WO2016010118A1

WO2016010118A1 - Gas barrier film and method for producing gas barrier film

Info

Publication number: WO2016010118A1
Application number: PCT/JP2015/070423
Authority: WO
Inventors: 晃矢子和地
Original assignee: コニカミノルタ株式会社
Priority date: 2014-07-16
Filing date: 2015-07-16
Publication date: 2016-01-21
Also published as: JPWO2016010118A1

Abstract

Provided is a gas barrier film with which a degradation in barrier performance due to a difference in degree of reforming is prevented even when a long body is produced. The present invention provides a gas barrier film that has, atop a resin substrate, a barrier layer including a silicon compound and metal atoms, wherein said barrier layer includes a region A of film thickness Th1 in which the ratio Si:M of the silicon element content Si to the metallic element content M is 1:x, where x ≥ 2, and a region B of film thickness Th2 in which the ratio Si:M of the silicon element content Si to the metallic element content M is 1:1-1:0.1, and Th1 and Th2 satisfy formulas (1) and (2): (1) Th1/Th2 ≥ 2, (2) 20 nm ≤ Th1 < 300 nm.

Description

Gas barrier film and method for producing gas barrier film

The present invention relates to a gas barrier film and a method for producing the gas barrier film. More specifically, the present invention relates to a gas barrier film with reduced barrier property deterioration and a method for producing the same.

In the fields of food, packaging materials, pharmaceuticals, etc., a gas barrier film that prevents the permeation of water vapor, oxygen, etc., which has been provided with a metal oxide deposition film or resin coating film on the surface of a resin film. It has been known. In recent years, in the field of electronic devices such as liquid crystal display elements (LCD), solar cells (PV), and organic electroluminescence (EL), resin base materials have been used for the purpose of providing lightness, resistance to cracking, and flexibility. There is a growing demand for gas barrier films. These electronic devices are required to have a higher level of water vapor gas barrier properties that can withstand even under high temperature and high humidity, depending on their usage.

As a method for producing such a gas barrier film, a gas barrier layer is mainly formed on a substrate such as a film by a plasma CVD method (chemical vapor deposition method) as a dry method. As a method for forming a gas barrier layer, a coating solution containing polysilazane as a main component is applied on a substrate, and then a surface treatment (modification treatment) is performed on the coating film. Unlike the dry method, the wet method does not require large-scale equipment, is not affected by the surface roughness of the base material, and cannot be pinholed. Therefore, it is attracting attention as a method for obtaining a uniform gas barrier film with good reproducibility. .

Conventionally known methods for modifying polysilazane include a plasma treatment method and a vacuum ultraviolet light irradiation method (for example, JP-A-8-281861, JP-A-2009-255040, and International Publication No. 2011). / 007543).

Japanese Patent Application Laid-Open No. 8-281186 discloses a gas barrier property comprising a silicon oxide layer having a thickness of 10 to 200 nm formed by plasma CVD and a silicon oxide layer having a thickness of 0.1 to 2 μm formed by converting polysilazane. A film is disclosed. However, the performance is not sufficient as a barrier film that requires high barrier properties such as when used for an organic EL substrate.

JP-A-2009-255040 describes that a flexible gas barrier film is produced by laminating a polysilazane film irradiated with a vacuum ultraviolet excimer lamp. The gas barrier film obtained by this method has no defects, has a smooth surface, does not easily crack, and has excellent gas barrier properties.

International Publication No. 2011/007543 describes that a gas barrier film is produced by irradiating a polysilazane film with plasma or ultraviolet light in an atmosphere substantially free of oxygen or water vapor. The gas barrier film obtained by this method is excellent in gas barrier properties such as water vapor gas barrier properties and oxygen gas barrier properties and scratch resistance.

However, in the conventional technology that uses the modified polysilazane film, there is a difference in the degree of modification of the polysilazane film in the longitudinal direction, particularly when the elongated body is used by being wound around a roll. Thus, it has been found that there is a problem of deteriorating the barrier performance. In addition, when placed in a high-temperature and high-humidity environment, cracks may occur in the gas barrier film and the barrier performance may deteriorate. Further, as a method for producing a gas barrier film using a coating method, a method with higher productivity has been required.

The present invention has been made in view of the above problems, and prevents the occurrence of a difference in the degree of modification of the polysilazane film even when a long body is formed, and further generates cracks under high temperature and high humidity. An object of the present invention is to provide a gas barrier film having excellent gas barrier performance capable of preventing the above. Furthermore, another object is to provide a production method capable of producing such a gas barrier film with high productivity.

The inventor of the present invention has made the present invention as a result of intensive studies to solve the above-mentioned problems. The above object of the present invention is achieved by the following means.

That is, the first aspect of the present invention has a barrier layer containing a silicon compound and a metal atom on a resin substrate,
The region A of the film thickness Th1 in which the ratio Si: M of the silicon element amount Si and the metal element amount M is 1: x and x ≧ 2,
A ratio B of silicon element amount Si and metal element amount M Si: M is 1: 1 to 1: 0.1, and region B of film thickness Th2 includes:
The Th1 and Th2 are the following formulas (1) and (2):
(1) Th1 / Th2 ≧ 2
(2) 20 nm ≦ Th1 <300 nm
It is a gas barrier film that satisfies the above.

The second aspect of the present invention is the first barrier layer precursor liquid containing a silicon compound precursor and a solvent having a solubility parameter of 15.5 to 20.0 on the resin substrate, the metal compound and the solubility parameter being A method for producing a gas barrier film, comprising a film forming step including applying a second barrier layer precursor liquid containing a solvent of 26.0 to 32.0.

It is sectional drawing which shows schematic structure of the gas barrier film of this invention. In FIG. 1, 10 represents a gas barrier film, 11 represents a (resin) substrate, 12 represents an inorganic barrier layer, 13 represents a barrier layer, 14 represents a region derived from the first barrier layer, 15 represents a region B, 16 represents a region A, 17 represents a region derived from the second barrier layer, 18 represents a first barrier layer, 19 represents a second barrier layer, and 20 represents a precursor film. Represents. It is a schematic diagram which shows an example of the manufacturing apparatus used for formation of the inorganic barrier layer which concerns on this invention. 2, 1 represents a gas barrier film, 2 represents a (resin) substrate, 3 represents an inorganic barrier layer, 31 represents a production apparatus, 32 represents a feed roller, 33, 34, 35, 36 represents a transport roller, 39 and 40 represent film forming rollers, 41 represents a gas supply pipe, 42 represents a plasma generation power source, 43 and 44 represent a magnetic field generator, and 45 represents a take-up roller. To express. It is a schematic diagram which shows an example of the other manufacturing apparatus (vacuum plasma CVD apparatus) used for formation of the inorganic barrier layer which concerns on this invention. 3, 101 represents a (vacuum) plasma CVD apparatus, 102 represents a vacuum chamber, 103 represents a cathode electrode, 105 represents a susceptor, 106 represents a heat medium circulation system, and 107 represents a vacuum exhaust system. 108 represents a gas introduction system, 109 represents a high-frequency power source, 110 represents a base material, and 160 represents a heating and cooling device.

Hereinafter, modes for carrying out the present invention will be described. First, features and elements of the gas barrier film of the present invention will be described, and then a method for producing the gas barrier film will be described.

[Gas barrier film]
The gas barrier film of the present invention has a barrier layer containing a silicon compound and a metal atom on a resin substrate, and the amount of silicon element and the amount of metal element satisfy the predetermined relationship described above.

According to the present invention, when the barrier layer includes a layer containing a metal atom that satisfies a specific thickness condition, it is possible to prevent the barrier property from being lowered due to a difference in the degree of modification of the polysilazane film. There is provided a gas barrier film capable of preventing the occurrence of cracks at high temperature and high humidity. In addition, according to the production method of the present invention, by using solvents having different solubility parameters for the coating solutions of the first barrier layer and the second barrier layer, respectively, the gas barrier property with higher productivity and superior barrier performance. A film can be produced. Moreover, the electronic device using the gas barrier film of the present invention can improve durability by using a film having high barrier performance.

FIG. 1 is a schematic cross-sectional view showing the structure of an example of the gas barrier film 10 of the present invention. The gas barrier film 10 of the present invention is obtained by modifying the precursor film 20. In the gas barrier film 10, a resin base material 11, an inorganic barrier layer 12, and a barrier layer 13 are laminated in this order. The precursor film 20 includes a resin base material 11, an inorganic barrier layer 12, a first barrier layer 18 that is a coating film containing a silicon compound precursor before modification, and a second barrier layer 19 that is a coating film containing a metal compound. They are stacked in this order. The barrier layer 13 of the gas barrier film 10 is configured by modifying the first barrier layer 18 and the second barrier layer 19 of the precursor film 20. The barrier layer 13 of the gas barrier film 10 is a film having a region 14 derived from the first barrier layer 18 and a ratio Si: M between the silicon element amount Si and the metal element amount M of 1: 1 to 1: 0.1. It is composed of a region B15 having a thickness Th2 and a region 17 derived from the second barrier layer. Further, the region 17 of the barrier layer 13 includes a region A16 having a thickness Th1 in which the ratio Si: M between the silicon element amount Si and the metal element amount M is 1: x and x ≧ 2. Hereinafter, the components of the gas barrier film 10 will be described.

<Resin substrate>
As the gas barrier film according to the present invention, a resin base material (plastic film or sheet) is usually used, and a film or sheet (resin base material) made of a colorless and transparent resin is preferably used as the base material. The resin substrate used is not particularly limited in material, thickness, and the like as long as it is a film that can hold a barrier layer, a hard coat layer, and the like, and can be appropriately selected according to the purpose of use. Specific examples of the resin substrate include polyester resin, methacrylic resin, methacrylic acid-maleic acid copolymer, polystyrene resin, transparent fluororesin, polyimide, fluorinated polyimide resin, polyamide resin, polyamideimide resin, and polyether. Imide resin, cellulose acylate resin, polyurethane resin, polyether ether ketone resin, polycarbonate resin, alicyclic polyolefin resin, polyarylate resin, polyether sulfone resin, polysulfone resin, cycloolefin copolymer, fluorene ring modified polycarbonate resin, fat Examples thereof include thermoplastic resins such as a ring-modified polycarbonate resin, a fluorene ring-modified polyester resin, and an acryloyl compound.

In the present invention, the substrates disclosed in paragraphs “0056” to “0075” of JP2012-116101A, paragraphs “0125” to “0131” of JP2013-226758A, etc. are also appropriately employed. Is done.

The thickness of the resin substrate used in the gas barrier film according to the present invention is not particularly limited because it is appropriately selected depending on the application, but is typically 1 to 800 μm, preferably 5 μm to 500 μm, more preferably. Is 25 to 250 μm. These resin base materials may have functional layers such as a transparent conductive layer and a primer layer. As the functional layer, those described in paragraph numbers “0036” to “0038” of JP-A-2006-289627 can be preferably used.

The substrate preferably has a high surface smoothness. As the surface smoothness, those having an average surface roughness (Ra) of 2 nm or less are preferable. Although there is no particular lower limit, it is practically 0.01 nm or more. If necessary, both surfaces of the substrate, at least the side on which the barrier layer is provided, may be polished to improve smoothness.

At least on the side of the substrate on which the gas barrier layer (inorganic barrier layer and second layer) according to the present invention is provided, various known treatments for improving adhesion, such as corona discharge treatment, flame treatment, oxidation treatment, or plasma. It is preferable to perform treatment, lamination of a primer layer, which will be described later, and more preferably to combine the above treatments as necessary.

Further, an anchor coat layer (easy adhesion layer) may be formed on the substrate. It is also possible to expect a higher adhesion by forming a thin film of monomolecular level to nano level like silane coupling agent and providing an anchor coat layer with a material capable of forming a molecular bond at the layer interface. It can be preferably used. In addition, a stress relaxation layer made of resin, etc., a smoothing layer for smoothing the surface of the resin base material, a bleed out prevention layer for preventing bleed out from the resin base material, etc. are additionally provided on the base material. Also good.

<Barrier layer>
The barrier layer of the present invention contains a silicon compound and a metal atom. In the barrier layer, the ratio Si: M between the silicon element amount Si and the metal element amount M is 1: x, and x ≧ 2, the region A of the film thickness Th1, and the silicon element amount Si and the metal element amount M And a region B having a thickness Th2 in which the ratio Si: M is 1: 1 to 1: 0.1. Furthermore, Th1 and Th2 are the following formulas (1) and (2):
(1) Th1 / Th2 ≧ 2
(2) 20 nm ≦ Th1 <300 nm
Meet.

In the gas barrier film of the present invention, the barrier layer is mainly derived from the first barrier layer before modification, the region mainly containing a silicon compound, and the second barrier layer, mainly a metal compound (compound containing a metal atom). And a region in which the first barrier layer and the second barrier layer in between are slightly mixed and the silicon compound and metal atoms are mixed. A region B where the ratio Si: M of the silicon element amount Si to the metal element amount M is 1: 1 to 1: 0.1 corresponds to a region where a silicon compound and metal atoms are mixed. The region A in which the ratio Si: M between the silicon element amount Si and the metal element amount M is 1: x and x ≧ 2 is included in a region mainly composed of a metal compound with a large amount of metal element. The film thickness Th1 in the region A is thicker than the film thickness Th2 in the region B, and Th1 and Th2 satisfy the formula (1) Th1 / Th2 ≧ 2. That is, the region A mainly composed of the metal compound has a thickness that is twice or more that of the region B mixed with the silicon compound, so to speak, it remains without being mixed with the lower layer. In other words, in the present invention, it is preferable that the mixed region has a smaller film thickness and the silicon compound and the metal atom are not mixed as much as possible. Furthermore, the film thickness Th1 of the region A satisfies the formula (2) 20 nm ≦ Th1 <300 nm. That is, the region A mainly composed of a metal compound is more than twice as large as the region B and remains with a certain substantial film thickness.

Thus, the region A mainly composed of the metal compound remains with a predetermined film thickness, so that the gas barrier film becomes an unmodified silicon compound precursor, particularly under high temperature and high humidity. The region A can absorb the distortion generated by the modification. Therefore, generation of cracks in the gas barrier film under high temperature and high humidity is prevented, and a gas barrier film with high gas barrier performance is obtained. The effect of preventing cracks is particularly remarkable when the thickness of the second barrier layer containing a silicon compound is thick.

Further, when producing a long gas barrier film, the region B is thinner, and the region A remains with a certain thickness, so that the above condition is satisfied. It was found that differences in the degree of modification of the compound precursor can be prevented. This is presumably because the low-molecular component of the silicon compound volatilizes during the modification, adheres to the reforming lamp, and the illuminance of the lamp decreases, resulting in a difference in the degree of modification over time. It is considered that the region A remaining at a predetermined thickness prevents volatilization and scattering of low molecular components of the silicon compound and suppresses a decrease in illuminance of the reforming lamp. As a result, the gas barrier film of the present invention is a film that exhibits excellent barrier performance over the entire elongated body.

Conventionally, for example, when a first barrier layer coating solution containing a silicon compound precursor and a second barrier layer coating solution containing a metal compound are applied simultaneously, two layers are formed before the barrier layer is modified. As a result of mixing, a portion containing a large amount of metal atoms did not remain in the thickness as in the region A. Further, in order to leave the layer containing the metal compound, the lower layer containing the silicon compound precursor had to be modified in advance. Therefore, it is considered that the low-molecular silicon compound was volatilized or scattered during the modification, resulting in a decrease in lamp illuminance and a difference in the degree of modification.

The ratio of Th1 and Th2 is more preferably 5.0 ≧ Th1 / Th2 ≧ 2.5, and further preferably 4.0 ≧ Th1 / Th2 ≧ 3.2. It is preferable that the ratio of Th1 and Th2 is in such a range because the desired effects of the present invention, prevention of cracking at high temperature and high humidity, and realization of uniform barrier performance by suppressing the difference in the degree of modification are higher. The film thickness of Th1 is 20 nm or more, preferably more than 20 nm, and more preferably 50 nm or more. Further, Th1 <300 nm, preferably Th1 ≦ 200 nm, and more preferably satisfies Th1 ≦ 100 nm. When Th1 is 20 nm or more, the effect of preventing the volatilization or scattering of the low-molecular silicon compound is more reliable, and when it is 200 nm or less, the flexibility of the gas barrier film is high.

In order to obtain Th1 and Th2, the XPS depth profile is measured, and the distribution of the Si element amount and the metal element amount is obtained. Based on this distribution, the thickness of the region B where Si: M is 1: 1 to 1: 0.1 and the region A where Si: M is 1: x and x ≧ 2 is calculated. As specific measurement conditions, the conditions described in Examples described later are used.

(Silicon compound)
The silicon compound forming the barrier layer has the following general formula (1):

In the general formula (1), R ¹ , R ² and R ³ each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, aryl group, vinyl group or (trialkoxysilyl) alkyl group. ,
It is preferable that it is obtained by modifying the silicon compound precursor having the structure represented by the following by irradiating with active energy rays.

As a silicon compound precursor, the silicon compound precursor which has a structure shown by the said General formula (1) is mentioned. The silicon compound of the general formula (1) is a polymer having a silicon-nitrogen (Si—N) bond in the structure, and has SiO ₂ , Si ₃ N having a bond such as Si—N, Si—H, or N—H. ₄ and their intermediate solid solution SiO _x N _{y and} other ceramic precursor inorganic polymers. In the present specification, the silicon compound precursor of the general formula (1) is also referred to as “polysilazane”. The silicon compound precursor having the structure represented by the general formula (1) may be used alone or two or more silicon compound precursors of the formula (1) may be included.

Here, examples of the alkyl group include linear, branched or cyclic alkyl groups having 1 to 8 carbon atoms. More specifically, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, neopentyl group, n -Hexyl group, n-heptyl group, n-octyl group, 2-ethylhexyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group and the like. Examples of the aryl group include aryl groups having 6 to 30 carbon atoms. More specifically, non-condensed hydrocarbon groups such as phenyl group, biphenyl group, terphenyl group; pentarenyl group, indenyl group, naphthyl group, azulenyl group, heptaenyl group, biphenylenyl group, fluorenyl group, acenaphthylenyl group, preadenenyl group , Condensed polycyclic hydrocarbon groups such as acenaphthenyl group, phenalenyl group, phenanthryl group, anthryl group, fluoranthenyl group, acephenanthrenyl group, aceantrirenyl group, triphenylenyl group, pyrenyl group, chrysenyl group, naphthacenyl group, etc. Can be mentioned. The (trialkoxysilyl) alkyl group includes an alkyl group having 1 to 8 carbon atoms having a silyl group substituted with an alkoxy group having 1 to 8 carbon atoms. More specific examples include 3- (triethoxysilyl) propyl group and 3- (trimethoxysilyl) propyl group. The substituent optionally present in R ¹ to R ³ is not particularly limited, and examples thereof include an alkyl group, a halogen atom, a hydroxyl group (—OH), a mercapto group (—SH), a cyano group (—CN), There are a sulfo group (—SO ₃ H), a carboxyl group (—COOH), a nitro group (—NO ₂ ) and the like. Note that the optionally present substituent is not the same as R ¹ to R ³ to be substituted. For example, when R ¹ to R ³ are alkyl groups, they are not further substituted with an alkyl group. Among these, R ¹ , R ² and R ³ are preferably a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a phenyl group, a vinyl group, 3 -(Triethoxysilyl) propyl group or 3- (trimethoxysilylpropyl) group. Perhydropolysilazane (PHPS) in which all of R ¹ , R ² and R ³ are hydrogen atoms is particularly preferred. A gas barrier layer (gas barrier film) formed from such polysilazane exhibits high density.

In the general formula (1), n is an integer representing the number of structural units of the formula: — [Si (R ¹ ) (R ² ) —N (R ³ )] —, and the general formula (1) It is preferable that the polysilazane having the structure represented by the formula is determined so as to have a number average molecular weight of 150 to 150,000 g / mol.

Perhydropolysilazane, in which all of R ¹ , R ² and R ³ are hydrogen atoms, is particularly preferred from the viewpoint of denseness as a gas barrier layer film. Perhydropolysilazane is presumed to have a linear structure and a ring structure centered on a 6-membered ring and an 8-membered ring. Its molecular weight is about 600 to 2000 in terms of number average molecular weight (Mn) (gel Polystyrene conversion by permeation chromatography), which is a liquid or solid substance. Polysilazane is commercially available in the form of a solution dissolved in an organic solvent, and a commercially available product can be used as it is as a polysilazane-containing coating solution. Examples of commercially available polysilazane solutions include AQUAMICA (registered trademark) NN120-10, NN120-20, NAX120-20, NN110, NN310, NN320, NL110A, NL120A, NL120-20, NL150A, and NP110 manufactured by AZ Electronic Materials Co., Ltd. NP140, SP140 and the like.

Examples of polysilazane used in the present invention are not particularly limited and include known ones. For example, those disclosed in paragraphs “0043” to “0058” of JP2013-022799A, paragraphs “0038” to “0056” of JP2013-226758A are appropriately adopted. Of these, perhydropolysilazane is most preferably used.

Other examples of polysilazane include, but are not limited to, for example, silicon alkoxide-added polysilazane obtained by reacting the above polysilazane with silicon alkoxide (Japanese Patent Laid-Open No. 5-238827), glycidol addition obtained by reacting glycidol Polysilazane (JP-A-6-122852), alcohol-added polysilazane obtained by reacting an alcohol (JP-A-6-240208), metal carboxylate-added polysilazane obtained by reacting a metal carboxylate 6-299118), acetylacetonate complex-added polysilazane obtained by reacting a metal-containing acetylacetonate complex (JP-A-6-306329), metal fine particle-added polysilazane obtained by adding metal fine particles (specialty) Kaihei 7- Publication), etc. No. 96986, include polysilazane ceramic at low temperatures.

(Silazane compound)
The silicon compound precursor for forming the barrier layer is not particularly limited as long as the coating liquid can be prepared. In addition to the polysilazane represented by the general formula (1), a silazane compound, an aminosilane compound, A silylacetamide compound, a silylimidazole compound, or the like is used.

Examples of silazane compounds preferably used in the present invention include dimethyldisilazane, trimethyldisilazane, tetramethyldisilazane, pentamethyldisilazane, hexamethyldisilazane, and 1,3-divinyl-1,1,3,3. -Examples include, but are not limited to, tetramethyldisilazane.

(Metal compound)
The metal compound is not particularly limited as long as it is a compound containing a metal atom.

(Metal atom)
The metal atom contained in the barrier layer of the present invention is not particularly limited as long as it has the above effects. Specifically, boron atom (B), aluminum atom (Al), titanium atom (Ti), zirconium atom (Zr), zinc atom (Zn), gallium atom (Ga), indium atom (In), chromium atom ( Cr), iron atom (Fe), magnesium atom (Mg), tin atom (Sn), nickel atom (Ni), palladium atom (Pd), lead atom (Pb), manganese atom (Mn), lithium atom (Li) , Germanium atoms (Ge), copper atoms (Cu), sodium atoms (Na), potassium atoms (K), calcium atoms (Ca), and cobalt atoms (Co). Among these, a boron atom (B), an aluminum atom (Al), a titanium atom (Ti), and a zirconium atom (Zr) are more preferable. The metal atoms may be used alone or in the form of a mixture of two or more. By containing these metal atoms, it is possible to further improve the effects of preventing volatilization and scattering of low-molecular silicon compounds and preventing cracking at high temperatures and high humidity.

Metal atoms are contained in the metal compound contained in the barrier layer. The metal compound is preferably a compound having a metal atom, an oxygen atom and a carbon atom. The metal compound may be contained singly or two or more metal compounds may be contained.

When the metal compound contains an oxygen (O) atom, it is possible to form a gas barrier layer having a high oxygen composition ratio with less dangling bonds when the silicon compound precursor is modified by irradiation with active energy rays. Here, the metal compound is not particularly limited as long as it has a metal atom, an oxygen atom, and a carbon atom. Specifically, an alkali metal alkoxide, the following general formula (2):

And metal compounds having a structural unit represented by The above metal compounds may be used alone or in the form of a mixture of two or more.

The alkali metal alkoxide is not particularly limited, but an alkali metal having an alkoxy group having 1 to 10 carbon atoms bonded to the alkali metal is preferable. Specific examples include sodium methoxide, sodium ethoxide, sodium propoxide, sodium isopropoxide, sodium butoxide, potassium methoxide, potassium ethoxide, potassium propoxide, potassium isopropoxide, potassium butoxide and the like.

Moreover, the metal compound which has a structural unit shown by the said General formula (2) can be used as a metal compound. In the general formula (2), M represents boron (B), aluminum (Al), titanium (Ti), zirconium (Zr), zinc (Zn), gallium (Ga), indium (In), chromium (Cr). , Iron (Fe), magnesium (Mg), tin (Sn), nickel (Ni), palladium (Pd), lead (Pb), manganese (Mn), lithium (Li), germanium (Ge), copper (Cu) , Sodium (Na), potassium (K), calcium (Ca), or cobalt (Co). Here, n is 2 or more ^{_{(i.e., - [M (R 4)}} m1] - there are a plurality) in case each ^{_{- [M (R 4) m1}} ] - M in the unit, respectively, It may be the same or different. Among these, M is preferably boron (B), aluminum (Al), titanium (Ti), or zirconium (Zr) from the viewpoints of VUV light transmittance, reactivity with polysilazane, and the like, and aluminum (Al), Titanium (Ti) and zirconium (Zr) are more preferable.

Y represents a single bond or an oxygen atom (—O—).

R ⁴ , R ^5, and R ⁶ are a hydrogen atom, a halogen atom, a cyano group (—CN), a nitro group (—NO ₂ ), a mercapto group (—SH), an epoxy group (a 3-membered ring ether oxacyclo Propyl group), a hydroxyl group (—OH), a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 2 to 10 carbon atoms, or Unsubstituted alkenyl group, substituted or unsubstituted alkynyl group having 2 to 10 carbon atoms, substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms, acetoacetate group (—O—C (CH ₃ ) ═CH —C (═O) —CH ₃ ), a substituted or unsubstituted (alkyl) acetoacetate group having 4 to 25 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, Alternatively, it represents an unsubstituted heterocyclic group or an amino group (—NH ₂ ). Here, R ⁴ , R ⁵ and R ⁶ may be the same or different. Also, n is 2 or more in the case of (i.e., - there are a plurality ^{_{- [M (R 4) m1}} ]), each ^{_{- [M (R 4) m1}} ] - R 4 in the units, respectively, It may be the same or different.

Here, the halogen atom may be a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.

The alkyl group having 1 to 10 carbon atoms is not particularly limited, but is a linear or branched alkyl group having 1 to 10 carbon atoms. For example, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group, hexyl group, heptyl group, octyl group, Nonyl group, decyl group, 2-ethylhexyl group and the like can be mentioned. Among these, from the viewpoints of VUV light permeability, film density, etc., linear or branched alkyl groups having 1 to 6 carbon atoms are preferred, and linear or branched alkyl groups having 1 to 5 carbon atoms. An alkyl group is more preferred.

The cycloalkyl group having 3 to 10 carbon atoms is not particularly limited, and examples thereof include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group.

The alkenyl group having 2 to 10 carbon atoms is not particularly limited, but is a linear or branched alkenyl group having 2 to 10 carbon atoms. For example, vinyl group, allyl group, 1-propenyl group, isopropenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, 1-pentenyl group, 2-pentenyl group, 3-pentenyl group, 1-hexenyl Group, 2-hexenyl group, 3-hexenyl group, 1-heptenyl group, 2-heptenyl group, 5-heptenyl group, 1-octenyl group, 3-octenyl group, 5-octenyl group and the like.

The alkynyl group having 2 to 10 carbon atoms is not particularly limited, but is a linear or branched alkynyl group having 2 to 10 carbon atoms. For example, acetylenyl group, 1-propynyl group, 2-propynyl group, 1-butynyl group, 2-butynyl group, 3-butynyl group, 1-pentethyl group, 2-pentethyl group, 3-pentethyl group, 1-hexynyl group, Examples include 2-hexynyl group, 3-hexynyl group, 1-heptynyl group, 2-heptynyl group, 5-heptynyl group, 1-octynyl group, 3-octynyl group, and 5-octynyl group.

The alkoxy group having 1 to 10 carbon atoms is not particularly limited, but is a linear or branched alkoxy group having 1 to 10 carbon atoms. For example, methoxy group, ethoxy group, propoxy group, isopropoxy group, n-butoxy group, sec-butoxy group, tert-butoxy group, pentyloxy group, hexyloxy group, 2-ethylhexyloxy group, octyloxy group, nonyloxy group And decyloxy group. Of these, a linear or branched alkoxy group having 1 to 8 carbon atoms is preferable from the viewpoint of VUV light permeability, reactivity with polysilazane, and film denseness, and has 1 to 5 carbon atoms. A linear or branched alkoxy group is preferred.

The (alkyl) acetoacetate group having 4 to 25 carbon atoms is not particularly limited, but represents a group in which a hydrogen atom or a linear or branched alkyl group having 1 to 6 carbon atoms is bonded to the acetoacetate group. For example, an acetoacetate group (—O—C (CH ₃ ) ═CH—C (═O) —OH), a methyl acetoacetate group (—O—C (CH ₃ ) ═CH—C (═O) —C— O—CH ₃ ), ethyl acetoacetate group (—O—C (CH ₃ ) ═CHC (═O) —C—O—C ₂ H ₅ ), propyl acetoacetate group, isopropyl acetoacetate group, octadecyl acetoacetate group Etc. Of these, ethyl acetoacetate group, methyl acetoacetate group, and acetoacetate group are preferable from the viewpoints of VUV light permeability and film density.

The aryl group having 6 to 30 carbon atoms is not particularly limited, and examples thereof include a phenyl group, a naphthyl group, a biphenyl group, a fluorenyl group, an anthryl group, a pyrenyl group, an azulenyl group, an acenaphthylenyl group, a terphenyl group, and a phenanthryl group. Is mentioned.

The heterocyclic group is not particularly limited, but thiophene ring, dithienothiophene ring, cyclopentadithiophene ring, phenylthiophene ring, diphenylthiophene ring, imidazole ring, oxazole ring, isoxazole ring, thiazole ring, pyrrole ring, furan Ring, benzofuran ring, isobenzofuran ring, coumarin ring (for example, 3,4-dihydrocoumarin), benzimidazole ring, benzoxazole ring, rhodanine ring, pyrazolone ring, imidazolone ring, pyran ring, pyridine ring, pyrazine ring, pyrazole ring , Pyrimidine ring, pyridazine ring, triazine ring, fluorene ring, benzothiophene ring, benzo (c) thiophene ring, benzimidazole ring, benzoxazole ring, benzoisoxazole ring, benzothiazole ring, indole ring, lid Gin ring, sinanoline ring, quinazoline ring, carbazole ring, carboline ring, diazacarboline ring (in which one of carbon atoms of carboline is replaced by nitrogen atom), 1,10-phenanthroline ring, quinone ring, rhodanine ring, Examples include a group derived from a dirhodanine ring, a thiohydantoin ring, a pyrazolone ring, and a pyrazoline ring.

Moreover, the substituent which exists depending on the case in R ⁴ , R ⁵ and R ⁶ is not particularly limited. Specifically, a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), a linear or branched alkyl group having 1 to 24 carbon atoms, a cycloalkyl group having 3 to 24 carbon atoms (for example, Cyclopentyl group, cyclohexyl group), hydroxyalkyl group having 1 to 24 carbon atoms (for example, hydroxymethyl group, hydroxyethyl group), alkoxyalkyl group having 2 to 24 carbon atoms (for example, methoxyethyl group), carbon atom An alkoxy group of 1 to 24 (for example, methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, pentyloxy group, hexyloxy group, 2-ethylhexyloxy group, octyloxy group, dodecyloxy group, etc.), A cycloalkoxy group having 3 to 24 carbon atoms (for example, cyclopentyloxy group, cyclohexane Siloxy group) alkenyl group, alkynyl group, amino group, aryl group, aryloxy group having 6 to 24 carbon atoms (for example, phenoxy group, naphthyloxy group), alkylthio group having 1 to 24 carbon atoms (for example, methylthio group) , Ethylthio group, propylthio group, pentylthio group, hexylthio group, octylthio group, dodecylthio group), cycloalkylthio group having 3 to 24 carbon atoms (eg, cyclopentylthio group, cyclohexylthio group), arylthio having 6 to 24 carbon atoms A group (eg, phenylthio group, naphthylthio group), an alkoxycarbonyl group having 1 to 24 carbon atoms (eg, methyloxycarbonyl group, ethyloxycarbonyl group, butyloxycarbonyl group, octyloxycarbonyl group, dodecyloxycarbonyl group), carbon Aryloxycarbonyl group having 7 to 24 members (eg, phenyloxycarbonyl group, naphthyloxycarbonyl group), hydroxyl group (—OH), carboxyl group (—COOH), thiol group (—SH), cyano group (—CN) Etc. In addition, since an alkyl group, an alkenyl group, an alkynyl group, an amino group, and an aryl group have the same definition as described above, a description thereof is omitted here. The number of substituents is not particularly limited, and can be appropriately selected in consideration of desired effects (VUV light permeability, solubility, reactivity with polysilazane, etc.). In the above, it is not substituted with the same substituent. That is, a substituted alkyl group is not substituted with an alkyl group.

Of these, at least one of R ⁴ , R ⁵ and R ⁶ preferably represents a hydroxyl group, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms. In the compound containing an alkoxy group or a hydroxyl group, the bond of the alkoxy group part or the hydroxyl group part is easily cleaved by VUV light, and the cleaved alkoxy group part or hydroxyl group part reacts quickly with polysilazane. Great reaction promotion effect. In addition, a compound containing an alkyl group can form a flexible film. Further, at least one of R ⁴ , R ⁵ and R ⁶ is an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms or an (alkyl) acetoacetate group having 4 to 25 carbon atoms. More preferably, it represents an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, and even more preferably represents an alkoxy group having 1 to 10 carbon atoms.

In the above general formula (2), m1 and m2 are integers of 1 or more, and m1 + m2 is an integer defined by M, and is uniquely defined by the number of M bonds. Here, m1 and m2 may be the same integer or different integers. n is an integer of 1 or more, and is preferably an integer of 1 to 10, more preferably 1 to 4, from the viewpoints of VUV light permeability, film density, and the like.

Examples of the metal compound represented by the general formula (2) include triisopropyl borate, aluminum isopropoxide, aluminum-sec-butyrate, titanium isopropoxide, aluminum triethylate, aluminum triisopropylate, aluminum tritert-butylate. , Aluminum tri-n-butylate, aluminum trisec-butyrate, aluminum ethyl acetoacetate diisopropylate, acetoalkoxyaluminum diisopropylate, calcium isopropylate, titanium tetraisopropoxide (titanium (IV) isopropylate), zirconium tetraacetyl Acetonate, aluminum diisopropylate monoaluminum t-butylate, aluminum trisethylacetoacetate Aluminum oxide isopropoxide trimer, zirconium (IV) isopropylate, tris (2,4-pentandionato) titanium (V), tetrakis (2,4-pentandionato) zirconium (IV), tris (2,4- Pentandionato) cobalt (III), tris (2,4-pentandionato) iron (III), bis (2,4-pentadionato) palladium (II), tris (2,4-pentandionato) iridium (III ), Tris (2,4-pentanedionato) aluminum (III), bis (2,4-pentanedionato) nickel (II), bis (2,4-pentandedionato) copper (II), bis (2 , 4-Pentandionato) Zinc (II), Tris (2,4-pentandionato) Manganese (III), Tris 2,4-pentanedionato) chromium (III), tris (2,4-pentandionato) indium (III), tris (2,4-pentandionato) calcium (III), magnesium ethoxide, sodium ethoxide Potassium ethoxide, trimethylgallium, di-n-butyldimethoxytin, tetraethyllead, manganese (III) acetylacetonate, diethyldiethoxygermane and the like.

Of these, from the viewpoint of VUV light transmission, etc., triisopropyl borate, aluminum ethyl acetoacetate diisopropylate, aluminum sec-butyrate, titanium isopropoxide, titanium tetraisopropoxide (titanium (IV) isopropylate) ) Are preferred, and triisopropyl borate, aluminum ethyl acetoacetate diisopropylate, and titanium tetraisopropoxide (titanium (IV) isopropylate) are more preferred. The metal compound may be synthesized or a commercially available product may be used.

<Inorganic barrier layer>
The gas barrier film of the present invention preferably further includes an inorganic barrier layer formed by a chemical vapor deposition (CVD) method between the resin base material and the barrier layer. By providing the inorganic barrier layer, it is possible to suppress / prevent moisture from entering the barrier layer from the resin substrate side, so that the gas barrier performance of the entire gas barrier film is further improved. Also, the modification (oxidation) reaction of the silicon compound precursor in the barrier layer can proceed slowly (at a slower rate) under low humidity conditions. For this reason, the softness | flexibility and bending resistance of a gas barrier film can also be improved.

By including an inorganic compound, the inorganic barrier layer has high density and further has gas barrier properties. When the gas barrier property of the inorganic barrier layer is calculated with a laminate in which the inorganic barrier layer is formed on the substrate, the water vapor permeability (WVTR) is preferably 0.1 g / (m ² · day) or less, More preferably, it is 0.01 g / (m ² · day) or less.

The inorganic barrier layer contains an inorganic compound. Here, the inorganic compound is not particularly limited, and examples thereof include metal oxides, metal nitrides, metal carbides, metal oxynitrides, and metal oxycarbides. Among these, oxides, nitrides, carbides, oxynitrides or oxycarbides containing one or more metals selected from Si, Al, In, Sn, Zn, Ti, Cu, Ce and Ta in terms of gas barrier performance Are preferably used, and an oxide, nitride or oxynitride of a metal selected from Si, Al, In, Sn, Zn and Ti is more preferable, and in particular, an oxide of at least one of Si and Al, Nitride or oxynitride is preferred. Specific examples of suitable inorganic compounds include composites such as silicon oxide, silicon nitride, silicon oxynitride, silicon carbide, silicon oxycarbide, aluminum oxide, titanium oxide, or aluminum silicate. You may contain another element as a secondary component.

The content of the inorganic compound contained in the inorganic barrier layer is not particularly limited, but is preferably 50% by mass or more, more preferably 80% by mass or more, and 95% by mass or more in the inorganic barrier layer. Is more preferably 98% by mass or more, and most preferably 100% by mass (that is, the inorganic barrier layer is made of an inorganic compound).

The film thickness per layer of the inorganic barrier layer is preferably 20 to 3000 nm, more preferably 50 to 2500 nm, and particularly preferably 30 to 1000 nm. With such a film thickness, the gas barrier film can exhibit excellent gas barrier properties and the effect of suppressing / preventing cracking during bending. In addition, when the inorganic barrier layer formed by said plasma CVD method is comprised from 2 or more layers, it is preferable that each inorganic barrier layer has a film thickness as mentioned above.

The inorganic barrier layer does not need to be formed on the surface of the resin base material. The base layer (smooth layer, primer layer), anchor coat layer (anchor layer), protective layer, hygroscopic layer and antistatic layer are not required between the resin base material. A functional layer or the like of the layer may be provided.

The formation method of the inorganic barrier layer is not limited to the chemical vapor deposition method (CVD method). A vacuum film-forming method such as a physical vapor deposition method (PVD method) or a method of forming a film by modifying a coating film formed by applying a liquid containing an inorganic compound, preferably a liquid containing a silicon compound ( Hereinafter, it is also simply referred to as a coating method). Of these, physical vapor deposition or chemical vapor deposition is more preferred, and chemical vapor deposition is particularly preferred.

(Smooth layer (underlayer, primer layer))
The gas barrier film of the present invention may have a smooth layer between the substrate and the barrier layer. The smooth layer used in the present invention flattens the rough surface of the transparent resin film support with protrusions or the like, or fills the irregularities and pinholes generated in the transparent inorganic compound layer with the protrusions present on the transparent resin film support. Provided for flattening. The materials, methods, etc. disclosed in paragraphs “0233” to “0248” of JP2013-52561A are appropriately employed as the constituent material, forming method, surface roughness, film thickness, etc. of the smooth layer.

(Anchor coat layer (anchor layer))
On the surface of the substrate according to the present invention, an anchor coat layer (anchor layer) may be formed as an easy adhesion layer for the purpose of improving adhesiveness (adhesion). Examples of the anchor coating agent used in this anchor coat layer include polyester resin, isocyanate resin, urethane resin, acrylic resin, ethylene vinyl alcohol resin, vinyl modified resin, epoxy resin, modified styrene resin, modified silicon resin, and alkyl titanate. One type or two or more types can be used in combination. A commercially available product may be used as the anchor coating agent. Specifically, siloxane-based UV curable polymer solution (manufactured by Shin-Etsu Chemical Co., Ltd., 3% isopropyl alcohol solution of “X-12-2400”), UV curable organic / inorganic hybrid hard coat material (manufactured by JSR Corporation) OPSTARZ7501) or the like can be used.

Conventionally known additives can be added to these anchor coating agents. Then, the above-mentioned anchor coating agent is coated on a substrate by a known method such as roll coating, gravure coating, knife coating, dip coating, spray coating, etc., and is coated by drying and removing the solvent, diluent, etc. Can do. The application amount of the anchor coating agent is preferably about 0.1 to 5 g / m ² (dry state). A commercially available base material with an easy-adhesion layer may be used.

Alternatively, the anchor coat layer can be formed by a vapor phase method such as physical vapor deposition or chemical vapor deposition. For example, as described in JP-A-2008-142941, an inorganic film mainly composed of silicon oxide can be formed for the purpose of improving adhesion and the like.

The thickness of the anchor coat layer is not particularly limited, but is preferably about 0.5 to 10.0 μm.

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

The bleed-out prevention layer is for the purpose of suppressing the phenomenon that, when a film having a smooth layer is heated, unreacted oligomers etc. migrate from the film having the smooth layer to the surface and contaminate the contact surface. , Provided on the opposite surface of the substrate having a smooth layer. The bleed-out prevention layer may basically have the same configuration as the smooth layer as long as it has this function.

The material, method, and the like disclosed in paragraphs “0249” to “0262” of JP2013-52561A are appropriately employed as the constituent material, formation method, film thickness, and the like of the bleedout prevention layer.

(Middle layer)
In the present invention, when two or more barrier layers are laminated, an intermediate layer may be formed between each barrier layer or between the barrier layer and the substrate. In the present invention, a method of forming a polysiloxane modified layer can be applied as a method of forming the intermediate layer. In this method, a coating solution containing polysiloxane is applied onto the barrier layer by a wet coating method and dried, and then the dried coating film is irradiated with vacuum ultraviolet light to form a polysiloxane modified layer. It is a method of forming.

The coating solution used for forming the intermediate layer in the present invention mainly contains polysiloxane and an organic solvent. As specific forms of the constituent material and forming method of the intermediate layer, for example, the materials and methods disclosed in paragraphs “0161” to “0185” of JP-A-2014-046272 can be appropriately employed.

(Protective layer)
In the gas barrier film according to the present invention, a protective layer containing an organic compound may be provided on the barrier layer. As the organic compound used in the protective layer, an organic resin such as an organic monomer, oligomer or polymer, or an organic-inorganic composite resin layer using a siloxane or silsesquioxane monomer, oligomer or polymer having an organic group is preferably used. Can do.

[Method for producing gas barrier film]
In the method for producing a gas barrier film of the present invention, a first barrier layer precursor liquid containing a silicon compound precursor and a solvent having a solubility parameter of 15.5 to 20.0 on a resin substrate, a metal compound and a solubility parameter are provided. A film forming process including applying a second barrier layer precursor liquid containing a solvent of 26.0 to 32.0. In the present invention, by appropriately controlling the solvent (solubility parameter), the coating method, the thickness of the coating film, etc., the above-mentioned Th1 and Th2 satisfy the relationship of the above formulas (1) and (2) The gas barrier film of the present invention having the following can be achieved.

As an embodiment, after the first barrier layer precursor liquid is applied and the first barrier layer is formed, the second barrier layer precursor liquid is applied and the second barrier layer is formed. . That is, the film forming step includes applying a first barrier layer precursor liquid including a silicon compound precursor and a solvent having a solubility parameter of 15.5 to 20.0 on a resin substrate. A first film-forming step to be formed, and a second film-forming to form a second barrier layer, comprising applying a second barrier layer precursor liquid containing a metal compound and a solvent having a solubility parameter of 26.0 to 32.0 You may have a process. As another embodiment, in the film forming step, the first barrier layer precursor liquid and the second barrier layer precursor liquid are applied by a simultaneous multilayer coating method, and the first barrier layer and the second barrier layer are formed simultaneously. May be.

The solubility parameter (SP value) is a value defined by the regular solution theory introduced by Hildebrand, and is used as an indicator of the solubility and compatibility of solvents and organic compounds. When the solubility parameters of the two types of solvents are the same, the solvents are likely to be mixed, and when the solubility parameters are different from each other, the solvents are difficult to mix. The solubility parameter can be determined by a known method from the structure and physical properties of the chemical substance.

Here, the first barrier layer refers to a coating film formed by applying a first barrier layer precursor liquid, and the second barrier layer refers to a coating film formed by applying a second barrier layer precursor liquid. Say. The first barrier layer and the second barrier layer are slightly mixed at the interface during the modification. Therefore, the barrier layer of the gas barrier film of the present invention includes a part mainly containing a silicon compound derived from the first barrier layer, a part mainly containing a metal compound derived from the second barrier layer, and a first barrier layer therebetween. It is comprised with the part which the 2nd barrier layer mixed.

As shown in the above formulas (1) and (2), in the gas barrier film of the present invention, the region A containing a large amount of metal atoms remains in a predetermined thickness, and the region B in which the silicon compound and the metal atoms are mixed. However, it exists in a thinner film thickness that satisfies the predetermined relationship. It is preferable that the silicon compound and the metal atom are not mixed as much as possible. Therefore, in the production method of the present invention, the first barrier layer precursor liquid containing the silicon compound precursor and the second barrier layer precursor liquid containing the metal compound are difficult to mix with each other. That is, solvents having different solubility parameters are used for the first barrier layer precursor liquid and the second barrier layer precursor liquid, respectively. More specifically, a solvent having a solubility parameter of 15.5 to 20.0 is used for the first barrier layer precursor liquid, and a solubility parameter of 26.0 to 32.0 is used for the second barrier layer precursor liquid. Use a solvent. By using each of the solvents having the solubility parameter range, the region A containing the metal atoms derived from the second barrier layer can be left in a predetermined thickness, and the first barrier layer and the second barrier layer The mixing area can be made thinner. By the presence of the layer containing such a metal compound, it is possible to prevent the low-molecular silicon compound from being volatilized or scattered during the reforming and adhering to the reforming lamp. Therefore, even when producing a long gas barrier film, a reduction in lamp illuminance is prevented, there is no difference in the degree of modification, and a gas barrier film having a uniform and excellent barrier performance is provided.

In addition, according to the present invention, the first barrier layer precursor liquid and the second barrier layer precursor liquid each use a solvent having different solubility parameters, so that the first barrier layer and the second barrier layer precursor liquid It can prevent mixing with a 2nd barrier layer more than predetermined amount. Therefore, the manufacturing process is simpler and shorter than the conventional method of forming the second barrier layer after modifying the first barrier layer, and the productivity is improved. Even in the case of the sequential coating method, there is no need for modification for each film formation, and drying can be completed in a short time, so that an effect of improving productivity can be obtained.

Further, the difference between the solubility parameter of the solvent contained in the first barrier layer precursor liquid and the solubility parameter of the solvent contained in the second barrier layer precursor liquid is more preferably 7.5 to 17.5, It is preferably 11 to 17.5. When the difference in solubility parameter is 7.5 to 17.5, the desired effect of the present invention is to prevent the generation of cracks under high temperature and high humidity, and to achieve uniform barrier performance by preventing the difference in the degree of modification. The effect of improving productivity and productivity is higher. If the solubility parameter difference is 11 or more, the first barrier layer is reliably formed, and if the solubility parameter difference is 17.5 or less, the second barrier layer reliably remains at a predetermined thickness, and the film is formed. Is done. In particular, when the first barrier layer and the second barrier layer are formed by simultaneous multilayer coating, if the difference in solubility parameter is 11 or more, the above Th1 and Th2 are related to the above formulas (1) and (2). A barrier layer that satisfies the above can be obtained more efficiently.

<Inorganic barrier layer deposition process>
The method for producing a gas barrier film of the present invention preferably further includes an inorganic barrier layer film forming step of forming an inorganic barrier layer on the resin substrate by a chemical vapor deposition (CVD) method before the film forming step. Have. The method for forming the inorganic barrier layer is not particularly limited, but a vacuum film formation method such as physical vapor deposition (PVD method) or chemical vapor deposition (CVD), or a liquid containing an inorganic compound, preferably a silicon compound And a method of reforming and forming a coating film formed by applying a liquid containing a liquid (hereinafter also simply referred to as a coating method). Of these, physical vapor deposition or chemical vapor deposition is more preferred, and chemical vapor deposition is particularly preferred. That is, the inorganic barrier layer is preferably formed by a chemical vapor deposition (CVD) method. Hereinafter, the vacuum film forming method will be described.

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

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

The inorganic barrier layer obtained by the vacuum plasma CVD method, or the plasma CVD method under atmospheric pressure or a pressure near atmospheric pressure, has conditions such as the metal compound (decomposition material), decomposition gas, decomposition temperature, and input power as raw materials. This is preferable because the desired compound can be produced.

For example, if a silicon compound is used as a raw material compound and oxygen is used as a 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.

As a raw material compound, it is preferable to use a silicon compound, a titanium compound, and an aluminum compound. These raw material compounds can be used alone or in combination of two or more.

Among these, as silicon compounds, silane, tetramethoxysilane, tetraethoxysilane, tetra n-propoxysilane, tetraisopropoxysilane, tetra n-butoxysilane, tetra t-butoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, Diethyldimethoxysilane, diphenyldimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, phenyltriethoxysilane, (3,3,3-trifluoropropyl) trimethoxysilane, hexamethyldisiloxane (HMDSO), bis (dimethylamino) ) Dimethylsilane, bis (dimethylamino) methylvinylsilane, bis (ethylamino) dimethylsilane, N, O-bis (trimethylsilyl) acetamide, bis (trimethylsilyl) carbonate Bodiimide, diethylaminotrimethylsilane, dimethylaminodimethylsilane, hexamethyldisilazane, hexamethylcyclotrisilazane, heptamethyldisilazane, nonamethyltrisilazane, octamethylcyclotetrasilazane, tetrakisdimethylaminosilane, tetraisocyanatosilane, tetramethyldi Silazane, 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, phenyltri Tylsilane, propargyltrimethylsilane, tetramethylsilane, trimethylsilylacetylene, 1- (trimethylsilyl) -1-propyne, tris (trimethylsilyl) methane, tris (trimethylsilyl) silane, vinyltrimethylsilane, hexamethyldisilane, octamethylcyclotetrasiloxane, tetra Examples include methylcyclotetrasiloxane, hexamethylcyclotetrasiloxane, and M silicate 51. In addition, a silicon compound that is a raw material compound used in the formation of a barrier layer that satisfies the requirements (i) to (iii), which are preferred forms described later, can be used.

Examples of titanium compounds include titanium methoxide, titanium ethoxide, titanium isopropoxide, titanium tetraisopropoxide, titanium n-butoxide, titanium diisopropoxide (bis-2,4-pentanedionate), titanium dioxide. Examples thereof include isopropoxide (bis-2,4-ethylacetoacetate), titanium di-n-butoxide (bis-2,4-pentanedionate), titanium acetylacetonate, and butyl titanate dimer.

Examples of the aluminum compound include aluminum ethoxide, aluminum triisopropoxide, aluminum isopropoxide, aluminum n-butoxide, aluminum s-butoxide, aluminum t-butoxide, aluminum acetylacetonate, triethyldialuminum tri-s-butoxide, and the like. Can be mentioned.

In addition, as a decomposition gas for decomposing a raw material gas containing these metals to obtain an inorganic compound, hydrogen gas, methane gas, acetylene gas, carbon monoxide gas, carbon dioxide gas, nitrogen gas, ammonia gas, nitrous oxide Examples include gas, nitrogen oxide gas, nitrogen dioxide gas, oxygen gas, and water vapor. Further, the decomposition gas may be mixed with an inert gas such as argon gas or helium gas.

A desired inorganic barrier layer can be obtained by appropriately selecting a source gas containing a source compound and a decomposition gas. The inorganic barrier layer formed by the CVD method is preferably a layer containing oxide, nitride, oxynitride, or oxycarbide.

Hereinafter, the vacuum plasma CVD method, which is a preferred form among the CVD methods, will be described in detail.

FIG. 3 is a schematic view showing an example of a vacuum plasma CVD apparatus used for forming the inorganic barrier layer according to the present invention.

3, the vacuum plasma CVD apparatus 101 has a vacuum chamber 102, and a susceptor 105 is disposed on the bottom surface inside the vacuum chamber 102. A base material 110 to be deposited is placed on the susceptor 105. Further, a cathode electrode 103 is disposed on the ceiling side inside the vacuum chamber 102 at a position facing the susceptor 105. A heat medium circulation system 106, a vacuum exhaust system 107, a gas introduction system 108, and a high-frequency power source 109 are disposed outside the vacuum chamber 102. A heat medium is disposed in the heat medium circulation system 106. The heat medium circulation system 106 stores a pump for moving the heat medium, a heating device for heating the heat medium, a cooling device for cooling, a temperature sensor for measuring the temperature of the heat medium, and a set temperature of the heat medium. A heating / cooling device 160 having a storage device is provided.

As a preferred embodiment of the inorganic barrier layer formed by the CVD method according to the present invention, the inorganic barrier layer preferably contains carbon, silicon, and oxygen as constituent elements. A more preferable form is a layer that satisfies the following requirements (i) to (iii).

(I) the distance (L) from the surface of the inorganic barrier layer in the film thickness direction of the inorganic barrier layer, and the ratio of the amount of silicon atoms to the total amount of silicon atoms, oxygen atoms, and carbon atoms (atom ratio of silicon) The silicon distribution curve showing the relationship of L, the oxygen distribution curve showing the relationship between the L and the ratio of the amount of oxygen atoms to the total amount of silicon atoms, oxygen atoms and carbon atoms (atomic ratio of oxygen), and the L and silicon In a carbon distribution curve showing a relationship with the ratio of the amount of carbon atoms to the total amount of atoms, oxygen atoms, and carbon atoms (carbon atomic ratio), 90% or more of the film thickness of the inorganic barrier layer (upper limit: 100% ) In the order of (atomic ratio of oxygen), (atomic ratio of silicon), (atomic ratio of carbon) (atomic ratio is O>Si>C);
(Ii) the carbon distribution curve has at least two extreme values;
(Iii) The absolute value of the difference between the maximum value and the minimum value of the carbon atomic ratio in the carbon distribution curve (hereinafter also simply referred to as “C _max −C _min difference”) is 3 at% or more.

Hereinafter, the requirements (i) to (iii) will be described.

The inorganic barrier layer is (i) the distance (L) from the surface of the inorganic barrier layer in the film thickness direction of the inorganic barrier layer, and the ratio of the amount of silicon atoms to the total amount of silicon atoms, oxygen atoms, and carbon atoms. The silicon distribution curve showing the relationship with (atom ratio of silicon), the oxygen distribution showing the relationship between the L and the ratio of the amount of oxygen atoms to the total amount of silicon atoms, oxygen atoms and carbon atoms (oxygen atomic ratio) In the carbon distribution curve showing the relationship between the curve and the ratio of the amount of carbon atoms to the total amount of L and silicon atoms, oxygen atoms, and carbon atoms (the atomic ratio of carbon), the thickness of the inorganic barrier layer is 90%. % (Upper limit: 100%) in the order of (atomic ratio of oxygen), (atomic ratio of silicon), and (atomic ratio of carbon) (atomic ratio is preferably O> Si> C). When the above condition (i) is satisfied, the gas barrier property and flexibility of the obtained gas barrier film can be improved. Here, in the carbon distribution curve, the relationship of the above (atomic ratio of oxygen), (atomic ratio of silicon) and (atomic ratio of carbon) is at least 90% or more of the film thickness of the inorganic barrier layer (upper limit: 100 %), More preferably at least 93% or more (upper limit: 100%). Here, at least 90% or more of the film thickness of the inorganic barrier layer does not have to be continuous in the inorganic barrier layer, and only needs to satisfy the above-described relationship at 90% or more.

In the inorganic barrier layer, it is preferable that (ii) the carbon distribution curve has at least two extreme values. The inorganic barrier layer preferably has at least three extreme values in the carbon distribution curve, more preferably has at least four extreme values, but may have five or more extreme values. When the extreme value of the carbon distribution curve is two or more, the gas barrier property when the obtained gas barrier film is bent can be improved. Although the upper limit of the extreme value of the carbon distribution curve is not particularly limited, for example, it is preferably 30 or less, more preferably 25 or less, but the number of extreme values is also caused by the film thickness of the inorganic barrier layer. It cannot be stipulated in general.

Here, in the case of having at least three extreme values, from the surface of the inorganic barrier layer in the film thickness direction of the inorganic barrier layer at one extreme value that the carbon distribution curve has and the extreme value adjacent to the extreme value. The absolute value of the difference in distance (L) (hereinafter also simply referred to as “distance between extreme values”) is preferably 200 nm or less, more preferably 100 nm or less, and 75 nm or less. Is particularly preferred. If the distance is between such extreme values, the inorganic barrier layer has a portion having a large carbon atom ratio (maximum value) at an appropriate period, so that the inorganic barrier layer is provided with appropriate flexibility and gas barrier properties. Generation of cracks when the film is bent can be more effectively suppressed / prevented. In the present specification, the “extreme value” refers to the maximum value or the minimum value of the atomic ratio of the element to the distance (L) from the surface of the inorganic barrier layer in the film thickness direction of the inorganic barrier layer. Further, in this specification, the “maximum value” means that the value of the atomic ratio of an element (oxygen, silicon or carbon) changes from increasing to decreasing when the distance from the surface of the inorganic barrier layer is changed. And the atomic ratio of the element at a position where the distance from the surface of the inorganic barrier layer in the film thickness direction of the inorganic barrier layer is further changed within the range of 4 to 20 nm from the value of the atomic ratio of the element at that point. This is the point at which the value decreases by 3 at% or more. That is, it is sufficient that the atomic ratio value of the element is reduced by 3 at% or more in any range when changing in the range of 4 to 20 nm. Similarly, in this specification, “minimum value” means that the value of the atomic ratio of an element (oxygen, silicon, or carbon) changes from decrease to increase when the distance from the surface of the inorganic barrier layer is changed. And the atom of the element at a position where the distance from the surface of the inorganic barrier layer in the film thickness direction of the inorganic barrier layer is further changed within the range of 4 to 20 nm from the value of the atomic ratio of the element at that point. This is the point where the ratio value increases by 3 at% or more. That is, when changing in the range of 4 to 20 nm, the atomic ratio value of the element only needs to increase by 3 at% or more in any range. Here, the lower limit of the distance between the extreme values in the case of having at least three extreme values is particularly high because the smaller the distance between the extreme values, the higher the effect of suppressing / preventing crack generation when the gas barrier film is bent. Although not limited, it is preferably 10 nm or more, more preferably 30 nm or more in consideration of the flexibility of the inorganic barrier layer, the effect of suppressing / preventing cracks, thermal expansion, and the like.

Further, the inorganic barrier layer has (iii) an absolute value of a difference between a maximum value and a minimum value of the atomic ratio of carbon in the carbon distribution curve (hereinafter, also simply referred to as “C _max −C _min difference”) of 3 at% or more. It is preferable that When the absolute value is 3 at% or more, the gas barrier property when the obtained gas barrier film is bent can be improved. The C _max −C _min difference is more preferably 5 at% or more, further preferably 7 at% or more, and particularly preferably 10 at% or more. By setting the C _max −C _min difference, the gas barrier property can be further improved. In the present specification, the “maximum value” is the atomic ratio of each element that is maximum in the distribution curve of each element, and is the highest value among the maximum values. Similarly, in this specification, the “minimum value” is the atomic ratio of each element that is the minimum in the distribution curve of each element, and is the lowest value among the minimum values. Here, the upper limit of the C _max -C _min difference is not particularly limited, but it is preferably 50 at% or less in consideration of the effect of suppressing / preventing crack generation during bending of the gas barrier film, and is preferably 40 at% or less. It is more preferable that

In the present invention, the oxygen distribution curve of the inorganic barrier layer preferably has at least one extreme value, more preferably has at least two extreme values, and more preferably has at least three extreme values. When the oxygen distribution curve has at least one extreme value, the gas barrier property when the obtained gas barrier film is bent is further improved as compared with a gas barrier film having no extreme value. The upper limit of the extreme value of the oxygen distribution curve is not particularly limited, but is preferably 20 or less, more preferably 10 or less, for example. Even in the number of extreme values of the oxygen distribution curve, there is a portion caused by the film thickness of the inorganic barrier layer, and it cannot be specified unconditionally. In the case of having at least three extreme values, the distance from the surface of the inorganic barrier layer in the film thickness direction of the inorganic barrier layer at one extreme value of the oxygen distribution curve and the extreme value adjacent to the extreme value The absolute value of the difference is preferably 200 nm or less, and more preferably 100 nm or less. With such a distance between extreme values, the occurrence of cracks during bending of the gas barrier film can be more effectively suppressed / prevented. Here, the lower limit of the distance between the extreme values in the case of having at least three extreme values is not particularly limited, but considering the improvement effect of crack generation suppression / prevention when the gas barrier film is bent, the thermal expansion property, etc. The thickness is preferably 10 nm or more, and more preferably 30 nm or more.

In addition, the absolute value of the difference between the maximum value and the minimum value of the atomic ratio of oxygen in the oxygen distribution curve of the inorganic barrier layer (hereinafter also simply referred to as “O _max −O _min difference”) is 3 at% or more. Is preferably 6 at% or more, and more preferably 7 at% or more. When the absolute value is 3 at% or more, the gas barrier property when the obtained gas barrier film is bent is further improved. Here, the upper limit of the O _max -O _min difference is not particularly limited, but is preferably 50 at% or less, and is preferably 40 at% or less in consideration of the effect of suppressing / preventing crack generation when the gas barrier film is bent. It is more preferable that

The absolute value of the difference between the maximum value and the minimum value of the atomic ratio of silicon in the silicon distribution curve of the inorganic barrier layer (hereinafter, also simply referred to as “Si _max −Si _min difference”) is preferably 10 at% or less, It is more preferably 7 at% or less, and further preferably 3 at% or less. When the absolute value is 10 at% or less, the gas barrier property of the obtained gas barrier film is further improved. The lower _limit of Si max _{-Si min} _difference, because the effect of improving the crack generation suppression / prevention during bending of Si max _{-Si min} as gas barrier property difference is small film is high, is not particularly limited, and gas barrier property In consideration, it is preferably 1 at% or more, and more preferably 2 at% or more.

The total amount of carbon and oxygen atoms with respect to the film thickness direction of the inorganic barrier layer is preferably substantially constant. Thereby, an inorganic barrier layer exhibits moderate flexibility, and generation | occurrence | production of the crack at the time of bending of a gas barrier film is suppressed and prevented more effectively. More specifically, the total amount of oxygen atoms and carbon atoms with respect to the distance (L) from the surface of the inorganic barrier layer in the film thickness direction of the inorganic barrier layer and the total amount of silicon atoms, oxygen atoms, and carbon atoms. In the oxygen-carbon distribution curve showing the relationship with the ratio (atomic ratio of oxygen and carbon), the absolute value of the difference between the maximum value and the minimum value of the oxygen-carbon atomic ratio in the oxygen-carbon distribution curve (hereinafter simply referred to as “ OC _max -OC _min difference ") is preferably less than 5 at%, more preferably less than 4 at%, and even more preferably less than 3 at%. When the absolute value is less than 5 at%, the gas barrier property of the obtained gas barrier film is further improved. _The lower limit of the OC max _{-OC min} _difference, since preferably as OC max _{-OC min} difference is small, but is 0 atomic%, it is sufficient if more than 0.1 at%.

The silicon distribution curve, the oxygen distribution curve, the carbon distribution curve, and the oxygen carbon distribution curve are a combination of X-ray photoelectron spectroscopy (XPS) measurement and rare gas ion sputtering such as argon. By doing so, it can be created by so-called XPS depth profile measurement in which surface composition analysis is sequentially performed while exposing the inside of the sample. A distribution curve obtained by such XPS depth profile measurement can be created, for example, with the vertical axis as the atomic ratio (unit: at%) of each element and the horizontal axis as the etching time (sputtering time). In the element distribution curve with the horizontal axis as the etching time, the etching time is generally correlated with the distance (L) from the surface of the inorganic barrier layer in the film thickness direction of the inorganic barrier layer in the film thickness direction. Therefore, as the “distance from the surface of the inorganic barrier layer in the film thickness direction of the inorganic barrier layer”, the surface of the inorganic barrier layer calculated from the relationship between the etching rate and the etching time employed in the XPS depth profile measurement The distance from can be adopted. The silicon distribution curve, oxygen distribution curve, carbon distribution curve, and oxygen carbon distribution curve can be prepared under the following measurement conditions.

(Measurement condition)
Etching ion species: Argon (Ar ⁺ )
Etching rate (SiO ₂ thermal oxide equivalent value): 0.05 nm / sec
Etching interval (SiO ₂ equivalent value): 10 nm
X-ray photoelectron spectrometer: Model name “VG Theta Probe” manufactured by Thermo Fisher Scientific
Irradiation X-ray: Single crystal spectroscopy AlKα
X-ray spot and its size: 800 × 400 μm oval.

The film thickness (dry film thickness) of the inorganic barrier layer formed by the above plasma CVD method is not particularly limited. For example, the thickness of the inorganic barrier layer per layer is preferably 20 to 3000 nm, more preferably 50 to 2500 nm, and particularly preferably 30 to 1000 nm. With such a film thickness, the gas barrier film can exhibit excellent gas barrier properties and the effect of suppressing / preventing cracking during bending. In addition, when the inorganic barrier layer formed by said plasma CVD method is comprised from 2 or more layers, it is preferable that each inorganic barrier layer has a film thickness as mentioned above.

In the present invention, from the viewpoint of forming an inorganic barrier layer having a uniform and excellent gas barrier property over the entire film surface, the inorganic barrier layer is substantially in the film surface direction (direction parallel to the surface of the inorganic barrier layer). Preferably it is uniform. Here, the inorganic barrier layer is substantially uniform in the film surface direction means that the oxygen distribution curve, the carbon distribution curve, and the carbon distribution curve at any two measurement points on the film surface of the inorganic barrier layer by XPS depth profile measurement. When an oxygen carbon distribution curve is created, the number of extreme values of the carbon distribution curve obtained at any two measurement points is the same, and the maximum and minimum carbon atomic ratios in each carbon distribution curve The absolute value of the difference between the values is the same as each other or within 5 at%.

Furthermore, in the present invention, it is preferable that the carbon distribution curve is substantially continuous. Here, the carbon distribution curve is substantially continuous means that the carbon distribution curve does not include a portion where the atomic ratio of carbon changes discontinuously. Specifically, the carbon distribution curve is calculated from the etching rate and the etching time. Between the distance (x, unit: nm) from the surface of the inorganic barrier layer in the film thickness direction of at least one of the inorganic barrier layers to be applied and the atomic ratio of carbon (C, unit: at%) Means satisfying the condition represented by the following formula 1.

In the gas barrier film according to the present invention, the inorganic barrier layer that satisfies all of the above conditions (i) to (iii) may include only one layer or two or more layers. Furthermore, when two or more such inorganic barrier layers are provided, the materials of the plurality of inorganic barrier layers may be the same or different.

In the silicon distribution curve, the oxygen distribution curve, and the carbon distribution curve, the silicon atomic ratio, the oxygen atomic ratio, and the carbon atomic ratio are 90% or more of the film thickness of the inorganic barrier layer. When the condition represented by i) is satisfied, the atomic ratio of the content of silicon atoms to the total amount of silicon atoms, oxygen atoms, and carbon atoms in the inorganic barrier layer is 20 to 45 at%. Preferably, it is 25 to 40 at%. The atomic ratio of the oxygen atom content to the total amount of silicon atoms, oxygen atoms, and carbon atoms in the inorganic barrier layer is preferably 45 to 75 at%, more preferably 50 to 70 at%. preferable. Further, the atomic ratio of the carbon atom content to the total amount of silicon atoms, oxygen atoms and carbon atoms in the inorganic barrier layer is preferably 0.5 to 25 at%, and preferably 1 to 20 at%. Is more preferable.

In the present invention, the method for forming the inorganic barrier layer is not particularly limited, and the conventional method and the method can be applied in the same manner or appropriately modified. The inorganic barrier layer is preferably formed by a chemical vapor deposition (CVD) method, particularly a plasma chemical vapor deposition method (plasma CVD, plasma-enhanced chemical vapor deposition (PECVD), hereinafter also simply referred to as “plasma CVD method”). More preferably, the substrate is formed by a plasma CVD method in which a base material is disposed on a pair of film forming rollers and plasma is generated by discharging between the pair of film forming rollers.

In the following, a method for forming an inorganic barrier layer on a base material by a plasma CVD method in which the base material is disposed on a pair of film forming rollers and plasma is generated by discharging between the pair of film forming rollers will be described. .

(Method of forming inorganic barrier layer by plasma CVD method)
As a method for forming the inorganic barrier layer according to the present invention on the surface of the substrate, it is preferable to employ a plasma CVD method from the viewpoint of gas barrier properties. The plasma CVD method may be a Penning discharge plasma type plasma CVD method.

Further, when plasma is generated in the plasma CVD method, it is preferable to generate plasma discharge in a space between a plurality of film forming rollers. A pair of film forming rollers is used, and each of the pair of film forming rollers is used. More preferably, a substrate is placed and discharged between a pair of film forming rollers to generate plasma. In this way, by using a pair of film forming rollers, placing a base material on the pair of film forming rollers, and discharging between the pair of film forming rollers, one film forming roller It is possible not only to produce a thin film efficiently because it is possible to form a film on the surface part of the base material existing in the film while simultaneously forming a film on the surface part of the base material present on the other film forming roller. The film formation rate can be doubled compared to the plasma CVD method without using any roller, and since it is possible to form a film having a structure that is substantially the same, it is possible to at least double the extreme value in the carbon distribution curve, It is possible to efficiently form a layer that satisfies all of the above conditions (i) to (iii).

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

In addition, the gas barrier film according to the present invention preferably has the inorganic barrier layer formed on the surface of the substrate by a roll-to-roll method from the viewpoint of productivity. In addition, an apparatus that can be used when manufacturing the inorganic barrier layer by such a plasma CVD method is not particularly limited, and includes at least a pair of film forming rollers and a plasma power source, and the pair of components. It is preferable that the apparatus has a configuration capable of discharging between film rollers. For example, when the manufacturing apparatus shown in FIG. 2 is used, the apparatus is manufactured by a roll-to-roll method using a plasma CVD method. It is also possible to do.

Hereinafter, with reference to FIG. 2, a base material is disposed on a pair of film forming rollers, and a method for forming an inorganic barrier layer by a plasma CVD method in which plasma is generated by discharging between the pair of film forming rollers. This will be described in detail. FIG. 2 is a schematic view showing an example of a manufacturing apparatus that can be suitably used for manufacturing an inorganic barrier layer by this manufacturing method. In the following description and drawings, the same or corresponding elements are denoted by the same reference numerals, and redundant description is omitted.

The manufacturing apparatus 31 shown in FIG. 2 includes a delivery roller 32,

transport rollers

33, 34, 35, and 36,

film formation rollers

39 and 40, a gas supply pipe 41, a plasma generation power source 42, and a film formation roller 39. And

magnetic field generators

43 and 44 installed inside 40 and a winding roller 45. In such a manufacturing apparatus, at least the

film forming rollers

39 and 40, the gas supply pipe 41, the plasma generating power source 42, and the magnetic

field generating apparatuses

43 and 44 are arranged in a vacuum chamber (not shown). ing. Further, in such a manufacturing apparatus 31, the vacuum chamber is connected to a vacuum pump (not shown), and the pressure in the vacuum chamber can be appropriately adjusted by the vacuum pump.

In such a manufacturing apparatus, each film-forming roller has a power source for plasma generation so that the pair of film-forming rollers (the film-forming roller 39 and the film-forming roller 40) can function as a pair of counter electrodes. 42. Therefore, in such a manufacturing apparatus 31, it is possible to discharge into the space between the film forming roller 39 and the film forming roller 40 by supplying electric power from the plasma generating power source 42. Plasma can be generated in the space between the film roller 39 and the film formation roller 40. In this way, when the film forming roller 39 and the film forming roller 40 are also used as electrodes, the material and design thereof may be appropriately changed so that they can also be used as electrodes. Moreover, in such a manufacturing apparatus, it is preferable to arrange | position a pair of film-forming roller (film-forming rollers 39 and 40) so that the central axis may become substantially parallel on the same plane. Thus, by arranging a pair of film forming rollers (film forming rollers 39 and 40), the film forming rate can be doubled and a film having the same structure can be formed. Can be at least doubled. And according to such a manufacturing apparatus, it is possible to form the inorganic barrier layer 3 on the surface of the base material 2 by CVD method, and the inorganic barrier layer on the surface of the base material 2 on the film-forming roller 39. While depositing the components, the inorganic barrier layer component can be deposited on the surface of the substrate 2 also on the film forming roller 40, so that the inorganic barrier layer can be efficiently formed on the surface of the substrate 2. it can.

In the film forming roller 39 and the film forming roller 40,

magnetic field generators

43 and 44 fixed so as not to rotate even when the film forming roller rotates are provided, respectively.

The

magnetic field generators

43 and 44 provided on the film forming roller 39 and the film forming roller 40 are respectively a magnetic field generating device 43 provided on one film forming roller 39 and a magnetic field generating device provided on the other film forming roller 40. It is preferable to arrange the magnetic poles so that the magnetic field lines do not cross between them and the

magnetic field generators

43 and 44 form a substantially closed magnetic circuit. By providing such

magnetic field generators

43 and 44, it is possible to promote the formation of a magnetic field in which magnetic lines of force swell near the opposing surface of each

film forming roller

39 and 40, and the plasma is converged on the bulging portion. Since it becomes easy, it is excellent at the point which can improve the film-forming efficiency.

The

magnetic field generators

43 and 44 provided in the film forming roller 39 and the film forming roller 40 respectively have racetrack-shaped magnetic poles that are long in the roller axis direction, and one magnetic field generator 43 and the other magnetic field generator. It is preferable to arrange the magnetic poles so that the magnetic poles facing to 44 have the same polarity. By providing such

magnetic field generators

43 and 44, the opposing space along the length direction of the roller shaft without straddling the magnetic field generator on the roller side where the magnetic lines of force of each of the

magnetic field generators

43 and 44 are opposed. A racetrack-like magnetic field can be easily formed in the vicinity of the roller surface facing the (discharge region), and the plasma can be focused on the magnetic field, so that a wide base wound around the roller width direction can be obtained. The material 2 is excellent in that the inorganic barrier layer 3 that is a vapor deposition film can be efficiently formed.

As the film formation roller 39 and the film formation roller 40, known rollers can be used as appropriate. As such

film forming rollers

39 and 40, those having the same diameter are preferably used from the viewpoint of forming a thin film more efficiently. Further, the diameter of the

film forming rollers

39 and 40 is preferably in the range of 300 to 1000 mmφ, particularly in the range of 300 to 700 mmφ, from the viewpoint of discharge conditions, chamber space, and the like. If the diameter of the film forming roller is 300 mmφ or more, the plasma discharge space will not be reduced, so that the productivity will not be deteriorated and it is possible to avoid applying the total amount of heat of the plasma discharge to the substrate 2 in a short time. It is preferable because damage to the material 2 can be reduced. On the other hand, if the diameter of the film forming roller is 1000 mmφ or less, it is preferable because practicality can be maintained in terms of apparatus design including uniformity of plasma discharge space.

In such a manufacturing apparatus 31, the base material 2 is disposed on a pair of film forming rollers (the film forming roller 39 and the film forming roller 40) so that the surfaces of the base material 2 face each other. By disposing the base material 2 in this manner, when the plasma is generated by performing discharge in the facing space between the film formation roller 39 and the film formation roller 40, the base existing between the pair of film formation rollers is present. Each surface of the material 2 can be formed simultaneously. That is, according to such a manufacturing apparatus, the inorganic barrier layer component is deposited on the surface of the substrate 2 on the film forming roller 39 by the plasma CVD method, and further the inorganic barrier layer component is formed on the film forming roller 40. Therefore, it is possible to efficiently form an inorganic barrier layer on the surface of the substrate 2.

As the feed roller 32 and the

transport rollers

33, 34, 35, and 36 used in such a manufacturing apparatus, known rollers can be appropriately used. Further, the take-up roller 45 is not particularly limited as long as it can take up the gas barrier film 1 in which the inorganic barrier layer 3 is formed on the substrate 2, and a known roller is appropriately used. Can do.

Further, as the gas supply pipe 41 and the vacuum pump, those capable of supplying or discharging the raw material gas at a predetermined speed can be appropriately used.

The gas supply pipe 41 as a gas supply means is preferably provided in one of the facing spaces (discharge region; film formation zone) between the film formation roller 39 and the film formation roller 40, and is a vacuum as a vacuum exhaust means. A pump (not shown) is preferably provided on the other side of the facing space. As described above, by providing the gas supply pipe 41 as the gas supply means and the vacuum pump as the vacuum exhaust means, the film formation gas is efficiently supplied to the facing space between the film formation roller 39 and the film formation roller 40. It is excellent in that the film formation efficiency can be improved.

Furthermore, as the plasma generating power source 42, a known power source of a plasma generating apparatus can be used as appropriate. Such a plasma generating power supply 42 supplies power to the film forming roller 39 and the film forming roller 40 connected thereto, and makes it possible to use these as counter electrodes for discharge. Such a plasma generating power source 42 can perform plasma CVD more efficiently, and can alternately reverse the polarity of the pair of film forming rollers (AC power source or the like). Is preferably used. In addition, since the plasma generating power source 42 can perform plasma CVD more efficiently, the applied power can be set to 100 W to 10 kW, and the AC frequency can be set to 50 Hz to 500 kHz. More preferably, it is possible to do this. As the

magnetic field generators

43 and 44, known magnetic field generators can be used as appropriate. Furthermore, as the base material 2, in addition to the base material used in the present invention, a material in which the inorganic barrier layer 3 is previously formed can be used. As described above, the inorganic barrier layer 3 can be made thicker by using the substrate 2 in which the inorganic barrier layer 3 is previously formed.

Using such a manufacturing apparatus 31 shown in FIG. 2, for example, the type of source gas, the power of the electrode drum of the plasma generator, the pressure in the vacuum chamber, the diameter of the film forming roller, and the transport of the film (base material) The inorganic barrier layer according to the present invention can be produced by appropriately adjusting the speed. That is, using the manufacturing apparatus 31 shown in FIG. 2, a discharge is generated between the pair of film forming rollers (film forming rollers 39 and 40) while supplying a film forming gas (raw material gas, etc.) into the vacuum chamber. As a result, the film-forming gas (raw material gas or the like) is decomposed by plasma, and the inorganic barrier layer 3 is plasma on the surface of the base material 2 on the film-forming roller 39 and the surface of the base material 2 on the film-forming roller 40. It is formed by the CVD method. At this time, a racetrack-shaped magnetic field is formed in the vicinity of the roller surface facing the facing space (discharge region) along the length direction of the roller axes of the

film forming rollers

39 and 40, and the plasma is converged on the magnetic field. For this reason, when the base material 2 passes through the point A of the film forming roller 39 and the point B of the film forming roller 40 in FIG. 2, the maximum value of the carbon distribution curve is formed in the inorganic barrier layer. On the other hand, when the base material 2 passes the points C1 and C2 of the film forming roller 39 and the points C3 and C4 of the film forming roller 40 in FIG. 2, the minimum value of the carbon distribution curve in the inorganic barrier layer. Is formed. For this reason, five extreme values are usually generated for two film forming rollers. Further, the distance between extreme values of the inorganic barrier layer (the distance (L) from the surface of the inorganic barrier layer in the film thickness direction of the inorganic barrier layer at one extreme value of the carbon distribution curve and the extreme value adjacent to the extreme value) (The absolute value of the difference) can be adjusted by the rotation speed of the film forming rollers 39 and 40 (base material transport speed). In such film formation, the substrate 2 is conveyed by the delivery roller 32, the film formation roller 39, and the like, respectively, so that the surface of the substrate 2 is formed by a roll-to-roll continuous film formation process. Thus, the inorganic barrier layer 3 is formed.

As the film forming gas (raw material gas or the like) supplied from the gas supply pipe 41 to the facing space, a raw material gas, a reactive gas, a carrier gas, or a discharge gas can be used alone or in combination of two or more. The source gas in the film forming gas used for forming the inorganic barrier layer 3 can be appropriately selected and used according to the material of the inorganic barrier layer 3 to be formed. As such a source gas, for example, an organic silicon compound containing silicon or an organic compound gas containing carbon can be used. Examples of such organosilicon compounds include hexamethyldisiloxane (HMDSO), hexamethyldisilane (HMDS), 1,1,3,3-tetramethyldisiloxane, vinyltrimethylsilane, methyltrimethylsilane, hexamethyldisilane. , Methylsilane, dimethylsilane, trimethylsilane, diethylsilane, propylsilane, phenylsilane, vinyltriethoxysilane, vinyltrimethoxysilane, tetramethoxysilane (TMOS), tetraethoxysilane (TEOS), phenyltrimethoxysilane, methyltriethoxy Examples include silane and octamethylcyclotetrasiloxane. Among these organosilicon compounds, hexamethyldisiloxane and 1,1,3,3-tetramethyldisiloxane are preferable from the viewpoints of handling properties of the compound and gas barrier properties of the resulting inorganic barrier layer. These organosilicon compounds can be used alone or in combination of two or more. Examples of the organic compound gas containing carbon include methane, ethane, ethylene, and acetylene. As these organic silicon compound gas and organic compound gas, an appropriate source gas is selected according to the type of the inorganic barrier layer 3.

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

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

When such a film-forming gas contains a source gas and a reactive gas, the ratio of the source gas and the reactive gas is the reaction gas that is theoretically necessary for completely reacting the source gas and the reactive gas. It is preferable not to make the ratio of the reaction gas excessive rather than the ratio of the amount. By not making the ratio of the reaction gas excessive, the formed inorganic barrier layer 3 is excellent in that excellent gas barrier properties and bending resistance can be obtained. Further, when the film forming gas contains the organosilicon compound and oxygen, the amount is less than the theoretical oxygen amount necessary for complete oxidation of the entire amount of the organosilicon compound in the film forming gas. It is preferable.

Hereinafter, a gas containing hexamethyldisiloxane (organosilicon compound, HMDSO, (CH ₃ ) ₆ Si ₂ O) as a source gas and oxygen (O ₂ ) as a reaction gas is used as the film forming gas. Taking a case of producing a silicon-oxygen-based thin film as an example, the preferred ratio of the raw material gas to the reactive gas in the film forming gas will be described in more detail.

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

In such a reaction, the amount of oxygen required to completely oxidize 1 mol of hexamethyldisiloxane is 12 mol. Therefore, a uniform silicon dioxide film is formed when oxygen is contained in the film forming gas in an amount of 12 moles or more per mole of hexamethyldisiloxane and a uniform silicon dioxide film is formed (a carbon distribution curve exists). Therefore, it becomes impossible to form an inorganic barrier layer that satisfies all the above conditions (i) to (iii). Therefore, in the present invention, when the inorganic barrier layer is formed, the oxygen amount is set to a stoichiometric ratio with respect to 1 mol of hexamethyldisiloxane so that the reaction of the reaction formula 1 does not proceed completely. Preferably less than 12 moles. In the actual reaction in the plasma CVD chamber, 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, so the molar amount of oxygen in the reaction gas Even if the (flow rate) is 12 times the molar amount (flow rate) of the raw material hexamethyldisiloxane (flow rate), the reaction cannot actually proceed completely, and the oxygen content is reduced. It is considered that the reaction is completed only when a large excess is supplied compared to the stoichiometric ratio (for example, in order to obtain silicon oxide by complete oxidation by CVD, the molar amount (flow rate) of oxygen is changed to the hexamethyldioxide raw material. (It may be about 20 times or more the molar amount (flow rate) of siloxane). 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 at such a ratio, carbon atoms and hydrogen atoms in hexamethyldisiloxane that have not been completely oxidized are taken into the inorganic barrier layer, and the above conditions (i) to ( It becomes possible to form an inorganic barrier layer satisfying all of iii), and it is possible to exhibit excellent gas barrier properties and bending resistance in the obtained gas barrier film. From the viewpoint of use as a flexible substrate for devices that require transparency, such as organic EL elements and solar cells, the molar amount of oxygen relative to the molar amount (flow rate) of hexamethyldisiloxane in the deposition gas The lower limit of (flow rate) is preferably greater than 0.1 times the molar amount (flow rate) of hexamethyldisiloxane, more preferably greater than 0.5 times.

Further, the pressure (degree of vacuum) in the vacuum chamber can be appropriately adjusted according to the type of the raw material gas, but is preferably in the range of 0.5 Pa to 50 Pa.

In such a plasma CVD method, in order to discharge between the film forming roller 39 and the film forming roller 40, an electrode drum connected to the plasma generating power source 42 (in this embodiment, the film forming roller 39) is used. The power applied to the power source can be adjusted as appropriate according to the type of the source gas, the pressure in the vacuum chamber, and the like. It is preferable to be in the range. If such an applied power is 100 W or more, the generation of particles can be sufficiently suppressed. On the other hand, if the applied power is 10 kW or less, the amount of heat generated at the time of film formation can be suppressed. An increase in surface temperature can be suppressed. Therefore, it is excellent in that wrinkles can be prevented during film formation without causing the substrate to lose heat.

The conveyance speed (line speed) of the base material 2 can be appropriately adjusted according to the type of source gas, the pressure in the vacuum chamber, etc., but is preferably in the range of 0.25 to 100 m / min. More preferably, it is in the range of 5 to 20 m / min. If the line speed is 0.25 m / min or more, generation of wrinkles due to heat in the substrate can be effectively suppressed. On the other hand, if it is 100 m / min or less, it is excellent at the point which can ensure sufficient film thickness as an inorganic barrier layer, without impairing productivity.

As described above, as a more preferable aspect of this embodiment, the inorganic barrier layer according to the present invention is formed by a plasma CVD method using the plasma CVD apparatus (roll-to-roll method) having the counter roll electrode shown in FIG. It is characterized by forming a film. This is excellent in flexibility (flexibility) and mechanical strength, especially when transported by roll-to-roll, when mass-produced using a plasma CVD apparatus (roll-to-roll method) having a counter roll electrode. This is because it is possible to efficiently produce an inorganic barrier layer in which gas barrier performance is compatible. Such a manufacturing apparatus is also excellent in that it can inexpensively and easily mass-produce gas barrier films that are required for durability against temperature changes used in solar cells and electronic components.

<Barrier layer deposition process>
<First film forming step>
As one embodiment of the present invention, the film forming process can be performed by dividing it into a first film forming process and a second film forming process. The first film forming step is a step of forming a first barrier layer, and includes applying a first barrier layer precursor liquid containing a silicon compound precursor and a solvent having a solubility parameter of 15.5 to 20.0. As the silicon compound precursor, those described in the above item (Silicon compound) can be used.

The first barrier layer precursor solution (coating solution) can be prepared by dissolving the silicon compound precursor and, if necessary, a catalyst in a solvent having a solubility parameter of 15.5 to 20.0. Here, the solvent for preparing the coating solution is preferably a solvent capable of dissolving the silicon compound precursor (polysilazane) of the general formula (1). An organic solvent that does not contain water and reactive groups (for example, hydroxyl group or amine group) that easily react with polysilazane and is inert to polysilazane is preferable, and an aprotic organic solvent is more preferable.

Specific examples of the solvent having a solubility parameter of 15.5 to 20.0 include aliphatic hydrocarbons such as cyclohexane, dodecane, methylcyclohexane, octane, and hydrogenated triisobutylene; benzene, ethylbenzene, toluene, o-xylene, and the like. Aromatic hydrocarbons; aliphatic ethers such as dibutyl ether, dioxane and tetrahydrofuran; ethers such as alicyclic ethers; pyridine, 1-methylpiperidine, 1-ethylpiperidine, 2-hydroxymethylpiperidine, 3-hydroxymethylpiperidine And amine compounds such as N, N′-dimethylpiperazine; and halogenated hydrocarbons such as chloroform, 1,2 dichloroethane, and trichloroethylene. Of these, o-xylene (SP value: 18.1), toluene (SP value: 18.2), cyclohexane (SP value: 17.3), n-butyl acetate (SP value: 17.4), diethyl, etc. Ether (SP value: 15.5), dibutyl ether (SP value: 15.9), and piperidine (SP value: 19.7) are preferable. The said solvent may be used independently or may be used with the form of a 2 or more types of mixture.

In addition, it is preferable to reduce the oxygen concentration and water content of the solvent before use. Means for reducing the oxygen concentration and water content in the solvent are not particularly limited, and conventionally known methods can be applied.

The concentration of the silicon compound precursor of the general formula (1) in the first barrier layer precursor liquid is not particularly limited and varies depending on the film thickness of the gas barrier layer and the pot life of the coating liquid, but is preferably 0.2 to 80 mass. %, More preferably 1 to 50% by mass, particularly preferably 1.5 to 35% by mass.

The first barrier layer precursor liquid may contain a catalyst together with polysilazane in order to promote modification to silicon oxynitride. As the catalyst applicable to the present invention, a basic catalyst is preferable, and in particular, N, N-diethylethanolamine, N, N-dimethylethanolamine, triethanolamine, triethylamine, 3-morpholinopropylamine, N, N, Amine catalysts such as N ′, N′-tetramethyl-1,3-diaminopropane, N, N, N ′, N′-tetramethyl-1,6-diaminohexane, Pt compounds such as Pt acetylacetonate, propion Examples thereof include metal catalysts such as Pd compounds such as acid Pd, Rh compounds such as Rh acetylacetonate, and N-heterocyclic compounds. Of these, it is preferable to use an amine catalyst. The concentration of the catalyst added at this time is preferably in the range of 0.1 to 10% by mass, more preferably 0.5 to 5% by mass, based on polysilazane. By setting the addition amount of the catalyst within this range, it is possible to avoid excessive silanol formation due to rapid progress of the reaction, reduction in film density, increase in film defects, and the like.

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

The method for forming the first barrier layer (coating film) is not particularly limited and may be formed by any method. However, the first barrier layer (coating film) may be formed by wet coating with a first barrier layer precursor liquid containing a silicon compound precursor. It is preferable. As a coating method, a conventionally known appropriate wet coating method can be adopted. Specific examples include spin coating method, roll coating method, flow coating method, ink jet method, spray coating method, printing method, dip coating method, casting film forming method, bar coating method, wireless bar coating method, gravure printing method, etc. Is mentioned. The first barrier layer may be a laminate of two or more layers. The method for forming a coating film when the first barrier layer is a laminate of two or more layers is not particularly limited, and may be a sequential multilayer coating method or a simultaneous multilayer coating method.

As another embodiment of the present invention, the first barrier layer precursor liquid is applied onto a resin substrate together with a second barrier layer precursor liquid described later by a simultaneous multilayer coating method, and the first barrier layer and the second barrier liquid are applied. The layers may be formed simultaneously. The simultaneous multi-layer coating method uses multiple coaters to apply the next layer before drying the already applied layer and simultaneously dry multiple layers, or use slide coating or curtain coating to apply multiple layers on the slide surface. There is a method of laminating and applying liquids. According to the present invention, since the solubility parameters of the solvents are different, the first barrier layer and the second barrier layer are not mixed in a certain amount or more even by the simultaneous multilayer coating method, and the above-described region A Remains at a predetermined thickness. Therefore, the simultaneous multi-layer coating method with higher productivity can be preferably applied.

The thickness (application thickness) of the coating film of the first barrier layer is not particularly limited, and can be appropriately set according to the desired thickness (dry film thickness) of the first barrier layer. For example, the thickness (coating thickness) of the coating film is preferably about 1 nm to 100 μm, more preferably about 5 nm to 10 μm, and more preferably 10 nm to 1 μm, as the thickness after drying (dry film thickness). It is even more preferable that the thickness is 30 to 500 nm. If the thickness of the coating film is 1 nm or more, gas barrier properties (for example, low oxygen permeability and low water vapor permeability) can be obtained, and if it is 100 μm or less, stable coating properties when forming the first barrier layer. And high light transmittance can be realized. In addition, when a coating film is laminated | stacked, it is preferable that the thickness of the whole coating film becomes thickness as mentioned above.

In the present specification, the thickness (dry film thickness) of a layer (coating film) is measured by making a TEM observation of a cross section of each sample after producing a flake with the following FIB processing apparatus. Also, the presence or absence of modification of the layer (coating film) is the same as described above, and after producing a flake with the following FIB processing apparatus, if this sample is continuously irradiated with an electron beam, A contrast difference appears in the other part. At this time, the portion that has undergone the modification treatment is densified and thus is less susceptible to electron beam damage, but the other portion is damaged by electron beam damage, and alteration is confirmed. By the cross-sectional TEM observation confirmed in this way, the film thicknesses of the modified portion and the unmodified portion can be calculated.

After applying the first barrier layer precursor liquid, the first barrier layer is formed by drying the coating film. Here, the drying conditions are not particularly limited as long as a coating film is formed. Specifically, the drying temperature is preferably 50 to 150 ° C, more preferably 80 to 100 ° C. The drying time is preferably 0.5 to 60 minutes, more preferably 1 to 10 minutes.

<Second film forming step>
In one embodiment of the present invention, after forming the first barrier layer as described above, applying a second barrier layer precursor solution containing a metal compound and a solvent having a solubility parameter of 26.0 to 32.0 is included. Then, the second film forming step for forming the second barrier layer is performed. As the metal compound, those described in the above section (Metal compound) can be used as appropriate.

The second barrier layer precursor liquid (coating liquid) can be prepared by dissolving a metal compound in a solvent. Here, the solvent for preparing the coating solution is not particularly limited as long as it satisfies the above solubility parameter range and can dissolve the metal compound. However, water that easily reacts with the metal compound and reactive groups (for example, amine groups) are not included, and an organic solvent inert to the metal compound is preferable, and a polar organic solvent is more preferable.

Specifically, as a solvent for preparing the second barrier layer precursor liquid, for example, a divalent solvent such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, diethylene glycol, 1,3-propanediol, etc. Alcohol, glycerin, diglycerin, triglycerin, polyglycerin, trimethylolpropane and other trihydric alcohols, pentaerythritol and other tetravalent alcohols, sorbitol and other hexitols, glucose and other aldoses, and sugar skeletons such as sucrose Examples include compounds, lower alcohols such as isopropanol, butanol, and ethanol. Of these, ethanol (SP value: 26.5), propylene glycol (SP value: 29.1), 1,3-propanediol (SP value: 31.7), diethylene glycol (SP value: 27.9), Dipropylene glycol (SP value: 26.4) and methoxymethanol (SP value: 26.1) are preferred. One or more of these may be used in combination.

The concentration of the metal compound in the second barrier layer precursor liquid is not particularly limited and varies depending on the film thickness of the barrier layer and the pot life of the coating liquid, but is preferably 0.2 to 80% by mass, and more preferably 1 to 50%. % By mass, particularly preferably 1.5 to 35% by mass.

The second barrier layer precursor liquid containing the metal compound is wet-applied on the first barrier layer to form a coating film. As a coating method, a conventionally known appropriate wet coating method can be adopted. Specific examples include spin coating method, roll coating method, flow coating method, ink jet method, spray coating method, printing method, dip coating method, casting film forming method, bar coating method, wireless bar coating method, gravure printing method, etc. Is mentioned.

Further, the second barrier layer may be a laminate of two or more layers. The method for forming a coating film when the second barrier layer is a laminate of two or more layers is not particularly limited, and may be a sequential multilayer coating method or a simultaneous multilayer coating method.

As another embodiment of the present invention, as described above, the second barrier layer precursor liquid is simultaneously applied onto the resin substrate together with the first barrier layer precursor liquid by the simultaneous multilayer coating method, Two barrier layers may be formed simultaneously. The simultaneous multi-layer coating method uses multiple coaters to apply the next layer before drying the already applied layer and simultaneously dry multiple layers, or use slide coating or curtain coating to apply multiple layers on the slide surface. There is a method of laminating and applying liquids. According to the present invention, the first barrier layer precursor liquid and the second barrier layer precursor liquid have different solvent solubility parameters, so that the first barrier layer and the second barrier layer can be obtained by the simultaneous multilayer coating method. Never mix more than a certain amount. Therefore, the above-described region A remains with a predetermined thickness.

(Reforming process)
In a preferred embodiment of the present invention, the silicon compound precursor is represented by the following general formula (1):

In the general formula (1), R ¹ , R ² and R ³ each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, aryl group, vinyl group or (trialkoxysilyl) alkyl group. ,
A precursor having a structure represented by:
After the film forming step, a modification step of modifying the silicon compound precursor (first barrier layer) by irradiating active energy rays is included.

That is, in a preferable manufacturing method of the present invention, after the first barrier layer is applied and formed, the second barrier layer is applied and formed before the modification, and then the active energy rays are irradiated through the second barrier layer, Modify the barrier layer. Alternatively, after the first barrier layer and the second barrier layer are simultaneously formed by simultaneous multilayer coating, the first barrier layer is modified by irradiating active energy rays through the second barrier layer. In the present invention, since solvents having different solubility parameters are used, the first barrier layer and the second barrier layer are only slightly mixed in the vicinity of the interface at the time of modification. Remains at a predetermined thickness. Therefore, the first barrier layer and the second barrier layer can be laminated by the simultaneous multilayer coating method, and after the two layers are laminated, the modification process can be performed to complete the barrier layer. Conventionally, the modification process was performed after the first barrier layer was formed, and the second barrier layer was formed. Therefore, the lamp illuminance decreased due to volatilization and scattering of low-molecular silicon compounds during the modification of the first barrier layer. However, it is inevitable that a difference occurs in the degree of modification. However, according to the method of the present embodiment, since the reforming process is performed in a state where the second barrier layer is formed on the first barrier layer, volatilization or scattering of the silicon compound can be prevented, and the barrier performance is uniform and excellent. The gas barrier film can be produced.

(Modification process)
The modification treatment in the present invention refers to a reaction in which part or all of the silicon compound precursor (polysilazane) is converted into silicon oxide or silicon oxynitride. Thus, an inorganic thin film of a level that can contribute to the development of the gas barrier property (water vapor permeability of 1 × 10 ⁻³ g / m ² · day or less) as a whole of the gas barrier film of the present invention can be formed. Specifically, the modification treatment includes heat treatment, plasma treatment, active energy ray irradiation treatment, and the like. Among these, from the viewpoint that it can be modified at a low temperature and has a high degree of freedom in selecting a base material species, a treatment with active energy ray irradiation is preferable.

(Heat treatment)
As a heat treatment method, for example, a method of heating a coating film by heat conduction by bringing a substrate into contact with a heating element such as a heat block, a method of heating an environment in which the coating film is placed by an external heater such as a resistance wire, Although the method using the light of infrared region, such as IR heater, is mentioned, It is not limited to these. What is necessary is just to select suitably the method which can maintain the smoothness of a coating film, when performing heat processing.

The temperature for heating the coating film is preferably in the range of 40 to 250 ° C, more preferably in the range of 60 to 150 ° C. The heating time is preferably in the range of 10 seconds to 100 hours, and more preferably in the range of 30 seconds to 5 minutes.

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

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

(Active energy ray irradiation treatment)
As the active energy rays, for example, infrared rays, visible rays, ultraviolet rays, X rays, electron rays, α rays, β rays, γ rays and the like can be used, but electron rays or ultraviolet rays are preferable, and ultraviolet rays are more preferable. Ozone and active oxygen atoms generated by ultraviolet light (synonymous with ultraviolet light) have high oxidation ability, and can form a silicon-containing film having high density and insulating properties at low temperatures.

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

By this ultraviolet irradiation, the base material is heated, and O ₂ and H ₂ O contributing to ceramicization (silica conversion), an ultraviolet absorber, and polysilazane itself are excited and activated. The conversion to ceramics is promoted, and the obtained first barrier layer becomes denser. Irradiation with ultraviolet rays is effective at any time after the formation of the coating film.

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

It is preferable that the irradiation intensity and the irradiation time be set within the range where the substrate carrying the first barrier layer to be irradiated is not damaged. Taking the case of using a plastic film as a base material, for example, a 2 kW (80 W / cm × 25 cm) lamp is used, and the strength of the base material surface is 20 to 300 mW / cm ² , preferably 50 to 200 mW / cm. The distance between the base material and the ultraviolet irradiation lamp is set so as to be ^2, and irradiation can be performed for 0.1 seconds to 10 minutes.

Examples of such ultraviolet ray generating means include metal halide lamps, high pressure mercury lamps, low pressure mercury lamps, xenon arc lamps, carbon arc lamps, and excimer lamps (single wavelengths of 172 nm, 222 nm, and 308 nm, for example, USHIO INC. Manufactured by MD Excimer Co., Ltd.), UV light laser, and the like. In addition, when irradiating the generated ultraviolet rays to the first barrier layer, from the viewpoint of achieving efficiency improvement and uniform irradiation, the ultraviolet rays from the generation source are reflected by the reflector and then applied to the first barrier layer. Is preferred.

UV irradiation can be applied to both batch processing and continuous processing, and can be appropriately selected depending on the shape of the substrate used. For example, in the case of batch processing, the laminated body having the first barrier layer on the surface can be processed in an ultraviolet baking furnace equipped with the above-described ultraviolet ray generation source. The ultraviolet baking furnace itself is generally known. For example, an ultraviolet baking furnace manufactured by I-Graphics Co., Ltd. can be used. Moreover, when the laminated body which has a 1st barrier layer on the surface is a long film form, by conveying this, continuously irradiating with an ultraviolet-ray in the drying zone equipped with the above ultraviolet-ray generation sources. It can be made into ceramics. The time required for ultraviolet irradiation is generally 0.1 seconds to 10 minutes, preferably 0.5 seconds to 3 minutes, depending on the base material used and the composition and concentration of the first barrier layer.

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

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

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

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

¡Excimer lamps have high light generation efficiency and can be lit with low power. In addition, light having a long wavelength that causes a temperature increase due to light is not emitted, and energy is irradiated in the ultraviolet region, that is, in a short wavelength, so that the increase in the surface temperature of the target object is suppressed. For this reason, it is suitable for flexible film materials such as PET that are easily affected by heat.

Oxygen is required for the reaction at the time of ultraviolet irradiation, but since vacuum ultraviolet rays are absorbed by oxygen, the efficiency in the ultraviolet irradiation process tends to decrease. It is preferable to perform in a state where the water vapor concentration is low. That is, the oxygen concentration at the time of irradiation with vacuum ultraviolet rays is preferably 10 to 20,000 volume ppm, more preferably 50 to 10,000 volume ppm. Also, the water vapor concentration during the conversion process is preferably in the range of 1000 to 4000 ppm by volume.

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

In the vacuum ultraviolet irradiation step, the illuminance of the vacuum ultraviolet light on the coating surface received by the polysilazane coating is preferably 1 mW / cm ² to 10 W / cm ² , more preferably 30 mW / cm ² to 200 mW / cm ^2. ^preferably, further preferably at 50mW / cm 2 ~ 160mW / cm 2. If it is 1 mW / cm ² or more, sufficient reforming efficiency is obtained, and if it is 10 W / cm ² or less, it is difficult to cause ablation in the coating film and damage the substrate.

Irradiation energy amount of the VUV in the coated surface (integrated quantity of light), it preferably from 10 ~ 10000mJ / cm ^2, more preferably 100 ~ 8000mJ / cm ^2, a 200 ~ 6000mJ / cm ² Is more preferable. If it is 10 mJ / cm ² or more, the modification can proceed sufficiently. If it is 10,000 mJ / cm ² or less, cracking due to over-reformation and thermal deformation of the substrate are unlikely to occur.

In addition, the oxygen concentration at the time of irradiation with vacuum ultraviolet light (VUV) is preferably 300 to 10000 volume ppm (1 volume%), more preferably 500 to 5000 volume ppm. By adjusting to such an oxygen concentration range, it is possible to prevent the formation of an excessive oxygen barrier layer and to prevent the deterioration of the barrier property.

The Xe excimer lamp is excellent in luminous efficiency because it emits ultraviolet light having a short wavelength of 172 nm at a single wavelength. Since this light has a large oxygen absorption coefficient, it can generate radical oxygen atom species and ozone at a high concentration with a very small amount of oxygen. In addition, it is known that the energy of light having a short wavelength of 172 nm for dissociating the bonds of organic substances has high ability. The coating layer containing the polysilazane compound can be modified in a short time by the high energy of the active oxygen, ozone and ultraviolet radiation. Therefore, compared to low-pressure mercury lamps with wavelengths of 185 nm and 254 nm and plasma cleaning, shortening process time and equipment area associated with high throughput, irradiation to organic materials, plastic substrates, resin films, etc. that are easily damaged by heat. It is possible.

The layer formed by the above coating has a composition of SiO _x N _y M _z as a whole layer by modifying at least part of the polysilazane in the step of irradiating the coating film containing the polysilazane compound with vacuum ultraviolet rays. A barrier layer comprising the silicon oxynitride shown is formed.

The film composition can be measured by measuring the atomic composition ratio using an XPS surface analyzer. Alternatively, the barrier layer formed by applying a solution containing a polysilazane compound is cut, and the cut surface can be measured by measuring the atomic composition ratio with an XPS surface analyzer.

Further, the film density can be appropriately set according to the purpose. For example, the film density of the barrier layer formed by applying a solution containing a polysilazane compound is preferably in the range of 1.5 to 2.6 g / cm ³ . Within this range, the density of the film can be improved and deterioration of gas barrier properties and film deterioration under high temperature and high humidity conditions can be prevented.

Further, the vacuum ultraviolet light used for reforming, CO, may be generated by plasma formed in a gas containing at least one of CO ₂ and CH _4. Further, as the gas containing at least one of CO, CO ₂ and CH ₄ (hereinafter also referred to as carbon-containing gas), the carbon-containing gas may be used alone, but carbon containing rare gas or H ₂ as the main gas. It is preferable to add a small amount of the contained gas. Examples of plasma generation methods include capacitively coupled plasma.

By performing the modification treatment as described above, the barrier layer is completed, and the gas barrier film of the present invention is obtained.

(Post-processing)
The barrier layer formed by applying a solution containing a polysilazane compound may be subjected to post-treatment after coating or after modification, in particular after modification. The post-treatment described here includes temperature treatment (heat treatment) at a temperature of 40 to 120 ° C. or humidity: 30% to 100%, or humidity treatment immersed in a water bath, and the treatment time is from 30 seconds to 100 hours. It is defined as a range selected from the range. Both temperature and humidity treatments may be performed, or only one of them may be performed, but at least temperature treatment (heat treatment) is preferably performed. Preferred conditions are a temperature of 40 to 120 ° C., a humidity of 30% to 85%, and a treatment time of 30 seconds to 100 hours.

When performing the temperature treatment, any method such as a contact method such as placing on a hot plate or a non-contact method standing on an oven may be used.

In addition, the barrier layer formed by applying a solution containing a polysilazane compound may form only one layer or may laminate two or more layers. By providing a plurality of coating layers in this way, the gas barrier property can be further improved. Preferably, two or more barrier layers formed by applying a solution containing a polysilazane compound containing an additive element on a substrate and then forming a barrier layer formed by vapor phase film formation, for example, Two or three layers are stacked.

[Electronic device]
The gas barrier film of the present invention can be preferably used for a device whose performance is deteriorated by chemical components (oxygen, water, nitrogen oxide, sulfur oxide, ozone, etc.) in the air. Accordingly, the present invention also provides an electronic device comprising the electronic device body and the gas barrier film produced by the method of the present invention or the gas barrier film according to the present invention.

Examples of the devices include electronic devices such as organic EL elements, liquid crystal display elements (LCD), thin film transistors, touch panels, electronic paper, solar cells (PV), and the like. From the viewpoint that the effect of the present invention can be obtained more efficiently, it is preferably used for an organic EL device or a solar cell, and particularly preferably used for an organic EL device.

The gas barrier film of the present invention can also be used for device film sealing. That is, the present invention also provides an electronic device including the electronic device body and the gas barrier film of the present invention. Specifically, the gas barrier film of the present invention is provided on the surface of the device itself as a support. Note that the device may be covered with a protective layer before providing the gas barrier film.

The gas barrier film of the present invention can also be used as a device substrate or a film for sealing by a solid sealing method. The solid sealing method is a method in which after a protective layer is formed on a device, an adhesive layer and a gas barrier film are stacked and cured. Although there is no restriction | limiting in particular in an adhesive agent, A thermosetting epoxy resin, a photocurable acrylate resin, etc. are illustrated.

As the organic EL element, an example of an organic EL element using a gas barrier film is described in detail in JP-A-2007-30387.

As a liquid crystal display element, a reflective liquid crystal display device is composed of a lower substrate, a reflective electrode, a lower alignment film, a liquid crystal layer, an upper alignment film, a transparent electrode, an upper substrate, a λ / 4 plate, and a polarizing film in order from the bottom. It has a configuration. The gas barrier film in the present invention can be used as the transparent electrode substrate and the upper substrate.

As a solar cell, the gas barrier film of the present invention can also be used as a sealing film for solar cell elements. Here, the gas barrier film of the present invention is preferably sealed so that the barrier layer is closer to the solar cell element.

As other application examples, the thin film transistor described in JP-T-10-512104, the touch panel described in JP-A-5-127822, JP-A-2002-48913, etc., and described in JP-A-2000-98326 Electronic paper and the like.

The gas barrier film of the present invention can also be used as an optical member. Examples of the optical member include a circularly polarizing plate.

The circularly polarizing plate can be produced by laminating a λ / 4 plate and a polarizing plate using the gas barrier film in the present invention as a substrate. In this case, the lamination is performed so that the angle formed by the slow axis of the λ / 4 plate and the absorption axis of the polarizing plate is 45 °. As such a polarizing plate, one that is stretched in a direction of 45 ° with respect to the longitudinal direction (MD) is preferably used. For example, those described in JP-A-2002-865554 can be suitably used. .

Hereinafter, the present invention will be specifically described using examples and comparative examples, but the present invention is not limited to the following examples. In addition, although the display of "part" or "%" is used in an Example, unless otherwise indicated, "part by mass" or "mass%" is represented.

<Example 1-1>
<< Production of gas barrier film >>
[Preparation of gas barrier film 1]
(Preparation of resin base material)
A polyethylene terephthalate (PET) film having a thickness of 125 μm (trade name “Teijin Tetron Film” manufactured by Teijin DuPont Films Ltd.) was used as a resin substrate.

(Formation of anchor layer)
On the easy-adhesion surface side of the resin base material, a UV curable organic / inorganic hybrid hard coat material OPSTARZ5011 manufactured by JSR Corporation was used, and after applying with a bar coater so that the layer thickness after drying was 4 μm, drying conditions As a result, drying was performed at 80 ° C. for 3 minutes. Next, curing was performed under an air atmosphere using a high-pressure mercury lamp under curing conditions: 500 mW / cm ² · 250 mJ / cm ² to form an anchor layer.

(Formation of inorganic barrier layer: Roller CVD method)
Using the inter-roller discharge plasma CVD apparatus to which the magnetic field shown in FIG. 2 is applied (hereinafter, this method is referred to as “roller CVD method”), the back surface of the resin substrate (the surface opposite to the side on which the anchor layer is provided) A resin base material is attached to the apparatus so as to be in contact with the film forming roller, and an inorganic barrier layer is formed on the anchor layer under a condition that the thickness is 100 nm under the following film forming conditions (plasma CVD conditions). did.

<Plasma CVD conditions>
Feed rate of raw material gas (hexamethyldisiloxane, abbreviation: HMDSO): 50 sccm (Standard Cubic Centimeter per Minute)
Supply amount of oxygen gas (O ₂ ): 500 sccm
Degree of vacuum in the vacuum chamber: 3Pa
Applied power from the power source for plasma generation: 0.8 kW
Frequency of power source for plasma generation: 70 kHz
Resin substrate transport speed: 2 m / min
(Formation of first barrier layer: silazane layer)
Subsequently, the following first barrier layer precursor liquid was applied and formed as a hexamethyldisilazane (also referred to as silazane) layer on the inorganic barrier layer by a die coater method, and then dried at 80 ° C. In this way, a first barrier layer having a thickness of 50 nm was formed on the inorganic barrier layer.

<Preparation of first barrier layer precursor liquid (coating liquid)>
Hexamethyldisilazane (manufactured by Momentive Performance Materials Japan GK) was prepared into a solution having a solid content concentration of 5% by mass using n-butyl acetate as a solvent.

(Formation of second barrier layer: metal compound layer)
Subsequently, a solution obtained by diluting [B (OCH (CH ₃ ) ₂ ) ₃ ] (manufactured by Tokyo Chemical Industry Co., Ltd., triisopropyl borate) with methoxymethanol to 2% by mass on the first barrier layer by a die coater method. A coating film was formed. Thereafter, by drying at 80 ° C., a second barrier layer having a thickness of 80 nm was formed on the first barrier layer as the second layer. Thereafter, the following vacuum ultraviolet ray treatment was performed to modify the second layer (first barrier layer) and the third layer (second barrier layer).

Furthermore, a 2000 m long film was continuously formed by the above method.

(Vacuum ultraviolet (VUV light) irradiation treatment conditions)
In the present invention, irradiation with vacuum ultraviolet rays (VUV light) was performed under the following conditions, using the following apparatus, placing the sample so that the distance between the lamp and the sample (also referred to as Gap) was 6 mm.

In addition, the oxygen concentration during irradiation with vacuum ultraviolet rays (VUV light) is adjusted by measuring the flow rate of nitrogen gas and oxygen gas introduced into the irradiation chamber with a flow meter, and nitrogen gas / oxygen gas of the gas introduced into the chamber. The flow rate ratio was adjusted.

Vacuum ultraviolet irradiation equipment: Xenon excimer irradiation equipment (MD excimer, MECL-M-1-200)
Illuminance: 140 mW / cm ² (172 nm)
Processing environment: Under dry nitrogen gas atmosphere Oxygen concentration in processing environment: 0.1% by volume
Substrate transport speed: 5 m / min
Excimer light exposure integrated amount: 6000 mJ / cm ²
<Examples 1-2 to 1-8>
A gas barrier film was produced in the same manner as in Example 1-1 except that the materials and conditions listed in Table 1-1 were used. In the table, ALCH means aluminum ethyl acetoacetate diisopropylate manufactured by Kawaken Fine Chemical Co., Ltd. In the table, R in Ti (OR) ₄ means a propyl group. In the table, DBE means dibutyl ether, and PHPS means perhydropolysilazane.

In addition, the formation method of the 1st barrier layer at the time of using PHPS is as follows. The following are examples of formation methods when n-butyl acetate is used as a solvent. In each example, the solvents listed in Table 1-1 were used as the solvent.

(Formation of first barrier layer using PHPS: polysilazane layer)
After forming the inorganic barrier layer, the following first barrier layer precursor solution using PHPS was coated on the inorganic barrier layer as a perhydropolysilazane layer by a die coater method, and then dried at 80 ° C. . In this way, a first barrier layer having a thickness of 50 nm was formed on the inorganic barrier layer.

<Preparation of First Barrier Layer Precursor Solution (Coating Solution) Using PHPS>
Perhydropolysilazane (PHPS) solution is a non-catalytic perhydropolysilazane 20% by weight dibutyl ether solution (manufactured by AZ Electronic Materials, Aquamica (registered trademark) NN120-20), amine catalyst (N, N, N ′ , N′-tetramethyl-1,6-diaminohexane) perhydropolysilazane in an amount of 5% by mass with respect to perhydropolysilazane, 20% by mass dibutyl ether solution (manufactured by AZ Electronic Materials Co., Ltd., Aquamica NAX120-20) Were used as a mixture. This mixed solution was appropriately diluted with n-butyl acetate to prepare an n-butyl acetate solution containing 1% by mass of the amine catalyst with respect to perhydropolysilazane and 1.7% by mass of perhydropolysilazane.

Incidentally, first barrier layers of Comparative Examples 1-1 to 1-5, Examples 2-1 to 2-3, Comparative Example 2-1, Examples 3-1 to 3-3, and Comparative Example 3-1, which will be described later. In the same manner as in the above (Formation of first barrier layer using PHPS: polysilazane layer), except that the solvents and conditions are those shown in Table 1-1, Table 2-1, and Table 3-1. It was prepared using.

<Comparative Examples 1-1 to 1-5>
A gas barrier film was produced in the same manner as in Example 1-1 except that the materials and conditions listed in Table 1-1 were used. In Comparative Examples 1-4 to 1-5, the second barrier layer was not formed. In Comparative Example 1-5, no inorganic barrier layer was formed.

<Examples 2-1 to 2-3>
A gas barrier film was produced in the same manner as in Example 1-1 except that the materials and conditions described in Table 2-1 were used. For Examples 2-1 to 2-3, a film having a thick second barrier layer of 200 nm was manufactured.

<Comparative Example 2-1>
A gas barrier film was produced in the same manner as in Example 1-1 except that the materials and conditions described in Table 2-1 were used. In Comparative Example 2-1, the second barrier layer was not formed.

<Examples 3-1 to 3-3>
A gas barrier film was produced in the same manner as in Example 1-1 except that the materials and conditions shown in Table 3-1 were used. In Examples 3-1 to 3-3, the first barrier layer and the second barrier layer were formed by the simultaneous multilayer coating method.

<Comparative Example 3-1>
A gas barrier film was produced in the same manner as in Example 1-1 except that the materials and conditions shown in Table 3-1 were used. In Comparative Example 3-1, the second barrier layer was not formed.

<Evaluation method>
Obtained in Examples 1-1 to 1-8, 2-1 to 2-3, 3-1 to 3-3, and Comparative Examples 1-1 to 1-5, 2-1, 3-1 The gas barrier film was evaluated according to the following items. The evaluation results are shown in Tables 1-2, 2-2 and 3-2 below.

(Th1 / Th2 calculation method)
About each obtained gas-barrier film, XPS depth profile was measured on the following measuring conditions.

(Measurement condition)
Etching ion species: Argon (Ar ⁺ )
Etching rate (converted to SiO ₂ thermal oxide film): 0.01 nm / sec
X-ray photoelectron spectrometer: Model name “VG Theta Probe” manufactured by Thermo Fisher Scientific
Irradiation X-ray: Single crystal spectroscopy AlKα
X-ray spot and its size: 800 × 400 μm oval.

The distribution of the amount of Si element and the amount of metal (M) element contained in the metal compound was obtained from the XPS measurement result in the film thickness direction. From the distribution, the thickness of the region where M / Si ≧ 2 is Th1, and the thickness of the region where 0.1 ≦ M / Si ≦ 1 is Th2.

(Evaluation of water vapor barrier properties)
The water vapor barrier property was evaluated for each gas barrier film in two states immediately after the start of film formation and after 2000 m film formation. The evaluation results are listed in the item “WVTR” in the following table.

・ Evaporation equipment: Vacuum evaporation equipment 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 (φ3-5mm, granular)
-Preparation of water vapor barrier property evaluation cell Using a vacuum vapor deposition apparatus (JEOL-made vacuum vapor deposition apparatus JEE-400), metallic calcium was vapor-deposited on the surface of each gas barrier film. After that, in a dry nitrogen gas atmosphere, the metal calcium vapor deposition surface is bonded and bonded to quartz glass having a thickness of 0.2 mm via a sealing ultraviolet curable resin (manufactured by Nagase ChemteX) and irradiated with ultraviolet rays. An evaluation cell was produced.

The obtained sample (evaluation cell) was stored under high temperature and high humidity of 85 ° C. and 85% RH, and the time taken for the metal calcium to corrode 100% was measured.

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 vapor-depositing metallic calcium using a quartz glass plate having a thickness of 0.2 mm instead of the gas barrier film as a comparative sample was used. The same storage at 85 ° C. and 85% RH under high temperature and high humidity was conducted, and it was confirmed that no corrosion of metallic calcium occurred even after 1000 hours.

The 100% corrosion time of each gas barrier film thus obtained was evaluated in the following 6 stages.
×: 30 hours or less Δ ×: 30 hours to 100 hours or less Δ: 100 hours to 300 hours or less ○ Δ: 300 hours to 600 hours or less ○: 600 hours to 1000 hours or less ◎: 1000 Over time.

(Bending evaluation)
Each of the obtained gas barrier films was stored at 85 ° C. and 85% RH for 100 hours, and then a total of five 3 cm × 12 cm samples were wound around a 5 mm diameter rod, and the number of cracks generated was measured. Was measured and evaluated. The evaluation results are listed in the item “Crack” in the table below.
×: 21 or more △: 11 to 20 △: 4 to 10 ○: 1 to 3 ◎: No occurrence.

(Lamp illuminance)
After each gas barrier film was formed over 2000 m, the illuminance of the lamp used for the modification was measured by measuring with a UV (VUV) illuminometer. The ratio of the UV illuminance after 2000 m film formation to the UV illuminance before 2000 m film formation was calculated. The lamp illuminance was evaluated according to the following evaluation criteria.
A: 98% or more B: 93% or more, less than 98% Δ: 85% or more, less than 93% Δ ×: 70% or more, less than 85% ×: less than 70%

As shown in Table 1-2 above, Examples 1-1 to 1-8 were compared by using a solvent having a solubility parameter within a specific range in each of the first barrier layer formation and the second barrier layer formation. Compared to Examples 1-3 to 1-5, it can be seen that excellent barrier performance was exhibited even under high temperature and high humidity, and the occurrence of cracks could be prevented. Further, in comparison with Comparative Examples 1-3 to 1-5, in Examples 1-1 to 1-8, even when a 2000 m long film was produced, the barrier performance derived from the difference in the degree of modification It can be seen that the decrease in the is suppressed.

Further, in Comparative Example 1-1 in which the solubility parameter of the solvent of the first barrier layer precursor liquid is smaller than that of the production method of the present invention, the first barrier layer (second layer) was not formed. In Comparative Example 1-2, where the solubility parameter of the solvent of the second barrier layer precursor liquid is larger than the specified range of the production method of the present invention, the second barrier layer (third layer) was not formed.

Further, when Examples 2-1 to 2-3 in Table 2-2 are compared with Comparative Example 2-1, the thickness of the second barrier layer is 200 nm in Examples 2-1 to 2-3. It turns out that even if it becomes thick, the barrier performance fall by the crack generation under high temperature and high humidity is suppressed, and also the barrier performance fall after forming a long body is also controlled.

In the example of Table 3-2 above, the first barrier layer and the second barrier layer are formed by simultaneous multilayer coating. In the case of the simultaneous multi-layer coating method, the first barrier layer and the second barrier layer are mostly used by using a solvent having a solubility parameter in a specific range for each of the solvent for the first barrier layer and the solvent for the second barrier layer. Th1 is formed with a predetermined thickness without mixing. Therefore, it can be seen that a decrease in barrier performance due to the occurrence of cracks at high temperature and high humidity and a decrease in lamp illuminance over time are suppressed.

Note that this application is based on Japanese Patent Application No. 2014-146138 filed on July 16, 2014, the disclosure of which is incorporated by reference in its entirety.

Claims

On the resin substrate, it has a barrier layer containing a silicon compound and a metal atom, the barrier layer,
The region A of the film thickness Th1 in which the ratio Si: M of the silicon element amount Si and the metal element amount M is 1: x and x ≧ 2,
A ratio B of silicon element amount Si and metal element amount M Si: M is 1: 1 to 1: 0.1, and region B of film thickness Th2 includes:
The Th1 and Th2 are the following formulas (1) and (2):
(1) Th1 / Th2 ≧ 2
(2) 20 nm ≦ Th1 <300 nm
Satisfying gas barrier film.
The gas barrier film according to claim 1, wherein the metal atom is at least one selected from the group consisting of a boron atom (B), an aluminum atom (Al), a titanium atom (Ti), and a zirconium atom (Zr).
The silicon compound has the following general formula (1):

In the general formula (1), R 1 , R 2 and R 3 each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, aryl group, vinyl group or (trialkoxysilyl) alkyl group. ,
The gas barrier film according to claim 1, which is obtained by modifying a silicon compound precursor having a structure represented by the following: irradiation with active energy rays.
The gas barrier film according to any one of claims 1 to 3, further comprising an inorganic barrier layer formed by a chemical vapor deposition (CVD) method between the resin substrate and the barrier layer.
A first barrier layer precursor solution containing a silicon compound precursor and a solvent having a solubility parameter of 15.5 to 20.0, and a metal compound and a solvent having a solubility parameter of 26.0 to 32.0 are formed on the resin substrate. The manufacturing method of a gas barrier film which has a film-forming process including apply | coating a 2nd barrier layer precursor liquid.
6. The difference between the solubility parameter of the solvent contained in the first barrier layer precursor solution and the solubility parameter of the solvent contained in the second barrier layer precursor solution is 7.5 to 17.5. The manufacturing method as described.
The silicon compound precursor is represented by the following general formula (1):

In the general formula (1), R 1 , R 2 and R 3 each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, aryl group, vinyl group or (trialkoxysilyl) alkyl group. ,
A precursor having a structure represented by:
The manufacturing method of Claim 5 or 6 including the modification | reformation process which modify | reforms the said silicon compound precursor by irradiating an active energy ray after the said film-forming process.
The inorganic barrier layer forming step of forming an inorganic barrier layer on the resin base material by a chemical vapor deposition (CVD) method before the film forming step. The manufacturing method as described in.
An electronic device comprising the gas barrier film according to any one of claims 1 to 4 or the gas barrier film obtained by the production method according to any one of claims 5 to 8.