing gas may be used alone, but carbon containing rare gas or H ₂ as the main gas. It is preferable to add a small amount of the contained gas. Examples of plasma generation methods include capacitively coupled plasma.

[Gas barrier layer]
The gas barrier film according to the present invention has a gas barrier layer which is in contact with the anchor coat layer and formed by a vacuum film formation method on the anchor coat layer.

  As a vacuum film forming method which is a preferable method for forming the gas barrier layer, there are a physical vapor deposition method (PVD method) and a chemical vapor deposition method (CVD method).

<Gas deposition method>
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 are methods for generating plasma and the like, and well-known CVD methods such as a thermal CVD method, catalytic chemical vapor deposition method, photo CVD method, vacuum plasma CVD method and the like can be mentioned. Although not particularly limited, it is preferable to apply a vacuum plasma CVD method from the viewpoints of film formation speed, processing area, flexibility of the obtained gas barrier layer, and gas barrier properties.

  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.

  In the following, a case where a gas barrier layer is manufactured by using a facing roll type roll-to-roll film forming apparatus that forms a thin film by a vacuum plasma CVD method will be described as an example.

  1 and 2 are schematic configuration diagrams illustrating an example of a film forming apparatus. The film forming apparatus 101 illustrated in FIG. 2 has a basic structure in which two film forming apparatuses 100 illustrated in FIG. 1 are joined in tandem. Here, the case where the gas barrier layer is formed will be described using the film forming apparatus illustrated in FIG. 2 as an example. However, the description regarding the film forming apparatus illustrated in FIG. 2 is the same as the description regarding the film forming apparatus illustrated in FIG. However, it is considered as appropriate.

  As shown in FIG. 2, the film forming apparatus 101 includes a delivery roll 10, transport rolls 11 to 14, first, second, third, and fourth film forming rolls 15, 16, 15 ′, 16 ′, Take-off roll 17, gas supply pipes 18, 18 ', plasma generation power sources 19, 19', magnetic field generators 20, 21, 20 ', 21', vacuum chamber 30, vacuum pumps 40, 40 ' And a control unit 41.

  The delivery roll 10, the transport rolls 11 to 14, the first, second, third and fourth film forming rolls 15, 16, 15 ′, 16 ′ and the take-up roll 17 are accommodated in the vacuum chamber 30.

  The feed roll 10 feeds the base material 1 a installed in a state of being wound in advance toward the transport roll 11. The delivery roll 10 is a cylindrical roll extending in a direction perpendicular to the paper surface, and is wound around the delivery roll 10 by rotating counterclockwise (see an arrow in FIG. 2) by a drive motor (not shown). The base material 1a is sent out toward the transport roll 11.

  The transport rolls 11 to 14 are cylindrical rolls configured to be rotatable around a rotation axis substantially parallel to the delivery roll 10. The transport roll 11 is a roll for transporting the base material 1 a from the feed roll 10 to the film forming roll 15 while applying an appropriate tension to the base material 1 a. The transport rolls 12 and 13 are rolls for transporting the base material 1 b from the film forming roll 15 to the film forming roll 16 while applying an appropriate tension to the base material 1 b formed by the film forming roll 15. The transporting rolls 12 ′ and 13 ′ are for supplying the base material 1e from the film forming roll 15 ′ to the film forming roll 16 ′ while applying an appropriate tension to the base material 1e formed by the film forming roll 15 ′. It is a roll of. Further, the transport roll 14 is a roll for transporting the base material 1 c from the film forming roll 16 to the take-up roll 17 while applying an appropriate tension to the base material 1 c formed by the film forming roll 16 ′. .

  The first film-forming roll 15 and the second film-forming roll 16 are a pair of film-forming rolls that have a rotation axis substantially parallel to the delivery roll 10 and are opposed to each other by a predetermined distance. Similarly, the third film-forming roll 15 ′ and the fourth film-forming roll 16 ′ have a rotation axis that is substantially parallel to the delivery roll 10, and are formed by a pair of film-forming rolls that are opposed to each other by a predetermined distance. is there. The film forming roll 16 forms the substrate 1b and conveys the substrate 1d to the film forming roll 15 'while applying an appropriate tension to the formed substrate 1d. The film forming roll 16 ′ forms the base material 1 e and transports the base material 1 c to the transport roll 14 while applying an appropriate tension to the formed base material 1 c.

  In the example shown in FIG. 2, the separation distance between the first film-forming roll 15 and the second film-forming roll 16 is a distance connecting the point A and the point B, and the third film-forming roll 15 ′ and the second film-forming roll. The separation distance from the roll 16 ′ is a distance connecting the point A ′ and the point B ′. The first to fourth film forming rolls 15, 16, 15 ′, 16 ′ are discharge electrodes formed of a conductive material, and the first film forming roll 15, the second film forming roll 16, and the third film forming roll. The 15 ′ and the fourth film forming roll 16 ′ are insulated from each other. The materials and configurations of the first to fourth film forming rolls 15, 16, 15 ′, 16 ′ can be appropriately selected so that a desired function can be achieved as an electrode.

  Further, the first to fourth film forming rolls 15, 16, 15 ', 16' may be independently temperature controlled. The temperature of the first to fourth film forming rolls 15, 16, 15 ′, 16 ′ is not particularly limited, but is, for example, −30 to 100 ° C., but exceeds the glass transition temperature of the base material 1a. If the temperature is set too high, the substrate may be deformed by heat.

  Magnetic field generators 20, 21, 20 'and 21' are installed in the first to fourth film forming rolls 15, 16, 15 'and 16', respectively. The first film forming roll 15 and the second film forming roll 16 are supplied with a plasma generating power source 19, and the third film forming roll 15 ′ and the fourth film forming roll 16 ′ are supplied with a plasma generating power supply 19 ′. A generating high frequency voltage is applied. Thereby, the film forming section S between the first film forming roll 15 and the second film forming roll 16 or the film forming section S ′ between the third film forming roll 15 ′ and the fourth film forming roll 16 ′. An electric field is formed in the film, and discharge plasma of the film forming gas supplied from the gas supply pipe 18 or 18 'is generated. The voltage applied by the plasma generating power supply 19 and the voltage applied by the plasma generating power supply 19 ′ may be the same or different. The power source frequency of the plasma generating power source 19 or 19 ′ can be arbitrarily set. However, the apparatus of this configuration is, for example, 60 to 100 kHz, and the applied power is, for example, 1 to 1 m with respect to the effective film forming width 1 m. 10 kW.

  The take-up roll 17 has a rotation axis substantially parallel to the feed roll 10 and takes up the base material 1c and accommodates it in a roll shape. The take-up roll 17 takes up the substrate 1c by rotating counterclockwise by a drive motor (not shown) (see the arrow in FIG. 2).

  The substrate 1a fed from the feed roll 10 is wound around the transport rolls 11 to 14 and the first to fourth film forming rolls 15, 16, 15 ′ and 16 ′ between the feed roll 10 and the take-up roll 17. It is conveyed by rotation of each of these rolls while maintaining an appropriate tension by being applied. In addition, the conveyance direction of the base materials 1a, 1b, 1c, 1d, and 1e (hereinafter, the base materials 1a, 1b, 1c, 1d, and 1e are also collectively referred to as “base materials 1a to 1e”) is indicated by arrows. . The conveyance speed (line speed) of the base materials 1a to 1e (for example, the conveyance speed at the point C or the point C ′ in FIG. The conveyance speed is adjusted by controlling the rotation speeds of the drive motors of the delivery roll 10 and the take-up roll 17 by the control unit 41. When the conveyance speed is decreased, the thickness of the formed region is increased.

  When this film forming apparatus is used, the transport direction of the base materials 1a to 1e is set to a direction (hereinafter referred to as a reverse direction) opposite to a direction indicated by an arrow in FIG. 2 (hereinafter referred to as a forward direction). A gas barrier film forming step can also be performed. Specifically, the control unit 41 rotates the rotation direction of the drive motors of the feed roll 10 and the take-up roll 17 in the direction opposite to that described above in a state where the substrate 1c is taken up by the take-up roll 17. Control to do. When controlled in this way, the base material 1c sent out from the take-up roll 17 is transported between the feed roll 10 and the take-up roll 17, and the transport rolls 11 to 14, the first to fourth film forming rolls 15 and 16, While being wound around 15 'and 16', appropriate tension is maintained, and the rolls are conveyed in the reverse direction by rotation of these rolls.

  When forming a gas barrier layer using the film forming apparatus 101, the base material 1a is transported in the forward direction and the reverse direction, and the film forming unit S or the film forming unit S ′ is reciprocated to form a gas barrier layer. The (film) step can be repeated multiple times.

  The gas supply pipes 18 and 18 ′ supply a film forming gas such as a plasma CVD source gas into the vacuum chamber 30. The gas supply pipe 18 has a tubular shape extending in the same direction as the rotation axes of the first film forming roll 15 and the second film forming roll 16 above the film forming section S, and is provided at a plurality of locations. A film forming gas is supplied to the film forming part S from the opened opening. Similarly, the gas supply pipe 18 ′ has a tubular shape extending above the film forming section S ′ in the same direction as the rotation axes of the third film forming roll 15 ′ and the fourth film forming roll 16 ′. The film forming gas is supplied to the film forming part S ′ from the openings provided at a plurality of locations. The film forming gas supplied from the gas supply pipe 18 and the film forming gas supplied from the gas supply pipe 18 'may be the same or different. Further, the supply gas pressure supplied from these gas supply pipes may be the same or different.

  A silicon compound can be used as the source gas. Examples of the silicon compound include hexamethyldisiloxane (HMDSO), 1,1,3,3-tetramethyldisiloxane, vinyltrimethylsilane, methyltrimethylsilane, hexamethyldisilane, methylsilane, dimethylsilane, trimethylsilane, and diethylsilane. Propylsilane, phenylsilane, vinyltriethoxysilane, vinyltrimethoxysilane, tetramethoxysilane, dimethyldisilazane, trimethyldisilazane, tetramethyldisilazane, pentamethyldisilazane, hexamethyldisilazane, and the like. In addition to this, the compounds described in paragraph “0075” of JP2008-056967 A can also be used. Among these silicon compounds, HMDSO is preferably used in the formation of the gas barrier layer from the viewpoint of easy handling of the compound and high gas barrier properties of the resulting gas barrier film. Two or more of these silicon compounds may be used in combination. The source gas may contain monosilane in addition to the silicon compound.

  As the film forming gas, a reactive gas may be used in addition to the source gas. As the reaction gas, a gas that reacts with the raw material gas to become a silicon compound such as oxide or nitride is selected. As a reactive gas for forming an oxide as a thin film, for example, oxygen gas or ozone gas can be used. In addition, you may use these reaction gas in combination of 2 or more type.

  As the film forming gas, a carrier gas may be further used to supply the source gas into the vacuum chamber 30. Further, as a film forming gas, a discharge gas may be further used to generate plasma. As the carrier gas and the discharge gas, for example, a rare gas such as argon, hydrogen, or nitrogen is used.

  The magnetic field generators 20 and 21 are members that form a magnetic field in the film forming unit S between the first film forming roll 15 and the second film forming roll 16, and the magnetic field generating apparatuses 20 ′ and 21 ′ are similarly configured. It is a member that forms a magnetic field in the film forming section S ′ between the third film forming roll 15 ′ and the fourth film forming roll 16 ′. These magnetic field generators 20, 20 ', 21, 21' do not follow the rotation of the first to fourth film forming rolls 15, 16, 15 ', 16', and are stored at predetermined positions.

  The vacuum chamber 30 maintains the decompressed state by sealing the delivery roll 10, the transport rolls 11 to 14, the first to fourth film forming rolls 15, 16, 15 ′, 16 ′, and the take-up roll 17. The pressure (degree of vacuum) in the vacuum chamber 30 can be adjusted as appropriate according to the type of source gas. The pressure of the film forming part S or S ′ is preferably 0.1 to 50 Pa.

  The vacuum pumps 40 and 40 ′ are communicably connected to the control unit 41 and appropriately adjust the pressure in the vacuum chamber 30 in accordance with a command from the control unit 41.

  The control unit 41 controls each component of the film forming apparatus 101. The control unit 41 is connected to the drive motors of the feed roll 10 and the take-up roll 17 and adjusts the conveyance speed of the substrate 1a by controlling the rotation speed of these drive motors. Moreover, the conveyance direction of the base material 1a is changed by controlling the rotation direction of the drive motor. The control unit 41 is connected to a film-forming gas supply mechanism (not shown) so as to be communicable, and controls the supply amount of each component gas of the film-forming gas. The control unit 41 is communicably connected to the plasma generation power sources 19 and 19 ′ and controls the output voltage and output frequency of the plasma generation power source 19. Further, the control unit 41 is communicably connected to the vacuum pumps 40 and 40 ′, and controls the vacuum pump 40 so as to maintain the inside of the vacuum chamber 30 in a predetermined reduced pressure atmosphere.

  The control unit 41 includes a CPU (Central Processing Unit), an HDD (Hard Disk Drive), a RAM (Random Access Memory), and a ROM (Read Only Memory). The HDD stores a software program describing a procedure for controlling each component of the film forming apparatus 101 and realizing a method for producing a gas barrier film. When the film forming apparatus 101 is turned on, the software program is loaded into the RAM and sequentially executed by the CPU. The ROM stores various data and parameters used when the CPU executes the software program.

  The gas barrier layer may be a single layer or a laminated structure of two or more layers. When the gas barrier layer has a laminated structure of two or more layers, the gas barrier layers may have the same composition or different compositions.

The gas barrier layer formed by the vacuum film formation method according to the present invention preferably has a composition distribution region having a high density in the thickness direction of the gas barrier layer and a high carbon concentration. That is, the gas barrier layer preferably has a region having a composition distribution represented by SiC _x in the thickness direction, where x is 0.8 to 1.2. x is more preferably 0.9 to 1.1. By having a region having such a composition, the gas barrier property can be further improved.

  The measurement of the composition distribution in the thickness direction of the gas barrier layer and the measurement of the thickness of the region can be performed by XPS analysis employing the same conditions as the measurement of the N / Si ratio of the entire anchor coat layer.

The lower limit of the thickness of the region where the composition is represented by SiC _{x and} where x is 0.8 to 1.2 is not particularly limited because it varies depending on the application. From the viewpoint of improving the properties, it is preferably 1 nm or more, more preferably 30 nm or more, still more preferably 50 nm or more, and even more preferably 90 nm or more. The upper limit is also not particularly limited because it varies depending on the application, but is preferably 300 nm or less, more preferably 200 nm or less, and even more preferably 150 nm or less from the viewpoint of ensuring optical characteristics.

The thickness of the region in which the composition is represented by SiC _x and the composition distribution is represented by SiC _x, where x is 0.8 to 1.2, is, for example, the amount and ratio of the film forming raw material and oxygen supplied, It is possible to control by appropriately combining the conveyance speed, the number of times of film formation, and the like.

  The formation of the gas barrier layer is shown by (2) a method of performing aging after the modification treatment of the layer containing polysilazane, or (3) a method of performing an additional modification treatment after the modification treatment of the layer containing polysilazane. About the sample which did not perform the composition adjustment process of the N / Si ratio of the anchor coat layer, it is preferable to carry out within 1 to 2 days after forming the anchor coat layer. On the other hand, about the sample which performed the composition adjustment process of the anchor coat layer, it is preferable to carry out within 1 to 2 days after adjustment of N / Si ratio.

  The thickness of the gas barrier layer (the total thickness in the case of a laminated structure of two or more layers) is not particularly limited, but is preferably 5 to 1000 nm, more preferably 20 to 500 nm, and 50 to 300 nm. More preferably it is. If it is this range, the advantage of coexistence of productivity and gas barrier property will be acquired. The thickness of the gas barrier layer can be measured by TEM observation.

  In another embodiment, it is preferable to further provide a layer obtained by applying energy to the layer containing polysilazane and modifying it on the surface of the gas barrier layer opposite to the substrate side. .

  The formation and modification treatment of the polysilazane-containing layer further provided on the gas barrier layer can be performed by the same method as the formation of the anchor coat layer. For example, the type of polysilazane used is preferably perhydropolysilazane because it has a small amount of residual organic matter. The energy is preferably applied by irradiation with vacuum ultraviolet light from the viewpoint that the modification treatment can be performed at a relatively low temperature.

  The thickness of the layer obtained by modifying the layer containing polysilazane further provided on the gas barrier layer is also preferably within the preferable range as the thickness of the anchor coat layer.

  Further providing a layer obtained by modifying such a layer containing polysilazane on the gas barrier layer is a gas barrier property, in-plane uniformity of the gas barrier property, or durability of an electronic device in a high temperature and high humidity environment. Can be further improved.

[Layers with various functions]
In the gas barrier film of the present invention, layers having various functions can be provided.

(Clear hard coat layer)
In the gas barrier film of the present invention, a clear hard coat layer may be provided on the substrate.

  The clear hard coat layer improves adhesion between the base material and the anchor coat layer, relieves internal stress caused by the difference in expansion and contraction between the base material and the anchor coat layer under high temperature and high humidity, and a base material on which the anchor coat layer is provided It is possible to provide functions such as flattening and prevention of bleeding out of low molecular weight components such as monomers and oligomers from the substrate. Moreover, an antiblock function can also be provided by giving the surface of a clear hard-coat layer a little roughness. The anti-blocking function refers to a function of avoiding sticking (= blocking) that occurs when a substrate having a smooth clear hard coat layer formed on both sides is wound.

  The clear hard coat layer may be provided between the substrate and the anchor coat layer, or may be provided on the surface of the substrate opposite to the surface having the gas barrier layer. In the gas barrier film according to the present invention, it is preferably provided on the surface opposite to the surface having the gas barrier layer of the base material from the viewpoint of preventing bleeding out, and more preferably clear hard having an anti-block function. It is a coat layer.

  Such a clear hard coat layer is basically produced by curing a photosensitive material or a thermosetting material.

  As specific constituent materials, forming methods, film thicknesses, and the like of the clear hard coat layer, materials, methods, and the like disclosed in paragraphs “0141” to “0152” of JP2013-226758A are appropriately employed.

(Bleed-out prevention layer)
The gas barrier film of the present invention may have a bleed-out preventing layer on the surface of the substrate opposite to the surface on which the anchor coat layer is provided.

  The bleed-out prevention layer is used for the purpose of suppressing the phenomenon that unreacted oligomers migrate from the film to the surface and contaminate the contact surface when the film is heated. It is provided on the surface opposite to the provided surface. The bleed-out prevention layer may basically have the same configuration as the clear hard coat layer as long as it has this function.

  As the constituent material, forming method, film thickness and the like of the bleed-out prevention layer, materials, methods and the like disclosed in paragraphs “0249” to “0262” of JP2013-52561A are appropriately employed.

[Electronic device body]
The gas barrier film of the present invention can be preferably applied to a device whose performance is deteriorated by chemical components (oxygen, water, nitrogen oxide, sulfur oxide, ozone, etc.) in the air. That is, this invention provides the electronic device containing the gas barrier film of this invention, and the electronic device main body formed on this gas barrier film.

  Examples of the electronic device body used in the electronic device of the present invention include, for example, an organic electroluminescence element (organic EL element), a liquid crystal display element (LCD), a thin film transistor, a touch panel, electronic paper, a solar cell (PV), and the like. be able to. From the viewpoint that the effects of the present invention can be obtained more efficiently, the electronic device body is preferably an organic EL element or a solar cell, and more preferably an organic EL element. By forming the organic EL element on the gas barrier film according to the present invention, it is possible to obtain an organic EL panel that is excellent in durability in a high-temperature and high-humidity environment and has few dark spots.

  Hereinafter, an organic EL element and an organic EL panel using the same will be described as an example of a specific electronic device body.

  Although the preferable specific example of the layer structure of an organic EL element is shown below, this invention is not limited to these.

(1) Anode / light emitting layer / cathode (2) Anode / hole transport layer / light emitting layer / cathode (3) Anode / light emitting layer / electron transport layer / cathode (4) Anode / hole transport layer / light emitting layer / electron Transport layer / cathode (5) Anode / anode buffer layer (hole injection layer) / hole transport layer / light emitting layer / electron transport layer / cathode buffer layer (electron injection layer) / cathode (anode)
As the anode (transparent electrode) in the organic EL element, an electrode material made of a metal, an alloy, an electrically conductive compound or a mixture thereof having a high work function (4 eV or more) is preferably used. Specific examples of such electrode materials include metals such as Au, and conductive transparent materials such as CuI, indium tin oxide (ITO), SnO ₂ , and ZnO. Alternatively, an amorphous material such as IDIXO (In ₂ O ₃ —ZnO) capable of forming a transparent conductive film may be used.

  For the anode, these electrode materials may be formed as a thin film by a method such as vapor deposition or sputtering, and the thin film may be formed into a desired shape pattern by photolithography, or if the pattern accuracy is not required ( The pattern may be formed through a mask having a desired shape when the electrode material is deposited or sputtered.

  When light emission is taken out from the anode, it is desirable that the transmittance be larger than 10%. The sheet resistance as the anode is preferably several hundred Ω / □ or less. Moreover, although the film thickness of an anode is based also on material, it is 10-1000 nm normally, Preferably it is chosen in the range of 10-200 nm.

(cathode)
As the cathode in the organic EL element, a material having a small work function (4 eV or less) metal (referred to as an electron injecting metal), an alloy, an electrically conductive compound, and a mixture thereof is used. Specific examples of such electrode materials include sodium, sodium-potassium alloy, magnesium, lithium, magnesium / copper mixture, magnesium / silver mixture, magnesium / aluminum mixture, magnesium / indium mixture, aluminum / aluminum oxide (Al ₂ O ₃ ) Mixtures, indium, lithium / aluminum mixtures, rare earth metals and the like. Among these, from the point of durability against electron injection and oxidation, a mixture of an electron injecting metal and a second metal which is a stable metal having a larger work function value than this, for example, a magnesium / silver mixture, Magnesium / aluminum mixtures, magnesium / indium mixtures, aluminum / aluminum oxide (Al ₂ O ₃ ) mixtures, lithium / aluminum mixtures, aluminum and the like are suitable as the cathode.

  The cathode can be produced by forming a thin film of these electrode materials by a method such as vapor deposition or sputtering. The sheet resistance as a cathode is preferably several hundred Ω / □ or less. The film thickness of the cathode is usually selected in the range of 10 nm to 5 μm, preferably 50 to 200 nm. In order to transmit the emitted light, if either the anode or the cathode of the organic EL element is transparent or translucent, the light emission luminance is improved, which is convenient.

  Moreover, after manufacturing the said metal quoted by description of the cathode with the film thickness of 1-20 nm, the transparent transparent or semi-transparent cathode is produced by producing the electroconductive transparent material quoted by description of the anode on it. By applying this, an element in which both the anode and the cathode are transmissive can be manufactured.

(Injection layer: electron injection layer, hole injection layer)
The injection layer includes an electron injection layer and a hole injection layer. An electron injection layer and a hole injection layer are provided as necessary, and between the anode and the light emitting layer or the hole transport layer, and between the cathode and the light emitting layer or the electron transport. Exist between the layers.

  An injection layer is a layer provided between an electrode and an organic layer in order to reduce drive voltage and improve light emission luminance. “Organic EL element and its forefront of industrialization (issued by NTT Corporation on November 30, 1998) 2), Chapter 2, “Electrode Materials” (pages 123 to 166) in detail, and includes a hole injection layer (anode buffer layer) and an electron injection layer (cathode buffer layer).

  The details of the anode buffer layer (hole injection layer) are also described in JP-A-9-45479, JP-A-9-260062, JP-A-8-288069, and the like. Examples thereof include a phthalocyanine buffer layer typified by phthalocyanine, an oxide buffer layer typified by vanadium oxide, an amorphous carbon buffer layer, and a polymer buffer layer using a conductive polymer such as polyaniline (emeraldine) or polythiophene.

  Details of the cathode buffer layer (electron injection layer) are described in JP-A-6-325871, JP-A-9-17574, JP-A-10-74586, and the like. Specifically, strontium Metal buffer layer typified by aluminum and aluminum, alkali metal compound buffer layer typified by lithium fluoride, alkaline earth metal compound buffer layer typified by magnesium fluoride, oxide buffer layer typified by aluminum oxide, etc. Is mentioned. The buffer layer (injection layer) is desirably a very thin film, and although it depends on the material, the film thickness is preferably in the range of 0.1 nm to 5 μm.

(Light emitting layer)
The light emitting layer in the organic EL element is a layer that emits light by recombination of electrons and holes injected from the electrode (cathode, anode) or electron transport layer, hole transport layer, and the light emitting portion is the light emitting layer. It may be in the layer or the interface between the light emitting layer and the adjacent layer.

  The light emitting layer of the organic EL device preferably contains the following dopant compound (light emitting dopant) and host compound (light emitting host). Thereby, the luminous efficiency can be further increased.

(Luminescent dopant)
There are two types of luminescent dopants: a fluorescent dopant that emits fluorescence and a phosphorescent dopant that emits phosphorescence.

  Representative examples of fluorescent dopants include coumarin dyes, pyran dyes, cyanine dyes, croconium dyes, squalium dyes, oxobenzanthracene dyes, fluorescein dyes, rhodamine dyes, pyrylium dyes, perylene dyes. Stilbene dyes, polythiophene dyes, rare earth complex phosphors, and the like.

  As a typical example of the phosphorescent dopant, preferably a complex compound containing a metal of Group 8, Group 9, or Group 10 in the periodic table of elements, more preferably an iridium compound or an osmium compound, Of these, iridium compounds are the most preferred. The light emitting dopant may be used by mixing a plurality of kinds of compounds.

(Light emitting host)
A light-emitting host (also simply referred to as a host) means a compound having the largest mixing ratio (mass) in a light-emitting layer composed of two or more kinds of compounds. It is also simply called a dopant). For example, if the light emitting layer is composed of two types of compound A and compound B and the mixing ratio is A: B = 10: 90, compound A is a dopant compound and compound B is a host compound. Furthermore, if a light emitting layer is comprised from 3 types of a compound A, a compound B, and the compound C and the mixing ratio is A: B: C = 5: 10: 85, the compound A and the compound B are dopant compounds, and a compound C is a host compound.

  The light emitting host is not particularly limited in terms of structure, but is typically a basic skeleton such as a carbazole derivative, a triarylamine derivative, an aromatic borane derivative, a nitrogen-containing heterocyclic compound, a thiophene derivative, a furan derivative, or an oligoarylene compound. Or a carboline derivative or a diazacarbazole derivative (herein, a diazacarbazole derivative is one in which at least one carbon atom of the hydrocarbon ring constituting the carboline ring of the carboline derivative is substituted with a nitrogen atom) For example). Of these, carboline derivatives, diazacarbazole derivatives and the like are preferably used.

  The light emitting layer can be formed by depositing the above compound by a known thinning method such as a vacuum deposition method, a spin coating method, a casting method, an LB method, or an ink jet method. Although the film thickness as a light emitting layer does not have a restriction | limiting in particular, Usually, 5 nm-5 micrometers, Preferably it is chosen in the range of 5-200 nm. This light emitting layer may have a single layer structure in which the dopant compound and the host compound are one kind or two or more kinds, or may have a laminated structure made up of a plurality of layers having the same composition or different compositions.

(Hole transport layer)
The hole transport layer is made of a hole transport material having a function of transporting holes, and in a broad sense, a hole injection layer and an electron blocking layer are also included in the 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 one 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 and pyrazolone derivatives, phenylenediamine derivatives, arylamine derivatives, amino-substituted chalcone derivatives, oxazole derivatives, styrylanthracene derivatives, fluorenone derivatives, hydrazone derivatives, Examples thereof include stilbene derivatives, silazane derivatives, aniline copolymers, and conductive polymer oligomers, particularly thiophene oligomers. The above-mentioned materials can be used as the hole transport material, but it is preferable to use a porphyrin compound, an aromatic tertiary amine compound and a styrylamine compound, particularly an aromatic tertiary amine compound. Furthermore, a polymer material in which these materials are introduced into a polymer chain or these materials are used as a polymer main chain can also be used. In addition, inorganic compounds such as p-type-Si and p-type-SiC can also be used as the hole injection material and the hole transport material.

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

(Electron transport layer)
The electron transport layer is made of an electron transport 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 or a plurality of layers.

  The electron transport material only needs to have a function of transmitting electrons injected from the cathode to the light emitting layer, and the material can be selected and used from conventionally known compounds. Examples include nitro-substituted fluorene derivatives, diphenylquinone derivatives, thiopyran dioxide derivatives, carbodiimides, fluorenylidenemethane derivatives, anthraquinodimethane and anthrone derivatives, oxadiazole derivatives, and the like. 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 an electron transport material. Furthermore, a polymer material in which these materials are introduced into a polymer chain or these materials are used as a polymer main chain can also be used. In addition, metal complexes of 8-quinolinol derivatives such as tris (8-quinolinol) aluminum (Alq3), 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 (Znq), and the like, and the central metal of these metal complexes is In, Mg, Metal complexes replaced with Cu, Ca, Sn, Ga or Pb can also be used as the electron transport material. In addition, metal-free or metal phthalocyanine, or those having terminal ends substituted with an alkyl group or a sulfonic acid group can be preferably used as the electron transporting material. Similarly to the hole injection layer and the hole transport layer, an inorganic semiconductor such as n-type-Si or n-type-SiC can also be used as the electron transport material.

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

(Method for producing organic EL element)
A method for manufacturing the organic EL element will be described.

  Here, as an example of the organic EL element, a method for manufacturing an organic EL element including an anode / hole injection layer / hole transport layer / light emitting layer / electron transport layer / electron injection layer / cathode will be described.

  First, a desired electrode material, for example, a thin film made of an anode material is formed on a gas barrier film so as to have a thickness of 1 μm or less, preferably 10 to 200 nm, for example, by vapor deposition, sputtering, plasma CVD, or the like. To produce an anode.

Next, an organic compound thin film of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer, which are organic EL element materials, is formed thereon. As a method for forming this organic compound thin film, there are a vapor deposition method, a wet process (spin coating method, casting method, ink jet method, printing method), etc., but a homogeneous film is easily obtained and pinholes are not easily generated. From the point of view, the vacuum deposition method, the spin coating method, the ink jet method, and the printing method are particularly preferable. Further, different film forming methods may be applied for each layer. When a vapor deposition method is employed for film formation, the vapor deposition conditions vary depending on the type of compound used, but generally a boat heating temperature of 50 to 450 ° C., a vacuum degree of 10 ⁻⁶ to 10 ⁻² Pa, and a vapor deposition rate of 0.01 to It is desirable to select appropriately within the range of 50 nm / second, substrate temperature −50 to 300 ° C., film thickness 0.1 nm to 5 μm, preferably 5 to 200 nm.

  After these layers are formed, a thin film made of a cathode material is formed thereon by a method such as vapor deposition or sputtering so as to have a film thickness of 1 μm or less, preferably 50 to 200 nm, and a cathode is provided. Thus, a desired organic EL element can be obtained.

  The organic EL device is preferably manufactured from the anode and the hole injection layer to the cathode consistently by a single evacuation, but may be taken out halfway and subjected to different film forming methods. At that time, it is necessary to consider that the work is performed in a dry inert gas atmosphere. In addition, it is also possible to reverse the production order and produce the cathode, the electron injection layer, the electron transport layer, the light emitting layer, the hole transport layer, the hole injection layer, and the anode in this order.

  When a DC voltage is applied to a multicolor display device (organic EL panel) provided with the organic EL element thus obtained, a voltage of about 2 to 40 V is applied with the positive polarity of the anode and the negative polarity of the cathode. Then luminescence can be observed. An alternating voltage may be applied. The alternating current waveform to be applied may be arbitrary.

  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 "part" or "%" is used in an Example, unless otherwise indicated, "part by mass" or "mass%" is represented.

<Manufacture of gas barrier film>
[Resin substrate]
Substrate 1: A 100 μm-thick polyethylene terephthalate film (Lumirror (registered trademark) (U48), manufactured by Toray Industries, Inc.) with easy adhesion treatment on both sides has a thickness of 0. A substrate 1 was formed by forming a clear hard coat layer having an antiblock function of 5 μm. That is, a UV curable resin (manufactured by Aika Kogyo Co., Ltd., product number: Z731L) was applied so as to have a dry film thickness of 0.5 μm, and then dried at 80 ° C. Then, using a high-pressure mercury lamp in air. Curing was performed under the condition of an irradiation energy amount of 0.5 J / cm ² .

Substrate 2: A clear hard coat layer having a thickness of 2 μm was formed on the surface of the substrate 1 on the side where the gas barrier layer was to be formed as follows. A UV curable resin OPSTAR (registered trademark) Z7527 manufactured by JSR Corporation was applied to a dry film thickness of 2 μm, dried at 80 ° C., and then irradiated with a high-pressure mercury lamp in air. Curing was performed under the condition of 0.5 J / cm ² .

[Formation of anchor coat layer]
The anchor coat layer was formed by applying a coating solution as shown below to form a coating film, and then performing modification by irradiation with vacuum ultraviolet rays.

  The coating solution was prepared as follows.

  Coating solution 1: a dibutyl ether solution containing 20% by mass of perhydropolysilazane (manufactured by AZ Electronic Materials, NN120-20) and an amine catalyst (N, N, N ″, N ″ -tetramethyl-1,6- Dihydrohexane (TMDAH))-containing perhydropolysilazane 20 mass% dibutyl ether solution (manufactured by AZ Electronic Materials Co., Ltd., NAX120-20) is mixed at a ratio of 4: 1 (mass ratio), and further dried film A coating solution was prepared by appropriately diluting with dibutyl ether to adjust the thickness.

  Coating solution 2: Aluminum ethyl acetoacetate diisopropylate (ALCH) is added to polysilazane so that the Al / Si ratio is 0.05 when preparing the coating solution 1, and the mixture is heated at room temperature (25 ° C.) for 6 hours. A coating solution was prepared by stirring.

  Coating liquid 3: Commercially available polysiloxane-based coating agent: Glasca (manufactured by JSR Corporation) was used.

  Thickness after drying the obtained coating liquid on the surface opposite to the surface on which the clear hard coat layer having the antiblock function of the substrate 1 is formed, or on the clear hard coat layer of the substrate 2 Was applied by a die coating method so as to have a thickness as shown in Table 1 below, and dried in air at a temperature shown in Table 1 below (dew point 5 ° C.) for 2 minutes. Next, the coating film obtained by drying was subjected to a vacuum ultraviolet ray irradiation treatment (modification treatment) using a Xe excimer lamp having a wavelength of 172 nm in a nitrogen atmosphere under the conditions shown in Table 1 below, and an anchor coat layer. Formed.

  Depending on the sample, the composition adjustment treatment of the anchor coat layer shown in Table 2 below was performed on the coating film.

  The layer containing polysilazane was modified under the following conditions.

・ Modification processing equipment Excimer irradiation equipment MODEL: MECL-M-1-200 manufactured by M.D.
Wavelength: 172nm
Lamp filled gas: Xe
-Modification treatment conditions Excimer light intensity: 130 mW / cm ² (172 nm)
Distance between sample and light source: 2mm
Stage heating temperature: 80 ° C
Oxygen concentration in the irradiation device: 0.3% by volume
Stage transport speed during excimer light irradiation: 10 mm / second Stage transport count during excimer light irradiation: 3 reciprocations The composition distribution (N / Si ratio) in the thickness direction of such an anchor coat layer is expressed by the following XPS ( Measurement was made by a method using photoelectron spectroscopy) analysis.

(XPS analysis conditions)
・ Equipment: ULVAC-PHI QUANTERASXM
・ X-ray source: Monochromatic Al-Kα
Measurement area: Si2p, C1s, N1s, O1s
・ Sputtering ion: Ar (2 keV)
Depth profile: after 1 minute sputtering, the measurement is repeated ※ corresponds to the thickness of about 2.8nm in the etching rate of SiO ₂ in terms and quantitative: seeking background Shirley method, the relative sensitivity coefficient method from the peak area obtained with And quantified. For data processing, MultiPak manufactured by ULVAC-PHI was used.

  In this way, a composition distribution profile in the film thickness direction in the anchor coat layer was obtained. The film thickness of the anchor coat layer was determined by observing the cross section of the layer with a TEM.

[Formation of gas barrier layer]
A gas barrier layer was formed on the anchor coat layer by a vacuum plasma CVD method.

  A roll-to-roll type CVD film forming apparatus in which two apparatuses each having a film forming unit composed of opposing film forming rolls shown in FIG. 2 are connected (having a first film forming unit and a second film forming unit) Was used. The effective film formation width is 1000 mm, and the film formation conditions are: conveyance speed, supply amount of source gas (HMDSO) of each of the first film formation unit and the second film formation unit, supply amount of oxygen gas, degree of vacuum, applied power, The frequency was adjusted by the frequency of the power supply and the number of film formation (number of passes of the apparatus). In contrast to the first pass, the substrate is transported in the direction of rewinding the substrate in the second pass. However, even when the pass directions are different, the first film forming unit passes through the first film forming unit, and the component that passes next. The film part was used as the second film forming part.

  As other conditions, the power supply frequency was 84 kHz, and the film forming roll temperatures were all 30 ° C. The film thickness was determined by cross-sectional TEM observation.

  Formation of the gas barrier layer was performed within 1-2 days after applying the anchor coat layer for the samples that were not subjected to the composition adjustment treatment of the anchor coat layer. About the sample which performed the composition adjustment process of the anchor coat layer represented by said M1, M2, and M3, it carried out within 1-2 days after a composition adjustment process.

  The gas barrier layer has a composition of SiC_xAny one of the three types of CVD1 to CVD3, in which the thicknesses of the regions having the composition distribution represented by ## EQU1 ## and the region where x is 0.8 to 1.2 are different. Table 3 shows the deposition conditions of each gas barrier layer, the thickness of the gas barrier layer, and SiC. _xThe thickness of the region where x is 0.8 to 1.2 is shown.

The composition distribution in the thickness direction of the gas barrier layer and the region of the composition distribution in which the composition is represented by SiC _x , where x is 0.8 to 1.2, the thickness of the anchor coat layer It measured by XPS on the same conditions as the measurement of the composition distribution of the thickness direction.

  A gas barrier film was produced by combining the above conditions. About the gas barrier film of Comparative Examples 1-7 and Examples 1-11, the below-mentioned "evaluation of the number of defects of a gas barrier layer" was performed. About Comparative Examples 8-12 and Examples 12-18, the organic EL element was produced on the gas-barrier film, and the below-mentioned "dark spot (DS) evaluation of an organic EL device" was implemented.

(Comparative Example 1)
On the surface of the resin substrate 2 on which the clear hard coat layer was formed, the gas barrier layer CVD2 shown in Table 2 was formed to produce a gas barrier film (sample No. 1).

(Comparative Example 2)
On the surface of the resin substrate 1 on which the gas barrier layer is formed, an anchor coat layer is formed under the conditions of U1 in Table 1 above, and further, the gas barrier layer CVD2 in Table 2 above is formed thereon to form a gas barrier film ( Sample No. 2) was produced.

(Comparative Example 3)
A gas barrier film (Sample No. 3) was produced in the same manner as in Comparative Example 2 except that the resin base material 2 was used and the anchor coat layer was formed under the conditions of U2 in Table 1 above.

(Comparative Example 4)
A gas barrier film (sample No. 4) was produced in the same manner as in Comparative Example 3 except that the anchor coat layer was formed under the conditions of U3 in Table 1 above.

(Comparative Example 5)
A gas barrier film (Sample No. 5) was produced in the same manner as in Comparative Example 3 except that the anchor coat layer was formed under the conditions of U8 in Table 1 above.

(Comparative Example 6)
A gas barrier film (Sample No. 6) was produced in the same manner as in Comparative Example 3 except that the anchor coat layer was formed under the conditions of U9 in Table 1 above.

Example 1
A gas barrier film (Sample No. 7) was produced in the same manner as in Comparative Example 2 except that the composition adjustment treatment M2 of the anchor coat layer was performed during the modification treatment of the layer containing polysilazane.

(Example 2)
A gas barrier film (Sample No. 8) was produced in the same manner as in Comparative Example 3 except that the composition adjustment treatment M1 of the anchor coat layer was performed during the modification treatment of the layer containing polysilazane.

(Example 3)
A gas barrier film (Sample No. 9) was produced in the same manner as in Comparative Example 3 except that the anchor coat layer was formed under the conditions of U4 in Table 1 above.

Example 4
A gas barrier film (Sample No. 10) was produced in the same manner as in Comparative Example 3 except that the anchor coat layer was formed under the conditions of U5 in Table 1 above.

(Example 5)
A gas barrier film (Sample No. 11) was produced in the same manner as in Comparative Example 3 except that the anchor coat layer was formed under the conditions of U6 in Table 1 above.

(Example 6)
A gas barrier film (Sample No. 12) was produced in the same manner as in Comparative Example 3 except that the anchor coat layer was formed under the conditions of U7 in Table 1 above.

(Example 7)
A gas barrier film (Sample No. 13) was produced in the same manner as in Example 3 except that the gas barrier layer was changed to CVD1.

(Example 8)
A gas barrier film (Sample No. 14) was produced in the same manner as in Example 3 except that the gas barrier layer was changed to CVD3.

(Comparative Example 7)
A gas barrier film (Sample No. 15) was produced in the same manner as in Comparative Example 3 except that the gas barrier layer was changed to CVD1.

Example 9
A gas barrier film (Sample No. 16) was produced in the same manner as in Comparative Example 3 except that the anchor coat layer was formed under the conditions of U10 in Table 1 above.

(Example 10)
A gas barrier film (sample No. 17) was formed in the same manner as in Example 4 except that a layer containing polysilazane was further formed on the gas barrier layer under the conditions of U2 in Table 1 above and the modification treatment was performed. Produced.

(Example 11)
In Comparative Example 3, the gas barrier film (Sample No. 18) was prepared in the same manner as Comparative Example 3 except that the anchor coat layer composition adjustment treatment M3 was performed during the modification treatment of the polysilazane-containing layer. Produced.

(Comparative Example 8)
A gas barrier film (Sample No. 19) was produced under the same conditions as in Comparative Example 3 above.

(Comparative Example 9)
A gas barrier film (Sample No. 20) was formed in the same manner as in Comparative Example 3 except that a layer containing polysilazane was further formed on the gas barrier layer under the conditions of U2 in Table 1 above and the modification treatment was performed. Produced.

(Comparative Example 10)
A gas barrier film (Sample No. 21) was produced in the same manner as in Comparative Example 9 except that the anchor coat layer was formed under the conditions of U3 in Table 1 above.

(Example 12)
A gas barrier film (Sample No. 22) was produced in the same manner as in Example 1 except that a layer containing polysilazane was further formed on the gas barrier layer under the conditions of U2 in Table 1 above and the modification treatment was performed. did.

(Comparative Example 11)
A gas barrier film (sample No. 23) was produced in the same manner as in Comparative Example 5 except that a layer containing polysilazane was further formed on the gas barrier layer under the conditions of U2 in Table 1 above and the modification treatment was performed. did.

(Example 13)
A gas barrier film (sample No. 24) was prepared in the same manner as in Example 3 except that a layer containing polysilazane was further formed on the gas barrier layer under the conditions of U2 in Table 1 and the modification treatment was performed. did.

(Example 14)
A gas barrier film (sample No. 25) was produced in the same manner as in Example 4 except that a layer containing polysilazane was further formed on the gas barrier layer under the conditions of U2 in Table 1 above and the modification treatment was performed. did.

(Example 15)
A gas barrier film (sample No. 26) was prepared in the same manner as in Example 5 except that a layer containing polysilazane was further formed on the gas barrier layer under the conditions of U2 in Table 1 and the reforming treatment was performed. did.

(Example 16)
A gas barrier film (sample No. 27) was prepared in the same manner as in Example 6 except that a layer containing polysilazane was further formed on the gas barrier layer under the conditions of U2 in Table 1 and the modification treatment was performed. did.

(Example 17)
A gas barrier film (Sample No. 28) was produced in the same manner as in Example 7 except that a layer containing polysilazane was further formed on the gas barrier layer under the conditions of U2 in Table 1 above and the modification treatment was performed. did.

(Comparative Example 12)
A gas barrier film (sample No. 29) was produced in the same manner as in Comparative Example 7 except that a layer containing polysilazane was further formed on the gas barrier layer under the conditions of U2 in Table 1 above and the modification treatment was performed. did.

(Example 18)
A gas barrier film (Sample No. 30) was produced in the same manner as in Comparative Example 7 except that the composition adjustment treatment M2 was performed during the modification treatment of the layer containing polysilazane.

"Evaluation method"
<Evaluation of number of defects in gas barrier layer by vacuum film formation>
With respect to the gas barrier film samples 1 to 18 produced above, an evaluation element having a Ca vapor deposition area of 50 mm was produced. The number of Ca corrosion points of 100 μm or more was determined in terms of a circle-equivalent diameter generated when stored at 85 ° C. and 85% RH for 6 hours.

  Each gas barrier film measured as described above was evaluated by the number of Ca corrosion points and ranked as follows. In addition, if the number of Ca corrosion points is 19 or less (△ evaluation or more), it means that it has high gas barrier properties and excellent in-plane uniformity of gas barrier properties, and there is no problem in practical use, and it is a pass product. It is.

(Rank evaluation)
◎: 2 or less ○: 3-5
Δ: 6 to 19
X: 20-39
XX: 40 or more.

  The above evaluation results are summarized in Table 4.

  From Table 4 above, the gas barrier films of the examples are Sample 1 that does not have an anchor coat layer, Samples 2 to 5 that have A × B> 60, and Sample 15, and the anchor coat layer is formed by modifying polysiloxane. It was found that the film 6 had high gas barrier properties and excellent in-plane uniformity of gas barrier properties as compared to the sample 6 formed.

<Dark spot (DS) evaluation of organic EL devices>
Using the gas barrier film samples 19 to 30 produced above, a bottom emission type organic electroluminescence device (organic EL device) is produced by the method shown below so that the area of the light emitting region is 5 cm × 5 cm. did.

(Formation of underlayer and first electrode)
The gas barrier film is fixed to a substrate holder of a commercially available vacuum deposition apparatus, compound 118 is placed in a resistance heating boat made of tungsten, and the substrate holder and the heating boat are attached in the first vacuum chamber of the vacuum deposition apparatus. It was. 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 118 was energized and heated, and the deposition rate was 0.1 nm / second to 0.2 nm / second. The underlayer of the first electrode was provided with a thickness of 10 nm.

  Next, the base material formed up to the base layer is transferred to the second vacuum chamber while being vacuumed, and the second vacuum chamber is moved to 4 × 10. ^-4After reducing the pressure to Pa, the heating boat containing silver was energized and heated. Thus, a first electrode 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.

(Organic functional layer-second electrode)
Subsequently, the pressure was reduced to 1 × 10 ⁻⁴ Pa using a commercially available vacuum deposition apparatus, and then the compound HT-1 was deposited at a deposition rate of 0.1 nm / second while moving the base material. A transport layer (HTL) was provided.

  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 wt% to 5 wt%, and the compound A-1 and the compound A-2 each had a concentration of 0.2 wt% without depending on the film thickness. Thus, at a deposition rate of 0.0002 nm / sec, the compound H-1 was co-deposited to a thickness of 70 nm by changing the deposition rate from 64.6 wt% to 94.6 wt% depending on the location. A light emitting layer 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 was formed.

  The compound 118, compound HT-1, compound A-1 to compound 3, compound H-1, and compound ET-1 are the compounds shown below.

(Solid sealing)
Next, an aluminum foil with a thickness of 25 μm is used as a sealing member, and a thermosetting sheet adhesive (epoxy resin) is bonded as a sealing resin layer on one surface of the aluminum foil with a thickness of 20 μm. The stopper member was used to superimpose the sample up to the second electrode. At this time, the adhesive forming surface of the sealing member and the organic functional layer surface of the element were continuously overlapped so that the end portions of the extraction electrodes of the first electrode and the second electrode were exposed.

  Next, the sample was placed in a decompression device, and the laminated base material and the sealing member were pressed and held for 5 minutes under a decompression condition of 0.1 MPa at 90 ° C. Subsequently, the sample was returned to an atmospheric pressure environment and further heated at 120 ° C. for 30 minutes to cure the adhesive.

  The sealing step is performed under atmospheric pressure and in a nitrogen atmosphere with a water content of 1 ppm or less in accordance with JIS B 9920: 2002. The measured cleanliness is class 100, the dew point temperature is −80 ° C. or less, and the oxygen concentration is 0.00. It was performed at an atmospheric pressure of 8 ppm or less. In addition, the description regarding formation of the lead-out wiring from an anode and a cathode is abbreviate | omitted.

(Dark spot (DS) evaluation)
The organic EL device obtained as described above was energized for 100 hours in an environment of 85 ° C. and 85% RH, issued and photographed, and the size and number of dark spots were measured from the photograph image. The number of dark spots of 300 μm or more was obtained. The number of dark spots was converted to an issue area of 100 cm ² and ranked as follows. In addition, if the number of dark spots is 19 or less (Δ evaluation or more), it means that the electronic device has excellent durability in a high-temperature and high-humidity environment, and the gas barrier film used has a high gas barrier property and It means having excellent in-plane uniformity of gas barrier properties. Further, if the number of dark spots is 19 or less (Δevaluation or more), there is no problem in actual use and the product is acceptable.

(Rank evaluation)
◎: 2 or less ○: 3-5
Δ: 6 to 19
X: 20-39
XX: 40.

  The above evaluation results are summarized in Table 5.

From Table 5 above, the organic EL element samples 22 and 24-28 having the gas barrier films of Examples in which the anchor coat layer satisfies A × B ≦ 60 showed good results in the dark spot evaluation in a high temperature and high humidity environment. . On the other hand, in an organic EL element sample using a gas barrier film whose anchor coat layer does not satisfy A × B ≦ 60, a modified layer of polysilazane is further provided on the gas barrier layer (samples 20 and 21), and the composition is SiC. _{Even if} the thickness of the region of the gas barrier layer in which x is 0.8 to 1.2 (sample 29) is increased (Sample 29), the darkness is remarkable in a high-temperature and high-humidity environment. Spots were observed, indicating that the durability was poor.

  This application is based on Japanese Patent Application No. 2014-144294 filed on July 14, 2014, the disclosure of which is incorporated by reference in its entirety.

S deposition space,
1, 1a base material,
1b, 1c, 1d, 1e film-formed substrate,
10 Delivery roll,
11, 12, 13, 14 transport rolls,
15, 15 ′ first film forming roll,
16, 16 ′ second film forming roll,
17 winding roll,
18, 18 'gas supply pipe,
19, 19 'power source for plasma generation,
20, 20 ′, 21, 21 ′ magnetic field generator,
30 vacuum chamber,
40, 40 'vacuum pump,
41 Control unit.

Claims (7)

On the base material, an anchor coat layer, a gas barrier film having a gas barrier layer in contact with the anchor coat layer and formed in this order by a vacuum film forming method,
The anchor coat layer is a layer obtained by applying energy to a layer containing polysilazane and performing a modification treatment, and the thickness of the anchor coat layer is A (nm), and the entire anchor coat layer A gas barrier film in which A × B ≦ 60 when the atomic ratio (N / Si) of nitrogen atoms to silicon atoms is B.   The gas barrier film according to claim 1, wherein the gas barrier layer is a gas barrier layer formed by a vacuum plasma CVD method. The gas barrier layer is a composition distribution region whose composition is represented by SiC _x ,
The gas barrier film according to claim 1 or 2, wherein x has a region in the thickness direction of 0.8 to 1.2.   The gas barrier film according to any one of claims 1 to 3, wherein the energy is applied by irradiation with vacuum ultraviolet light.   Any one of Claims 1-4 which has a layer obtained by applying energy to the layer containing polysilazane, and performing a modification process on the surface on the opposite side to the base material side of the said gas barrier layer. The gas barrier film according to Item.   The gas barrier film according to claim 5, wherein the energy is applied by irradiation with vacuum ultraviolet light. The gas barrier film according to any one of claims 1 to 6,
An electronic device body formed on the gas barrier film;
Including electronic devices.