JP2017222071A - Gas barrier film, method for producing the same and organic electroluminescent device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a gas barrier film which suppresses fine foams generated on a boundary surface between a gas barrier layer and another constituent layer when storing an electronic device comprising a gas barrier film in a curved state under high temperature and high humidity .SOLUTION: There is provided a gas barrier film which comprises a base layer (Y) and a gas barrier layer (X) on a resin substrate, wherein the base layer (Y) contains a metal oxide (A), a phosphorus compound (B) and a cation (Z) having an ionic valence (F) of 1 to 3, wherein the phosphorus compound (B) is a compound having a site reactive with the metal oxide (A) and a relationship between the number of moles (N) of a metal atom (M) constituting the metal oxide (A) and the number of moles (N) of a phosphorus atom derived from the phosphorus compound (B) and a relationship among the number of moles (N) of the metal atom (M), the number of moles (N) of the cation (Z) and the ionic valence (F) satisfy specific relational expressions.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a gas barrier film, a manufacturing method thereof, and an organic electroluminescence device. More specifically, the present invention suppresses fine foaming that occurs at the interface between the gas barrier layer and other constituent layers when the electronic device including the gas barrier film is stored in a curved state under high temperature and high humidity. The present invention relates to a gas barrier film, a manufacturing method thereof, and an organic electroluminescence device.

  In recent years, gas barrier films have been demanded to be developed for flexible electronic devices such as solar cell elements, organic electroluminescence (hereinafter abbreviated as EL) elements, and liquid crystal display elements such as liquid crystal display elements. Consideration is being made in various fields. However, in these flexible electronic devices, a very high gas barrier property at the glass substrate level is required.

  In such a gas barrier film, as a method for forming a gas barrier layer on a substrate, for example, an organosilicon compound represented by hexamethyldisiloxane (hereinafter abbreviated as HMDSO) is used under reduced pressure. Chemical vapor deposition (CVD: Chemical Vapor Deposition, also referred to as chemical vapor deposition) that forms a gas barrier layer on a substrate while being oxidized with oxygen plasma, or by vaporizing metal Si using a semiconductor laser and oxygen There is known a vapor phase growth method such as a physical vapor deposition method (PVD method: Physical Vapor Deposition, for example, a vacuum vapor deposition method or a sputtering method) in which a gas barrier layer is formed by depositing on a substrate in the presence of.

  A gas barrier film in which a gas barrier layer is formed on a resin substrate using an organic silicon compound by the above chemical vapor deposition method, vacuum deposition method or sputtering method can certainly realize a high gas barrier property. When used as a base material of an element, if it is placed in an environment such as high temperature and high humidity while being curved, fine foam may appear at the gas barrier layer-element boundary or the gas barrier layer-lower layer boundary. When the fine foaming occurs, the gas barrier property is lowered. For example, in the case of an organic EL element, a light emission defect such as a dark spot is likely to occur. Recently, an organic EL display having a curved screen has appeared, and in some cases, the dark spot is a problem since it may be stored in a curved state under high temperature and high humidity.

  According to the study of the present inventor, this is caused by the generation of fine cracks at the boundary of the gas barrier layer due to the physical stress of bending, and the moisture that oozes out from the substrate side due to the pinhole of the gas barrier layer itself. It was inferred that fine foaming occurred at the corresponding portion of the barrier layer interface.

  Patent Document 1 discloses that a gas barrier film having a higher water vapor barrier property than a conventional gas barrier layer has a specific composition ratio including a metal atom such as aluminum, an oxygen atom, and a sulfur atom or a phosphorus atom. Although it is described that it can be realized by a gas barrier layer composed of a compound, according to the study of the present inventors, the electronic device equipped with the gas barrier film is stored in an environment such as high temperature and high humidity while being curved. In this case, the generation of fine cracks and the suppression of the fine foaming due to pinholes were insufficient.

  In Patent Document 2, a coating liquid containing a metal oxide, a phosphorus compound and a cation having an ionic value of 1 or more and 3 or less in a specific molar ratio is prepared and applied onto a substrate to form a precursor. A technique for forming a multilayer structure having a high gas barrier property by post-heat treatment has been disclosed, but the gas barrier layer when the electronic device is stored in an environment such as high temperature and high humidity while being curved- There is no description of the fine foaming that appears at the device boundary or at the gas barrier layer-lower layer boundary.

  Therefore, when an electronic device having a gas barrier film is curved and stored in an environment such as high temperature and high humidity, a gas barrier that suppresses fine foaming generated at the gas barrier layer-element boundary or gas barrier layer-lower layer boundary. A film is desired.

JP 2003-251732 A International Publication No. 2015/141226

  The present invention has been made in view of the above-described problems and situations, and a solution to the problem is that the gas barrier layer and the other when the electronic device including the gas barrier film is stored in a curved state under high temperature and high humidity. The object is to provide a gas barrier film in which fine foaming generated at the interface with the constituent layer is suppressed, a production method thereof, and an organic electroluminescence device.

In order to solve the above problems, the present inventor includes a base layer (Y) laminated on a resin base material and a gas barrier layer (X) in contact with the base layer in the process of examining the cause of the above problems. A gas barrier film, wherein the underlayer (Y) comprises a metal oxide (A), a phosphorus compound (B), and a cation ( _Z ) having an ionic value (F _Z ) in the range of 1 to 3. When the electronic device having the gas barrier film is stored in a curved state under high temperature and high humidity, it is generated at the boundary between the gas barrier layer (X) and other constituent layers. It was found that fine foaming can be suppressed.

  That is, the said subject which concerns on this invention is solved by the following means.

1. A gas barrier film comprising a base layer (Y) laminated on a resin substrate and a gas barrier layer (X) in contact with the underlayer (Y),
The underlayer (Y) contains a metal oxide (A), a phosphorus compound (B), and a cation ( _Z ) having an ionic value (F _Z ) in the range of 1 to 3,
The phosphorus compound (B) is a compound having a site capable of reacting with the metal oxide (A), and in the base layer (Y), the metal atom (M) constituting the metal oxide (A) The number of moles (N _M ) and the number of moles of phosphorus atoms derived from the phosphorus compound (B) (N _P ) satisfy the relationship represented by the following relational expression (1), and
In the underlayer (Y), the number of moles (N _M ), the number of moles of the cation (Z) (N _Z ), and the ion valence (F _Z ) are expressed by the following relational expression (2). A gas barrier film characterized by satisfying the above relationship.

Relational expression (1) 0.8 ≦ N _M / N _P ≦ 4.5
Relational expression (2) 0.001 ≦ F _Z × N _Z / N _M ≦ 0.60
2. When the gas barrier layer (X) represents the average composition by SiO _x C _y (x and y are stoichiometric coefficients), the relationship represented by the following relational expression (3) and the following relational expression (4) The gas barrier film according to item 1, which satisfies the relationship represented by the formula (1) and has a layer thickness in the range of 15 to 50 nm.

Relational expression (3) 1.6 ≦ x ≦ 1.9, 0.15 ≦ y ≦ 0.40
Relational expression (4) 4.0 ≦ 2x + 2y <4.3
3. A method for producing a gas barrier film comprising forming at least an underlayer (Y) on a resin substrate and a gas barrier layer (X) in contact with the underlayer (Y),
The underlayer (Y) contains a metal oxide (A), a phosphorus compound (B), and a cation ( _Z ) having an ionic value (F _Z ) in the range of 1 to 3,
The phosphorus compound (B) is a compound having a site capable of reacting with the metal oxide (A), and in the base layer (Y), the metal atom (M) constituting the metal oxide (A) The number of moles (N _M ) and the number of moles of phosphorus atoms derived from the phosphorus compound (B) (N _P ) satisfy the relationship represented by the following relational expression (1), and
In the underlayer (Y), the number of moles (N _M ), the number of moles of the cation (Z) (N _Z ), and the ion valence (F _Z ) are expressed by the following relational expression (2). A method for producing a gas barrier film, which is adjusted so as to satisfy the above relationship.

Relational expression (1) 0.8 ≦ N _M / N _P ≦ 4.5
Relational expression (2) 0.001 ≦ F _Z × N _Z / N _M ≦ 0.60
4). When the average composition of the gas barrier layer (X) is represented by SiO _x C _y (x and y are stoichiometric coefficients), the relationship represented by the following relational expression (3) and the following relational expression (4) 4. The method for producing a gas barrier film according to item 3, wherein the relationship represented by the formula (1) is satisfied and the layer thickness is adjusted within a range of 15 to 50 nm.

Relational expression (3) 1.6 ≦ x ≦ 1.9, 0.15 ≦ y ≦ 0.40
Relational expression (4) 4.0 ≦ 2x + 2y <4.3
5. The gas barrier layer (X) is formed by a vacuum plasma CVD method using a counter-roller type roll-to-roll film forming apparatus, The production of a gas barrier film according to claim 3 or 4, Method.

  6). An organic electroluminescence device comprising the gas barrier film according to item 1 or 2.

  By the above means of the present invention, when the electronic device having the gas barrier film is stored in a curved state under high temperature and high humidity, the gas barrier which suppresses fine foaming generated at the boundary between the gas barrier layer and the other constituent layers A film, a production method thereof, and an organic electroluminescence device can be provided.

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

  When an organic silicon compound is used as a base material for an organic device such as an organic EL element, a gas barrier film in which a gas barrier layer is formed by chemical vapor deposition, vacuum deposition, or sputtering is used to bend the electronic device. If left in an environment such as high temperature and high humidity, fine foaming may occur at the gas barrier layer-element boundary or gas barrier layer-underlying layer boundary. Defects such as dark spots are likely to occur in the element.

  According to the study of the present inventor, this is caused by the occurrence of fine cracks at the boundary of the gas barrier layer due to physical stress when the electronic device is bent and placed under high temperature and high humidity, or the gas barrier layer itself It was inferred that minute foaming occurred at the gas barrier layer-element boundary and gas barrier layer-lower layer boundary when a small amount of water oozes out from the base material side to the relevant part of the gas barrier layer boundary due to the pinholes having .

  While examining the means for suppressing the occurrence of fine foaming, the present inventor forms a thin gas barrier layer (X) by chemical vapor deposition, and further forms the gas barrier layer (X ) And a base material, a base layer containing a specific metal compound such as aluminum phosphate is provided, so that the metal compound of the base layer adsorbs a trace amount of moisture, thereby allowing the trace moisture to be applied to the gas barrier layer. It was found that the movement was blocked and fine foaming at the gas barrier layer boundary could be suppressed.

  The thin gas barrier layer (X) formed using the organosilicon compound or the like of the present invention is capable of forming a gas barrier layer that is flexible and dense, so that the generation of cracks when the device is bent, and the gas barrier It is considered advantageous for suppressing pinholes in the layer itself. However, since the film is originally a thin film, when a defect such as a pinhole is formed in the gas barrier layer (X), there is a drawback that it is easily affected by moisture from the substrate side.

  In the present invention, a trace amount of moisture is contained in the base layer by providing a base layer containing the specific metal compound between the gas barrier layer (X) and the substrate in contact with the thin gas barrier layer (X). Since it can be trapped in, the flexibility of the thin gas barrier layer (X) can be utilized, the occurrence of cracks and pinholes can be suppressed, and when the electronic device is stored in a curved state at high temperature and high humidity, It is assumed that the fine foaming generated at the boundary between the gas barrier layer and the other constituent layers could be suppressed.

Sectional drawing which shows the example of the gas barrier film of this invention The 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 Schematic diagram showing another example of a vacuum plasma CVD apparatus Sectional drawing of the organic EL element which comprises the gas barrier film of this invention

The gas barrier film of the present invention is a gas barrier film comprising a base layer (Y) laminated on a resin substrate and a gas barrier layer (X) in contact with the base layer (Y), wherein the base layer (Y) A metal oxide (A), a phosphorus compound (B), and a cation ( _Z ) having an ionic value (F _Z ) in the range of 1 to 3, and the phosphorus compound (B) A compound having a site capable of reacting with the product (A), the number of moles (N _M ) of the metal atom (M) constituting the metal oxide (A) in the base layer (Y), and the phosphorus compound The number of moles of phosphorus atoms derived from (B) (N _P ) satisfies the relationship represented by the relational expression (1), and in the underlayer (Y), the number of moles (N _M ) the number of moles of the cation (Z) and _{(N Z),} the ionic valence and _{(F Z),} but the function And satisfies the relation expressed by the formula (2). This feature is a technical feature common to or corresponding to the claimed invention.

As an embodiment of the present invention, from the viewpoint of expression of the effect of the present invention, when the gas barrier layer (X) represents an average composition by SiO _x C _y (x and y are stoichiometric coefficients), Satisfying the relationship represented by the relational expression (3) and the relation represented by the relational expression (4) and having a layer thickness in the range of 15 to 50 nm is excellent in flexibility as a gas barrier layer, and is a thin film From the viewpoint of realizing a high gas barrier property.

The method for producing a gas barrier film of the present invention is a method for producing a gas barrier film in which at least a base layer (Y) and a gas barrier layer (X) are formed on and in contact with a resin base material. The formation (Y) contains a metal oxide (A), a phosphorus compound (B), and a cation ( _Z ) having an ionic value (F _Z ) in the range of 1 to 3, and the phosphorus compound (B) Is a compound having a site capable of reacting with the metal oxide (A), and in the base layer (Y), the number of moles (N _M ) of metal atoms (M) constituting the metal oxide (A) And the number of moles (N _P ) of phosphorus atoms derived from the phosphorus compound (B) satisfy the relationship represented by the relational expression (1), and the number of moles in the underlayer (Y) (N _M ), the number of moles of the cation (Z) (N _Z ), and the ionic value (F _Z ) is adjusted so as to satisfy the relationship represented by the relational expression (2).

Further, when the gas barrier layer (X) has an average composition represented by SiO _x C _y (x and y are stoichiometric coefficients), the relation represented by the relational expression (3) and the relational expression ( 4) From the viewpoint of satisfying the relationship represented by 4) and adjusting the layer thickness within the range of 15 to 50 nm to form a gas barrier layer that balances transparency, gas barrier properties, and flexibility. ,preferable.

  Further, the gas barrier layer (X) is formed by a vacuum plasma CVD method using a counter-roller type roll-to-roll film forming apparatus, thereby producing a dense gas barrier layer in which the generation of pinholes is suppressed. It can be manufactured well and is preferable.

    The gas barrier film of the present invention is preferably provided in an organic electroluminescence device, and even when the device is curved and stored under high temperature and high humidity, it can prevent defects such as dark spots due to the trace amount of moisture. Is possible.

  Hereinafter, the present invention, its components, and modes and modes for carrying out the present invention will be described in detail. In addition, in this application, "-" is used in the meaning which includes the numerical value described before and behind that as a lower limit and an upper limit.

<< Outline of Gas Barrier Film of the Present Invention >>
The gas barrier film of the present invention is a gas barrier film comprising a base layer (Y) laminated on a resin substrate and a gas barrier layer (X) in contact with the base layer (Y), wherein the base layer (Y) A metal oxide (A), a phosphorus compound (B), and a cation ( _Z ) having an ionic value (F _Z ) in the range of 1 to 3, and the phosphorus compound (B) A compound having a site capable of reacting with the product (A), the number of moles (N _M ) of the metal atom (M) constituting the metal oxide (A) in the base layer (Y), and the phosphorus compound The number of moles of phosphorus atoms derived from (B) (N _P ) satisfies the relationship represented by the following relational expression (1), and in the base layer (Y), the number of moles (N _M ) the number of moles of the cation (Z) and _{(N Z),} the ionic valence and _{(F Z)} but, following function The gas barrier layer and other constituent layers when the electronic device having the gas barrier film is stored in a curved state under high temperature and high humidity, characterized by satisfying the relationship represented by the formula (2) A gas barrier film in which fine foaming generated at the boundary is suppressed.

Relational expression (1) 0.8 ≦ N _M / N _P ≦ 4.5
Relational expression (2) 0.001 ≦ F _Z × N _Z / N _M ≦ 0.60
The gas barrier film of the present invention was measured by a method according to JIS K 7129-1992 when the gas barrier property was calculated as a laminate in which the gas barrier layer (X) was formed on a base material. It is preferably a gas barrier film having a water vapor permeability of 0.01 g / m ² · 24 h or less in an environment of 0.5 ° C. and 90 ± 2% RH, and further, by a method based on JIS K 7126-2006. The measured oxygen permeability under an environment of 85 ° C. and 85% RH is 1 × 10 ⁻³ mL / m ² · 24 h · atm or less, and the water vapor permeability is 1 × 10 ⁻³ g / m ² · 24 h. A gas barrier film having the following high gas barrier properties is preferred.

Moreover, expressing the average composition of the gas barrier layer (X) as “SiO _x C _y ” means the compound constituting the gas barrier layer (X) or the average composition of the compound.

<Composition analysis by XPS>
The composition x and y in SiO _x C _y contained in the gas barrier layer (X) according to the present invention was measured for the element concentration distribution in the layer thickness direction by X-ray photoelectron spectroscopy (XPS). It can be obtained by averaging.

  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 the resolution in the layer thickness direction, and the etching depth per measurement point (corresponding to the conditions of the following sputter ion and depth profile) is 3 nm or less. Is preferably 2 nm or less, and more preferably 1 nm or less.

  An example of specific conditions for XPS analysis applicable to the present invention is shown below.

・ Analyzer: QUANTERA SXM manufactured by ULVAC-PHI
・ X-ray source: Monochromatic Al-Kα
・ Sputtering ion: Ar (2 keV)
Depth profile: Measurement is repeated at a predetermined thickness interval with a SiO ₂ equivalent sputtering thickness to obtain a depth profile in the depth direction. The thickness interval was 1 nm (data every 1 nm is obtained in the depth direction).

  Quantification: The background was determined by the Shirley method, and quantified using the relative sensitivity coefficient method from the obtained peak area. Data processing uses MultiPak manufactured by ULVAC-PHI.

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

  FIG. 1 shows a minimum configuration of a gas barrier film F of the present invention in which a base layer (Y) 2 is formed on a resin substrate 1 and a gas barrier layer (X) 3 is laminated thereon.

  Although other functional layers are not shown in FIG. 1, an antistatic layer, a backcoat layer, a bleedout prevention layer, a hard coat layer, and the like may be appropriately laminated. Furthermore, the structure which formed the base layer 2 and the gas barrier layer 3 which concern on this invention on the both sides of the resin base material 1 may be sufficient.

  In the present invention, an organic EL device described later is formed directly on the gas barrier layer (X) 3 of the gas barrier film F of the present invention or via another functional layer such as a smooth layer, It is preferable to do.

[1] Resin base material The material of the resin base material is not particularly limited, and base materials made of various materials can be used. Examples of the material of the resin base material include resins such as thermoplastic resins and thermosetting resins. Among these, a thermoplastic resin and a fiber assembly are preferable, and a thermoplastic resin is more preferable. The form of the resin substrate is not particularly limited, and may be a layer such as a film or a sheet. As a resin base material, a single layer may be sufficient and a multilayer may be sufficient.

Examples of the thermoplastic resin used for the resin base material include polyolefin resins such as polyethylene and polypropylene; polyester resins such as polyethylene terephthalate (PET), polyethylene-2,6-naphthalate, polybutylene terephthalate, and copolymers thereof. Resin; Polyamide-based resin such as nylon-6, nylon-66, nylon-12, etc .; Hydroxy group-containing polymer such as polyvinyl alcohol and ethylene-vinyl alcohol copolymer; Polystyrene; Poly (meth) acrylic acid ester; Polyacrylonitrile; Poly Polyvinylate; Polycarbonate; Polyarylate; Regenerated cellulose; Cellulose ester; Polyimide; Polyetherimide; Polysulfone; Polyethersulfone; Polyetheretherketone; Ionomer tree Etc. The. As a material for the resin base material, at least one thermoplastic resin selected from the group consisting of polyethylene, polypropylene, polyethylene terephthalate, nylon-6, and nylon-66 is preferable.
When a film made of the thermoplastic resin is used as a resin substrate, the resin substrate may be a stretched film or an unstretched film. A stretched film, particularly a biaxially stretched film is preferred because the processability (eg, suitability for printing and laminating) of the resulting gas barrier film is excellent. The biaxially stretched film may be a biaxially stretched film produced by any one of a simultaneous biaxial stretching method, a sequential biaxial stretching method, and a tubular stretching method.

  The thickness of the resin base material is preferably about 5 to 500 μm, more preferably 15 to 250 μm.

  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.

[2] Underlayer (Y)
The underlayer (Y) according to the present invention contains a metal oxide (A), a phosphorus compound (B), and a cation ( _Z ) having an ionic value (F _Z ) in the range of 1 to 3, The phosphorus compound (B) is a compound having a site capable of reacting with the metal oxide (A), and in the base layer (Y), the moles of metal atoms (M) constituting the metal oxide (A) The number (N _M ) and the number of moles of phosphorus atoms (N _P ) derived from the phosphorus compound (B) satisfy the relationship represented by the following relational expression (1), and the underlayer (Y) The number of moles (N _M ), the number of moles of the cation (Z) (N _Z ), and the ionic valence (F _Z ) satisfy the relationship represented by the following relational expression (2). It is characterized by.

Relational expression (1) 0.8 ≦ N _M / N _P ≦ 4.5
Relational expression (2) 0.001 ≦ F _Z × N _Z / N _M ≦ 0.60
[2.1] Metal oxide (A)
The metal atom (M) constituting the metal oxide (A) preferably has a valence of 2 or more. Examples of the metal atom (M) include a metal atom of Group 2 of the periodic table such as magnesium and calcium; a metal atom of Group 4 of the periodic table such as titanium and zirconium; a metal atom of Group 12 of the periodic table such as zinc; There can be mentioned group 13 metal atoms of the periodic table such as boron and aluminum; group 14 metal atoms of the periodic table such as silicon. Note that boron and silicon may be classified as metalloid atoms, but in this specification, these are included in the metal atoms. The metal atom (M) may be one type or two or more types. Among these, since the productivity of the metal oxide (A) and the gas barrier property and water vapor barrier property of the resulting gas barrier film are more excellent, the metal atom (M) is from the group consisting of aluminum, titanium, and zirconium. At least one selected from the above is preferable, and aluminum is more preferable. That is, the metal atom (M) preferably contains aluminum.
The total proportion of aluminum, titanium and zirconium in the metal atom (M) is usually 60 mol% or more and may be 100 mol%. Further, the proportion of aluminum in the metal atom (M) is usually 50 mol% or more, and may be 100 mol%. The metal oxide (A) is produced by a method such as a liquid phase synthesis method, a gas phase synthesis method, or a solid pulverization method.

The metal oxide (A) may be a hydrolysis condensate of the compound (L) having a metal atom (M) to which a hydrolyzable characteristic group is bonded. Examples of the characteristic group include R _{1 of} the general formula [I] described later. The hydrolysis condensate of compound (L) can be substantially regarded as the metal oxide (A). Therefore, in this specification, "metal oxide (A)" can be read as "hydrolysis condensate of compound (L)", and "hydrolysis condensate of compound (L)" It can also be read as “metal oxide (A)”.
<Compound (L) containing a metal atom (M) to which a hydrolyzable characteristic group is bonded>
Since the control of the reaction with the phosphorus compound (B) becomes easy and the gas barrier property of the resulting gas barrier film is excellent, the compound (L) is a compound represented by the following general formula [I] (L ₁ ) It is preferable to contain at least one kind.

Formula [I] M ₁ (R ₁ ) _m (R ₂ ) _nm
In the formula, M ₁ is selected from the group consisting of aluminum, titanium, and zirconium. R ₁ may have a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), NO ₃ , an optionally substituted alkoxy group having 1 to 9 carbon atoms, or a substituent. An acyloxy group having 1 to 9 carbon atoms, an alkenyloxy group having 3 to 9 carbon atoms which may have a substituent, a β-diketonato group having 5 to 15 carbon atoms which may have a substituent, or a substituent It is a diacylmethyl group having a C 1-9 acyl group which may have a group. R ₂ is an optionally substituted alkyl group having 1 to 9 carbon atoms, an optionally substituted aralkyl group having 7 to 10 carbon atoms, and an optionally substituted carbon. It is a C2-C10 aryl group which may have a C2-C9 alkenyl group or a substituent. m is an integer of 1 to n. n is equal to the valence of M ₁ . When a plurality of R ₁ are present, R ₁ may be the same as or different from each other. If R ₂ there are a plurality, R ₂ may be different may be identical or different.

Examples of the alkoxy group for R ₁ include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group, benzyloxy group, diphenylmethoxy group, Trityloxy group, 4-methoxybenzyloxy group, methoxymethoxy group, 1-ethoxyethoxy group, benzyloxymethoxy group, 2-trimethylsilylethoxy group, 2-trimethylsilylethoxymethoxy group, phenoxy group, 4-methoxyphenoxy group, etc. It is done.

Examples of the acyloxy group for R ₁ include an acetoxy group, ethylcarbonyloxy group, n-propylcarbonyloxy group, isopropylcarbonyloxy group, n-butylcarbonyloxy, isobutylcarbonyloxy group, sec-butylcarbonyloxy group, tert- A butylcarbonyloxy group, an n-octylcarbonyloxy group, etc. are mentioned.

Examples of the alkenyloxy group for R ₁ include allyloxy group, 2-propenyloxy group, 2-butenyloxy group, 1-methyl-2-propenyloxy group, 3-butenyloxy group, 2-methyl-2-propenyloxy group, 2-pentenyloxy group, 3-pentenyloxy group, 4-pentenyloxy group, 1-methyl-3-butenyloxy group, 1,2-dimethyl-2-propenyloxy group, 1,1-dimethyl-2-propenyloxy group 2-methyl-2-butenyloxy group, 3-methyl-2-butenyloxy group, 2-methyl-3-butenyloxy group, 3-methyl-3-butenyloxy group, 1-vinyl-2-propenyloxy group, 5-hexenyl An oxy group etc. are mentioned.

Examples of the β-diketonato group for R ₁ include a 2,4-pentandionato group, a 1,1,1-trifluoro-2,4-pentandionato group, 1,1,1,5,5,5. -Hexafluoro-2,4-pentanedionato group, 2,2,6,6-tetramethyl-3,5-heptaneedionate group, 1,3-butanedionato group, 2-methyl-1,3-butanedionato group, 2 -Methyl-1,3-butanedionato group, benzoylacetonato group and the like.

Examples of the acyl group of the diacylmethyl group of R ₁ include 1 to 6 carbon atoms such as formyl group, acetyl group, propionyl group (propanoyl group), butyryl group (butanoyl group), valeryl group (pentanoyl group), and hexanoyl group. An aliphatic acyl group (aroyl group) such as a benzoyl group or a toluoyl group.

Examples of the alkyl group for R ₂ include 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, Examples include n-hexyl group, isohexyl group, 3-methylpentyl group, 2-methylpentyl group, 1,2-dimethylbutyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group and the like.

Examples of the aralkyl group for R ₂ include a benzyl group and a phenylethyl group (phenethyl group).

Examples of the alkenyl group for R ₂ include a vinyl group, 1-propenyl group, 2-propenyl group, isopropenyl group, 3-butenyl group, 2-butenyl group, 1-butenyl group, and 1-methyl-2-propenyl group. 1-methyl-1-propenyl group, 1-ethyl-1-ethenyl group, 2-methyl-2-propenyl group, 2-methyl-1-propenyl group, 3-methyl-2-butenyl group, 4-pentenyl group Etc.

The aryl group of R _2, for example, phenyl, 1-naphthyl, 2-naphthyl group and the like.

Examples of the substituent in R ₁ and R ₂ include an alkyl group having 1 to 6 carbon atoms; a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, a sec-butoxy group, an alkoxy group having 1 to 6 carbon atoms such as a tert-butoxy group, an n-pentyloxy group, an isopentyloxy group, an n-hexyloxy group, a cyclopropyloxy group, a cyclobutyloxy group, a cyclopentyloxy group, a cyclohexyloxy group; Methoxycarbonyl group, ethoxycarbonyl group, n-propoxycarbonyl group, isopropoxycarbonyl group, n-butoxycarbonyl group, isobutoxycarbonyl group, sec-butoxycarbonyl group, tert-butoxycarbonyl group, n-pentyloxycarbonyl group, iso Pentyloxycarbo Group, cyclopropyloxycarbonyl group, cyclobutyloxycarbonyl group, cyclopentyloxycarbonyl group, etc., C1-C6 alkoxycarbonyl group; phenyl group, tolyl group, naphthyl group, etc. aromatic hydrocarbon group; fluorine atom, Halogen atoms such as chlorine atom, bromine atom and iodine atom; acyl group having 1 to 6 carbon atoms; aralkyl group having 7 to 10 carbon atoms; aralkyloxy group having 7 to 10 carbon atoms; alkylamino group having 1 to 6 carbon atoms A dialkylamino group having an alkyl group having 1 to 6 carbon atoms.

R ₁ includes a halogen atom, NO ₃ , an optionally substituted alkoxy group having 1 to 6 carbon atoms, an optionally substituted acyl group having 1 to 6 carbon atoms, and a substituent. A diacylmethyl group having an optionally substituted β-diketonato group having 5 to 10 carbon atoms or an optionally substituted acyl group having 1 to 6 carbon atoms is preferable.

As R < ₂ >, the C1-C6 alkyl group which may have a substituent is preferable. The M _1, aluminum is preferred. When M ₁ is aluminum, m is preferably 3.

Specific examples of the compound (L ₁ ) include, for example, aluminum nitrate, aluminum acetate, tris (2,4-pentanedionato) aluminum, trimethoxyaluminum, triethoxyaluminum, tri-n-propoxyaluminum, triisopropoxyaluminum. , Aluminum compounds such as tri-n-butoxyaluminum, tri-sec-butoxyaluminum, tri-tert-butoxyaluminum; tetrakis (2,4-pentanedionato) titanium, tetramethoxytitanium, tetraethoxytitanium, tetraisopropoxytitanium , Tetra-n-butoxytitanium, tetrakis (2-ethylhexoxy) titanium, etc .; tetrakis (2,4-pentanedionato) zirconium, tetra-n-propoxyzirconium, te Zirconium compounds such as La -n- butoxy zirconium and the like. Among these, as the compound (L ₁ ), at least one compound selected from triisopropoxy aluminum and tri-sec-butoxy aluminum is preferable. A compound (L) may be used individually by 1 type, and may use 2 or more types together.

In the compound (L), the ratio of the compound (L ₁ ) in the compound (L) is not particularly limited as long as the effect of the present invention is obtained. The proportion of the compound other than the compound (L ₁ ) in the compound (L) is, for example, preferably 20 mol% or less, more preferably 10 mol% or less, further preferably 5 mol% or less, and even 0 mol%. Good.

  By hydrolyzing the compound (L), at least a part of the hydrolyzable characteristic group of the compound (L) is converted into a hydroxy group. Furthermore, the hydrolyzate condenses to form a compound in which the metal atom (M) is bonded through the oxygen atom (O). When this condensation is repeated, a compound that can be substantially regarded as a metal oxide is formed. In addition, a hydroxy group usually exists on the surface of the metal oxide (A) thus formed.

  In the present specification, a compound having a ratio of [number of moles of oxygen atom (O) bonded only to metal atom (M)] / [number of moles of metal atom (M)] of 0.8 or more is metal. It shall be included in oxide (A). Here, the oxygen atom (O) bonded only to the metal atom (M) is the oxygen atom (O) in the structure represented by MOM, and the structure represented by MOH. Oxygen atoms bonded to metal atoms (M) and hydrogen atoms (H) such as oxygen atoms (O) in are excluded. The ratio in the metal oxide (A) is preferably 0.9 or more, more preferably 1.0 or more, and further preferably 1.1 or more. Although the upper limit of this ratio is not particularly limited, it is usually represented by n / 2, where n is the valence of the metal atom (M).

  In order for the hydrolysis condensation to occur, it is important that the compound (L) has a hydrolyzable characteristic group. When these groups are not bonded, the hydrolysis condensation reaction does not occur or becomes extremely slow, making it difficult to prepare the target metal oxide (A).

  The hydrolyzed condensate of compound (L) may be produced from a specific raw material by a method employed in a known sol-gel method, for example. The raw materials include compound (L), partial hydrolyzate of compound (L), complete hydrolyzate of compound (L), partial hydrolyzed condensate of compound (L), and complete hydrolysis of compound (L). At least one selected from the group consisting of products in which a part of the product is condensed can be used.

[2.2] Phosphorus compound (B)
The phosphorus compound (B) has a site capable of reacting with the metal oxide (A), and typically has a plurality of such sites. As a phosphorus compound (B), an inorganic phosphorus compound is preferable. As the phosphorus compound (B), a compound having 2 to 20 sites (atomic groups or functional groups) capable of reacting with the metal oxide (A) is preferable. Such a part includes a part capable of undergoing a condensation reaction with a functional group (for example, a hydroxy group) present on the surface of the metal oxide (A). Examples of such a site include a halogen atom directly bonded to a phosphorus atom, an oxygen atom directly bonded to a phosphorus atom, and the like. A functional group (for example, a hydroxy group) present on the surface of the metal oxide (A) is usually bonded to a metal atom (M) constituting the metal oxide (A).

  Examples of the phosphorus compound (B) include phosphoric acid, polyphosphoric acid condensed with 4 or more molecules of phosphoric acid, phosphorous acid, phosphonic acid, phosphonous acid, phosphinic acid, phosphinic acid, and the like, and These salts (for example, sodium phosphate), and derivatives thereof (for example, halides (for example, phosphoryl chloride), dehydrates (for example, diphosphorus pentoxide)) and the like can be mentioned.

  A phosphorus compound (B) may be used individually by 1 type, and may use 2 or more types together. Among these phosphorus compounds (B), it is preferable to use phosphoric acid alone or to use phosphoric acid and other phosphorus compounds (B) in combination. By using phosphoric acid, the stability of the first coating liquid (U) described later and the gas barrier property and water vapor barrier property of the resulting underlayer are improved.

<Ratio of metal oxide (A) and phosphorus compound (B)>
In the base layer according to the present invention (Y), and the _{N M} and the _{N P} is, which satisfies the relationship _{0.8 ≦ N M / N P ≦} 4.5, 1.0 ≦ N M / N Those satisfying the relationship of _P ≦ 3.6 are preferable, and those satisfying the relationship of 1.1 ≦ N _M / N _P ≦ 3.0 are more preferable. When the value of N _M / _{N P} is more than 4.5, becomes excessive metal oxide (A) with respect to the phosphorus compound (B), the binding of the metal oxide (A) and phosphorus compound (B) not In addition, since the amount of hydroxy groups present on the surface of the metal oxide (A) increases, the gas barrier property and its stability tend to decrease. On the other hand, when the value of N M _/ N _P is less than 0.8, a phosphorus compound (B) is a metal oxide becomes excessive relative to (A), a surplus that is not involved in binding of the metal oxide (A) The amount of the phosphorus compound (B) increases, and the amount of the hydroxy group derived from the phosphorus compound (B) tends to increase, and the gas barrier property and its stability tend to decrease.

In addition, the said ratio can be adjusted with ratio of the quantity of a metal oxide (A) and the quantity of a phosphorus compound (B) in the 1st coating liquid (U) for forming a base layer (Y). The ratio between the number of moles (N _M ) and the number of moles (N _P ) in the underlayer (Y) is usually the ratio in the first coating liquid (U) and the metal atoms (A) constituting the metal oxide (A) ( It is the same as the ratio between the number of moles of M) and the number of moles of phosphorus atoms constituting the phosphorus compound (B).

<Reaction product (D)>
A reaction product (D) is obtained by reaction of a metal oxide (A) and a phosphorus compound (B). Here, the compound produced by the reaction of the metal oxide (A), the phosphorus compound (B), and another compound is also included in the reaction product (D). The reaction product (D) may partially contain a metal oxide (A) and / or a phosphorus compound (B) that is not involved in the reaction.

[2.3] Cation (Z)
The ionic value (F Z) of the cation ( _Z ) is in the range of 1 to 3. The cation (Z) is a cation containing an element in the second to seventh periods of the periodic table. Examples of the cation (Z) include lithium ion, sodium ion, potassium ion, magnesium ion, calcium ion, titanium ion, zirconium ion, lanthanoid ion (for example, lanthanum ion), vanadium ion, manganese ion, iron ion, and cobalt. Examples include ions, nickel ions, copper ions, zinc ions, boron ions, aluminum ions, and ammonium ions. Among them, lithium ions, sodium ions, potassium ions, magnesium ions, calcium ions, and zinc ions are preferable. One kind of cation (Z) may be included, or two or more kinds may be included. Regarding the action of the cation (Z), the cation (Z) is smaller by suppressing the enlargement of the inorganic compound particles by the interaction with the hydroxy group of the metal oxide (A) or the phosphorus compound (B). As a result of the denseness of the gas barrier layer being improved by the particle filling, it is assumed that the performance degradation of the electronic device is suppressed. Therefore, when a higher performance deterioration suppressing function is required, it is preferable to use a cation having a small ion valence (F _Z ) capable of forming an ionic bond.

In addition, when a cation (Z) contains several types of cation from which an ionic valence differs, the value of said _FZ * _NZ is obtained by totaling the value calculated for every cation. For example, when the cation (Z) includes 1 mol of sodium ion (Na ⁺ ) and 2 mol of calcium ion (Ca ²⁺ ), F _Z × N _Z = 1 × 1 + 2 × 2 = 5.

  The cation (Z) can be added to the underlayer (Y) by dissolving the ionic compound (E) that generates the cation (Z) when dissolved in the solvent in the first coating liquid (U). . Examples of the cation (Z) counter ions include inorganic anions such as hydroxide ions, chloride ions, sulfate ions, hydrogen sulfate ions, nitrate ions, carbonate ions and hydrogen carbonate ions; acetate ions and stearate ions. And organic acid anions such as oxalate ion and tartrate ion. The ionic compound (E) of the cation (Z) is a metal compound (Ea) or metal oxide (Eb) (excluding the metal oxide (A)) that generates a cation (Z) when dissolved. Also good.

<Ratio of metal oxide (A) to cation (Z)>
In accordance with the present invention (Y), and the FZ and _{N Z} and _{N M} is, which satisfy the relation of _{0.001 ≦ F Z × N Z /} N M ≦ 0.60, 0.001 ≦ F Z Those satisfying the relationship of × N _Z / N _M ≦ 0.30 are preferable, and those satisfying the relationship of 0.01 ≦ F _Z × N _Z / N _M ≦ 0.30 are more preferable.

<Ratio of phosphorus compound (B) to cation (Z)>
In the base layer according to the present invention (Y), the _{F Z} and _{N Z} and _{N P} is preferably satisfy the relation of _{0.0008 ≦ F Z × N Z /} N P ≦ 1.35, 0.001 ≦ Those satisfying the relationship of F _Z × N _Z / N _P ≦ 1.00 are more preferable, those satisfying the relationship of 0.0012 ≦ F _Z × N _Z / N _P ≦ 0.35 are further preferable, and 0.012 ≦ Those satisfying the relationship of F _Z × N _Z / N _P ≦ 0.29 are particularly preferable.

[2.4] Polymer (C)
The underlayer (Y) may further contain a specific polymer (C). The polymer (C) is, for example, a polymer containing at least one functional group selected from the group consisting of a carbonyl group, a hydroxy group, a carboxy group, a carboxylic anhydride group, and a salt of a carboxy group.

  Specific examples of the polymer (C) having a hydroxy group include polyketone; polyvinyl alcohol, modified polyvinyl alcohol containing 1 to 50 mol% of an α-olefin unit having 4 or less carbon atoms, polyvinyl acetal (for example, polyvinyl butyral), and the like. Polyvinyl alcohol polymers such as: polysaccharides such as cellulose, starch, cyclodextrin; (meth) acrylic acid heavy polymers such as hydroxyethyl poly (meth) acrylate, poly (meth) acrylic acid, and ethylene-acrylic acid copolymers Maleic polymers such as hydrolyzate of ethylene-maleic anhydride copolymer, hydrolyzate of styrene-maleic anhydride copolymer, hydrolyzate of alternating isobutylene-maleic anhydride copolymer, etc. Can be mentioned. Among these, a polyvinyl alcohol polymer is preferable, and specifically, modified polyvinyl alcohol containing 1 to 15 mol% of polyvinyl alcohol and an α-olefin unit having 4 or less carbon atoms is preferable.

  Although it does not specifically limit as a saponification degree of a polyvinyl alcohol-type polymer, 75.0-99.85 mol% is preferable and 80.0-99.5 mol% is more preferable. 100-4000 are preferable and, as for the viscosity average polymerization degree of a polyvinyl alcohol-type polymer, 300-3000 are more preferable. Moreover, 1.0-200 mPa * s is preferable and, as for the viscosity of the 4 mass% aqueous solution at 20 degreeC of a polyvinyl alcohol-type polymer, 11-90 mPa * s is more preferable. The saponification degree, the viscosity average polymerization degree, and the viscosity of the 4% by mass aqueous solution are values obtained according to JIS K 6726 (1994).

  The polymer (C) may be a homopolymer of a monomer having a polymerizable group (for example, vinyl acetate or acrylic acid), or may be a copolymer of two or more monomers. It may be a copolymer of a monomer having a carbonyl group, a hydroxy group and / or a carboxy group and a monomer having no such group.

  There is no restriction | limiting in particular in the molecular weight of a polymer (C). In order to obtain a base layer having better gas barrier properties and physical properties (for example, scratch resistance), the number average molecular weight of the polymer (C) is preferably 5000 or more, more preferably 8000 or more. Preferably, it is 10,000 or more. The upper limit of the number average molecular weight of a polymer (C) is not specifically limited, For example, it is 1500000 or less.

  In order to further improve the gas barrier properties, the content of the polymer (C) in the underlayer (Y) may be 50% by mass or less based on the mass of the underlayer (Y) (100% by mass). Preferably, it is 40 mass% or less, more preferably 30 mass% or less, and may be 20 mass% or less. The polymer (C) may or may not react with other components in the underlayer (Y).

[2.5] Other components in the underlayer (Y) The underlayer (Y) comprises a metal oxide (A), a compound (L), a phosphorus compound (B), a reaction product (D), a cation ( In addition to Z) or a compound (E) thereof, an acid (an acid catalyst used for hydrolysis condensation, an acid during peptization, and the like), and the polymer (C), other components may be included. Examples of other components include inorganic acid metal salts such as carbonates, hydrochlorides, nitrates, hydrogen carbonates, sulfates, hydrogen sulfates, borates and the like that do not contain cations (Z); cations (Z) Organic acid metal salts such as acetates, stearates, oxalates, tartrates, etc. that do not contain amides; layered clay compounds; crosslinking agents; polymer compounds other than polymer (C); plasticizers; antioxidants; Agents; flame retardants and the like.

  The content of the other components in the underlayer (Y) is preferably 50% by mass or less, more preferably 20% by mass or less, and more preferably 10% by mass with respect to the mass of the underlayer (Y). More preferably, it is more preferably 5% by mass or less, and may be 0% by mass (excluding other components).

[2.6] Physical properties of base layer (Y) Thickness of base layer (Y) (when the base layer has two or more base layers (Y), the total thickness of each base layer (Y)) Is preferably 0.05 to 4.0 μm, more preferably 0.1 to 2.0 μm. By reducing the thickness of the underlayer (Y), flexibility is increased, so that the mechanical characteristics can be brought close to the mechanical characteristics of the substrate itself. When the foundation layer according to the present invention has two or more layers (Y), the thickness per foundation layer (Y) is preferably 0.05 μm or more from the viewpoint of gas barrier properties. The thickness of the underlayer (Y) can be controlled by the concentration of a first coating liquid (U) (described later) used for forming the underlayer (Y) and the coating method.

In the infrared absorption spectrum of the underlying layer (Y), the maximum absorption wave number in the region of 800～1400Cm ^-1 is preferably in the range of 1,080~1130cm ^-1. In the process in which the metal oxide (A) and the phosphorus compound (B) react to form a reaction product (D), the metal atom (M) derived from the metal oxide (A) and the phosphorus compound (B) To form a bond represented by M-O-P bonded with an oxygen atom (O). As a result, a characteristic absorption band derived from the bond is generated in the infrared absorption spectrum. As a result of the study by the present inventors, when the absorption band based on the M—O—P bond is seen in the region of 1,080 to 1,130 cm ⁻¹ , the obtained gas barrier film exhibits excellent gas barrier properties. I understood it. In particular, when the characteristic absorption band is the strongest absorption in a region of 800 to 1400 cm ^{−1 in which} absorption derived from bonds between various atoms and oxygen atoms is generally observed, the obtained gas barrier film further It was found that excellent gas barrier properties were exhibited.

In contrast, when a metal compound such as a metal alkoxide or metal salt and a phosphorus compound (B) are mixed in advance and then hydrolytically condensed, the metal atom derived from the metal compound and the phosphorus compound (B) are derived. A complex in which phosphorus atoms are mixed and reacted almost uniformly is obtained. In that case, in the infrared absorption spectrum, the maximum absorption wave number in the region of 800～1400Cm ^-1 comes to deviate from the scope of 1080~1130cm ^-1.

In the infrared absorption spectrum of the underlying layer (Y), the half-value width of the maximum absorption band in the region of 800～1400Cm ^-1, from the viewpoint of gas barrier properties of the resulting gas barrier film, 200 cm ^-1 or less is preferable, 150 cm ^-1 The following is more preferable, 100 cm ⁻¹ or less is further preferable, and 50 cm ⁻¹ or less is particularly preferable.

  The infrared absorption spectrum of the underlayer (Y) can be measured by an attenuated total reflection method using a Fourier transform infrared spectrophotometer. As an example, the measurement conditions are as follows.

Device: Spectrum One manufactured by PerkinElmer Co., Ltd.
Measurement mode: attenuated total reflection method Measurement region: 800 to 1400 cm ⁻¹
[2.7] Underlayer (W)
In addition to the underlayer (Y) according to the present invention, an underlayer (W) may be further included. The underlayer (W) preferably contains a polymer (G1) having a functional group containing a phosphorus atom. The underlayer (W) is preferably disposed adjacent to the underlayer (Y). That is, it is preferable that the base layer (W) and the base layer (Y) are arranged so as to be in contact with each other to form the base layer. Moreover, it is preferable that a base layer (W) is arrange | positioned on the opposite side (preferably the surface on the opposite side) with respect to a resin base material on both sides of a base layer (Y).

  The underlayer (W) may further include a polymer (G2) having a hydroxy group and / or a carboxy group. As the polymer (G2), the same polymer (C) can be used. The polymer (G1) will be described below.

<Polymer (G1)>
Examples of the functional group containing a phosphorus atom that the polymer (G1) having a functional group containing a phosphorus atom has include a phosphoric acid group, a phosphorous acid group, a phosphonic acid group, a phosphonous acid group, a phosphinic acid group, Examples thereof include phosphinic acid groups and salts thereof, and functional groups derived therefrom (for example, (partial) ester compounds, halides (for example, chloride), dehydrates) and the like. Among these, a phosphoric acid group and / or a phosphonic acid group are preferable, and a phosphonic acid group is more preferable.

  Examples of the polymer (G1) include 6-[(2-phosphonoacetyl) oxy] hexyl acrylate, 2-phosphonooxyethyl methacrylate, phosphonomethyl methacrylate, 11-phosphonoundecyl methacrylate, and methacrylic acid 1 Polymers of phosphono (meth) acrylates such as 1,1-diphosphonoethyl; heavy phosphonic acids such as vinylphosphonic acid, 2-propene-1-phosphonic acid, 4-vinylbenzylphosphonic acid, 4-vinylphenylphosphonic acid Polymers of phosphinic acids such as vinyl phosphinic acid and 4-vinylbenzyl phosphinic acid; phosphorylated starch and the like. The polymer (G1) may be a homopolymer of a monomer having at least one phosphorus atom-containing functional group, or may be a copolymer of two or more types of monomers. Further, as the polymer (G1), two or more kinds of polymers composed of a single monomer may be mixed and used. Among these, polymers of phosphono (meth) acrylic acid esters and / or polymers of vinyl phosphonic acids are preferable, and polymers of vinyl phosphonic acids are more preferable. The polymer (G1) is preferably poly (vinylphosphonic acid) or poly (2-phosphonooxyethyl methacrylate), and may be poly (vinylphosphonic acid). The polymer (G1) can also be obtained by hydrolyzing after vinylphosphonic acid derivatives such as vinylphosphonic acid halides and vinylphosphonic acid esters are used alone or copolymerized.

  The polymer (G1) may be a copolymer of a monomer having at least one phosphorus atom-containing functional group and another vinyl monomer. Other vinyl monomers that can be copolymerized with a monomer having a phosphorus atom-containing functional group include, for example, (meth) acrylic acid, (meth) acrylic acid esters, acrylonitrile, methacrylonitrile, styrene, Examples include nucleus-substituted styrenes, alkyl vinyl ethers, alkyl vinyl esters, perfluoroalkyl vinyl ethers, perfluoroalkyl vinyl esters, maleic acid, maleic anhydride, fumaric acid, itaconic acid, maleimide, and phenylmaleimide. Among these, (meth) acrylic acid esters, acrylonitrile, styrene, maleimide, and phenylmaleimide are preferable.

  In order to obtain a gas barrier film having superior bending resistance, the proportion of the structural unit derived from the monomer having a phosphorus atom-containing functional group in the total structural unit of the polymer (G1) is 10 mol% or more. It is preferably 20 mol% or more, more preferably 40 mol% or more, particularly preferably 70 mol% or more, and may be 100 mol%.

  Although there is no restriction | limiting in particular in the molecular weight of a polymer (G1), It is preferable that a number average molecular weight exists in the range of 1000-100000. When the number average molecular weight is in this range, the improvement effect of bending resistance by laminating the underlayer (W) and the viscosity stability of the second coating liquid (V) described later are compatible at a high level. Can do. Moreover, when laminating | stacking a base layer (Y), when the molecular weight of the polymer (G1) per phosphorus atom exists in the range of 100-500, the improvement effect of a bending resistance can be heightened more.

  The underlayer (W) may be composed only of the polymer (G1), may be composed only of the polymer (G1) and the polymer (G2), or may further include other components. Other components contained in the underlayer (W) include, for example, inorganic acid metal salts such as carbonates, hydrochlorides, nitrates, hydrogen carbonates, sulfates, hydrogen sulfates, borates; acetates, stearic acid Organic acid metal salts such as salts, oxalates, and tartrate salts; metal complexes such as cyclopentadienyl metal complexes (eg, titanocene) and cyano metal complexes (eg, Prussian blue); layered clay compounds; cross-linking agents; Polymer compounds other than (G1) and the polymer (G2): plasticizers; antioxidants; ultraviolet absorbers; flame retardants and the like. The content of the other components in the underlayer (W) is preferably 50% by mass or less, more preferably 20% by mass or less, further preferably 10% by mass or less, and more preferably 5% by mass. % Or less is particularly preferable, and may be 0% by mass (excluding other components).

  The thickness per layer of the underlayer (W) is preferably 0.003 μm or more from the viewpoint of better resistance to physical stress (for example, bending) of the gas barrier film of the present invention. The upper limit of the thickness of the underlayer (W) is not particularly limited, but the effect of improving resistance to physical stress reaches saturation at 1.0 μm or more. Therefore, the upper limit of the total thickness of the base layer (W) is preferably 1.0 μm from the viewpoint of economy. The thickness of the underlayer (W) can be controlled by the concentration of a second coating liquid (V) described later used for forming the underlayer (W) and the coating method.

[2.8] Manufacturing method of base layer (Y) The manufacturing method of the base layer (Y) according to the present invention is such that the base layer (Y) includes a metal oxide (A), a phosphorus compound (B), and an ionic value. (F _Z ) contains a cation (Z) in the range of 1 to 3, and the phosphorus compound (B) is a compound having a site capable of reacting with the metal oxide (A), In the underlayer (Y), the number of moles (N _M ) of the metal atoms (M) constituting the metal oxide (A) and the number of moles of phosphorus atoms (N _P ) derived from the phosphorus compound (B) Satisfying the relationship represented by the relational expression (1), and in the underlayer (Y), the number of moles (N _M ) and the number of moles of the cation (Z) (N _Z ), The ion valence (F _Z ) is adjusted so as to satisfy the relationship represented by the relational expression (2), and the process [I] , [II] and [III] are preferably included.

  In the step [I], the metal oxide (A), the phosphorus compound (B), and the ionic compound (E) of the cation (Z) are mixed, whereby the metal oxide (A), the phosphorus compound ( A first coating liquid (U) containing B) and a cation (Z) is prepared. In step [II], the precursor layer of the base layer (Y) is formed on the resin substrate by applying the first coating liquid (U) on the resin substrate. In step [III], the precursor layer is heat-treated at a temperature of 110 ° C. or higher to form a base layer (Y) on the resin substrate.

<Step [I] Preparation of First Coating Liquid (U)>
In the step [I], the metal oxide (A), the phosphorus compound (B), and the ionic compound (E) of the cation (Z) are mixed. In mixing these, a solvent may be added. In the first coating liquid (U), a cation (Z) is generated from the ionic compound (E). The first coating liquid (U) may contain other compounds in addition to the metal oxide (A), the phosphorus compound (B), and the cation (Z).

The first coating solution in (U), and the N _M and N _P preferably satisfies the relational expression. Further, with the _{N M} and _{N Z} and _{F Z} preferably satisfies the relational expression. Furthermore, said _{N P} and _{N Z} and _{F Z} preferably satisfies the relational expression.

  The step [I] preferably includes the following steps [Ia] to [Ic].

Step [Ia]: a step of preparing a liquid containing the metal oxide (A),
Step [Ib]: a step of preparing a solution containing the phosphorus compound (B),
Step [Ic]: A step of mixing the liquid containing the metal oxide (A) obtained in the steps [Ia] and [Ib] and the solution containing the phosphorus compound (B).

  Step [Ib] may be performed either before or after step [Ia], or may be performed simultaneously with step [Ia]. Hereinafter, each step will be described more specifically.

  In the step [Ia], a liquid containing the metal oxide (A) is prepared. The liquid is a solution or a dispersion. The liquid is, for example, mixed with the above-described compound (L), water, and, if necessary, an acid catalyst or an organic solvent in accordance with a technique employed in a known sol-gel method, and compound (L) is mixed. It can be prepared by condensation or hydrolysis condensation. When a dispersion of the metal oxide (A) is obtained by condensing or hydrolyzing the compound (L), a specific treatment (such as peptization or concentration as described above) is performed on the dispersion as necessary. The solvent may be adjusted for control). Step [Ia] may include a step of condensing (for example, dehydrating condensation) at least one selected from the group consisting of compound (L) and a hydrolyzate of compound (L). There is no restriction | limiting in particular in the kind of organic solvent which can be used in process [Ia], For example, alcohol, such as methanol, ethanol, isopropanol, water, and these mixed solvents are preferable. The content of the metal oxide (A) in the liquid is preferably in the range of 0.1 to 30% by mass, more preferably in the range of 1 to 20% by mass, and 2 to 15% by mass. More preferably, it is in the range.

  For example, when the metal oxide (A) is aluminum oxide, the preparation of the aluminum oxide dispersion is performed by first hydrolyzing and condensing the aluminum alkoxide in an aqueous solution adjusted to pH with an acid catalyst as necessary. A slurry is obtained. Next, the slurry is peptized in the presence of a specific amount of acid to obtain a dispersion of aluminum oxide. In addition, the dispersion liquid of the metal oxide (A) containing metal atoms other than aluminum can also be manufactured by the same method. As the acid, for example, hydrochloric acid, sulfuric acid, nitric acid, acetic acid, lactic acid and butyric acid are preferable, and nitric acid and acetic acid are more preferable.

  In step [Ib], a solution containing the phosphorus compound (B) is prepared. The solution can be prepared by dissolving the phosphorus compound (B) in a solvent. When the solubility of the phosphorus compound (B) is low, dissolution may be promoted by heat treatment or ultrasonic treatment. The solvent may be appropriately selected according to the type of the phosphorus compound (B), but preferably contains water. The solvent may contain an organic solvent (for example, methanol) as long as it does not hinder the dissolution of the phosphorus compound (B).

  The content of the phosphorus compound (B) in the solution containing the phosphorus compound (B) is preferably in the range of 0.1 to 99% by mass, more preferably in the range of 45 to 95% by mass, 55 More preferably, it is in the range of -90% by mass.

  In the step [Ic], a liquid containing the metal oxide (A) and a solution containing the phosphorus compound (B) are mixed. By maintaining the temperature at the time of mixing at 30 ° C. or lower (for example, 20 ° C.), the first coating liquid (U) excellent in storage stability can be obtained.

  The compound (E) containing a cation (Z) may be added in at least one step selected from the group consisting of the step [Ia], the step [Ib], and the step [Ic]. However, it may be added in any one of them. For example, the compound (E) may be added to the liquid containing the metal oxide (A) in the step [Ia] or the solution containing the phosphorus compound (B) in the step [Ib]. -C] may be added to a mixed solution of the liquid containing the metal oxide (A) and the solution containing the phosphorus compound (B).

  Further, the first coating liquid (U) may contain a polymer (C). The method for including the polymer (C) in the first coating liquid (U) is not particularly limited. For example, the polymer (C) may be added and mixed as a solution to any one of a liquid containing the metal oxide (A), a solution containing the phosphorus compound (B), and a mixed solution thereof. You may make it melt | dissolve, after adding in the state of a pellet. Metal oxide (A) when liquid containing metal oxide (A) and solution containing phosphorus compound (B) are mixed by containing polymer (C) in a solution containing phosphorus compound (B) As a result, the first coating liquid (U) having excellent stability over time can be obtained.

  The first coating liquid (U) may contain at least one acid compound (J) selected from hydrochloric acid, nitric acid, acetic acid, trifluoroacetic acid, and trichloroacetic acid, if necessary. The content of the acid compound (J) is preferably in the range of 0.1 to 5.0% by mass, and more preferably in the range of 0.5 to 2.0% by mass. Within these ranges, the effect of adding the acid compound (J) can be obtained, and the acid compound (J) can be easily removed. When the acid component remains in the liquid containing the metal oxide (A), the addition amount of the acid compound (J) may be determined in consideration of the residual amount.

  The mixed liquid obtained in the step [Ic] can be used as it is as the first coating liquid (U). In this case, normally, the solvent contained in the liquid containing the metal oxide (A) or the solution containing the phosphorus compound (B) is the solvent for the first coating liquid (U). Further, the first coating liquid (U) may be prepared by performing treatments such as addition of an organic solvent, adjustment of pH, adjustment of viscosity, addition of additives, and the like on the mixed solution. As an organic solvent, the solvent etc. which are used for preparation of the solution containing a phosphorus compound (B) are mentioned, for example.

  From the viewpoint of the storage stability of the first coating liquid (U) and the coating properties of the first coating liquid (U) on the resin substrate, the solid content concentration of the first coating liquid (U) is 1 to 20% by mass. Preferably, it is in the range of 2 to 15% by mass, more preferably in the range of 3 to 10% by mass. The solid content concentration of the first coating liquid (U) is, for example, adding a predetermined amount of the first coating liquid (U) to the petri dish, heating the petri dish to remove volatile components such as a solvent, and the remaining solid mass Is calculated by dividing by the mass of the first coating liquid (U) added first.

  The first coating liquid (U) has a viscosity measured by a Brookfield type rotational viscometer (SB type viscometer: rotor No. 3, rotation speed 60 rpm) of 3000 mPa · s or less at the coating temperature. Is preferably 2500 mPa · s or less, and more preferably 2000 mPa · s or less. When the said viscosity is 3000 mPa * s or less, the leveling property of a 1st coating liquid (U) improves and the base layer which is excellent in an external appearance can be obtained. Moreover, as a viscosity of a 1st coating liquid (U), 50 mPa * s or more is preferable, 100 mPa * s or more is more preferable, 200 mPa * s or more is further more preferable.

In the first coating liquid (U), the NM and NP satisfy the relationship of 0.8 ≦ N _M / N _P ≦ 4.5. The first coating liquid in (U), and the _{N M} and _{N Z} and _{F Z} satisfy the relationship of _{0.001 ≦ F Z × N Z /} N M ≦ 0.60. Furthermore, the first coating liquid in (U), the _{F Z} and _{N Z} and _{N P} is, preferably satisfy the relation of _{0.0008 ≦ F Z × N Z /} N P ≦ 1.35.

<[Step [II] Coating of First Coating Liquid (U)>
In step [II], the precursor layer of the base layer (Y) is formed on the resin substrate by applying the first coating liquid (U) on the resin substrate. You may apply a 1st coating liquid (U) directly on the at least one surface of a resin base material. In addition, before applying the first coating liquid (U), the surface of the resin substrate is treated with a known anchor coating agent, or a known adhesive is applied to the surface of the resin substrate. An easy-adhesion layer may be formed on the surface of the resin base material.

  The method for coating the first coating liquid (U) on the resin substrate is not particularly limited, and a known method can be employed. Coating methods include, for example, casting method, dipping method, roll coating method, gravure coating method, screen printing method, reverse coating method, spray coating method, kiss coating method, die coating method, metalling bar coating method, chamber doctor combined coating Method, curtain coating method, and the like.

  Usually, in the step [II], the precursor layer of the underlayer (Y) is formed by removing the solvent in the first coating liquid (U). There is no restriction | limiting in particular in the removal method of a solvent, A well-known drying method is applicable. Examples of the drying method include a hot air drying method, a hot roll contact method, an infrared heating method, and a microwave heating method. The drying treatment temperature is preferably 0 to 15 ° C. or lower than the flow start temperature of the resin base material. When the first coating liquid (U) contains the polymer (C), the drying treatment temperature is preferably 15 to 20 ° C. lower than the thermal decomposition start temperature of the polymer (C). The drying treatment temperature is preferably in the range of 70 to 200 ° C, more preferably in the range of 80 to 180 ° C, and further preferably in the range of 90 to 160 ° C. The removal of the solvent may be carried out under normal pressure or reduced pressure. Further, the solvent may be removed by a heat treatment in step [III] described later.

  When laminating the base layer (Y) on both surfaces of the layered resin base material, the first coating liquid (U) is applied to one surface of the resin base material, and then the first layer ( The first layer (Y) precursor layer) is formed, and then the first coating liquid (U) is applied to the other surface of the resin substrate, and then the solvent is removed to remove the second layer. (Precursor layer of second underlayer (Y)) may be formed. The composition of the first coating liquid (U) applied to each surface may be the same or different.

<[Process [III] Treatment of Precursor Layer of Underlayer (Y)>
In step [III], the base layer (Y) is formed by heat-treating the precursor layer (precursor layer of base layer (Y)) formed in step [II] at a temperature of 140 ° C. or higher. This heat treatment temperature is preferably higher than the drying treatment temperature after the application of the first coating liquid (U).

  In the step [III], a reaction in which the metal oxides (A) are bonded through phosphorus atoms (phosphorus atoms derived from the phosphorus compound (B)) proceeds. From another point of view, in the step [III], the reaction reaction of the reaction product (D) proceeds. In order to sufficiently proceed with the reaction, the temperature of the heat treatment is preferably 140 ° C. or higher, more preferably 170 ° C. or higher, and further preferably 180 ° C. or higher. If the heat treatment temperature is low, it takes a long time to obtain a sufficient degree of reactivity, which causes a decrease in productivity. The preferable upper limit of the temperature of heat processing changes with the kind etc. of resin base material. For example, when a thermoplastic resin film made of polyamide resin is used as the resin base material, the heat treatment temperature is preferably 270 ° C. or lower. Moreover, when using the thermoplastic resin film which consists of polyester resins as a resin base material, it is preferable that the temperature of heat processing is 240 degrees C or less. The heat treatment can be performed in air, in a nitrogen atmosphere, or in an argon atmosphere.

  The heat treatment time is preferably in the range of 0.1 second to 1 hour, more preferably in the range of 1 second to 15 minutes, and still more preferably in the range of 5 to 300 seconds.

  Moreover, you may include the process of irradiating a precursor layer of a base layer (Y), or a base layer (Y) with an ultraviolet-ray. For example, the ultraviolet irradiation may be performed after the step [II] (for example, after the removal of the solvent of the coated first coating liquid (U) is almost completed).

  In order to arrange an easy-adhesion layer between the resin substrate and the base layer (Y), the surface of the resin substrate is treated with a known anchor coating agent before applying the first coating liquid (U). Alternatively, a known adhesive may be applied to the surface of the resin base material.

  The underlayer manufacturing method according to the present invention may further include steps [i] and [ii]. In process [i], the 2nd coating liquid (V) containing the polymer (G1) containing a phosphorus atom and a solvent is prepared. In the step [ii], the base layer (W) disposed adjacent to the base layer (Y) is formed using the second coating liquid (V). The order of the step [i] is not particularly limited, and may be performed in parallel with the step [I], [II] or [III], or may be performed after the step [I], [II] or [III]. Good. Step [ii] can be performed after step [II] or [III]. A base layer laminated on the base layer (Y) so as to be in contact with the base layer (Y) by applying the second coating liquid (V) to the base layer (Y) or a precursor layer of the base layer (Y) (W) can be formed. When forming the base layer (W) containing the polymer (G2), the second coating liquid (V) contains the polymer (G2). In the second coating liquid (V), the mass ratio of the polymer (G1) and the polymer (G2) is such that the polymer (G1): polymer (G2) is in the range of 15:85 to 100: 0. Is preferable, and it is more preferable that it is in the range of 15:85 to 99: 1. By using the 2nd coating liquid (V) of the said mass ratio, the base layer (W) in which the mass ratio of a polymer (G1) and a polymer (G2) exists in the said range can be formed. The second coating liquid (V) can be prepared by dissolving the polymer (G1) (and the polymer (G2) as necessary) in a solvent.

  The solvent used in the second coating liquid (V) may be appropriately selected according to the type of polymer contained, but is preferably water, alcohols, or a mixed solvent thereof. As long as the dissolution of the polymer is not hindered, the solvent is ether such as tetrahydrofuran, dioxane, trioxane, dimethoxyethane; ketone such as acetone or methyl ethyl ketone; glycol such as ethylene glycol or propylene glycol; methyl cellosolve, ethyl cellosolve, n-butyl cellosolve. Glycerin; acetonitrile; amides such as dimethylformamide; dimethyl sulfoxide; sulfolane and the like.

  The concentration of the solid content (polymer (G1) and the like) in the second coating liquid (V) is preferably in the range of 0.01 to 60% by mass from the viewpoint of storage stability and coating property of the solution, More preferably, it is in the range of 0.1 to 50% by mass, and further preferably in the range of 0.2 to 40% by mass. The solid content concentration can be determined by a method similar to the method described for the first coating liquid (U).

  Usually, in process [ii], the base layer (W) is formed by removing the solvent in the second coating liquid (V). The method for removing the solvent of the second coating liquid (V) is not particularly limited, and a known drying method can be applied. Examples of the drying method include a hot air drying method, a hot roll contact method, an infrared heating method, and a microwave heating method. The drying temperature is preferably 0 to 15 ° C. or more lower than the flow start temperature of the resin base material. The drying temperature is preferably in the range of 70 to 200 ° C, more preferably in the range of 150 to 200 ° C. The removal of the solvent may be carried out under normal pressure or reduced pressure. Moreover, when implementing process [ii] between the above-mentioned process [II] and process [III], you may remove a solvent by the heat processing in process [III].

  You may form a base layer (W) on both surfaces of a resin base material through a base layer (Y). In an example in that case, the first undercoat layer (W) is formed by applying the second coating liquid (V) to one surface and then removing the solvent. Next, the second undercoat layer (W) is formed by applying the second coating liquid (V) to the other surface and then removing the solvent. The composition of the second coating liquid (V) applied to each surface may be the same or different.

[3] Gas barrier layer (X)
The gas barrier film of the present invention comprises an underlayer (Y) laminated on a resin substrate and a gas barrier layer (X) in contact therewith. In other words, the gas barrier layer (X) functioning as a gas barrier layer is laminated on the base layer (Y) formed on the resin base material to constitute a gas barrier film.

The gas barrier layer (X) according to the present invention has a relation represented by the following relational expression (3) and the following relational expression when the average composition is represented by SiO _x C _y (x and y are stoichiometric coefficients). It is preferable that the relationship represented by (4) is satisfied and the layer thickness is in the range of 15 to 50 nm. By setting it as this range, transparency, gas barrier property, and a softness | flexibility (flexibility) can be balanced.

Relational expression (3) 1.6 ≦ x ≦ 1.9, 0.15 ≦ y ≦ 0.40
Relational expression (4) 4.0 ≦ 2x + 2y <4.3
The ranges of the values of the oxygen component x and the carbon component y are regions optimized from the viewpoints of transparency, gas barrier properties, and flexibility. When the oxygen component x increases, the transparency tends to improve, and when it decreases, the gas barrier property improves. Further, when the carbon component y increases, the flexibility tends to increase, but the transparency tends to deteriorate. Therefore, if it is in the range of the value of said x and y, it is guessed that transparency, gas barrier property, and a softness | flexibility can be balanced.

In addition, for example, in the formation of a gas barrier layer by a CVD method using hexamethyldisiloxane (HMDSO) as a raw material, the gas barrier layer mainly includes Si—O—Si bonds or Si—CH ₂ —Si bonds. It is thought to have. If all are Si—O—Si bonds or Si—CH ₂ —Si bonds, 2x + 2y = 4, but in reality, since a small amount of Si—CH ₃ exists, it is considered that 4 <2x + 2y. . Therefore, when 2x + 2y is 4.3 or more, it is considered that Si—CH ₃ is excessively present, and the gas barrier property is greatly lowered. When 2x + 2y is less than 4, a so-called oxygen deficiency state occurs and transparency deteriorates.

Accordingly, the gas barrier layer according to the present invention, defines the average composition of the compounds contained in the gas barrier layer when expressed in SiO _x C _y, a range of values of the x and y, and in 2x + 2y It is presumed that the gas barrier property and the transparency can be improved by controlling the content of Si—CH ₃ .

  Furthermore, the gas barrier layer (X) according to the present invention has a gas barrier property that the product of the y and the thickness (nm) of the gas barrier layer (X) is in the range of 4 to 12. From the viewpoint of balancing transparency, it is preferable.

  Particularly in the case of a gas barrier layer, when the product of the y and the thickness (nm) increases, the gas barrier property improves, and conversely, the wave transparency deteriorates. The y and the thickness (nm) When the product of is smaller, the gas barrier property is deteriorated and the transparency is improved, and a good performance balance is obtained when the product of y and thickness (nm) is within the range of 4 to 12. Is presumed to be obtained.

  The gas barrier layer (X) according to the present invention is preferably formed by a chemical vapor deposition method (CVD method).

  The chemical vapor deposition method is a method in which a raw material gas containing a target thin film component is supplied onto the substrate, and the film is deposited by a chemical reaction on the surface of the substrate or in the gas phase. 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, the vacuum plasma CVD method is applied to the film formation rate, the processing area, and the gas barrier layer (X) obtained from the viewpoint of the flexibility of the gas barrier layer and the gas barrier property. It is preferable to do.

  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 order to control the oxygen component x and the carbon component _y in the average composition SiO _x C _y , it is preferable to use a vacuum plasma CVD method. This can be achieved by controlling.

  For example, it can be controlled by appropriately combining the supply amount and ratio of the film forming raw material and oxygen, the transport speed during film formation, the number of film formations, and the like.

  Hereinafter, a case where a gas barrier layer is manufactured by a vacuum plasma CVD method using a counter roller type roll-to-roll film forming apparatus will be described as an example.

  FIG. 2 is a schematic view showing an example of a vacuum plasma CVD apparatus preferably used for forming the gas barrier layer (X) according to the present invention.

  As shown in FIG. 2, the film forming apparatus 100 includes a delivery roller 10, transport rollers 11 to 14, first and second film forming rollers 15 and 16, a take-up roller 17, a gas supply pipe 18, and plasma. The power supply 19 for generation | occurrence | production, the magnetic field generators 20 and 21, the vacuum chamber 30, the vacuum pump 40, and the control part 41 are provided.

  The delivery roller 10, the transport rollers 11 to 14, the first and second film forming rollers 15 and 16, and the take-up roller 17 are accommodated in the vacuum chamber 30.

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

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

  The first film forming roller 15 and the second film forming roller 16 are a pair of film forming rollers having a rotation axis substantially parallel to the delivery roller 10 and facing each other with a predetermined distance therebetween. The film forming roller 15 forms the base material 1 a and conveys the base material 1 b to the film forming roller 16 while applying an appropriate tension to the formed base material 1 b. The film formation roller 16 forms the base material 1b, and conveys the base material 1c to the conveyance roller 14 while applying an appropriate tension to the film-formed base material 1c.

  In the example shown in FIG. 2, the separation distance between the first film forming roller 15 and the second film forming roller 16 is a distance connecting the point A and the point B. The first and second film forming rollers 15 and 16 are discharge electrodes formed of a conductive material, and the first film forming roller 15 and the second film forming roller 16 are insulated from each other. In addition, the material and structure of the first and second film forming rollers 15 and 16 can be appropriately selected so as to achieve a desired function as an electrode.

  Further, the first film forming roller 15 and the second film forming roller 16 may be independently temperature controlled. Although the temperature of the 1st film-forming roller 15 and the 2nd film-forming roller 16 is not specifically limited, For example, although it is -30-100 degreeC, it exceeds the glass transition temperature of the base material 1a, and becomes too high temperature. If set, the substrate may be deformed by heat.

  Magnetic field generators 20 and 21 are installed in the first and second film forming rollers 15 and 16, respectively. A high frequency voltage for plasma generation is applied to the first film formation roller 15 and the second film formation roller 16 by a plasma generation power source 19. As a result, an electric field is formed in the film forming section S between the first film forming roller 15 and the second film forming roller 16, and discharge plasma of the film forming gas supplied from the gas supply pipe 18 is generated. The power source frequency of the plasma generating power source 19 can be arbitrarily set, but the apparatus of this configuration is, for example, 60 to 100 kHz, and the applied power is, for example, 1 to 10 kW with respect to an effective film forming width of 1 m. .

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

  The substrate 1a fed from the feed roller 10 is appropriately wound around the transport rollers 11 to 14 and the first and second film forming rollers 15 and 16 between the feed roller 10 and the take-up roller 17. It is conveyed by the rotation of each of these rollers while maintaining the tension. In addition, the conveyance direction of the base materials 1a, 1b, and 1c (hereinafter, the base materials 1a, 1b, and 1c are also collectively referred to as “base materials 1a to 1c”) is indicated by arrows. The conveyance speed (line speed) of the base materials 1a to 1c (for example, the conveyance speed at the point C in FIG. 2) can be appropriately adjusted according to the type of the source gas, the pressure in the vacuum chamber 30, and the like. The conveyance speed is adjusted by controlling the rotation speeds of the drive motors of the delivery roller 10 and the take-up roller 17 by the control unit 41. When the conveyance speed is decreased, the thickness of the formed region is increased.

  The conveyance speed (line speed) of the base material can be appropriately adjusted according to the type of source gas, the pressure in the chamber, etc., but is preferably in the range of 0.25 to 100 m / min. More preferably, it is within the range of 5 to 20 m / min. If the line speed is within the above range, wrinkles due to the heat of the resin base material hardly occur, and the thickness of the formed gas barrier layer can be sufficiently controlled.

  When this film forming apparatus is used, the transport direction of the base materials 1a to 1c 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 directions of the drive motors of the feed roller 10 and the take-up roller 17 in the direction opposite to that described above in a state where the substrate 1c is taken up by the take-up roller 17. Control to do. When controlled in this way, the base material 1 c sent out from the take-up roller 17 is transferred to the transport rollers 11 to 14, the first and second film forming rollers 15 and 16 between the send-out roller 10 and the take-up roller 17. It is conveyed in the reverse direction by rotation of each of these rollers, maintaining appropriate tension by being wound.

  When the gas barrier layer is formed using the film forming apparatus 100, the gas barrier layer forming (film forming) step is performed by transporting the substrate 1a in the forward direction and the reverse direction and reciprocating the film forming unit S. It can be repeated multiple times.

  The gas supply pipe 18 supplies 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 that extends in the same direction as the rotation axes of the first film forming roller 15 and the second film forming roller 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. When the film forming apparatuses are connected (tandem type), the film forming gas supplied from the gas supply pipe 18 may be the same for each film forming apparatus, but may be 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, it is preferable to use HMDSO in the formation of the gas barrier layer from the viewpoint of easy handling of the compound and high gas barrier properties of the obtained 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.

Hereinafter, as a representative example, a system of hexamethyldisiloxane (organosilicon compound: HMDSO, (CH ₃ ) ₆ Si ₂ O) as a source gas and oxygen (O ₂ ) as a reaction gas will be described.

A film-forming gas containing hexamethyldisiloxane (HMDSO, (CH ₃ ) ₆ Si ₂ O) as a source gas and oxygen (O ₂ ) as a reaction gas is reacted by a plasma CVD method to form silicon- When an oxygen-based thin film is formed, a reaction represented by the following reaction formula (1) occurs by the film forming gas, and a thin film made of silicon dioxide SiO ₂ is formed.

Reaction formula (1): (CH ₃ ) ₆ Si ₂ O + 12O ₂ → 6CO ₂ + 9H ₂ O + 2SiO ₂
In such a reaction, the amount of oxygen required to completely oxidize 1 mol of hexamethyldisiloxane is 12 mol. Therefore, in the initial stage of film formation, a silicon dioxide film having a high oxygen atom ratio and a uniform composition can be obtained by completely reacting by adding 12 mol or more of oxygen to 1 mol of hexamethyldisiloxane in the film forming gas. However, the non-complete reaction is performed by controlling the gas flow rate ratio of the raw material during the film formation to the later stage to a flow rate equal to or lower than the theoretical reaction raw material ratio, and the SiO _{x according to the} present invention is performed. it is possible to increase the proportion of C _y.

  In the actual reaction in the chamber of the plasma CVD apparatus, the raw material hexamethyldisiloxane and the reaction gas, oxygen, are supplied from the gas supply unit to the film formation region to form a film. Even if the molar amount (flow rate) is 12 times the molar amount (flow rate) of the starting hexamethyldisiloxane, the reaction cannot actually proceed completely, and oxygen content It is considered that the reaction is completed only when the amount is supplied in a large excess compared to the stoichiometric ratio. For example, in order to obtain silicon oxide by complete oxidation by a CVD method, the molar amount (flow rate) of oxygen may be about 20 times or more the molar amount (flow rate) of hexamethyldisiloxane as a raw material. Therefore, the molar amount (flow rate) of oxygen with respect to the molar amount (flow rate) of the raw material hexamethyldisiloxane is preferably an amount of 12 times or less (more preferably 10 times or less) which is the stoichiometric ratio. . By containing hexamethyldisiloxane and oxygen in such a ratio, carbon atoms and hydrogen atoms in hexamethyldisiloxane that have not been completely oxidized are taken into the gas barrier layer to form a desired gas barrier layer. This makes it possible to exhibit excellent gas barrier properties and bending resistance in the obtained gas barrier film. If the molar amount (flow rate) of oxygen with respect to the molar amount (flow rate) of hexamethyldisiloxane in the deposition gas is too small, unoxidized carbon atoms and hydrogen atoms will be excessively taken into the gas barrier layer. become.

  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 roller 15 and the second film forming roller 16. These magnetic field generators 20 and 21 do not follow the rotation of the first and second film forming rollers 15 and 16 and are stored at predetermined positions.

  The vacuum chamber 30 seals the delivery roller 10, the transport rollers 11 to 14, the first and second film forming rollers 15 and 16, and the take-up roller 17 and maintains a decompressed state. The pressure (vacuum degree) in the vacuum chamber 30 can be appropriately adjusted according to the type of source gas. The pressure of the film forming unit S is preferably 0.1 to 50 Pa.

  The vacuum pump 40 is communicably connected to the control unit 41 and appropriately adjusts 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 100. The control unit 41 is connected to the drive motors of the feed roller 10 and the take-up roller 17 and adjusts the conveyance speed of the substrate 1a by controlling the number of rotations 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 generating power source 19 and controls the output voltage and output frequency of the plasma generating power source 19. Further, the control unit 41 is communicably connected to the vacuum pump 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), a 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 100 to realize a method for producing a gas barrier film. When the film forming apparatus 100 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 respective gas barrier layers may have the same composition or different compositions. In the case of a stacked structure, it is also preferable to use a tandem film formation apparatus in which the film formation apparatuses illustrated in FIG. 2 are connected.

  The thickness of the gas barrier layer (X) is preferably in the range of 15 to 50 nm as described above. If it is this range, the advantage of coexistence with gas-barrier property and a softness | flexibility will be acquired. The thickness of the gas barrier layer (X) can be measured by observation with a transmission electron microscope (TEM).

[4] Gas Barrier Layer Containing Transition Metal On the gas barrier layer (X) according to the present invention, a gas barrier layer further containing a transition metal is preferably laminated from the viewpoint of improving gas barrier properties.

  The gas barrier layer refers to a layer containing a transition metal as a main component, and a transition metal as a main component means that a component occupying 50% by mass or more in the gas barrier layer is a transition metal, A transition metal oxide is preferable.

  It does not restrict | limit especially as a transition metal used for this invention, Arbitrary transition metals are used individually or in combination. Here, the transition metal refers to a Group 3 element to a Group 11 element in the long-period periodic table, and the transition metal includes Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Y , Zr, Nb, Mo, Tc, Ru, Pd, Ag, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Hf, Ta, W , Re, Os, Ir, Pt, and Au.

  Among them, Nb, Ta, V, Zr, Ti, Hf, Y, La, Ce, and the like are listed as transition metals that can provide good gas barrier properties. Among these, Nb, Ta, and V, which are Group 5 elements, tend to be bonded to Si, which is a non-transition metal contained in the gas barrier layer (X), based on various examination results. A composite composition region of non-transition metal is formed. In particular, when the composite composition region has an oxygen deficient composition, a significant gas barrier property improvement effect can be obtained. This is presumably because the bond between Si and the Group 5 element (particularly Nb) is particularly likely to occur, and a dense gas barrier layer is formed in the composite composition region. Furthermore, from the viewpoint of optical properties, the transition metal is particularly preferably Nb and Ta, which are compounds with good transparency.

  The oxygen deficient composition is a condition in which at least a part of the composition of the composite composition region is defined by the following relational expression (5) when the composition of the composite composition region is expressed by the following chemical composition formula (1). Satisfying. As the oxygen deficiency index indicating the degree of oxygen deficiency in the composite composition region, the minimum value obtained by calculating (2y + 3z) / (a + bx) in the composite composition region is used.

Chemical composition formula (1): (M _a ) (M _b ) _x O _y N _z
Relational expression (5): (2y + 3z) / (a + bx) <1.0
(In the formula, M _a : non-transition metal, M _b : transition metal, O: oxygen, N: nitrogen, x, y, z: stoichiometric coefficient, 0.02 ≦ x ≦ 49, 0 <y, 0 ≦ z, a: represents the maximum valence of M1, and b: represents the maximum valence of M2.)
The relational expression (5) represents that the composite composition region of the gas barrier layer includes an oxygen deficient composition of _a non-transition metal (M _a ) and a transition metal (M _b ).

  The gas barrier layer containing the transition metal can be formed by a known vapor deposition method. The vapor deposition method is not particularly limited, and examples thereof include physical vapor deposition (PVD) methods such as sputtering, vapor deposition, ion plating, and ion assisted vapor deposition, plasma CVD (chemical vapor deposition), and ALD. Examples thereof include a chemical vapor deposition (CVD) method such as an (Atomic Layer Deposition) method. Among these, it is possible to form a film without damaging the functional element, and since it has high productivity, it is preferably formed by a physical vapor deposition (PVD) method, and more preferably formed by a sputtering method. .

  For the film formation by sputtering, bipolar sputtering, magnetron sputtering, dual magnetron sputtering (DMS) using an intermediate frequency region, ion beam sputtering, ECR sputtering, or the like can be used alone or in combination of two or more. The target application method is appropriately selected according to the target type, and either DC (direct current) sputtering or RF (high frequency) sputtering may be used.

  The sputtering method may be multi-source simultaneous sputtering using a plurality of sputtering targets including a single transition metal or an oxide thereof. Regarding the method for producing these sputtering targets and the method for producing a thin film made of a complex oxide using these sputtering targets, for example, JP 2000-160331 A, JP 2004-068109 A, JP The description of 2013-043761 gazette etc. can be referred suitably.

  The thickness of the gas barrier layer containing the transition metal is preferably in the range of 1 to 500 nm, more preferably in the range of 10 to 300 nm.

[5] Anchor layer, adhesion layer [5.1] Anchor layer In the present invention, having at least one anchor layer on the resin substrate improves adhesion between the resin substrate and the base layer (Y). From the viewpoint of improving and preventing layer damage and defects due to mechanical or thermal stress in use environment fluctuations, this is a preferred embodiment.

  The anchor layer used in the present invention is preferably an organic polymer layer containing a resin. Examples of the resin used include polyester resin, isocyanate resin, urethane resin, acrylic resin, ethylene vinyl alcohol resin, vinyl modified resin, and epoxy resin. , Modified styrene resin, modified silicone resin, alkyl titanate and the like can be used alone or in combination of two or more.

  Preferably, the polymerizable composition containing the following polymerizable compound, a silane coupling agent, and a polymerization initiator can be formed into a layer and then cured.

  As a method for layering the polymerizable composition, in the present invention, the polymerizable composition can be formed by applying the polymerizable composition on a resin substrate. Arbitrary appropriate methods may be employ | adopted as a method of apply | coating a coating composition. Specific examples include spin coating, roll coating, flow coating, ink jet, spray coating, printing, dip coating, cast film formation, bar coating, and gravure printing. 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. Regarding the forming method, refer to paragraphs “0058” to “0064” of JP-A-2014-151571, paragraphs “0052” to “0056” of JP-A-2011-183773, and the like. Can do.

  Among the above coating methods, since there is a concern that the electronic device may be deteriorated by moisture or a hydrophilic solvent, general solvent coating is not preferable, and the coating is performed in a nitrogen atmosphere, without solvent, or with a low content of hydrophilic solvent. An ink jet method using the composition can be preferably applied. The ink jet method can be adopted with reference to the technical contents described in International Publication No. 2014/176365, International Publication No. 2015/100375, International Publication No. 2015/112454, and the like. Specifically, it is also a preferred embodiment to form an anchor layer using YIELDjet (registered trademark) Platform manufactured by KATEEVA.

  Further, as another method for forming the polymerizable composition into a layer, a vapor phase film forming method such as a known flash vapor deposition method can be used.

  For example, a polymerizable composition containing a polymerizable compound, a silane coupling agent, and a polymerization initiator may be volatilized by heating in a reduced pressure atmosphere to form a deposited film on a substrate, an electrode layer, or an organic functional layer. preferable.

  As a method of forming the vapor deposition film, a known method as described in JP 2008-142941, JP 2004-314626 A, or the like can be used.

  As an example, a base material and an organic functional layer formed thereon are installed in a vacuum apparatus, and the polymerizable composition is placed in a heating boat installed in the vacuum apparatus, and the polymerization is performed under a reduced pressure of about 10 Pa. The vapor-deposited film can be formed to have a desired layer thickness while heating the composition to about 200 ° C. and covering the base material and the organic functional layer.

  The obtained deposited film is irradiated with ultraviolet rays using a high-pressure mercury lamp or the like in a vacuum environment, and the deposited polymerizable composition is cured to form an anchor layer.

(Polymerizable compound)
The polymerizable compound used in the present invention is a compound having an ethylenically unsaturated bond at the terminal or side chain, or a compound having epoxy or oxetane at the terminal or side chain. Of these, compounds having an ethylenically unsaturated bond at the terminal or side chain are preferred. Examples of the compound having an ethylenically unsaturated bond at the terminal or side chain include a (meth) acrylate compound, an acrylamide compound, a styrene compound, maleic anhydride and the like, and a (meth) acrylate compound is preferable. As the (meth) acrylate compound, (meth) acrylate, urethane (meth) acrylate, polyester (meth) acrylate, epoxy (meth) acrylate and the like are preferable. As the styrene compound, styrene, α-methylstyrene, 4-methylstyrene, divinylbenzene, 4-hydroxystyrene, 4-carboxystyrene and the like are preferable.

(Silane coupling agent)
Examples of the silane coupling agent used in the present invention include halogen-containing silane coupling agents (2-chloroethyltrimethoxysilane, 2-chloroethyltriethoxysilane, 3-chloropropyltrimethoxysilane, 3-chloropropyltriethoxysilane). Silane etc.), epoxy group-containing silane coupling agent [2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 3- (3,4-epoxy Cyclohexyl) propyltrimethoxysilane, 2-glycidyloxyethyltrimethoxysilane, 2-glycidyloxyethyltriethoxysilane, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, etc.], amino Group-containing silane coupling agent (2-aminoethyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2- [N- (2-aminoethyl) amino] ethyltrimethoxysilane, 3 -[N- (2-aminoethyl) amino] propyltrimethoxysilane, 3- (2-aminoethyl) amino] propyltriethoxysilane, 3- [N- (2-aminoethyl) amino] propyl methyldimethoxysilane, etc. ), Mercapto group-containing silane coupling agents (2-mercaptoethyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, etc.), vinyl group-containing silane coupling agents (vinyltrimethoxysilane, vinyl) Triethoxysilane) (Meth) acryloyl group-containing silane coupling agent (2-methacryloyloxyethyltrimethoxysilane, 2-methacryloyloxyethyltriethoxysilane, 2-acryloyloxyethyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-methacryloyl Oxypropyltriethoxysilane, 3-acryloyloxypropyltrimethoxysilane, etc.). In these, the silane coupling agent ((meth) acryloyl group containing silane coupling agent) containing a (meth) acryloyl group is used preferably.

  Other (meth) acryloyl group-containing silane coupling agents include 1,3-bis (acryloyloxymethyl) -1,1,3,3-tetramethyldisilazane, 1,3-bis (methacryloyloxymethyl). ) -1,1,3,3-tetramethyldisilazane, 1,3-bis (γ-acryloyloxypropyl) -1,1,3,3-tetramethyldisilazane, 1,3-bis (γ-methacryloyl) Oxypropyl) -1,1,3,3-tetramethyldisilazane, acryloyloxymethylmethyltrisilazane, methacryloyloxymethylmethyltrisilazane, acryloyloxymethylmethyltetrasilazane, methacryloyloxymethylmethyltetrasilazane, acryloyloxymethylmethylpolysilazane , Methacryloyloxymethyl Methylpolysilazane, 3-acryloyloxypropylmethyltrisilazane, 3-methacryloyloxypropylmethyltrisilazane, 3-acryloyloxypropylmethyltetrasilazane, 3-methacryloyloxypropylmethyltetrasilazane, 3-acryloyloxypropylmethylpolysilazane, 3-methacryloyl From the viewpoint that oxypropylmethylpolysilazane, acryloyloxymethylpolysilazane, methacryloyloxymethylpolysilazane, 3-acryloyloxypropylpolysilazane, and 3-methacryloyloxypropylpolysilazane are preferable, and further, 1,3- Bis (acryloyloxymethyl) -1,1,3,3-tetramethyldisilazane, 1,3-bis (methacrylic) Yloxymethyl) -1,1,3,3-tetramethyldisilazane, 1,3-bis (γ-acryloyloxypropyl) -1,1,3,3-tetramethyldisilazane, 1,3-bis ( γ-Methacryloyloxypropyl) -1,1,3,3-tetramethyldisilazane is particularly preferred.

  As the silane coupling agent used in the present invention, a compound represented by the following general formula is preferably used. For the method of synthesizing the silane coupling agent, JP-A-2009-67778 can be referred to.

（式中、ＲはＣＨ_２＝ＣＨＣＯＯＣＨ_２を表す。）。

(In the formula, R represents CH ₂ ═CHCOOCH ₂ ).

(Polymerization initiator)
The polymerizable composition in the present invention usually contains a polymerization initiator. When using a polymerization initiator, the content thereof is preferably 0.1 mol% or more, more preferably 0.5 to 2 mol% of the total amount of compounds involved in the polymerization. By setting it as such a composition, the polymerization reaction via an active component production | generation reaction can be controlled appropriately. Examples of photopolymerization initiators are Irgacure series (for example, Irgacure 651, Irgacure 754, Irgacure 184, Irgacure 2959, Irgacure 907, Irgacure 369, Irgacure 379, Irgacure 819, etc.) commercially available from BASF Japan. Darocur series (for example, Darocur TPO, Darocur 1173, etc.), Quantacure PDO, Ezacure series (for example, Ezacure TZM, Ezacure TZT, Ecure TZT, Ecure TZT, Ecure TZT, Ecure TZT, Ecure Etc.).

  In the present invention, a polymerizable composition containing a silane coupling agent, a polymerizable compound, and a polymerization initiator is cured with light (for example, ultraviolet rays), electron beams, or heat rays, but is preferably cured with light. . In particular, it is preferable to cure the polymerizable composition after heating it at a temperature of 25 ° C. or higher (for example, 30 to 130 ° C.). By adopting such a structure, the hydrolysis reaction of the silane coupling agent proceeds, the polymerizable composition is effectively cured, and the film is formed without damaging the base material or the organic functional layer. Can do.

The light to be irradiated is usually ultraviolet light from a high pressure mercury lamp or a low pressure mercury lamp. The radiation energy is preferably 0.1 J / cm ² or more, 0.5 J / cm ² or more is more preferable. When a (meth) acrylate compound is employed as the polymerizable compound, polymerization inhibition is caused by oxygen in the air, so that it is preferable to reduce the oxygen concentration or oxygen partial pressure during polymerization. When the oxygen concentration during polymerization is lowered by the nitrogen substitution method, the oxygen concentration is preferably 2% or less, and more preferably 0.5% or less. When the oxygen partial pressure during polymerization is reduced by the decompression method, the total pressure is preferably 1000 Pa or less, and more preferably 100 Pa or less. Further, it is particularly preferable to perform ultraviolet polymerization by irradiating energy of 0.5 J / cm ² or more under a reduced pressure condition of 100 Pa or less.

  The anchor layer used in the present invention is preferably smooth and has high film hardness. The smoothness of the anchor layer is preferably less than 1 nm as an average roughness (Ra value) of 1 μm square, and more preferably less than 0.5 nm. The polymerization rate of the monomer is preferably 85% or more, more preferably 88% or more, still more preferably 90% or more, and particularly preferably 92% or more. The polymerization rate here means the ratio of the reacted polymerizable group among all the polymerizable groups (for example, acryloyl group and methacryloyl group) in the monomer mixture. The polymerization rate can be quantified by an infrared absorption method.

  The layer thickness of the anchor layer is not particularly limited, but if it is too thin, it is difficult to obtain the uniformity of the layer thickness, and if it is too thick, cracks are generated due to external force and the gas barrier property is lowered. From this viewpoint, the thickness of the anchor layer is preferably 50 to 2000 nm, and more preferably 200 to 1500 nm.

  The surface of the anchor layer is required to be free of foreign matters such as particles and protrusions. For this reason, the anchor layer is preferably formed in a clean room. The degree of cleanness is preferably class 10000 or less, more preferably class 1000 or less.

  It is preferable that the organic layer has a high hardness. When the hardness of the organic layer is high, the inorganic layer is smoothly formed, and as a result, the gas barrier performance is improved. The hardness of the organic layer can be expressed as a microhardness based on the nanoindentation method. The microhardness of the organic layer is preferably 100 N / mm or more, and more preferably 150 N / mm or more.

[5.2] Adhesion layer It is also possible to form an adhesion layer that also serves as a smoothing layer between the gas barrier layer (X) according to the present invention and the organic EL element described later, between the gas barrier layer (X) and the element. It is preferable from the viewpoint of improving adhesion.

  As the adhesion layer, an adhesion layer containing an organosilicon compound having a polymerizable group is preferably formed, and the thickness of the adhesion layer is preferably 5 nm or less.

  The organosilicon compound having a polymerizable group is not particularly limited, but is preferably a silane coupling agent, such as a halogen-containing silane coupling agent (2-chloroethyltrimethoxysilane, 2-chloroethyl). Triethoxysilane, 3-chloropropyltrimethoxysilane, 3-chloropropyltriethoxysilane, etc.), epoxy group-containing silane coupling agent [2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3 4-epoxycyclohexyl) ethyltriethoxysilane, 3- (3,4-epoxycyclohexyl) propyltrimethoxysilane, 2-glycidyloxyethyltrimethoxysilane, 2-glycidyloxyethyltriethoxysilane, 3-glycidyloxypropyltrimethoxy Lan, 3-glycidyloxypropyltriethoxysilane, etc.], amino group-containing silane coupling agents (2-aminoethyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2- [N- (2-aminoethyl) amino] ethyltrimethoxysilane, 3- [N- (2-aminoethyl) amino] propyltrimethoxysilane, 3- (2-aminoethyl) amino] propyltriethoxysilane, 3- [N -(2-aminoethyl) amino] propyl methyldimethoxysilane), mercapto group-containing silane coupling agents (such as 2-mercaptoethyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane), Vinyl group-containing silane cup (Meth) acryloyl group-containing silane coupling agent (2-methacryloyloxyethyltrimethoxysilane, 2-methacryloyloxyethyltriethoxysilane, 2-acryloyloxyethyltri) Methoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-methacryloyloxypropyltriethoxysilane, 3-acryloyloxypropyltrimethoxysilane, and the like.

  In these, the silane coupling agent ((meth) acryloyl group containing silane coupling agent) containing a (meth) acryloyl group is preferable.

  As the (meth) acryloyl group-containing silane coupling agent, 1,3-bis (acryloyloxymethyl) -1,1,3,3-tetramethyldisilazane, 1,3-bis (methacryloyloxymethyl) -1, 1,3,3-tetramethyldisilazane, 1,3-bis (γ-acryloyloxypropyl) -1,1,3,3-tetramethyldisilazane, 1,3-bis (γ-methacryloyloxypropyl)- 1,1,3,3-tetramethyldisilazane, acryloyloxymethylmethyltrisilazane, methacryloyloxymethylmethyltrisilazane, acryloyloxymethylmethyltetrasilazane, methacryloyloxymethylmethyltetrasilazane, acryloyloxymethylmethylpolysilazane, methacryloyloxymethyl Methylpolysila Zane, 3-acryloyloxypropylmethyltrisilazane, 3-methacryloyloxypropylmethyltrisilazane, 3-acryloyloxypropylmethyltetrasilazane, 3-methacryloyloxypropylmethyltetrasilazane, 3-acryloyloxypropylmethylpolysilazane, 3-methacryloyloxy Propylmethylpolysilazane, acryloyloxymethylpolysilazane, methacryloyloxymethylpolysilazane, 3-acryloyloxypropylpolysilazane, and 3-methacryloyloxypropylpolysilazane are preferable, and further, 1,3-bis is preferred from the viewpoint of easy compound synthesis and identification. (Acryloyloxymethyl) -1,1,3,3-tetramethyldisilazane, 1,3-bis (methacryloyloxime) ) -1,1,3,3-tetramethyldisilazane, 1,3-bis (γ-acryloyloxypropyl) -1,1,3,3-tetramethyldisilazane, 1,3-bis (γ- (Methacryloyloxypropyl) -1,1,3,3-tetramethyldisilazane is particularly preferred.

  Examples of commercially available (meth) acryloyl group-containing silane coupling agents include KBM-5103, KBM-502, KBM-503, KBE-502, KBE-503, and KR-513 (manufactured by Shin-Etsu Chemical Co., Ltd.). Can be mentioned. One of these (meth) acryloyl group-containing silane coupling agents may be used alone, or two or more thereof may be used in combination.

  The adhesion layer can be formed by applying a polymerizable composition. For example, a solution in which the (meth) acryloyl group-containing compound is dissolved in an appropriate solvent is applied to the surface of the gas barrier layer (X). The method of drying is illustrated. At this time, a suitable photopolymerization initiator is added to the solution, and the coating obtained by applying the solution and drying is subjected to a light irradiation treatment, and a part of the (meth) acryloyl group-containing compound. May be polymerized to form a polymerizable polymer.

  Arbitrary appropriate methods may be employ | adopted as a method of apply | coating a coating composition. Specific examples include spin coating, roll coating, flow coating, ink jet, spray coating, printing, dip coating, cast film formation, bar coating, and gravure printing.

  Moreover, it can also form into a film by a vapor-phase film-forming method, and a vapor-phase film-forming method can be used by a well-known method. The vapor deposition method is not particularly limited. For example, physical vapor deposition (PVD) methods such as sputtering, vapor deposition, ion plating, ion assisted vapor deposition, plasma CVD, ALD (Atomic Layer Deposition). ) Method and the like. Of these, the plasma CVD method is preferable.

[6] Electronic device The gas barrier film of the present invention has excellent gas barrier, transparency, and bending resistance. For this reason, the gas barrier film of the present invention is a gas barrier film used for electronic devices such as packages such as electronic devices, photoelectric conversion elements (solar cell elements), organic electroluminescence (EL) elements, liquid crystal display elements, and the like. It can be used for various purposes such as an electronic device using the same.

  That is, this invention provides the electronic device containing an electronic device main body and the gas barrier film of this invention, or the gas barrier film obtained by the manufacturing method of this invention.

  Preferred examples of application of the electronic device include, but are not limited to, a liquid crystal display element (LCD), a solar cell (PV), a quantum dot film, an organic electroluminescence (EL) element, and the like. Among them, since the gas barrier film of the present invention has excellent gas barrier properties, it can be suitably used for quantum dot films and organic electroluminescence (EL) elements, and particularly suitable for organic electroluminescence (EL) elements. An organic electroluminescent device of the invention is provided.

[6.1] Quantum dot film Hereinafter, a quantum dot (also referred to as QD), a resin, and the like, which are main components of the quantum dot film (quantum dot-containing resin layer), will be described.

<Quantum dots>
In general, semiconductor nanoparticles exhibiting a quantum confinement effect with a nanometer-sized semiconductor material are also referred to as “quantum dots”. Such a quantum dot is a small lump within about 10 and several nanometers in which several hundred to several thousand semiconductor atoms are gathered, but when absorbing energy from an excitation source and reaching an energy excited state, the energy of the quantum dot Releases energy corresponding to the band gap.

  Therefore, it is known that quantum dots have unique optical characteristics due to the quantum size effect. Specifically, (1) By controlling the size of the particles, various wavelengths and colors can be emitted. (2) The absorption band is wide and fine particles of various sizes can be obtained with a single wavelength of excitation light. It has the characteristics that it can emit light, (3) it has a symmetrical fluorescence spectrum, and (4) it has excellent durability and fading resistance compared to organic dyes.

  The quantum dots contained in the QD-containing resin layer may be known, and can be generated using any method known to those skilled in the art. For example, suitable QDs and methods for forming suitable QDs include US Pat. No. 6,225,198, US 2002/0066401, US Pat. No. 6,207,229, US Pat. No. 6,322,901. Description, US Pat. No. 6,949,206, US Pat. No. 7,572,393, US Pat. No. 7,267,865, US Pat. No. 7,374,807, US Patent Application No. 11/299299, and US Pat. No. 6,861,155 Can be mentioned.

  The QD is generated from any suitable material, preferably an inorganic material and more preferably an inorganic conductor or semiconductor material. Suitable semiconductor materials include any type of semiconductor, including II-VI, III-V, IV-VI and IV semiconductors.

Suitable semiconductor materials include Si, Ge, Sn, Se, Te, B, C (including diamond), P, BN, BP, BAs, AlN, AlP, AlAs, AlSb, GaN, GaP, GaAs, GaSb. , InN, InP, InAs, InSb, AlN, AlP, AlAs, AlSb, GaN, GaP, GaAs, GaSb, ZnO, ZnS, ZnSe, ZnTe, CdS, CdSe, CdSeZn, CdTe, HgS, HgSe, HgTe, BeS, BeSe , BeTe, MgS, MgSe, GeS, GeSe, GeTe, SnS, SnSe, SnTe, PbO, PbS, PbSe, PbTe, CuF, CuCl, CuBr, CuI, Si ₃ N ₄ , Ge ₃ N ₄ , Al ₂ O ₃ , _{(Al, Ga, In) 2} (S, Se, Te) 3, Al 2 O, and include but are more than one suitable combination of such semiconductor, and the like.

  In the present invention, the following core / shell type quantum dots, for example, CdSe / ZnS, InP / ZnS, PbSe / PbS, CdSe / CdS, CdTe / CdS, CdTe / ZnS and the like can be preferably used.

<resin>
In the QD-containing resin layer, a resin can be used as a binder for holding QD. For example, polycarbonate, polyarylate, polysulfone (including polyethersulfone), polyester such as polyethylene terephthalate, polyethylene naphthalate, polyethylene, polypropylene, cellophane, cellulose diacetate, cellulose triacetate, cellulose Cellulose esters such as acetate propionate and cellulose acetate butyrate, polyvinylidene chloride, polyvinyl alcohol, ethylene vinyl alcohol, syndiotactic polystyrene, norbornene, polymethylpentene, polyether ketone, polyether Examples thereof include acrylic resins such as ketone imide, polyamide resin, fluororesin, nylon, and polymethyl methacrylate.

  The QD-containing resin layer preferably has a thickness in the range of 50 to 200 μm.

  The QD content in the QD-containing resin layer is preferably in the range of 15 to 60% by volume, although the optimum amount varies depending on the compound used.

[6.2] Organic EL device The organic EL device according to the present invention includes, for example, an anode, a first organic functional layer group, a light emitting layer, directly or via the adhesion layer on the gas barrier layer of the present invention, It is preferable that the second organic functional layer group and the cathode are laminated. The first organic functional layer group includes, for example, a hole injection layer, a hole transport layer, an electron blocking layer, and the like, and the second organic functional layer group includes, for example, a hole blocking layer, an electric transport layer, and an electron injection layer. Etc. Each of the first organic functional layer group and the second organic functional layer group may be composed of only one layer, or the first organic functional layer group and the second organic functional layer group may not be provided.

Below, although the following structures can be mentioned as a typical element structure which can be used for the organic EL element which concerns on this invention, It is not limited to these.
(1) Anode / light emitting layer / cathode (2) Anode / light emitting layer / electron transport layer / cathode (3) Anode / hole transport layer / light emitting layer / cathode (4) Anode / hole transport layer / light emitting layer / electron Transport layer / cathode (5) anode / hole transport layer / light emitting layer / electron transport layer / electron injection layer / cathode (6) anode / hole injection layer / hole transport layer / light emitting layer / electron transport layer / cathode ( 7) Anode / hole injection layer / hole transport layer / (electron blocking layer /) luminescent layer / (hole blocking layer /) electron transport layer / electron injection layer / cathode Among the above, the configuration of (7) is preferable. Although used, it is not limited to this.

  An organic EL device comprising the gas barrier film of the present invention will be described with reference to the drawings.

  FIG. 4 is a cross-sectional view of an organic EL device comprising the gas barrier film of the present invention.

  In the configuration of the representative element 200 described above, the first electrode 215 is formed on the gas barrier film 210 in which the resin base material 211, the base layer (Y) 212, and the gas barrier layer (X) 213 are laminated, and then An organic functional layer 216 having a light emitting property, which is a layer excluding the anode and the cathode, and the second electrode 217 are formed. In the organic EL device according to the present invention, the first electrode 215 or the second electrode 217 constitutes an anode or a cathode, respectively. It is also preferable to provide the anchor layer (not shown) between the resin base material 211 and the base layer (Y) 212.

  On the 2nd electrode, the sealing member 221 and the sealing layer 222 which seal the whole organic EL element are formed.

<Organic functional layer>
In the above structure, the light emitting layer is formed of a single layer or multiple layers. When there are a plurality of light emitting layers, a non-light emitting intermediate layer may be provided between the light emitting layers.

  If necessary, a hole blocking layer (hole blocking layer), an electron injection layer (cathode buffer layer), or the like may be provided between the light emitting layer and the cathode, and between the light emitting layer and the anode. An electron blocking layer (electron barrier layer), a hole injection layer (anode buffer layer), or the like may be provided.

  The electron transport layer is a layer having a function of transporting electrons. The electron transport layer includes an electron injection layer and a hole blocking layer in a broad sense. Further, the electron transport layer may be composed of a plurality of layers.

  The hole transport layer is a layer having a function of transporting holes. The hole transport layer includes a hole injection layer and an electron blocking layer in a broad sense. The hole transport layer may be composed of a plurality of layers.

<Tandem structure>
The organic functional layer may be a so-called tandem element in which a plurality of organic functional layers including at least one light emitting layer are stacked.

As typical element configurations of the tandem structure, for example, the following configurations can be given.
(1) Anode / first organic functional layer / intermediate functional layer / second organic functional layer / cathode (2) anode / first organic functional layer / intermediate functional layer / second organic functional layer / intermediate functional layer / third organic Functional layer / cathode Here, the first organic functional layer, the second organic functional layer, and the third organic functional layer may all be the same or different. Further, the two organic functional layers may be the same, and the remaining one may be different.

  Moreover, each organic functional layer may be laminated | stacked directly, or may be laminated | stacked through the intermediate functional layer. The intermediate functional layer is composed of, for example, an intermediate electrode, an intermediate conductive layer, a charge generation layer, an electron extraction layer, a connection layer, or an intermediate insulating layer. The intermediate functional layer has electrons in the adjacent layer on the anode side and holes in the adjacent layer on the cathode side. A known material structure can be used as long as the layer has a function of supplying.

Examples of materials used for the intermediate functional layer include ITO (indium tin oxide), IZO (indium zinc oxide), ZnO ₂ , TiN, ZrN, HfN, TiOX, VOX, CuI, InN, GaN, and CuAlO. ₂ , conductive inorganic compound layers such as CuGaO ₂ , SrCu ₂ O ₂ , LaB ₆ , RuO ₂ and Al, two-layer films such as Au / Bi ₂ O ₃ , SnO ₂ / Ag / SnO ₂ , ZnO / Ag / ZnO, Bi ₂ O ₃ / Au / Bi ₂ O ₃ , TiO ₂ / TiN / TiO ₂ , TiO ₂ / ZrN / TiO _{2 and} other multilayer films, C _{60 and} other fullerenes, conductive organic materials such as oligothiophene Examples include layers, conductive organic compound layers such as metal phthalocyanines, metal-free phthalocyanines, metal porphyrins, and metal-free porphyrins. However, the present invention is not limited to these.

  Specific examples of the tandem type organic functional layer include, for example, US Pat. No. 6,337,492, US Pat. No. 7,420,203, US Pat. No. 7,473,923, US Pat. No. 6,872,472, US Pat. No. 6,107,734. No. 6, U.S. Pat. No. 6,337,492, International Publication No. 2005/009087, JP-A 2006-228712, JP-A 2006-24791, JP-A 2006-49393, JP-A 2006-49394 Gazette, JP 2006-49396 A, JP 2011-96679 A, JP 2005-340187 A, JP 4711424 A, JP 34966681, JP 3884564 A, Japanese Patent No. 4213169, JP 2010-A. No. 192719, JP2009-076 29, JP 2008-078414, JP 2007-059848, JP 2003-272860, JP 2003-045676, WO 2005/094130, etc. Although a constituent material etc. are mentioned, it is not limited to these.

<Light emitting layer>
The light emitting layer used in the organic EL device according to the present invention is a layer that provides a field in which electrons and holes injected from an electrode or an adjacent layer are recombined to emit light via excitons. In the light emitting layer, the light emitting portion may be within the layer of the light emitting layer or may be the interface between the light emitting layer and the adjacent layer.

  The total sum of the thicknesses of the light emitting layers is not particularly limited, and is determined from the viewpoint of the uniformity of the film to be formed, the voltage required at the time of light emission, the stability of the light emission color with respect to the driving current, and the like. For example, the total thickness of the light emitting layers is preferably adjusted to a range of 2 nm to 5 μm, more preferably adjusted to a range of 2 to 500 nm, and further preferably adjusted to a range of 5 to 200 nm. Further, the individual layer thickness of the light emitting layer is preferably adjusted to a range of 2 nm to 1 μm, more preferably adjusted to a range of 2 to 200 nm, and further preferably adjusted to a range of 3 to 150 nm.

  The light-emitting layer preferably contains a light-emitting dopant (a light-emitting dopant compound, a dopant compound, also simply referred to as a dopant) and a host compound (a matrix material, a light-emitting host compound, also simply referred to as a host).

<Luminescent dopant>
As the light emitting dopant used in the light emitting layer, a fluorescent light emitting dopant (also referred to as a fluorescent dopant or a fluorescent compound) and a phosphorescent light emitting dopant (also referred to as a phosphorescent dopant or a phosphorescent compound) are preferably used. Of these, at least one light emitting layer preferably contains a phosphorescent dopant.

  The concentration of the light-emitting dopant in the light-emitting layer can be arbitrarily determined based on the specific dopant used and the device requirements. The concentration of the photodopant may be contained at a uniform concentration in the thickness direction of the light emitting layer, or may have an arbitrary concentration distribution.

  In addition, the light emitting layer may contain a plurality of types of light emitting dopants. For example, a combination of dopants having different structures, or a combination of a fluorescent luminescent dopant and a phosphorescent luminescent dopant may be used. Thereby, arbitrary luminescent colors can be obtained.

  The color emitted by the organic EL device according to the present invention is shown in FIG. 4.16 on page 108 of “New Color Science Handbook” (edited by the Japan Society for Color Science, University of Tokyo Press, 1985). It is determined by the color when the result measured with Konica Minolta Co., Ltd. is applied to the CIE chromaticity coordinates.

  In the organic EL device according to the present invention, it is also preferable that one or a plurality of light-emitting layers contain a plurality of light-emitting dopants having different emission colors and emit white light. There are no particular limitations on the combination of the light-emitting dopants that exhibit white, and examples include blue and orange, and a combination of blue, green, and red.

As the white color in the organic EL device according to the present invention, the chromaticity in the CIE 1931 color system at 1000 cd / m ² is x = 0.39 ± 0. 09, preferably in the region of y = 0.38 ± 0.08.

<Phosphorescent dopant>
The phosphorescent dopant is a compound in which light emission from an excited triplet is observed. Specifically, the phosphorescent dopant is a compound that emits phosphorescence at room temperature (25 ° C.), and has a phosphorescence quantum yield of 0 at 25 ° C. .01 or more compounds. In the phosphorescent dopant used for a light emitting layer, a preferable phosphorescence quantum yield is 0.1 or more.

  The phosphorescence quantum yield can be measured by the method described in Spectroscopic II, page 398 (1992 edition, Maruzen) of Experimental Chemistry Course 4 of the 4th edition. The phosphorescence quantum yield in a solution can be measured using various solvents. The phosphorescence emitting dopant used for the light emitting layer should just achieve the said phosphorescence quantum yield (0.01 or more) in any solvent.

  There are two types of light emission of the phosphorescent dopant in principle.

  First, an excited state of the host compound is generated by recombination of carriers on the host compound to which carriers are transported. It is an energy transfer type in which light is emitted from the phosphorescent dopant by transferring this energy to the phosphorescent dopant. The other is a carrier trap type in which a phosphorescent dopant becomes a carrier trap, carrier recombination occurs on the phosphorescent dopant, and light emission from the phosphorescent dopant is obtained. In any case, it is a condition that the excited state energy of the phosphorescent dopant is lower than the excited state energy of the host compound.

  The phosphorescent dopant can be appropriately selected from known materials used for the light emitting layer of the organic EL device according to the present invention.

  Specific examples of known phosphorescent dopants include compounds described in the following documents.

  Nature, 395, 151 (1998), Appl. Phys. Lett. 78, 1622 (2001), Adv. Mater. , 19, 739 (2007), Chem. Mater. 17, 3532 (2005), Adv. Mater. , 17, 1059 (2005), International Publication No. 2009/100991, International Publication No. 2008/101842, International Publication No. 2003/040257, US Patent Application Publication No. 2006/020202194, US Patent Application Publication No. 2007. No./0087321, U.S. Patent Application Publication No. 2005/0244673, Inorg. Chem. , 40, 1704 (2001), Chem. Mater. 16, 2480 (2004), Adv. Mater. 16, 2003 (2004), Angew. Chem. lnt. Ed. , 2006, 45, 7800, Appl. Phys. Lett. 86, 153505 (2005), Chem. Lett. , 34, 592 (2005), Chem. Commun. , 2906 (2005), Inorg. Chem. , 42, 1248 (2003), International Publication No. 2009/050290, International Publication No. 2002/015645, International Publication No. 2009/000673, US Patent Application Publication No. 2002/0034656, and US Pat. No. 7,332,232. United States Patent Application Publication No. 2009/0108737, United States Patent Application Publication No. 2009/0039776, United States Patent No. 6921915, United States Patent No. 6,687,266, United States Patent Application Publication No. 2007/0190359. No., US Patent Application Publication No. 2006/0008670, US Patent Application Publication No. 2009/0165846, US Patent Application Publication No. 2008/0015355, US Pat. No. 7,250,226, US Patent No. 7396598 Writing, U.S. Patent Application Publication No. 2006/0263635, U.S. Patent Application Publication No. 2003/0138657, U.S. Patent Application Publication No. 2003/0152802, U.S. Patent No. 7090928, Angew. Chem. lnt. Ed. 47, 1 (2008), Chem. Mater. , 18, 5119 (2006), Inorg. Chem. 46, 4308 (2007), Organometallics, 23, 3745 (2004), Appl. Phys. Lett. , 74, 1361 (1999), International Publication No. 2002/002714, International Publication No. 2006/009024, International Publication No. 2006/056418, International Publication No. 2005/019373, International Publication No. 2005/123873, International Publication. No. 2005/123873, International Publication No. 2007/004380, International Publication No. 2006/082742, US Patent Application Publication No. 2006/0251923, US Patent Application Publication No. 2005/0260441, US Pat. No. 7,393,599. No. 7, U.S. Pat. No. 7,534,505, U.S. Pat. No. 7,445,855, U.S. Patent Application Publication No. 2007/0190359, U.S. Patent Application Publication No. 2008/0297033, U.S. Pat. No. 7,338,722. Letter, United States Patent Application Publication No. 2002/0134984, US Patent No. 7279704, International Publication No. 2005/076380, International Publication No. 2010/032663, International Publication No. 2008/140115, International Publication No. 2007/052431. International Publication No. 2011/134013, International Publication No. 2011/157339, International Publication No. 2010/086089, International Publication No. 2009/113646, International Publication No. 2012/020327, International Publication No. 2011/051404, International Publication No. JP 2011/004639, WO 2011/073149, JP 2012-069737, JP 2012-195554, JP 2009-114086, JP 2003-81988, JP 2002. -30 671 JP is JP 2002-363552 Publication.

  Among these, preferable phosphorescent dopants include organometallic complexes having Ir as a central metal. More preferably, a complex containing at least one coordination mode of a metal-carbon bond, a metal-nitrogen bond, a metal-oxygen bond, or a metal-sulfur bond is preferable.

<Fluorescent luminescent dopant>
The fluorescent light-emitting dopant is a compound that can emit light from an excited singlet, and is not particularly limited as long as light emission from the excited singlet is observed.

  Examples of the fluorescent dopant include anthracene derivatives, pyrene derivatives, chrysene derivatives, fluoranthene derivatives, perylene derivatives, fluorene derivatives, arylacetylene derivatives, styrylarylene derivatives, styrylamine derivatives, arylamine derivatives, boron complexes, coumarin derivatives, pyran. Derivatives, cyanine derivatives, croconium derivatives, squalium derivatives, oxobenzanthracene derivatives, fluorescein derivatives, rhodamine derivatives, pyrylium derivatives, perylene derivatives, polythiophene derivatives, rare earth complex compounds, and the like.

  Moreover, you may use the light emission dopant etc. which used delayed fluorescence as a fluorescence light emission dopant.

  Specific examples of the luminescent dopant using delayed fluorescence include compounds described in, for example, International Publication No. 2011/156793, Japanese Patent Application Laid-Open No. 2011-213643, Japanese Patent Application Laid-Open No. 2010-93181, and the like.

<Host compound>
The host compound is a compound mainly responsible for charge injection and transport in the light emitting layer, and its own light emission is not substantially observed in the organic EL element.

  Preferably, it is a compound having a phosphorescence quantum yield of phosphorescence of less than 0.1 at room temperature (25 ° C.), more preferably a compound having a phosphorescence quantum yield of less than 0.01. Moreover, it is preferable that the mass ratio in the layer is 20% or more among the compounds contained in a light emitting layer.

  Moreover, it is preferable that the excited state energy of a host compound is higher than the excited state energy of the light emission dopant contained in the same layer.

  A host compound may be used independently or may be used in combination of multiple types. By using a plurality of types of host compounds, it is possible to adjust the movement of electric charges, and it is possible to increase the efficiency of the organic EL element.

  There is no restriction | limiting in particular as a host compound used for a light emitting layer, The compound used with the conventional organic EL element can be used. For example, a low molecular compound, a high molecular compound having a repeating unit, or a compound having a reactive group such as a vinyl group or an epoxy group may be used.

  As a known host compound, while having a hole transport ability or an electron transport ability, it prevents the light emission from becoming longer wavelength, and further, from the viewpoint of stability against heat generation during driving of the organic EL element at a high temperature or during element driving, It is preferable to have a high glass transition temperature (Tg). As a host compound, it is preferable that Tg is 90 degreeC or more, More preferably, it is 120 degreeC or more.

  Here, the glass transition point (Tg) is a value obtained by a method based on JIS K 7121-2012 using DSC (Differential Scanning Colorimetry).

  Specific examples of known host compounds used in the organic EL device according to the present invention include compounds described in the following documents, but the present invention is not limited thereto.

  JP-A-2001-257076, 2002-308855, 2001-313179, 2002-319491, 2001-357777, 2002-334786, 2002-8860, 2002-334787, 2002-15871, 2002-334788, 2002-43056, 2002-334789, 2002-75645, 2002-338579, 2002-105445 gazette, 2002-343568 gazette, 2002-141173 gazette, 2002-352957 gazette, 2002-203683 gazette, 2002-363227 gazette, 2002-231453 gazette, No. 003-3165, No. 2002-234888, No. 2003-27048, No. 2002-255934, No. 2002-286061, No. 2002-280183, No. 2002-299060, No. 2002. -302516, 2002-305083, 2002-305084, 2002-308837, US Patent Application Publication No. 2003/0175553, US Patent Application Publication No. 2006/0280965, US Patent Application Publication No. 2005/0112407, US Patent Application Publication No. 2009/0017330, US Patent Application Publication No. 2009/0030202, US Patent Application Publication No. 2005/0238919, International Publication First 001/039234, International Publication No. 2009/021126, International Publication No. 2008/056746, International Publication No. 2004/093207, International Publication No. 2005/089025, International Publication No. 2007/063796, International Publication No. 2007/2007 / No. 063754, International Publication No. 2004/107822, International Publication No. 2005/030900, International Publication No. 2006/114966, International Publication No. 2009/086028, International Publication No. 2009/003898, International Publication No. 2012/023947 JP 2008-074939 A, JP 2007-254297 A, EP 2034538, and the like.

<Electron transport layer>
Electron transport in the organic EL device according to the present invention is performed by a material having a function of transporting electrons, and has a function of transmitting electrons injected from the cathode to the light emitting layer.

  The electron transport material may be used alone or in combination of two or more.

  Although there is no restriction | limiting in particular about the total layer thickness of an electron carrying layer, Usually, it is the range of 2 nm-5 micrometers, More preferably, it is 2-500 nm, More preferably, it is 5-200 nm.

  In the organic EL device according to the present invention, when the light generated in the light emitting layer is extracted from the electrode, the light extracted directly from the light emitting layer and the light reflected from the electrode that is opposite to the electrode from which the light is extracted are extracted. It is known that light causes interference. When light is reflected by the cathode, this interference effect can be efficiently utilized by appropriately adjusting the total thickness of the electron transport layer between several nanometers and several micrometers.

On the other hand, when the layer thickness of the electron transport layer is increased, the voltage is likely to increase. Therefore, particularly when the layer thickness is thick, the electron mobility of the electron transport layer is preferably 10 ⁻⁵ cm ² / Vs or more. .

  As a material used for the electron transport layer (hereinafter referred to as an electron transport material), any material that has either an electron injection property or a transport property or a hole barrier property may be used. Any one can be selected and used.

  Examples thereof include nitrogen-containing aromatic heterocyclic derivatives, aromatic hydrocarbon ring derivatives, dibenzofuran derivatives, dibenzothiophene derivatives and silole derivatives.

  Examples of the nitrogen-containing aromatic heterocyclic derivatives include carbazole derivatives, azacarbazole derivatives (one or more carbon atoms constituting the carbazole ring are substituted with nitrogen atoms), pyridine derivatives, pyrimidine derivatives, pyrazine derivatives, pyridazine derivatives, triazine derivatives. Quinoline derivatives, quinoxaline derivatives, phenanthroline derivatives, azatriphenylene derivatives, oxazole derivatives, thiazole derivatives, oxadiazole derivatives, thiadiazole derivatives, triazole derivatives, benzimidazole derivatives, benzoxazole derivatives, and benzthiazole derivatives.

  Examples of the aromatic hydrocarbon ring derivative include naphthalene derivatives, anthracene derivatives, and triphenylene.

In addition, a metal complex having a quinolinol skeleton or a dibenzoquinolinol skeleton as a ligand, for example, tris (8-quinolinol) aluminum (Alq ₃ ), tris (5,7-dichloro-8-quinolinol) aluminum, tris (5,7 -Dibromo-8-quinolinol) aluminum, tris (2-methyl-8-quinolinol) aluminum, tris (5-methyl-8-quinolinol) aluminum, bis (8-quinolinol) zinc (Znq) and the like and their metal complexes A metal complex in which the central metal is replaced with In, Mg, Cu, Ca, Sn, Ga, or Pb can also be used as the electron transport material.

  In addition, metal-free or metal phthalocyanine or those in which the terminal thereof is substituted with an alkyl group or a sulfonic acid group can be preferably used as the electron transport material. In addition, the distyrylpyrazine derivative exemplified as the material of the light emitting layer can also be used as an electron transport material, and an inorganic semiconductor such as n-type-Si, n-type-SiC, etc. as in the case of the hole injection layer and the hole transport layer. Can also be used as an electron transporting material.

  Further, 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 the organic EL device according to the present invention, the electron transport layer may be doped as a guest material with a doping material to form an electron transport layer having a high n property (electron rich). Examples of the doping material include metal compounds such as metal complexes and metal halides, and other n-type dopants.

  Specific examples of the electron transport layer having such a structure include, for example, JP-A-4-297076, JP-A-10-270172, JP-A-2000-196140, 2001-102175, J. Pat. Appl. Phys. , 95, 5773 (2004) and the like.

  Specific examples of known preferable electron transport materials used in the organic EL device according to the present invention include, but are not limited to, compounds described in the following documents.

  US Pat. No. 6,528,187, US Pat. No. 7,230,107, US Patent Application Publication No. 2005/0025993, US Patent Application Publication No. 2004/0036077, US Patent Application Publication No. 2009/0115316 U.S. Patent Application Publication No. 2009/0101870, U.S. Patent Application Publication No. 2009/0179554, International Publication No. 2003/060956, International Publication No. 2008/132805, Appl. Phys. Lett. , 75, 4 (1999), Appl. Phys. Lett. 79, 449 (2001), Appl. Phys. Lett. 81, 162 (2002), Appl. Phys. Lett. 81, 162 (2002), Appl. Phys. Lett. 79,156 (2001), U.S. Pat. No. 7,964,293, International Publication No. 2004/080975, International Publication No. 2004/063159, International Publication No. 2005/085387, International Publication No. 2006/067931, International Publication. 2007/088652, International Publication No. 2008/114690, International Publication No. 2009/066942, International Publication No. 2009/066779, International Publication No. 2009/054253, International Publication No. 2011/086935, International Publication No. 2010 No./150593, International Publication No. 2010/047707, EP23111826, JP2010-251675A, JP2009-209133A, JP2009-124114A, JP2008-277810A, JP2006. − 56445, JP 2005-340122, JP 2003-45662, JP-2003-31367, JP 2003-282270, JP-WO 2012/115034, and the like.

  More preferable electron transport materials include pyridine derivatives, pyrimidine derivatives, pyrazine derivatives, triazine derivatives, dibenzofuran derivatives, dibenzothiophene derivatives, carbazole derivatives, azacarbazole derivatives, and benzimidazole derivatives.

<Hole blocking layer>
The hole blocking layer is a layer having a function of an electron transport layer in a broad sense. Preferably, it contains a material having a function of transporting electrons and a small ability to transport holes. By blocking holes while transporting electrons, the recombination probability of electrons and holes can be improved.

  Moreover, the structure of the above-mentioned electron carrying layer can be used as a hole-blocking layer as needed.

  The hole blocking layer provided in the organic EL device according to the present invention is preferably provided adjacent to the cathode side of the light emitting layer.

  In the organic EL device according to the present invention, the thickness of the hole blocking layer is preferably in the range of 3 to 100 nm, more preferably in the range of 5 to 30 nm.

  As the material used for the hole blocking layer, the material used for the above-described electron transport layer is preferably used, and the material used as the above-described host compound is also preferably used for the hole blocking layer.

<Electron injection layer>
The electron injection layer (also referred to as “cathode buffer layer”) is a layer provided between the cathode and the light emitting layer in order to lower the driving voltage and improve the light emission luminance. An example of an electron injection layer is described in the second chapter, Chapter 2, “Electrode Materials” (pages 123 to 166) of “Organic EL devices and their industrialization front line (issued by NTT Corporation on November 30, 1998)”. Have been described.

  In the organic EL device according to the present invention, the electron injection layer is provided as necessary, and is provided between the cathode and the light emitting layer or between the cathode and the electron transport layer as described above.

  The electron injection layer is preferably a very thin film layer, and the layer thickness is preferably in the range of 0.1 to 5 nm although it depends on the material. Moreover, the layer which consists of a nonuniform film | membrane in which a constituent material exists intermittently may be sufficient.

  Details of the electron injection layer are also described in JP-A-6-325871, JP-A-9-17574, JP-A-10-74586, and the like. Specific examples of materials preferably used for the electron injection layer include metals typified by strontium and aluminum, alkali metal compounds typified by lithium fluoride, sodium fluoride, and potassium fluoride, magnesium fluoride, and fluoride. Examples include alkaline earth metal compounds typified by calcium, metal oxides typified by aluminum oxide, metal complexes typified by lithium 8-hydroxyquinolate (Liq), and the like. Moreover, it is also possible to use the above-mentioned electron transport material.

  Moreover, the material used for said electron injection layer may be used independently, and may be used in combination of multiple types.

<Hole transport layer>
The hole transport layer is made of a material having a function of transporting holes. The hole transport layer is a layer having a function of transmitting holes injected from the anode to the light emitting layer.

  In the organic EL device according to the present invention, the total thickness of the hole transport layer is not particularly limited, but is usually in the range of 5 nm to 5 μm, more preferably 2 to 500 nm, and further preferably 5 to 200 nm. is there.

  A material used for the hole transport layer (hereinafter referred to as a hole transport material) may have any of a hole injection property or a transport property and an electron barrier property. As the hole transport material, an arbitrary material can be selected and used from conventionally known compounds. The hole transport material may be used alone or in combination of two or more.

  Hole transport materials include, for example, porphyrin derivatives, phthalocyanine derivatives, oxazole derivatives, oxadiazole derivatives, triazole derivatives, imidazole derivatives, pyrazoline derivatives, pyrazolone derivatives, phenylenediamine derivatives, hydrazone derivatives, stilbene derivatives, polyarylalkane derivatives, tria. Reelamine derivatives, carbazole derivatives, indolocarbazole derivatives, isoindole derivatives, acene derivatives such as anthracene and naphthalene, fluorene derivatives, fluorenone derivatives, polyvinyl carbazole, polymer materials having aromatic amine introduced in the main chain or side chain, or Oligomer, polysilane, conductive polymer or oligomer (for example, PEDOT: PSS, aniline copolymer, polyaniline, polythiophene, etc.) And the like.

  Examples of the triarylamine derivative include a benzidine type typified by α-NPD, a starburst type typified by MTDATA, and a compound having fluorene or anthracene in the triarylamine linking core part.

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

  Furthermore, a hole transport layer having a high p property doped with impurities can also be used. For example, JP-A-4-297076, JP-A-2000-196140, 2001-102175, J. Pat. Appl. Phys. 95, 5773 (2004), etc., can also be applied to the hole transport layer.

JP-A-11-251067, J. Org. Huang et. al. It is also possible to use so-called p-type hole transport materials and inorganic compounds such as p-type-Si and p-type-SiC as described in the literature (Applied Physics Letters, 80 (2002), p. 139). . Further, ortho-metalated organometallic complexes having Ir or Pt as the central metal as typified by Ir (ppy) ₃ are also preferably used.

  Although the above-mentioned materials can be used as the hole transport material, a triarylamine derivative, a carbazole derivative, an indolocarbazole derivative, an azatriphenylene derivative, an organometallic complex, or an aromatic amine is introduced into the main chain or side chain. The polymer materials or oligomers used are preferably used.

  Specific examples of the hole transport material used in the organic EL device according to the present invention include, but are not limited to, the compounds described in the following documents in addition to the documents listed above.

  Appl. Phys. Lett. 69, 2160 (1996); Lumin. 72-74, 985 (1997), Appl. Phys. Lett. 78, 673 (2001), Appl. Phys. Lett. , 90, 183503 (2007), Appl. Phys. Lett. , 90, 183503 (2007), Appl. Phys. Lett. 51, 913 (1987), Synth. Met. , 87, 171 (1997), Synth. Met. 91, 209 (1997), Synth. Met. , 111, 421 (2000), SID Symposium Digest, 37, 923 (2006), J. Am. Mater. Chem. 3,319 (1993), Adv. Mater. 6, 677 (1994), Chem. Mater. , 15, 3148 (2003), US Patent Application Publication No. 2003/0162053, US Patent Application Publication No. 2002/0158242, US Patent Application Publication No. 2006/0240279, US Patent Application Publication No. 2008. No. 0220265, U.S. Pat. No. 5,061,569, WO 2007/002683, WO 2009/018009, EP 650955, U.S. Patent Application Publication No. 2008/0124572, U.S. Patent Application Publication No. 2007. No. / 027898938, U.S. Patent Application Publication No. 2008/0106190, U.S. Patent Application Publication No. 2008/0018221, International Publication No. 2012/115034, Japanese Translation of PCT International Publication No. 2003-519432, Japanese Patent Laid-Open No. 2006-2006. 135145 Publication, such as U.S. Patent Application No. 13/585981 and the like.

<Electron blocking layer>
The electron blocking layer is a layer having a function of a hole transport layer in a broad sense. Preferably, it is made of a material having a function of transporting holes and a small ability to transport electrons. The electron blocking layer can improve the probability of recombination of electrons and holes by blocking electrons while transporting holes.

  Moreover, the structure of the above-mentioned hole transport layer can be used as an electron blocking layer of the organic EL device according to the present invention, if necessary. The electron blocking layer provided in the organic EL element is preferably provided adjacent to the anode side of the light emitting layer.

  The thickness of the electron blocking layer is preferably in the range of 3 to 100 nm, more preferably in the range of 5 to 30 nm.

  As the material used for the electron blocking layer, the materials used for the above-described hole transport layer can be preferably used. Moreover, the material used as the above-mentioned host compound can also be preferably used as the electron blocking layer.

<Hole injection layer>
The hole injection layer (also referred to as “anode buffer layer”) is a layer provided between the anode and the light emitting layer in order to lower the driving voltage and improve the light emission luminance. An example of the hole injection layer is “Organic EL device and its industrialization front line (November 30, 1998, issued by NTT)”, Chapter 2, Chapter 2, “Electrode material” (pages 123-166). It is described in.

  The hole injection layer is provided as necessary, and is provided between the anode and the light emitting layer or between the anode and the hole transport layer as described above.

  Details of the hole injection layer are described in JP-A-9-45479, JP-A-9-260062, and JP-A-8-288069.

  Examples of the material used for the hole injection layer include the materials used for the hole transport layer described above. Among them, phthalocyanine derivatives represented by copper phthalocyanine, hexaazatriphenylene derivatives as described in JP-T-2003-519432, JP-A-2006-135145, etc., metal oxides represented by vanadium oxide, amorphous Conductive polymers such as carbon, polyaniline (emeraldine) and polythiophene, orthometalated complexes represented by tris (2-phenylpyridine) iridium complex, and triarylamine derivatives are preferred.

  The materials used for the hole injection layer described above may be used alone or in combination of two or more.

<Additive>
The organic functional layer constituting the organic EL device according to the present invention may further contain other additives.

  Examples of the additive include halogen elements and halogenated compounds such as bromine, iodine and chlorine, alkali metals and alkaline earth metals such as Pd, Ca, and Na, transition metal compounds, complexes, and salts.

  The content of the additive can be arbitrarily determined, but is preferably 1000 ppm or less, more preferably 500 ppm or less, and further preferably 50 ppm or less with respect to the total mass% of the contained layer. .

  However, it is not within this range depending on the purpose of improving the transportability of electrons and holes or the purpose of favoring the exciton energy transfer.

<Method for forming organic functional layer>
A method for forming an organic functional layer (hole injection layer, hole transport layer, light emitting layer, hole blocking layer, electron transport layer, electron injection layer, etc.) of the organic EL device according to the present invention will be described.

  The method for forming the organic functional layer is not particularly limited, and can be formed by a conventionally known method such as a vacuum deposition method or a wet method (wet process).

  Examples of the wet method include a spin coating method, a casting method, an ink jet method, a printing method, a die coating method, a blade coating method, a roll coating method, a spray coating method, a curtain coating method, and an LB method (Langmuir-Blodgett method). From the viewpoint of obtaining a homogeneous thin film easily and high productivity, a method having high suitability for a roll-to-roll method such as a die coating method, a roll coating method, an ink jet method, or a spray coating method is preferable.

  Examples of the liquid medium for dissolving or dispersing the organic functional layer material in the wet method include ketones such as methyl ethyl ketone and cyclohexanone, fatty acid esters such as ethyl acetate, halogenated hydrocarbons such as dichlorobenzene, toluene, and xylene. Aromatic hydrocarbons such as mesitylene and cyclohexylbenzene, aliphatic hydrocarbons such as cyclohexane, decalin and dodecane, and organic solvents such as DMF and DMSO can be used.

  Moreover, it can disperse | distribute by dispersion methods, such as an ultrasonic wave, high shear force dispersion | distribution, and media dispersion | distribution.

  When employing a vapor deposition method for forming each layer constituting the organic functional layer, the vapor deposition conditions vary depending on the type of compound used, but generally a boat heating temperature of 50 to 450 ° C., a degree of vacuum of 10 −6 to 10 −2 Pa, It is desirable to appropriately select a deposition rate of 0.01 to 50 nm / second, a substrate temperature of −50 to 300 ° C., and a layer thickness of 0.1 nm to 5 μm, preferably 5 to 200 nm.

  In the formation of the organic EL device according to the present invention, it is preferable to consistently produce the organic functional layer to the cathode by one evacuation, but it may be taken out halfway and subjected to different film forming methods. In that case, it is preferable to perform the work in a dry inert gas atmosphere.

  Different formation methods may be applied for each layer.

<First electrode>
As the first electrode 215, 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, preferably 4.3 eV or more) is used. Specific examples of such an electrode substance include metals such as Au and Ag, alloys thereof, and conductive transparent materials such as CuI, ITO (indium tin oxide), SnO ₂ , and ZnO. Alternatively, an amorphous material such as IDIXO (In ₂ O ₃ —ZnO) that can form a transparent conductive film may be used.

  For the first electrode, a thin film is formed by depositing these electrode materials by a method such as vapor deposition or sputtering, and a pattern having a desired shape is formed by a photolithography method. Alternatively, when the pattern accuracy is not so high (about 100 μm or more), the pattern may be formed through a mask having a desired shape when the electrode material is formed by vapor deposition or sputtering.

  In the case of using a coatable material such as an organic conductive compound, a wet film forming method such as a printing method or a coating method can also be used.

  When the emitted light is extracted from the first electrode side, it is desirable that the transmittance be greater than 10%. The sheet resistance as the first electrode is several hundred Ω / sq. The following is preferred. Further, the thickness of the first electrode depends on the material, but is usually 10 nm to 1 μm, preferably 10 to 200 nm.

  In particular, the first electrode is a layer composed mainly of silver and is preferably composed of silver or an alloy composed mainly of silver. Examples of the method for forming the first electrode include a method using a wet process such as a coating method, an inkjet method, a coating method, a dip method, a vapor deposition method (resistance heating, EB method, etc.), a sputtering method, a CVD method, and the like. Examples include a method using a dry process. Of these, the vapor deposition method is preferably applied.

  As an example, the alloy mainly composed of silver (Ag) constituting the first electrode is silver magnesium (AgMg), silver copper (AgCu), silver palladium (AgPd), silver palladium copper (AgPdCu), silver indium (AgIn). Etc.

  The first electrode as described above may have a structure in which silver or an alloy layer mainly composed of silver is divided into a plurality of layers as necessary.

  Further, the first electrode preferably has a thickness in the range of 4 to 15 nm. A thickness of 15 nm or less is preferable because the absorption component and reflection component of the layer are kept low and the light transmittance of the first electrode is maintained. Further, when the thickness is 4 nm or more, the conductivity of the layer is also ensured.

  In the case where a layer composed mainly of silver is formed as the first electrode, another conductive layer containing Pd or the like, or an organic functional layer such as a nitrogen compound or a sulfur compound is used as a base layer for the first electrode. You may form as. By forming the base layer, it is possible to improve the film formation of a layer composed mainly of silver, to reduce the resistivity of the first electrode, and to improve the light transmittance of the first electrode 15.

<Second electrode>
As the second electrode 217, an electrode substance made of a metal having a small work function (4 eV or less) (referred to as an electron injecting metal), an alloy, an electrically conductive compound, or 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, aluminum, rare earth metals and the like.

Among these, a mixture of an electron injecting metal and a second metal having a work function value larger and more stable than that of the electron injecting metal, for example, magnesium / Silver mixtures, magnesium / aluminum mixtures, magnesium / indium mixtures, aluminum / aluminum oxide (Al ₂ O ₃ ) mixtures, lithium / aluminum mixtures, aluminum and the like are preferred.

  The second electrode can be produced using the above electrode material by a method such as vapor deposition or sputtering. The sheet resistance of the second electrode is several hundred Ω / sq. The following is preferred. The thickness of the second electrode is usually in the range of 10 nm to 5 μm, preferably 50 to 200 nm.

  Moreover, after producing the metal with a thickness of 1 to 20 nm on the second electrode, a transparent transparent or translucent second electrode is produced by producing a conductive transparent material mentioned in the description of the first electrode on the second electrode. can do. By applying this, an element in which both the first electrode and the second electrode are transmissive can be manufactured.

<Sealing member>
As shown in FIG. 4, the organic EL element according to the present invention may be solid-sealed by bonding a sealing member 221 and a sealing layer 222 that cover the entire organic functional layer.

  The sealing member 221 is provided in a state of covering at least the organic functional layer, and is provided in a state of exposing the terminal portions (not shown) of the first electrode and the second electrode. Moreover, an electrode may be provided on the sealing member 221 so that the terminal portions of the first electrode and the second electrode of the organic EL element are electrically connected to this electrode.

  The sealing member 221 is made of a resin sealing material for bonding the second electrode 217 and the sealing layer 222. In addition to the resin sealing material, an inorganic sealing material may be used. For example, the organic functional layer may be covered with an inorganic sealing material, and then the sealing layer and the second electrode may be bonded with a resin sealing material.

  The resin sealing material is used for fixing the sealing layer 222 to the second electrode 217 side. Moreover, it is used as a sealing material for sealing the organic functional layer sandwiched between the sealing member and the first electrode.

  In order to bond the sealing layer to the second electrode, it is preferable to bond the sealing layer using any curable resin sealing material. As the resin sealing material, a suitable adhesive can be appropriately selected from the viewpoint of improving the adhesion with the sealing member to be bonded.

  As such a resin sealing material, it is preferable to use a thermosetting resin.

  As the thermosetting adhesive, for example, a resin mainly composed of a compound having an ethylenic double bond at the molecular end or side chain and a thermal polymerization initiator can be used. More specifically, a thermosetting adhesive made of an epoxy resin, an acrylic resin, or the like can be used. Moreover, according to the bonding apparatus and hardening processing apparatus which are used by the manufacturing process of an organic EL element, you may use a fusion type thermosetting adhesive.

  Moreover, as such a resin sealing material, it is also preferable to use a photocurable resin. For example, photo-radically polymerizable resins mainly composed of various (meth) acrylates such as polyester (meth) acrylate, polyether (meth) acrylate, epoxy (meth) acrylate, polyurethane (meth) acrylate, epoxy, vinyl ether, etc. Examples thereof include a cationic photopolymerizable resin mainly composed of a resin and a thiol / ene addition type resin. Among these photo-curing resins, an epoxy resin-based photo-cationic polymerizable resin having a low shrinkage of the cured product, a small outgas, and excellent long-term reliability is preferable.

  In addition, as such a resin sealing material, a chemically curable (mixed two-component) resin can be used. Hot melt polyamide, polyester, and polyolefin can also be used. Moreover, a cationic curing type ultraviolet curing epoxy resin can be used.

  In addition, the organic material which comprises an organic EL element may deteriorate with heat processing. For this reason, it is preferable to use a resin sealing material that can be adhesively cured from room temperature to 80 ° C.

  The said inorganic sealing material is a member which seals the light emitting unit which consists of a 1st electrode, an organic functional layer, and a 2nd electrode with a resin sealing material. For this reason, it is preferable to use a material having a function of suppressing intrusion of moisture, oxygen, or the like that degrades the organic functional layer as the inorganic sealing material.

  In addition, since the inorganic sealing material has a configuration in direct contact with the organic functional layer, it is preferable to use a material having excellent bonding properties with the organic functional layer.

  The inorganic sealing material is preferably formed of a compound such as an inorganic oxide, inorganic nitride, or inorganic carbide having high sealing properties.

Specifically, it is made of SiO _x , Al ₂ O ₃ , In ₂ O ₃ , TiO _x , ITO (indium tin oxide), AlN, Si ₃ N ₄ , SiO _x N, TiO _x N, SiC, or the like. be able to.

  The inorganic sealing material can be formed by a known method such as a sol-gel method, a vapor deposition method, CVD, ALD (Atomic Layer Deposition), PVD, or a sputtering method.

  In addition, in the atmospheric pressure plasma method, the inorganic sealing material is selected from conditions such as an organometallic compound, a decomposition gas, a decomposition temperature, and an input power that are raw materials (also referred to as raw materials). Compositions such as mixtures of inorganic carbides, inorganic nitrides, inorganic sulfides and inorganic halides such as inorganic oxides or inorganic oxynitrides and inorganic oxide halides as the main component can be made.

  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. Further, if silazane or the like is used as a raw material compound, silicon oxynitride is generated. This is because highly active charged particles and active radicals exist in the plasma space at a high density, so that multi-step chemical reactions are accelerated very rapidly in the plasma space, and the elements in the plasma space are thermodynamically This is because it is converted into a stable compound in a very short time.

  As long as the raw material for forming such an inorganic sealing material is a silicon compound, it may be in a gas, liquid, or solid state at normal temperature and pressure. In the case of gas, it can be introduced into the discharge space as it is, but in the case of liquid or solid, it is used after being vaporized by means such as heating, bubbling, decompression or ultrasonic irradiation. Moreover, you may dilute and use by a solvent and can use organic solvents, such as methanol, ethanol, n-hexane, and these mixed solvents. In addition, since these dilution solvents are decomposed | disassembled into a molecule | numerator or an atom during a plasma discharge process, the influence can be almost disregarded.

  Examples of such silicon compounds include silane, tetramethoxysilane, tetraethoxysilane, tetra n-propoxysilane, tetraisopropoxysilane, tetra n-butoxysilane, tetrat-butoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, Diethyldimethoxysilane, diphenyldimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, phenyltriethoxysilane, (3,3,3-trifluoropropyl) trimethoxysilane, hexamethyldisiloxane, bis (dimethylamino) dimethylsilane Bis (dimethylamino) methylvinylsilane, bis (ethylamino) dimethylsilane, N, O-bis (trimethylsilyl) acetamide, bis (trimethylsilyl) carbodiimide, die Ruaminotrimethylsilane, dimethylaminodimethylsilane, hexamethyldisilazane, hexamethylcyclotrisilazane, heptamethyldisilazane, nonamethyltrisilazane, octamethylcyclotetrasilazane, tetrakisdimethylaminosilane, tetraisocyanatosilane, tetramethyldisilazane , Tris (dimethylamino) silane, triethoxyfluorosilane, allyldimethylsilane, allyltrimethylsilane, benzyltrimethylsilane, bis (trimethylsilyl) acetylene, 1,4-bistrimethylsilyl-1,3-butadiyne, di-t-butylsilane, 1,3-disilabutane, bis (trimethylsilyl) methane, cyclopentadienyltrimethylsilane, phenyldimethylsilane, phenyltrimethylsilane, pro Rugyltrimethylsilane, tetramethylsilane, trimethylsilylacetylene, 1- (trimethylsilyl) -1-propyne, tris (trimethylsilyl) methane, tris (trimethylsilyl) silane, vinyltrimethylsilane, hexamethyldisilane, octamethylcyclotetrasiloxane, tetramethyl Examples thereof include cyclotetrasiloxane, hexamethylcyclotetrasiloxane, M silicate 51, and the like.

  In addition, as a decomposition gas for decomposing these silicon-containing source gases to obtain an inorganic sealing material, hydrogen gas, methane gas, acetylene gas, carbon monoxide gas, carbon dioxide gas, nitrogen gas, ammonia gas, suboxide Examples thereof include nitrogen gas, nitrogen oxide gas, nitrogen dioxide gas, oxygen gas, water vapor, fluorine gas, hydrogen fluoride, trifluoroalcohol, trifluorotoluene, hydrogen sulfide, sulfur dioxide, carbon disulfide, and chlorine gas.

  An inorganic sealing material containing silicon oxide, nitride, carbide, or the like can be obtained by appropriately selecting the source gas containing silicon and the decomposition gas.

  In the atmospheric pressure plasma method, a discharge gas that tends to be in a plasma state is mainly mixed with these reactive gases, and the gas is sent to a plasma discharge generator. As such a discharge gas, nitrogen gas and / or Group 18 element of the periodic table, specifically, helium, neon, argon, krypton, xenon, radon, etc. are used. Among these, nitrogen, helium, and argon are preferably used.

  The discharge gas and the reactive gas are mixed and supplied to an atmospheric pressure plasma discharge generator (plasma generator) as a thin film forming (mixed) gas to form a film. Although the ratio of the discharge gas and the reactive gas varies depending on the properties of the film to be obtained, the reactive gas is supplied with the ratio of the discharge gas being 50% or more with respect to the entire mixed gas.

<Sealing layer>
The sealing layer 222 covers the organic EL element. For example, a plate-like (film-like) sealing layer 222 is fixed to the second electrode side via the sealing member 221.

  Specific examples of the plate-like (film-like) sealing member include a glass substrate and a polymer substrate, and these substrate materials may be used in the form of a thin film. Examples of the glass substrate include soda-lime glass, barium / strontium-containing glass, lead glass, aluminosilicate glass, borosilicate glass, barium borosilicate glass, and quartz. Examples of the polymer substrate include polycarbonate, acrylic, polyethylene terephthalate, polyether sulfide, and polysulfone.

  Moreover, it is preferable to use the metal foil by which the resin film was laminated (polymer film) as a sealing layer. A metal foil laminated with a resin film cannot be used as a substrate on the light extraction side, but is a low-cost and low moisture-permeable sealing material. For this reason, it is suitable as a sealing layer which does not intend light extraction.

  The metal foil refers to a metal foil or film formed by rolling or the like, unlike a metal thin film formed by sputtering or vapor deposition, or a conductive film formed from a fluid electrode material such as a conductive paste. .

  As metal foil, there is no limitation in particular in the kind of metal, for example, copper (Cu) foil, aluminum (Al) foil, gold (Au) foil, brass foil, nickel (Ni) foil, titanium (Ti) foil, copper alloy Examples thereof include foil, stainless steel foil, tin (Sn) foil, and high nickel alloy foil. Among these various metal foils, a particularly preferred metal foil is an Al foil.

  The thickness of the metal foil is preferably 6 to 50 μm. In the case of 6 μm or more, depending on the material used for the metal foil, the required gas barrier properties (moisture permeability, oxygen permeability) can be obtained without any pinholes during use. When the thickness is 50 μm or less, an increase in cost due to the material used for the metal foil can be suppressed, and the organic EL element can be prevented from becoming too thick. Therefore, there is an advantage of using a film-shaped sealing member.

  In the metal foil laminated with the resin film, as the resin film, various materials described in the new development of functional packaging materials (Toray Research Center, Inc.) can be used. For example, polyethylene resin, polypropylene resin, polyethylene terephthalate resin, polyamide resin, ethylene-vinyl alcohol copolymer resin, ethylene-vinyl acetate copolymer resin, acrylonitrile-butadiene copolymer resin, cellophane resin, vinylon Resin, vinylidene chloride resin and the like can be used. Resins such as polypropylene resins and nylon resins may be stretched and further coated with a vinylidene chloride resin. The polyethylene resin may be either low density or high density.

The sealing layer 222 has an oxygen permeability measured by a method according to JIS K 7126-1987 of 1 × 10 ⁻³ mL / m ² · 24 h · atm or less, and is measured by a method according to JIS K 7129-1992. Further, the water vapor permeability (25 ± 0.5 ° C., relative humidity (90 ± 2)% RH) is preferably 1 × 10 ⁻³ g / m ² · 24 h or less.

  Moreover, you may use the above sealing layers processed into a concave plate shape. In this case, the above-described substrate member is subjected to processing such as sand blasting or chemical etching to form a concave shape.

  Moreover, not only this but a metal material may be used. Examples of the metal material include one or more metals or alloys selected from the group consisting of stainless steel, iron, copper, aluminum, magnesium, nickel, zinc, chromium, titanium, molybdenum, silicon, germanium, and tantalum. By using such a metal material as a sealing layer in the form of a thin film, the entire light-emitting panel provided with the organic EL element can be thinned.

  Among them, since the device can be thinned, a polymer substrate (gas barrier film) having a gas barrier property in a thin film shape can be preferably used as the sealing layer, and the gas barrier film of the present invention is sealed. It can also be used as a layer.

The film-like polymer substrate has an oxygen permeability measured by a method in accordance with JIS K 7126-1987, measured by a method in accordance with JIS K 7129-1992, which is 1 × 10 ⁻³ mL / m ² · 24 h · atm or less. The water vapor permeability (25 ± 0.5 ° C., relative humidity (90 ± 2)% RH) is preferably 1 × 10 ⁻³ g / m ² · 24 h or less.

  Further, the above substrate material may be processed into a concave plate shape and used as a sealing member. In this case, the above-described substrate member is subjected to processing such as sand blasting or chemical etching to form a concave shape.

<Extraction electrode>
The extraction electrode (not shown) is for electrically connecting the first electrode and the external power source, and the material thereof is not particularly limited and a known material can be preferably used. A metal film such as a MAM electrode (Mo / Al · Nd alloy / Mo) having a layer structure can be used.

<Auxiliary electrode>
The auxiliary electrode (not shown) is provided for the purpose of reducing the resistance of the first electrode, and is provided in contact with the electrode layer of the first electrode. The material for forming the auxiliary electrode is preferably a metal having low resistance such as gold, platinum, silver, copper, or aluminum. Since these metals have low light transmittance, a pattern is formed within a range not affected by extraction of emitted light from the light extraction surface.

  Examples of a method for forming such an auxiliary electrode include a vapor deposition method, a sputtering method, a printing method, an ink jet method, and an aerosol jet method. The line width of the auxiliary electrode is preferably 50 μm or less from the viewpoint of the aperture ratio for extracting light, and the thickness of the auxiliary electrode is preferably 1 μm or more from the viewpoint of conductivity.

<Protective film, protective plate>
The organic EL element may further include a protective film or a protective plate on the sealing material.

  The protective film or the protective plate mechanically protects the organic EL element body by sandwiching an organic EL element body (organic functional layer, various electrodes and wiring) and a sealing material between the protective film or the protective plate. In particular, when a sealing film is used as the sealing material, it is preferable that a protective film or a protective plate is provided because mechanical protection of the organic EL element body is not sufficient.

  As the protective film or protective plate, a glass plate, a polymer plate, a thin polymer film, a metal plate, a thin metal film, or a polymer material film or a metal material film is used. Among these, a polymer film is preferably used from the viewpoint of light weight and thinning of the element.

  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, "mass part" or "mass%" is represented.

Example 1
<< Preparation of the first coating liquids U-1 to U-5 for the underlayer (Y) >>
First coating liquids U-1 to U-5 used for the underlayer (Y) were prepared by the following procedure.

<Preparation of first coating liquid U-1>
The temperature was raised to 70 ° C. while stirring 230 parts by mass of distilled water. To the distilled water, 88 parts by mass of triisopropoxyaluminum was added dropwise over 1 hour, the liquid temperature was gradually raised to 95 ° C., and the generated isopropanol was distilled off to carry out hydrolysis and condensation. To the obtained liquid, 4.0 parts by mass of a 60% by mass aqueous nitric acid solution was added and stirred at 95 ° C. for 3 hours to flocculate the aggregates of hydrolyzed condensate particles. Thereafter, 2.24 parts by mass of an aqueous sodium hydroxide solution having a concentration of 1.0 mol% was added to the liquid, and the solid content concentration was concentrated to 10% by mass in terms of aluminum oxide. With respect to 18.66 parts by mass of the liquid thus obtained, 58.19 parts by mass of distilled water, 19.00 parts by mass of methanol, and 5% by mass of a polyvinyl alcohol aqueous solution (PVA124 manufactured by Kuraray Co., Ltd .; degree of saponification 98.5) (Mole%, viscosity average polymerization degree 2400, 4% by weight aqueous solution viscosity at 20 ° C. 60 mPa · s) 0.50 part by mass is added and stirred uniformly, and the dispersion is a liquid containing the metal oxide (A). A liquid was obtained. Subsequently, 3.66 parts by mass of 85 mass% phosphoric acid aqueous solution, which is a solution containing the phosphorus compound (B), was added dropwise while stirring the dispersion while maintaining the liquid temperature at 15 ° C., and the addition was completed. Stirring was continued for another 30 minutes later to obtain a first coating liquid U-1 having values of F _Z × N _Z / N _M = 0.0005 and N _M / N _P = 1.15.

<Preparation of first coating liquid U-2>
In the preparation of the first coating liquid U-1, changes the amount of 1.0 mol% aqueous solution of sodium _{hydroxide, F Z × N Z / N} M = 0.20, N M / N P = 1.15 A first coating solution U-2 was prepared in the same manner except that the first coating solution U-2 was prepared.

<Preparation of first coating liquid U-3>
In the preparation of the first coating liquid U-1, changes the amount of 1.0 mol% aqueous solution of sodium _{hydroxide, F Z × N Z / N} M = 0.62, N M / N P = 1.15 A first coating solution U-3 was prepared in the same manner except that it was prepared as follows.

<Preparation of first coating liquid U-4>
In the preparation of the first coating liquid U-1, changes the amount of 1.0 mole% of sodium hydroxide aqueous _{solution, F Z × N Z / N} M = 0.20, N M / N P = 5.50 A first coating solution U-4 was prepared in the same manner except that the first coating solution U-4 was prepared.

<Preparation of first coating liquid U-5>
In the preparation of the first coating liquid U-1, changes the amount of 1.0 mol% aqueous solution of sodium _{hydroxide, F Z × N Z / N} M = 0.20, N M / N P = 0.30 A first coating solution U-5 was prepared in the same manner except that it was prepared as follows.

<< Production of Organic EL Element 101 >>
<Preparation of gas barrier film 101>
(Preparation of base material)
A polyethylene terephthalate (PET) film with a double-sided easy-adhesion layer having a thickness of 125 μm (UH13, manufactured by Toray Industries, Inc.) was used as a substrate. However, a high refractive index easy-adhesion layer is provided on one side of the substrate, and the organic layer and the gas barrier layer are formed on the high refractive index easy-adhesion layer side.

(Formation of anchor layer)
100 parts by mass of a polymerizable compound (manufactured by Daicel Cytec, trimethylolpropane triacrylate (TMPTA)), a photopolymerization initiator (manufactured by BASF Japan, Irgacure 184), 3 parts by mass of the organosilicon compound a1 represented by the above chemical formula 1 And a polymerizable composition containing methyl ethyl ketone (MEK). The content of MEK was adjusted so that the dry layer thickness was 1 μm, and the content of the photopolymerization initiator was 3% by mass in the polymerizable composition. The prepared polymerizable composition was applied onto a substrate with a bar coater, dried, and cured by ultraviolet irradiation to form an anchor layer.

  The organosilicon compound a1 was synthesized in consideration of the method described in JP2009-67778A.

(Formation of gas barrier layer (X))
Using the resin base material on which the anchor layer was formed, a gas barrier layer (X) was formed on the anchor layer by the following method at a film thickness of 30 nm under the film forming conditions B1 described in Table 1 below.

  A type in which two apparatuses each having a film forming unit composed of opposing film forming rolls shown in FIG. 2 are connected (FIG. 3: a tandem CVD film forming apparatus having a first film forming unit and a second film forming unit. The reference numerals with “'” are the same as those in FIG. 2, respectively))). The effective film formation width is 1000 mm, and the film formation conditions are as follows: transfer 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, and applied power It was adjusted. The number of film formation (the number of passes of the apparatus) was 1 pass. As other conditions, the power supply frequency was 84 kHz, and the film forming roll temperatures were all 10 ° C. The film thickness was determined by cross-sectional TEM observation.

<Preparation of organic EL element 101>
(Formation of first transparent electrode)
On the gas barrier layer (X) of the formed gas barrier film 101, ITO (Indium Tin Oxide) having a thickness of 150 nm is formed by sputtering using a commercially available sputtering apparatus, and photo Patterning was performed by a lithography method to form a first transparent electrode. The pattern was such that the light emission area was 50 mm square.

(Formation of organic light emitting layer)
(Formation of hole transport layer)
On the first transparent electrode, the following coating solution for forming a hole transport layer is applied with a spin coater in an environment of 25 ° C. and a relative humidity of 50% RH, and then dried and heated under the following conditions. And a hole transport layer was formed. The coating solution for forming the hole transport layer was applied so that the thickness after drying was 50 nm.

<Preparation of hole transport layer forming coating solution>
A solution obtained by diluting polyethylene dioxythiophene / polystyrene sulfonate (PEDOT / PSS, Clevios P VP AI 4083 manufactured by Helios Co., Ltd.) with pure water at 65% and methanol at 5% was prepared as a coating solution for forming a hole transport layer.

<Drying and heat treatment conditions>
After applying the hole transport layer forming coating solution, the solvent is removed at a height of 100 mm toward the film formation surface, a discharge air velocity of 1 m / s, a wide air velocity distribution of 5%, and a temperature of 100 ° C., followed by heat treatment. The back surface heat transfer type heat treatment was performed at a temperature of 150 ° C. using an apparatus to form a hole transport layer.

(Formation of light emitting layer)
On the hole transport layer formed above, the following coating solution for forming a white light emitting layer was applied with a spin coater under the following conditions, followed by drying and heat treatment under the following conditions to form a light emitting layer. . The white light emitting layer forming coating solution was applied so that the thickness after drying was 40 nm.

<White luminescent layer forming coating solution>
As a host material, 1.0 g of a compound represented by the following chemical formula HA, 100 mg of a compound represented by the following chemical formula DA as a dopant material, and 0.1 mg of a compound represented by the following chemical formula DB as a dopant material. 2 mg of a compound represented by the following chemical formula DC as a dopant material was dissolved in 0.2 mg and 100 g of toluene to prepare a white light emitting layer forming coating solution.

<Application conditions>
The coating process was performed in an atmosphere having a nitrogen gas concentration of 99% or more and the coating temperature was 25 ° C.

<Drying and heat treatment conditions>
After applying the white light emitting layer forming coating solution, the solvent was removed at a height of 100 mm toward the film formation surface, a discharge wind speed of 1 m / s, a wide wind speed distribution of 5%, and a temperature of 60 ° C., and then a temperature of 130 ° C. A heat treatment was performed to form a light emitting layer.

(Formation of electron transport layer)
On the light emitting layer formed above, the following coating liquid for forming an electron transport layer was applied with a spin coater under the following conditions, and then dried and heated under the following conditions to form an electron transport layer. The coating solution for forming an electron transport layer was applied so that the thickness after drying was 30 nm.

<Application conditions>
The coating process was performed in an atmosphere with a nitrogen gas concentration of 99% or more, and the coating temperature of the electron transport layer forming coating solution was 25 ° C.

<Coating liquid for electron transport layer formation>
The electron transport layer was prepared by dissolving a compound represented by the following chemical formula EA in 2,2,3,3-tetrafluoro-1-propanol to obtain a 0.5 mass% solution as a coating liquid for forming an electron transport layer.

<Drying and heat treatment conditions>
After applying the electron transport layer forming coating solution, the solvent is removed at a height of 100 mm toward the film formation surface, a discharge wind speed of 1 m / s, a wide wind speed distribution of 5%, and a temperature of 60 ° C. Then, heat treatment was performed at a temperature of 200 ° C. to form an electron transport layer.

(Formation of electron injection layer)
An electron injection layer was formed on the electron transport layer formed above. First, the substrate was put into a vacuum chamber and the pressure was reduced to 5 × 10 ⁻⁴ Pa. In advance, cesium fluoride prepared in a tantalum vapor deposition boat was heated in a vacuum chamber to form an electron injection layer having a thickness of 3 nm.

(Formation of second electrode (reflection electrode))
Aluminum (Al) is used as the second electrode forming material on the electron injection layer formed as described above, except for the portion to be the extraction electrode of the first transparent electrode, under a vacuum of 5 × 10 ⁻⁴ Pa. A mask pattern was formed so as to have a light emitting area of 50 mm square by vapor deposition so as to have an extraction electrode, and a second electrode having a thickness of 150 nm was laminated.

(Cutting)
As described above, each laminate including the second electrode was moved again to a nitrogen atmosphere, and cut to a specified size using an ultraviolet laser to produce an organic EL element.

(Electrode lead connection)
An anisotropic conductive film DP3232S9 manufactured by Sony Chemical & Information Device Co., Ltd. was used for the produced organic EL element, and a flexible printed board (base film: polyimide 12.5 μm, rolled copper foil 18 μm, coverlay: polyimide 12.5 μm). , Surface-treated NiAu plating).

  Pressure bonding conditions: Pressure bonding was performed at a temperature of 170 ° C. (ACF temperature 140 ° C. measured using a separate thermocouple), a pressure of 2 MPa, and 10 seconds.

(Sealing)
The organic EL element 101 was produced using the following PET base material with a gas barrier layer as a transparent sealing base material. As the PET base material, a 125 μm thick PET film (manufactured by Teijin DuPont Films Ltd., Teijin Tetron Film (registered trademark) K) was used.

Adhesion of the transparent sealing substrate using the PET substrate with the gas barrier layer uses an epoxy thermosetting adhesive (Elephan CS manufactured by Yodogawa Paper Co., Ltd.) as an adhesive, an oxygen concentration of 10 ppm or less, and a moisture concentration of 10 ppm. In the following glove box, PET with the gas barrier layer is directed toward the organic EL element under the conditions of 80 ° C., 0.04 MPa load, reduced pressure (1 × 10 ⁻³ MPa or less) suction 20 seconds, press 20 seconds. It vacuum-pressed so that the gas barrier layer of a base material might become an element side.

  Thereafter, the adhesive layer was thermally cured by heating on a hot plate at 110 ° C. for 30 minutes in the glove box.

<PET substrate with gas barrier layer>
As a coating solution containing an inorganic precursor compound, a catalyst-free perhydropolysilazane 20 mass% dibutyl ether solution (AZ Electronic Materials Co., Ltd. Aquamica NN120-20) and an amine catalyst containing 5 mass% of a solid content. Hydroamine silazane 20% by mass dibutyl ether solution (AZ Electronic Materials Co., Ltd. Aquamica NAX120-20) is used by mixing, and after adjusting the amine catalyst to 1% by mass of solid content, it is further diluted with dibutyl ether. This was prepared as a 5% by mass dibutyl ether solution.

  After coating to a PET substrate so that the film thickness after drying was 300 nm, it was dried with infrared rays at a substrate temperature of 80 ° C., a drying time of 5 minutes, and a dew point of 5 ° C. in a dry atmosphere.

  After drying, the resin substrate was gradually cooled to 25 ° C., and the coating surface was subjected to a modification treatment by irradiation with vacuum ultraviolet rays in a vacuum ultraviolet irradiation apparatus. As a light source of the vacuum ultraviolet irradiation device, an Xe excimer lamp having a double tube structure for irradiating vacuum ultraviolet rays of 172 nm was used.

<Modification processing equipment>
Ex. Irradiator MODEL: MECL-M-1-200, light wavelength 172 nm, lamp filled gas Xe
<Reforming treatment conditions>
Excimer light intensity 3J / cm ² (172nm)
Stage heating temperature 100 ° C
Oxygen concentration in the irradiation device 1000ppm
<< Production of Organic EL Element 102 >>
In the production of the gas barrier film 101, the gas barrier film 102 was produced in the same manner except that the base layer (Y) was formed in the following procedure between the anchor layer and the gas barrier layer (X). Produced.

<Formation of Underlayer (Y)>
On the anchor layer formed on the resin base material, the first coating liquid U-1 is coated using a bar coater so that the thickness after drying is 0.5 μm, and the film after coating is coated at 100 ° C. The precursor layer of the foundation layer (Y) was formed by drying for 5 minutes. Subsequently, the base layer (Y) was formed by heat treatment at 180 ° C. for 1 minute.

Resin base material / anchor layer / base layer (Y) results of measurement of infrared absorption spectrum of the laminated resin film, the maximum absorption wave number in the region of 800～1400Cm ^-1 is 1107Cm ^-1, the maximum absorption band in the region The half width of was 37 cm ⁻¹ .

<< Production of Organic EL Element 103 >>
In the production of the gas barrier film 101, the gas barrier film 103 was produced in the same manner except that the base layer (Y) was formed on the anchor layer by the following procedure and the gas barrier layer (X) was not formed. An EL element 103 was produced.

<Formation of Underlayer (Y)>
On the anchor layer formed on the resin base material, the first coating liquid U-2 is coated using a bar coater so that the thickness after drying becomes 0.5 μm, and the film after coating is coated at 100 ° C. The precursor layer of the foundation layer (Y) was formed by drying for 5 minutes. Subsequently, the base layer (Y) was formed by heat treatment at 180 ° C. for 1 minute.

<< Production of organic EL elements 104 to 106 >>
In the production of the gas barrier film 101, the same procedure was performed except that the anchor layer was coated with the first coating liquids U-3, U-4, and U-5 in the following procedure to form the base layer (Y). The gas barrier films 104 to 106 shown in Table 2 were produced, and the organic EL elements 104 to 106 were produced.

<Formation of Underlayer (Y)>
On the anchor layer formed on the resin base material, the first coating liquids U-3, U-4 and U-5 are respectively coated using a bar coater so that the thickness after drying is 0.5 μm. The film after coating was dried at 100 ° C. for 5 minutes to form a precursor layer of the base layer (Y). Subsequently, the base layer (Y) was formed by heat treatment at 180 ° C. for 1 minute.

<< Production of Organic EL Element 107 >>
In the production of the gas barrier film 101, the gas barrier film 107 was similarly formed except that the underlayer (Y) was formed on the anchor layer by the following procedure, and further the gas barrier layer (X) was formed under the film formation condition B1. The organic EL element 107 was produced.

<Formation of Underlayer (Y)>
On the anchor layer formed on the resin base material, the first coating liquid U-2 is coated using a bar coater so that the thickness after drying becomes 0.5 μm, and the film after coating is coated at 100 ° C. The precursor layer of the foundation layer (Y) was formed by drying for 5 minutes. Subsequently, the base layer (Y) was formed by heat treatment at 180 ° C. for 1 minute.

<< Production of organic EL elements 108-110 >>
In the production of the gas barrier film 107, the gas barrier layer (X) is formed in the same manner except that the gas barrier layer (X) is formed under the film forming conditions B2, B3, and B4 instead of the film forming conditions B1. 110 was produced, and organic EL elements 108 to 110 were produced.

<< Production of Organic EL Elements 111-113 >>
In the production of the organic EL element 107, gas barrier films 111 to 113 were produced in the same manner except that the following base material was used instead of the resin base material (PET) used for the gas barrier film 107. 113 was produced.

Polyethylene naphthalate film (PEN): Thickness 125μm, Teonex Q83 manufactured by Teijin DuPont Films Ltd.
Cycloolefin polymer film (COP): Thickness 125 μm, Zeonore film manufactured by Nippon Zeon Co., Ltd. Polycarbonate film (PC): Thickness 125 μm, Teijin Pure Ace << Preparation of organic EL elements 114-118 >>
In the production of the organic EL element 107, as shown in Table 2, except that the resin base material type, the film formation conditions (B5 and B6) of the gas barrier layer (X), and the layer thickness of the gas barrier layer (X) were changed. Similarly, gas barrier films 114 to 118 were produced, and organic EL elements 114 to 118 were produced.

≪Evaluation≫
The following evaluation was implemented using the produced said organic EL elements 101-118.

[Dark spot (black spot) evaluation after curved high temperature and high humidity storage]
Each of the produced organic EL elements is wound around a semicircular roll having a diameter of 50 mm by applying a force so as to be in the shape of the roll, and wound in a curved shape, and is 100 in an environment of 85 ° C. and 85% RH. After performing the accelerated deterioration process for a time, dark spot evaluation was performed with each organic EL element which was not subjected to the accelerated deterioration process.

A current of 1 mA / cm ² was applied to the organic EL element subjected to the accelerated deterioration treatment and the organic EL element not subjected to the accelerated deterioration treatment to emit light continuously for 24 hours. ) A part of the panel was enlarged with Moritex MS-804 and lens MP-ZE25-200), and photographing was performed. The photographed image was cut out in 2 mm square, the area ratio of dark spots (black spots) was determined, the element deterioration resistance rate was calculated according to the following formula, and evaluated according to the following criteria. If it is 3 or more in the following criteria, it can be determined that there is no practical problem.

Element degradation tolerance ratio = (area of black spots generated in organic EL elements not subjected to accelerated degradation processing / area of black spots generated in organic EL elements subjected to accelerated degradation processing) × 100 (%)
5: Element deterioration resistance rate is 98% or more 4: Element deterioration resistance ratio is 90% or more and less than 98% 3: Element deterioration resistance ratio is 60% or more and less than 90% 2: Element Deterioration resistance ratio is 20% or more and less than 60% 1: Element deterioration resistance ratio is less than 20% Table 2 shows the configuration contents and evaluation results of the above organic EL elements.

  From Table 2, the gas barrier films 107 to 118 of the present invention are excellent in suppressing the generation of dark spots (black spots) after storage at high temperature and high humidity, and the electronic device including the gas barrier film is heated at a high temperature. It can be seen that it has an excellent effect in suppressing fine foaming generated at the boundary between the gas barrier layer and other constituent layers when stored under high humidity.

Example 2
The gas barrier layer (X) of the gas barrier film 107 produced in Example 1 is used as the first layer, and a commercially available oxygen-deficient niobium oxide target (composition is Nb ₁₂ O ₂₉ ) is used to form the first layer by the DC method. A gas barrier film 201 having a four-layer structure including an anchor layer and a base layer (Y) was formed on a resin base material by sputtering to form a second gas barrier layer.

The sputtering power supply power was 4.0 W / cm ² , the oxygen partial pressure was 12%, and the film formation time was set so that the layer thickness was 10 nm.

  About the formed gas barrier layer, the composition distribution profile of the thickness direction was measured by XPS analysis. The XPS analysis conditions are as follows.

<XPS analysis conditions>
・ Device: QUANTERA SXM manufactured by ULVAC-PHI
・ X-ray source: Monochromatic Al-Kα
・ Sputtering ion: Ar (2 keV)
Depth profile: Measurement was repeated at a predetermined thickness interval with a SiO ₂ equivalent sputtering thickness to obtain a depth profile in the depth direction. The thickness interval was 1 nm (data every 1 nm is obtained in the depth direction).

  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.

<Measurement of composite composition thickness>
From the data obtained from the XPS composition analysis, the composition of the gas barrier layer can be represented by (Si) (Nb) _x O _y N _z . In the interface region between the first layer and the second layer, Si as a non-transition metal and Nb as a transition metal coexist, and the value x of the atomic number ratio of the transition metal Nb / Si is 0.02 ≦ x A region in the range of ≦ 49 was defined as a “composite composition region”, and the presence / absence of the region and its thickness (nm) were measured. As a result, a composite composition region having a thickness of 8 nm was formed.

<Calculation of oxygen deficiency index in the composite composition region>
Using the XPS analysis data, a value of (2y + 3z) / (a + bx) at each measurement point was calculated. Here, since the non-transition metal is Si, a = 4, and since the transition metal is Nb, b = 5. When the minimum value of (2y + 3z) / (a + bx) was obtained and used as an oxygen deficiency index, (2y + 3z) / (a + bx) <1.0 was obtained, indicating an oxygen deficient state.

  Using the produced gas barrier films 107 and 201, gas barrier properties (water vapor permeability) evaluation by the following method, and using the gas barrier film as a base material, an organic EL device was produced in the same manner as in Example 1. Evaluation of dark spot (black spot) generation after curved high temperature and high humidity storage was carried out.

<Gas barrier properties>
As a method for measuring the water vapor permeability of the gas barrier film of the present invention, the following Ca method was used.

(Preparation of water vapor barrier property evaluation cell)
On the gas barrier layer surface of each gas barrier film sample, use a vacuum vapor deposition device (JEOL-made vacuum vapor deposition device JEE-400) to mask the gas barrier film sample except for the portion to be vapor-deposited (9 x 12 mm x 12 mm). Metallic calcium was deposited. Thereafter, the mask was removed in a vacuum state, and aluminum was deposited from another metal deposition source on the entire surface of one side of the sheet. After aluminum sealing, the vacuum state is released, and immediately facing the aluminum sealing side through a UV-curable resin for sealing (made by Nagase ChemteX) on quartz glass with a thickness of 0.2 mm in a dry nitrogen gas atmosphere The cell for evaluation was produced by irradiating with ultraviolet rays.

  The obtained sample with both sides sealed was stored at 60 ° C. and 90% RH under high temperature and high humidity, and permeated into the cell from the corrosion amount of metallic calcium based on the method described in JP-A-2005-283561. The amount of water was calculated.

  In addition, in order to confirm that there is no permeation of water vapor from other than the gas barrier film surface, a sample obtained by depositing metallic calcium using a quartz glass plate having a thickness of 0.2 mm instead of the gas barrier film sample as a comparative sample Was stored under the same high temperature and high humidity conditions of 60 ° C. and 90% RH, and it was confirmed that no corrosion of metallic calcium occurred even after 1000 hours.

  The permeated water amount of each gas barrier film measured as described above was evaluated.

(Devices and materials used)
Vapor deposition apparatus: Vacuum vapor deposition apparatus JEE-400 manufactured by JEOL Ltd.
Constant temperature and humidity oven: Yamato Humidic Chamber IG47M
Metal that reacts with water and corrodes: Calcium (granular)
Water vapor impermeable metal: Aluminum (3-5mmφ, granular)

  From the results shown in Table 3, the gas barrier film 201 showed a significantly high gas barrier property by forming a “composite composition region” of Si and Nb with respect to the gas barrier property of the gas barrier film 107. In addition, the organic EL device having the gas barrier film 201 as a base material reproduced an excellent effect in suppressing the occurrence of dark spots (black spots) after curved high temperature and high humidity storage, as in Example 1.

F gas barrier film 1 resin base material 2 ground layer (Y)
3 Gas barrier layer (X)
DESCRIPTION OF SYMBOLS S Film-forming part 1a Resin base material 1b, 1c, 1d, 1e Film-formed base material 10 Delivery roller 11, 12, 13, 14 Conveyance roller 15 1st film-forming roller 16 2nd film-forming roller 17 Winding roller 18 Gas supply pipe 19 Plasma generation power source 20, 21 Magnetic field generator 30 Vacuum chamber 40 Vacuum pump 41 Control unit 100 Film formation apparatus 101 Film formation apparatus (tandem)
200 Organic EL element 211 Resin base material 212 Underlayer (Y)
213 Gas barrier layer (X)
215 First electrode 216 Light emitting unit layer 217 Second electrode 221 Sealing member 222 Sealing layer

Claims (6)

A gas barrier film comprising a base layer (Y) laminated on a resin substrate and a gas barrier layer (X) in contact with the underlayer (Y),
The underlayer (Y) contains a metal oxide (A), a phosphorus compound (B), and a cation ( _Z ) having an ionic value (F _Z ) in the range of 1 to 3,
The phosphorus compound (B) is a compound having a site capable of reacting with the metal oxide (A), and in the base layer (Y), the metal atom (M) constituting the metal oxide (A) The number of moles (N _M ) and the number of moles of phosphorus atoms derived from the phosphorus compound (B) (N _P ) satisfy the relationship represented by the following relational expression (1), and
In the underlayer (Y), the number of moles (N _M ), the number of moles of the cation (Z) (N _Z ), and the ion valence (F _Z ) are expressed by the following relational expression (2). A gas barrier film characterized by satisfying the above relationship.
Relational expression (1) 0.8 ≦ N _M / N _P ≦ 4.5
Relational expression (2) 0.001 ≦ F _Z × N _Z / N _M ≦ 0.60 When the gas barrier layer (X) represents the average composition by SiO _x C _y (x and y are stoichiometric coefficients), the relationship represented by the following relational expression (3) and the following relational expression (4) The gas barrier film according to claim 1, wherein the gas barrier film satisfies the relationship represented by the formula (1) and has a layer thickness in the range of 15 to 50 nm.
Relational expression (3) 1.6 ≦ x ≦ 1.9, 0.15 ≦ y ≦ 0.40
Relational expression (4) 4.0 ≦ 2x + 2y <4.3 A method for producing a gas barrier film comprising forming at least an underlayer (Y) on a resin substrate and a gas barrier layer (X) in contact with the underlayer (Y),
The underlayer (Y) contains a metal oxide (A), a phosphorus compound (B), and a cation ( _Z ) having an ionic value (F _Z ) in the range of 1 to 3,
The phosphorus compound (B) is a compound having a site capable of reacting with the metal oxide (A), and in the base layer (Y), the metal atom (M) constituting the metal oxide (A) The number of moles (N _M ) and the number of moles of phosphorus atoms derived from the phosphorus compound (B) (N _P ) satisfy the relationship represented by the following relational expression (1), and
In the underlayer (Y), the number of moles (N _M ), the number of moles of the cation (Z) (N _Z ), and the ion valence (F _Z ) are expressed by the following relational expression (2). A method for producing a gas barrier film, which is adjusted so as to satisfy the above relationship.
Relational expression (1) 0.8 ≦ N _M / N _P ≦ 4.5
Relational expression (2) 0.001 ≦ F _Z × N _Z / N _M ≦ 0.60 When the average composition of the gas barrier layer (X) is represented by SiO _x C _y (x and y are stoichiometric coefficients), the relationship represented by the following relational expression (3) and the following relational expression (4) 4. The method for producing a gas barrier film according to claim 3, wherein the layer thickness is adjusted within a range of 15 to 50 nm.
Relational expression (3) 1.6 ≦ x ≦ 1.9, 0.15 ≦ y ≦ 0.40
Relational expression (4) 4.0 ≦ 2x + 2y <4.3   The said gas barrier layer (X) is formed by a vacuum plasma CVD method using a counter roller type roll to roll film-forming apparatus, The manufacturing of the gas barrier film of Claim 3 or Claim 4 characterized by the above-mentioned. Method.   An organic electroluminescence device comprising the gas barrier film according to claim 1.

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