KR20160049002A - Functional film - Google Patents

Abstract

It is an object of the present invention to provide a functional film excellent in durability and bending resistance under high temperature and high humidity. The present invention relates to a cerium-zirconium oxide-based metal complex oxide represented by the following general formula (1): wherein M represents at least one kind selected from the group consisting of Group 13 elements of the long form periodic table and w, x, y and z represent M, (1) to (4)), and the absorption intensity derived from Si-O around 1050 cm ^-1 observed in the IR spectrum (I _[Si-H] / I _[Si-O] ) of the absorption intensity derived from Si-H near 2200 cm ^-1 is 0.03 or less.

Description

Functional film {FUNCTIONAL FILM}

The present invention relates to a functional film. The functional film of the present invention is a film having a function, and the function means an action performed through physical and / or chemical phenomena. The functional film of the present invention includes a film having various functions such as a gas barrier layer, an electric insulating layer, a hard coating layer (upper layer of abrasion resistance), a foreign matter prevention layer, and a refractive index control layer.

Conventionally, it is known that a silica-based ceramic film as an example of a functional film is useful in various fields such as semiconductor devices, liquid crystal display devices, organic EL display devices, and printed circuit boards.

10, No. 1, 2004 (JS Lewis and MS Weaver, " Thin-Film Permeation-Barrier Technology for Flexible Organic Light-Emitting Devices ", IEEE Journal of Selected Topics in Quantum Electronics, Vol. , pp. 45-57) discloses a method in which a plurality of silica-based ceramics films prepared by a method such as applying energy such as heat or light to a precursor of a silica-based ceramics film subjected to vacuum film formation or wet film formation, Lt; / RTI >

However, the silica-based ceramics film as described above is insufficient in durability under high temperature and high humidity, and is not sufficiently bend resistant when it is used for a very long period of time, severe high temperature and high humidity, or repeatedly bending.

SUMMARY OF THE INVENTION Accordingly, it is an object of the present invention to provide a functional film excellent in durability and bending resistance under high temperature and high humidity.

The present inventor has conducted intensive studies to solve the above problems. As a result, the following formula (1):

[Chemical Formula 1]

(Wherein M represents at least one member selected from the group consisting of Group 13 elements of the long form periodic table and w, x, y, and z are elemental ratios of M, oxygen, nitrogen, The following formulas (1) to (4)

[Equation 1]

Lt; / RTI >

Comprises a chemical composition, it expressed in, and also the vicinity of 1050cm ^-1 ratio (I _{[Si -H} of the absorption intensity derived from Si-H in the vicinity of 2200cm ^-1 to the absorption intensity derived from Si-O observed in the IR spectrum _] / I _{[ Si- O]} ) is 0.03 or less. The present invention has been accomplished on the basis of these findings.

BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic view schematically showing one embodiment of a CVD apparatus usable for the production of a gas barrier film comprising the functional film of the present invention. Fig. 1, reference numeral 10 denotes a plasma CVD (PECVD) apparatus, reference numeral 11 denotes a substrate for thin film formation, reference numeral 12 denotes a chamber, reference numeral 13 denotes an upper electrode, reference numeral 14 denotes a lower electrode, reference numeral 15 denotes a power supply apparatus 20a, 20b, 20c and 22 are valves for controlling the flow rate of the gas to be supplied to the valves, 16a and 16b for the source gas storage, 16c for the associated gas storage, 17 for the piping, 18 for the gas inlet, 19 for the plasma discharge region, And reference numeral 21 denotes a vacuum pump.
2 is a schematic view schematically showing one embodiment of a CVD apparatus usable for the production of the gas barrier film according to the present invention. 2, reference numeral 31 denotes a manufacturing apparatus, reference numeral 32 denotes a delivery roller, reference numerals 33, 34, 35 and 36 denote conveying rollers, reference numerals 39 and 40 denote deposition rollers, reference numeral 41 denotes a gas supply Reference numeral 42 denotes a power source for generating a plasma, reference numerals 43 and 44 denote magnetic field generating devices, and reference numeral 45 denotes a take-up roller.

Hereinafter, embodiments for carrying out the present invention will be described in detail. The present invention is not limited to the following embodiments. In addition, the dimensional ratios in the drawings are exaggerated for convenience of explanation, and may differ from actual ratios. In the present specification, " X to Y " representing the range means " X to Y or less ", and " weight ", " weight ", "Quot; is treated as a synonym. Unless otherwise noted, the measurement of the operation and physical properties is carried out under the conditions of room temperature (20 to 25 ° C) / relative humidity of 40 to 50%.

{Functional membrane}

According to a first aspect of the present invention, there is provided a compound represented by the following formula (1):

(2)

(Wherein M represents at least one member selected from the group consisting of Group 13 elements of the long form periodic table and w, x, y, and z are elemental ratios of M, oxygen, nitrogen, The following formulas (1) to (4)

&Quot; (2) "

Lt; / RTI >

Comprises a chemical composition, expressed in, and also the IR spectrum observed in the vicinity of 1050cm ^-1 of Si-O in the absorption intensity derived from Si-H in the vicinity of 2200cm ^-1 to the absorption intensity derived from the ratio (I _{[Si-H ]} / I _[Si-O] ) is 0.03 or less.

That is, having a chemical composition (SiM _w O _x N _y C _z), represented by the general formula (1) membrane functionality of the invention, M, the element ratio (atomic ratio) on oxygen, nitrogen, and each of the silicon-carbon, respectively The ratio of the absorption intensity derived from Si-H to the absorption intensity derived from Si-O observed in the IR spectrum (I _{[ Si- H]} / I (4) _[Si-O] ) is 0.03 or less. The functional film of the present invention having such a constitution can exhibit its function even after being stored under severe high temperature and high humidity conditions (that is, has durability under high temperature and high humidity), and has sufficient bending resistance even when used repeatedly.

In the functional film of the present invention as a whole, the chemical composition of the present invention (that is, the chemical composition expressed by the above-described chemical formula (1) that satisfies the above formulas (1) to (4) When the total thickness of the functional film is 100% or more, the effect of the present invention can be exhibited when it is 20% or more, preferably 50% or more, more preferably 80% or more. Lt; / RTI > From the viewpoint of avoiding the number of surface adsorption of the functional film and the influence of organic substance contamination, it is preferable that the above region is present from a portion of not more than 3% on the outermost surface of the functional film, and it is preferable that the above region exists from a portion of not more than 20%.

In the following description, the gas barrier layer (also referred to as " gas barrier film ") which is an example of the function of the functional film of the present invention is described, but the present invention is not limited thereto.

In the present invention, a functional element film each having SiM _w O _x N _y C _z is presumed that a composition to form a network by covalent bonds to each other. At this time, a hydrogen element derived from the raw material to be used or moisture in the air or the like may be present in the network.

A description will be given of the M, oxygen, meaning that defines the element for the non-nitrogen, and carbon, each of the silicon in the formula _{SiM w O x N y C z} .

By adding the metal component M to the SiO _x N _y C _z composition and forming the SiM _w O _x N _y C _z composition, a dense functional film is formed by the coordination effect of the metal M having Lewis acidity and oxygen and nitrogen having Lewis basicity And the effect of the present invention is estimated to be obtained. The metal M is not particularly limited as far as it is at least one metal selected from the group consisting of elements belonging to Group 13 of the long-form periodic table (namely, boron, aluminum, gallium, indium, thallium and un- , Indium and thallium, more preferably at least one metal selected from the group consisting of boron, aluminum and indium, and particularly preferably aluminum.

In the present invention, the element ratio w of M to silicon is preferably 0.01 <w <1.00, more preferably 0.03 <w <0.30. When w is less than 0.01, there is a possibility that the coordination bond is small and the strength of the film becomes insufficient. On the other hand, when w is 1.00 or more, since there are many metal components in the functional film, initial gas barrier properties may be deteriorated.

Oxygen component in SiM _w O _x N _y C _z composition has the effect of forming a stable bond with the Si element. The element ratio x of oxygen to silicon is preferably 1.00 < x < 2.40, more preferably 1.50 < x < 2.20. When it is in the range of 1.00 < x < 2.40, it is revealed that oxygen atoms and silicon atoms are alternately combined to form Si-O-Si bonds and form a stable composition such as SiO ₂ . On the other hand, when x is 1.00 or less, the stability is insufficient because the ratio of Si-O-Si bonds having high stability in the functional film is small, and gas barrier properties are likely to be deteriorated when stored under severe high temperature and high humidity conditions have. When the ratio of Si-O-Si bonds in the functional film is large when x is 2.40 or more, the Si-OH bond ratio in the hydrolyzate of the Si-O-Si bond also increases, There is a fear that it will be deteriorated.

The nitrogen component in the SiM _w O _x N _y C _z composition is too high, reduction in a stable structure of Si-O-Si ratio of the coupling, and is more a functional film within a Si-N-Si ratio of the combined, severe high-temperature high-humidity There is a possibility that Si-OH is produced by hydrolysis by moist heat when stored under the conditions, resulting in deterioration of gas barrier properties. On the other hand, the nitrogen atom has a higher Lewis basicity than the oxygen atom, forms a coordination bond with the metal element M, and the densifying effect of the film tends to be larger than that of oxygen. Therefore, the element ratio y of nitrogen to silicon is preferably 0.00? Y <0.40, more preferably 0.01? Y <0.20.

_W O _x C _y N _z SiM carbon component in the composition has the effect of improving the functional film bending resistance. It is preferable that 0.01 <z <1.00, and more preferably 0.04 <z <0.50 from the viewpoint of achieving both durability under high temperature and high humidity and bending tolerance of carbon to silicon with respect to silicon.

In the present invention, the element ratio (atomic ratio) in the film thickness direction of each component is measured by using the following apparatus and method for the values of w, x, y, and z described above You can decide.

XPS analysis conditions

Apparatus: QUANTERASXM (manufactured by ULVAC-PY)

X-ray source: Monochromated Al-Kα

Measurement area: Si2p, C1s, N1s, O1s, M *

(M * is the optimum measurement area for the metal, for example in the case of boron: B1s; in the case of aluminum: Al2p; in the case of gallium: Ga3d or Ga2p; in case of indium: In3d; Case: Tl4f)

Sputter ion: Ar (2 keV)

Depth profile: repeat the measurement after 1 minute of sputtering. The single measurement corresponds to a thickness of about 5 nm in terms of a SiO ₂ thin film standard sample. In the case where there are influences of the surface adsorption number of the functional film and the contamination of organic matter, the first measurement data is excluded.

Quantitation: The background was determined by the Shirley method and quantified using the relative sensitivity coefficient method from the obtained peak area.

Data processing: MultiPak (manufactured by ULVAC-PY)

The ratio (I _{[Si -H]} of the absorption intensity derived from Si-H in the vicinity of 2200cm ^-1 to the absorption intensity derived from Si-O in the vicinity of 1050cm ^-1 functional film was observed by the IR spectrum / I _{[Si -O]} ) should be 0.03 or less, more preferably 0.01 to 0.03. When the value of I _[Si-H] / I _[Si-O] exceeds 0.03, in a state of high Si-H bonds in the functional film, particularly in an environment of harsh high temperature and high humidity such as 95 deg. There is a possibility that Si-H bonds are hydrolyzed by the moist heat and the Si-OH is produced, resulting in deterioration of gas barrier properties. In particular, even in the case of being subjected to the above-mentioned severe high-temperature and high-humidity environment over a long period of time, deterioration of the gas barrier property can be suppressed.

Therefore, in order to achieve durability and bending resistance under severe high temperature and high humidity conditions with high gas barrier properties, the elemental ratio of silicon, oxygen, nitrogen and carbon in the formula SiM _w O _x N _y C _z is , The value of (I _[Si-H] / I _[Si-O] ) needs to be 0.03 or less in addition to satisfying all of the above-mentioned expressions (1) to (4).

In the present invention, the IR spectrum (infrared absorption) is measured by a method such as a transmission method or a reflection method. In the transmission method, since the infrared absorption based on the Si-O bond derived from the glass substrate affects the infrared absorption of the functional film, a functional film is formed on the KBr plate or the CaF plate instead of the glass substrate, or a substrate containing the functional film And can be measured. In addition, as the reflection method, attenuated total reflection (ATR) method is preferably used since the selection range of the substrate is wide. However, since the IR spectrum obtained by the ATR method differs in depth through the sample depending on the wavelength, it is necessary to correct the IR spectrum by the reciprocal of the wavelength (1 /?). Thus, the absorption intensity (absorption spectrum) obtained by the transmission method can be corrected. Usually, the correction is built in the software of the infrared absorption measuring device, and can be easily performed. In the IR spectrum, &quot; near &quot; is meant to be included in the numerical range of ± 30 cm ^-1 of the above-mentioned numerical value.

In the present specification, a value obtained by correcting the spectrum obtained by the transmission method and the ATR method with the spectrum obtained by the transmission method is adopted as the value of "I _{[ Si- H]} " and the value of "I _{[ Si- O]} " . In the transmission method, when the infrared absorption by the substrate used can not be ignored, a countermeasure such as providing a substrate on the reference light side is performed to cancel the absorption from the substrate. In addition, in the ATR method, since the reflection method penetrates deeper than the functional film, when the infrared absorption by the substrate to be used is detected, the infrared absorption of only the substrate is separately measured and the infrared absorption of the measurement sample (functional film containing the substrate) _Quot; I _{[ Si- H]} &quot; value and &quot; I _{[ Si- O]} &quot; value derived from the functional film can be measured by subtracting the absorption from the substrate in absorption.

Further, in the functional film having SiM _w O _x N _y C _z composition, may indicate a relationship of the respective components by the formula [(2x + 3y + 4z) / (4 + 3w)]. In this case, (4 + 3w) represents the bond of silicon and the metal element M, and (2x + 3y + 4z) represents the bond of oxygen, nitrogen and carbon. In the present invention, from the viewpoint of forming a stable functional film, the value of [(2x + 3y + 4z) / (4 + 3w)] exceeds 0.8, ) / (4 + 3w)] < 1.5, and the closer to 1, the more preferable. The most ideal form is that in which [(2x + 3y + 4z) / (4 + 3w)] has a value of 1, and in this case the binding of all elements forms the most stable bond (for example, A state in which a high element and a low element alternately form a bond) and becomes a very firm and dense functional film.

The thickness of the functional film of the present invention is not particularly limited as long as it does not impair the effect of the present invention, and can be set appropriately according to the intended use. For example, when the functional film of the present invention is used as a gas barrier layer, the thickness is preferably 1 to 500 nm, more preferably 5 to 300 nm, and further preferably 10 to 200 nm.

{Method of forming a functional film}

Next, a preferred method of forming the functional film of the present invention will be described. The functional film of the present invention can be formed on the surface of a substrate suitably selected according to the intended use. The term "on the surface of the substrate" when forming the functional film of the present invention means "on at least one surface of the substrate" and is not limited to a form in which a functional film is directly formed on at least one surface of the substrate , Or a functional film may be formed through another layer.

The vapor deposition method such as physical vapor deposition (PVD), atomic layer deposition (ALD) or chemical vapor deposition (CVD), or coating liquid containing an inorganic compound, (Hereinafter simply referred to as &quot; coating method &quot;) is preferably used in which a coating film formed by applying a coating liquid containing a polysilazane compound is subjected to a modification treatment.

Hereinafter, each of the vapor phase film formation method and the coating method will be described.

<Vapor Deposition Method>

Physical Vapor Deposition (PVD) is a method of depositing a thin film of a target material, for example, a carbon film, on the surface of a material in a vapor phase by a physical method. For example, a sputtering method (Such as 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.

In the sputtering method, a target is placed in a vacuum chamber, a rare gas (usually argon) ionized by high voltage is applied to a target such as, for example, silicon oxide (SiO _x ) . At this time, a reactive sputtering method may be used in which a nitrogen gas or an oxygen gas is flowed into the chamber to react an element separated from the target by argon gas with nitrogen or oxygen to form an inorganic layer.

Atomic Layer Deposition (ALD) is a method of using chemisorption and chemical reaction of a plurality of low-energy gases on the support surface. Since the sputtering method and the CVD method use high energy particles and cause pinholes and damage of the thin film produced, this method uses a plurality of low-energy gases, so that pinholes and damage are less likely to occur (Japanese Unexamined Patent Application, First Publication No. 2003-347042, Japanese Unexamined Patent Publication No. 2004-535514, International Publication No. 2004/105149, etc.).

Chemical Vapor Deposition (CVD) is a method in which a raw material gas containing a component of a target thin film is supplied onto the surface of a base material, and a film is deposited by chemical reaction on the surface of the base material or in the vapor phase . For the purpose of activating a chemical reaction, there is a method of generating a plasma or the like, and known CVD methods such as a thermal CVD method, a catalytic chemical vapor deposition method, a photo CVD method, a vacuum plasma CVD method, an atmospheric pressure plasma CVD method, . It is preferable to use a plasma CVD method such as a vacuum plasma CVD method or an atmospheric pressure plasma CVD method from the viewpoint of the deposition rate and the processing area.

As one mode of the embodiment of the present invention, a plasma CVD apparatus (a system in which a substrate is fixed instead of a roll-to-roll system) shown in Fig. 1 is used, The film is formed (formed).

The structure of the plasma CVD apparatus 10 is as shown in Fig. In the present invention, a substrate appropriately selected is mounted on the substrate 11 for forming a thin film of the lower electrode 14, and a film forming gas (for example, an organic silicon compound gas such as HMDSO gas (source gas) 22b, 22c, and 22 and the power application degree by the power source device 15 are controlled by appropriately employing the reaction gas and the carrier gas such as helium gas as described later, (For example, a flow rate or flow rate ratio of the organic silicon compound and oxygen gas), a plasma discharge amount (for example, a magnitude of the input power per unit flow rate of the organic silicon compound gas) May be adjusted within a predetermined range to form a desired functional film as a vapor deposition film on the appropriately selected substrate. The detailed operation of the plasma CVD apparatus 10 is not particularly limited, and examples of the present invention can be suitably referred to, for example.

As film forming gas for forming the functional film of the present invention, if there is a respective element components of the composition SiM _w O _x N _y C _z is contained is not particularly limited, for example, a compound containing silicon as a raw material gas gas, the long A gas of a compound containing at least one kind of metal M selected from the group consisting of elements belonging to Group 13 of the periodic table of the elements (hereinafter abbreviated simply as "metal M"), and a gas containing a compound containing carbon, A reaction gas for forming an oxide and a reaction gas for forming a nitride may be used together or a gas of a compound in which silicon, metal M and carbon coexist may be used as the source gas.

Examples of the gas of the silicon-containing compound used in the present invention include hexamethyldisiloxane (HMDSO), hexamethyldisilane siloxane (HMDS), 1,1,3,3-tetramethyldisiloxane, vinyltrimethylsilane , Methyltrimethylsilane, hexamethyldisilane, silane, methylsilane, dimethylsilane, trimethylsilane, tetramethylsilane, diethylsilane, propylsilane, phenylsilane, vinyltriethoxysilane, vinyltrimethoxysilane, tetramethoxy Silane (TMOS) and tetraethoxysilane (TEOS). Of these, hexamethyldisiloxane and 1,1,3,3-tetramethyldisiloxane are preferred from the viewpoints of handleability of the compound and properties of the resulting functional film such as gas barrier properties. These film forming gases may be used singly or in combination of two or more.

Examples of the gas of the carbon-containing compound used in the present invention include methane, ethane, ethylene and acetylene. These film forming gases may be used singly or in combination of two or more.

Examples of the gas of the compound containing the metal M used in the present invention include trimethylaluminum, triethylaluminum, trichloroaluminum, borane, diborane, trimethoxyborane, triethoxyborane, trichloroborane, trimethylgallium , Trimethoxy gallium, trichlor gallium, trimethyl indium, trimethoxy indium, trichloro indium, trimethyl thallium, trimethoxy thallium, trichlorotallium and the like. These film forming gases may be used singly or in combination of two or more.

Examples of the reaction gas for forming the oxide used in the present invention include oxygen and ozone. As the reaction gas for forming nitride, for example, nitrogen and ammonia can be mentioned. These reaction gases can be used singly or in combination of two or more. For example, in the case of forming an oxynitride, a reaction gas for forming an oxide and a reaction gas for forming a nitride are combined Can be used.

As the film forming gas, a carrier gas may be used, if necessary, in order to supply the raw material gas into the vacuum chamber. As the film forming gas, a discharge gas may be used, if necessary, in order to generate a plasma discharge. As the carrier gas and the discharge gas, any well-known gas may be used. For example, a rare gas such as helium, argon, neon, or xenon or hydrogen gas may be used.

In the formation of the functional film of the present invention, by adjusting the feed rate ratio or flow rate ratio of the above-described film-forming gas composition SiM _w O _x N _y C a in the _z w, x, y and z the above formulas (1) to ( 4) a satisfactory and also non-(I _{[Si -H]} of the absorption intensity derived from Si-H in the vicinity of 2200cm ^-1 to the absorption intensity derived from Si-O in the vicinity of 1050cm ^-1 were observed in the IR spectrum / I _{[ Si- O]} ) is 0.03 or less. When the film forming gas contains the raw material gas and the reactive gas, the ratio of the raw material gas to the reactive gas is preferably set such that the ratio of the reactive gas is excessively larger than the ratio of the amount of the reactive gas required for the complete reaction of the raw material gas and the reactive gas . This is because it is possible to effectively exhibit excellent barrier property and bending resistance in the formed functional film by controlling the ratio of the reactive gas so as not to excess. When the film forming gas contains the organic silicon compound and oxygen, it is preferable that the total amount of the organic silicon compound in the film forming gas is not more than the theoretical oxygen amount required for complete oxidation. Further, by increasing the supply amount such as hydrogen gas, ammonia gas _{(I [Si-H] /} I [Si-O]) and the value of it can be increased, by increasing the supply amount of oxygen gas, (I _{[Si-H ]} / I _[Si-O] ) can be decreased.

The functional film of the present invention can be formed by using the CVD apparatus shown in Fig. 1, but also by using a roll-to-roll vacuum film forming apparatus (CVD apparatus 31 shown in Fig. 2) It may also be a tabernacle. Hereinafter, the case where the functional film of the present invention is produced by the CVD apparatus 31 shown in Fig. 2 will be described as an example.

2 is a schematic structural view showing an example of a film forming apparatus.

2, the film forming apparatus 31 includes a feed roller 32, conveying rollers 33 to 36, first and second film-forming rollers 39 and 40, a take-up roller 45, A gas supply port 41, a plasma generating power source (not shown), magnetic field generators 43 and 44, a vacuum chamber (not shown), a vacuum pump (not shown) Not shown).

The feed roller 32, the conveying rollers 33 to 36, the first and second film forming rollers 39 and 40, and the winding roller 45 are housed in a vacuum chamber.

The feed roller 32 feeds the base material 2, which is installed in a previously wound state, toward the conveying roll 11. The delivery roller 32 is a cylindrical roll extending in the direction perpendicular to the paper surface and is rotated counterclockwise (see arrows in Fig. 1) by a drive motor (not shown) (1) toward the conveying roll (11). As the base material 2, a film or sheet containing a resin or a composite material containing a resin is preferably used.

The conveying rollers 33 to 36 are cylindrical rolls configured to be rotatable about a rotation axis substantially parallel to the feed-out roller 32. [ The conveying roller 33 is a roller for conveying the base material from the delivery roller 32 to the film forming roller 39 while giving a proper tension to the base material. The conveying rollers 34 and 35 are rollers for conveying the substrate from the film forming roller 39 to the film forming roller 40 while giving appropriate tension to the substrate formed by the film forming roller 39. [ The conveying roller 36 is a roll for conveying the substrate from the film forming roller 40 to the take-up roller 45 while imparting an appropriate tension to the substrate formed by the film forming roller 40. [

The first film-formation roller 39 and the second film-formation roller 40 are a pair of film-forming rolls having rotation axes substantially parallel to the feed-out rollers 32, and spaced apart from each other by a predetermined distance. The first film-formation roller 39 and the second film-formation roller 40 are discharge electrodes formed of a conductive material and are insulated from each other. The material and configuration of the first film-formation roller 39 and the second film-formation roller 40 can be appropriately selected so as to achieve a desired function as an electrode. In addition, magnetic field generators 43 and 44 are provided inside the first and second film-forming rollers 39 and 40, respectively. A high frequency voltage for generating plasma is applied to the first film forming roller (39) and the second film forming roller (40) by a plasma generating power source. Thereby, an electric field is formed in the film forming space between the first film forming roller 39 and the second film forming roller 40, and a discharge plasma of the film forming gas supplied from the gas supply port 41 is generated.

The take-up roller 45 has a rotation axis substantially parallel to the feed roller 32, and the base material is taken up and received in a roll shape. The winding roller 45 is rotated in a counterclockwise direction (see an arrow in Fig. 2) by a driving motor (not shown) to wind the base material.

The base material fed out from the delivery roller 32 is wound around the delivery rollers 32 to 45 by the delivery rollers 33 to 36, the first deposition roller 39 and the second deposition roller 40 Thereby being conveyed by the rotation of each of these rolls while maintaining an appropriate tension. In addition, the carrying direction of the substrate is indicated by an arrow. The transporting speed of the substrate can be appropriately adjusted in accordance with the kind of the raw material gas, the pressure in the vacuum chamber, and the like. The conveying speed is preferably 0.1 to 100 m / min, more preferably 0.5 to 20 m / min. The conveying speed is adjusted by controlling the rotation speed of the drive motor of the feed roller 32 and the take-up roller 45 by the control unit 41.

When the film forming apparatus is used, the transporting direction of the substrate is set to be opposite to the direction indicated by the arrow in Fig. 2 (hereinafter referred to as forward direction) (hereinafter referred to as reverse direction) . Specifically, the control unit controls the rotation direction of the drive motor of the feed-out roller 32 and the take-up roller 45 to rotate in a direction opposite to the above-described case in a state in which the substrate is wound by the takeup roller 45. [ The base material fed from the winding roller 45 is conveyed between the feeding roller 32 and the winding roller 45 by the conveying rollers 33 to 36, the first film forming roller 39 and the second film forming roller 40, and is conveyed in the reverse direction by the rotation of each of these rolls while maintaining an appropriate tension.

The gas supply port 41 supplies a film forming gas such as a source gas of plasma CVD to the vacuum chamber. The gas supply port 41 has a tubular shape extending in the same direction as the rotation axis of the first film formation roller 39 and the second film formation roller 40 above the film formation space, The film forming gas is supplied into the chamber.

The film forming gas such as a raw material gas is the same as the description of the film forming gas when the CVD apparatus shown in Fig. 1 is used, and therefore the description thereof is omitted here.

In the present invention, the feed rate of the deposition gas / the feed rate of the reactive gas is not particularly limited, but is preferably 0.04 to 0.2, more preferably 0.06 to 0.15 from the viewpoint of gas barrier properties.

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

The magnetic field generators 43 and 44 are members that form a magnetic field in the film forming space S between the first film forming roller 39 and the second film forming roller 40. The first film forming roller 39 and the second film forming roller 40, but is stored at a predetermined position.

The vacuum chamber keeps the depressurized state by sealing the delivery roller 32, the conveying rollers 33 to 36, the first and second film forming rollers 39 and 40, and the winding roller 45. The pressure (vacuum degree) in the vacuum chamber can be appropriately adjusted according to the kind of the raw material gas or the like. The pressure of the film forming space is preferably 0.1 to 50 Pa. Depending on the purpose of suppressing the gas phase reaction, when plasma CVD is performed by the low pressure plasma CVD method, it is usually 0.1 to 100 Pa.

The vacuum pump is communicably connected to the control unit, and appropriately adjusts the pressure in the vacuum chamber 30 in accordance with an instruction from the control unit.

The control unit controls each component of the film forming apparatus 31. The control unit is connected to the drive motor of the feed-out roller 32 and the take-up roller 45, and controls the rotation speed of these drive motors to adjust the conveying speed of the substrate. Further, by controlling the rotation direction of the drive motor, the transport direction of the substrate is changed. Further, the control unit is connected so as to be capable of communicating with a not-shown film forming gas supply mechanism, and controls the supply amount of each component gas of the film forming gas. Further, the control unit is connected to be capable of communicating with the plasma generating power source, and controls the output voltage and the output frequency of the plasma generating power source. Further, the control unit is communicably connected to the vacuum pump, and controls the vacuum pump 40 so as to maintain the inside of the vacuum chamber at a predetermined reduced-pressure atmosphere. The control unit includes a central processing unit (CPU), a hard disk drive (HDD), a random access memory (RAM), and a read only memory (ROM). A software program describing a procedure for realizing a method of manufacturing a gas barrier film by controlling each component of the film forming apparatus 31 is stored in the HDD. When the power of the film forming apparatus 31 is turned on, the software program is loaded into the RAM and executed in order by the CPU. In the ROM, various data and parameters used by the CPU to execute the software program are stored.

As described above, the functional film of the present invention having the chemical composition expressed by the chemical formula (1) can be formed by suitably selecting the film forming gas such as the raw material gas and the reactive gas to be used by using the above-described film forming apparatus. Thus, the carbon distribution curve showing the relationship between the distance from the surface of the functional film in the film thickness direction of the formed functional film and the carbon atom ratio to the total amount of silicon atoms, metal elements M, oxygen atoms, nitrogen atoms and carbon atoms is substantially And has at least one extremum. By determining the composition of the functional film so as to satisfy this condition, a functional film having sufficient gas barrier properties can be formed. Further, the relationship between the composition of the functional film obtained by the film forming apparatus and the gas barrier property and the details of the carbon distribution curve are well known and will not be described in detail.

<Coating method>

The functional film of the present invention can be formed by a coating method on the surface of a substrate appropriately selected according to the intended use. As the coating liquid that is used, if the each composition element component of the composition SiM _w O _x N _y C _z is contained is not particularly limited, for example, containing a compound containing silicon, a metal M, oxygen, nitrogen, and carbon A coating liquid containing a coating liquid, preferably a silicon compound containing nitrogen and a compound of metal M, more preferably a coating liquid containing a compound of polysilazane compound and organic metal M is applied and dried And a method of applying (modifying) energy to the coating film.

(Silicon compound containing nitrogen)

When preparing a coating liquid for forming the functional film of the present invention, a silicon compound containing nitrogen to be used in combination with a compound of the organometallic M can be used as long as it is possible to prepare a coating liquid containing a silicon compound containing the nitrogen For example, a polysilazane compound, a silazane compound, an aminosilane compound, a silyl acetamide compound, a silylimidazole compound, and a silicon compound containing nitrogen are used.

(Polysilazane compound)

In the present invention, the polysilazane compound is a polymer having a silicon-nitrogen bond. Specifically, it is a ceramic precursor inorganic polymer having bonds such as Si-N, Si-H, and NH in the structure thereof and SiO ₂ , Si ₃ N ₄ and both intermediate solid solution SiO _x N _y . In the present specification, the term "polysilazane compound" is also abbreviated as "polysilazane".

More specifically, the polysilazane compound preferably has a structure represented by the following general formula (I).

(3)

In the general formula (I), R ₁ , R ₂ and R ₃ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, an aryl group, a vinyl group or a (trialkoxysilyl) alkyl group. Here, R ₁ , R ₂ and R ₃ may be the same or different. Here, examples of the alkyl group include a straight chain, branched chain or cyclic alkyl group having 1 to 8 carbon atoms. Specific examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec- an n-hexyl group, an n-heptyl group, an n-octyl group, a 2-ethylhexyl group, a cyclopropyl group, a cyclopentyl group and a cyclohexyl group. Examples of the aryl group include an aryl group having 6 to 30 carbon atoms. More specifically, non-condensed hydrocarbon groups such as phenyl group, biphenyl group and terphenyl group; A naphthyl group, an azulenyl group, a heptalenyl group, a biphenylenyl group, a fluorenyl group, an acenaphthylenyl group, a playadenyl group, an acenaphthenyl group, a phenalenyl group, a phenanthryl group, A condensed polycyclic hydrocarbon group such as an anthryl group, a fluoranthenyl group, an acenetanthrylenyl group, an asanantrylenyl group, a triphenylenyl group, a pyrenyl group, a chrysenyl group and a naphthacenyl group. (Trialkoxysilyl) alkyl group include an alkyl group having 1 to 8 carbon atoms and having a silyl group substituted with an alkoxy group having 1 to 8 carbon atoms. More specifically, examples include a 3- (triethoxysilyl) propyl group and a 3- (trimethoxysilyl) propyl group. The substituent present depending on the case of 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) Sulfo group (-SO ₃ H), carboxyl group (-COOH), nitro group (-NO ₂ ) and the like. The substituents present in some cases are not the same as the substituents R ₁ to R ₃ in some cases. For example, when R ₁ to R ₃ are alkyl groups, they are not substituted with alkyl groups again. Of these groups, R ₁ , R ₂ and R _{3 preferably} represent a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert- Ethoxysilyl) propyl group or 3- (trimethoxysilylpropyl) group.

In the general formula (I), n is an integer representing the number of the structural unit of the formula: - [Si (R ₁ ) (R ₂ ) -N (R ₃ )] - Is determined to have a number average molecular weight of 150 to 150,000 g / mol.

In the present invention, one preferred form of the compound having the structure represented by the general formula (I) is a perhydro polysilazane in which all of R ₁ , R ₂ and R ₃ are hydrogen atoms.

Alternatively, as the polysilazane compound, for example, the structure represented by the general formula (II) or the general formula (III) described in paragraphs "0051" to "0056" of Japanese Patent Laid-Open Publication No. 2013-022799 is suitably employed .

Perhydro polysilazane is presumed to have a linear structure and a ring structure centered on 6 and 8-membered rings. Its molecular weight is about 600 to 2,000 (in terms of polystyrene) in terms of the number average molecular weight (Mn), and there is a liquid or solid substance, and the condition differs depending on the molecular weight.

Examples of commercially available polysilazane solutions include NN120-10, NN120-20, NAX120-20, NAX-120, and NN110 manufactured by AZ Electronic Materials Co., , NN310, NN320, NL110A, NL120A, NL120-20, NL150A, NP110, NP140, SP140.

Other examples of polysilazane compounds that can be used in the present invention include, but are not limited to, for example, a polysilazane having a silicon alkoxide group obtained by reacting a polysilazane with a silicon alkoxide (Japanese Laid- (Japanese Unexamined Patent Application Publication No. 6-122852) obtained by reacting glycidol with an alcohol-added polysilazane (Japanese Patent Laid-Open Publication No. 6-240208 (Japanese Unexamined Patent Publication No. 6-299118), an acetylacetonate complex addition product obtained by reacting an acetylacetonate complex containing a metal and a metal carboxylate addition product obtained by reacting a metal carboxylate salt (Japanese Patent Application Laid-Open No. 6-306329), a metal fine particle-added polysilazane obtained by adding metal fine particles Such flat piece No. 7-196986), there may be mentioned the polysilazane compound to a ceramic screen at a low temperature.

(Silazane compound)

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

(Aminosilane compound)

Examples of the aminosilane compound preferably used in the present invention include 3-aminopropyltrimethoxysilane, 3-aminopropyldimethylethoxysilane, 3-arylaminopropyltrimethoxysilane, propylethylenediaminesilane, N- [ Butylaminopropyltrimethylsilane, 3- (trimethoxysilyl) propyl] ethylenediamine, 3-butylaminopropyltrimethylsilane, 3-dimethylaminopropyldiethoxymethylsilane, 2- (2-aminoethylthioethyl) triethoxysilane and bis ) Dimethylsilane, but are not limited thereto.

(Silyl acetamide compound)

Examples of the silyl acetamide compound preferably used in the present invention include N, N-trimethylsilylacetamide, N, O-bis (tert-butyldimethylsilyl) acetamide, N, O- N, O-bis (trimethylsilyl) acetamide, N-trimethylsilylacetamide, and the like, but are not limited thereto.

(Silylimidazole compound)

Examples of silylimidazole compounds preferably used in the present invention include 1- (tert-butyldimethylsilyl) imidazole, 1- (dimethylethylsilyl) imidazole, 1- (dimethylisopropylsilyl) imidazole and N -Trimethylsilylimidazole, and the like, but are not limited thereto.

(Other nitrogen-containing silicon compounds)

In the present invention, in addition to the silicon compound containing nitrogen as described above, for example, bis (trimethylsilyl) carbodiimide, trimethylsilyl azide, N, O-bis (trimethylsilyl) hydroxylamine, 3-bromo-1- (triisopropylsilyl) pyrrole, N-methyl-N, O-bis (trimethylsilyl) Hydroxylamine, 3-isocyanatopropyltriethoxysilane, and silicon tetraisothiocyanate, but are not limited thereto.

Of the above-mentioned nitrogen-containing silicon compounds, polysilazane compounds such as perhydro polysilazane and organopolysilazane are preferred because of few defects such as film formability and cracks and few residual organic substances, Perhydro polysilazane is particularly preferable in that barrier performance is high and gas barrier performance is exhibited even under bending and high temperature and high humidity conditions.

(Compound of metal M)

In the present invention, the compound of the metal M is not particularly limited as long as it is a compound containing at least one metal selected from the group consisting of the Group 13 elements of the long-form periodic table, but a compound of the organic metal M is preferably used. Hereinafter, preferred compounds as the metal M compound are exemplified, but the present invention is not limited thereto.

[Aluminum compound]

In the present invention, an aluminum compound is particularly preferably used as a compound of the metal M from the viewpoint of durability at high temperature and high humidity.

The aluminum compound used in the present invention is not particularly limited, but an organic aluminum compound such as an alkoxide of aluminum or a chelate compound of aluminum can be mentioned. In the present invention, "aluminum alkoxide" refers to a compound having at least one alkoxy group bonded to aluminum.

Examples of the organoaluminum compound used in the present invention include aluminum trimethoxide, aluminum triethoxide, aluminum tri-n-propoxide, aluminum triisopropoxide, aluminum tri-n-butoxide, aluminum tri- , Aluminum tri-tert-butoxide, aluminum acetylacetonate, acetalkoxy aluminum diisopropylate, aluminum ethylacetoacetate diisopropylate, aluminum ethylacetoacetate di n-butyrate, aluminum diethylacetoacetate mono n-butyrate, Aluminum diisopropylate mono sec-butyrate, aluminum tris acetylacetonate, aluminum tris ethyl acetoacetate, bis (ethyl acetoacetate) (2,4-pentanedione) aluminum, aluminum alkyl acetoacetate diisopropylate, Seed Isopropoxide trimer and aluminum oxide octylate trimer, but the present invention is not limited thereto.

The aluminum compound according to the present invention may be a commercially available product or a synthetic product. Specific examples of the commercially available products include, for example, AMD (aluminum diisopropylate mono sec-butyrate), ASBD (aluminum sec-butyrate), ALCH (aluminum ethyl acetoacetate diisopropylate), ALCH- (Aluminum acetylacetate), aluminum chelate M (aluminum alkyl acetoacetate diisopropylate), aluminum chelate D (aluminum bis ethylacetoacetate monoacetylacetonate), aluminum chelate A (W) (aluminum trisacetylacetonate) (Manufactured by Kawaken Fine Chemicals Co., Ltd.), and Pren Act (registered trademark) AL-M (acetal alkoxyaluminum diisopropylate, manufactured by Ajinomoto Fine Chemical Co., Ltd.).

[Boron compound]

Examples of the boron compound used in the present invention include trimethoxyborane, triethoxyborane, tri-n-propyl borate, triisopropyl borate, tri-n-butyl borate, tri-tert- butyl borate and trichloroborane However, the present invention is not limited thereto.

[Gallium compound]

Examples of the gallium compound used in the present invention include, but are not limited to, trimethoxy gallium, triethoxy gallium, trimethyl gallium, trichlorogallium and the like.

[Indium compound]

Examples of the indium compound used in the present invention include, but are not limited to, trimethoxy indium, triethoxy indium, trimethyl indium, and trichloro indium.

[Thallium compound]

Examples of the thallium compound used in the present invention include, but are not limited to, trimethoxytaurium, triethoxytaurium, trimethalithium, trichlorotallium and the like.

The element ratio w of the metal M to silicon in the functional film of the present invention can be controlled by adjusting the amount of the compound of the metal M added to the amount of the silicon element contained in the above polysilazane. The value of w does not substantially change even if coating drying and excimer irradiation treatment for forming a functional film to be described later are performed. Thus, to satisfy the range specified for the value of w in the _w O _x N _y C _z SiM composition in the present invention can determine the added amount of the compound of the metal M.

Further, in the functional film of the present invention, the element ratio x of oxygen to silicon tends to increase at the same time as the addition amount of the compound of the metal M (in particular, the alkoxide of the metal M) increases. On the other hand, the element ratio y of nitrogen to silicon tends to decrease at the same time as the addition amount of the compound of the metal M increases. Thus, although not completely independent, can be controlled so as to satisfy the range specified for the value of x and y in, SiM _w O _x C _y N _z by the addition amount of the composition of a metal M compound in the present invention. The value of I _(Si-H) / I _[Si-O] ) in the IR spectrum of the functional film of the present invention can also be adjusted by the addition amount of the metal M.

The element ratio z of the carbon to silicon in the functional film of the present invention can be obtained by selecting a compound of the organometallic M having a different ratio of the metal M and the carbon contained therein or by increasing or decreasing the excimer irradiation energy, Can be controlled.

In addition to the silicon compound containing the nitrogen and the compound of the metal M described above, the coating liquid forming the functional film of the present invention may contain a silicon compound not containing nitrogen, as long as the effect of the present invention is not impaired. Specific examples thereof include silsesquioxane, tetramethylsilane, trimethylmethoxysilane, dimethyldimethoxysilane, methyltrimethoxysilane, and the like. These nitrogen-free silicon compounds may be used alone or in combination of two or more.

[Functional film-forming coating liquid]

The functional coating liquid for forming a film of the present invention can be prepared by dissolving the aforementioned compound containing silicon, metal M, oxygen, nitrogen and carbon in a suitable solvent. Preferably, the above-described nitrogen-containing silicon compound and organic metal M compound can be prepared by dissolving the compound in an appropriate solvent. The coating liquid for forming a functional film of the present invention may be prepared by mixing the silicon compound containing nitrogen and the compound of the organic metal M and then dissolving the compound in a suitable solvent to prepare the coating liquid. (2) containing a compound of an organic metal M by dissolving a silicon compound in an appropriate solvent to dissolve the coating liquid (1) containing a silicon compound containing nitrogen and a compound of the organic metal M in an appropriate solvent, To prepare a coating liquid. From the viewpoint of the stability of the liquid, it is preferable to prepare the coating liquid by mixing the coating liquid (1) containing the silicon compound containing nitrogen and the coating liquid (2) containing the compound of the organic metal M using the same solvent desirable. The coating liquid (1) may contain one kind of nitrogen-containing silicon compound, two or more kinds of nitrogen-containing silicon compounds, and the above-mentioned nitrogen-free silicon compound Or more. Similarly, the coating liquid (2) may contain one kind of organic metal M compound or two or more kinds of organic metal M compounds.

In the present invention, the solvent for producing the functional film-forming coating liquid is not particularly limited as long as it is capable of dissolving the silicon compound containing nitrogen and the compound of metal M, and examples thereof include silicon compounds containing nitrogen In the case of using a polysilazane compound, it is preferable that the polysilazane compound does not contain water and a reactive group (for example, a hydroxyl group or an amine group) that easily reacts with the polysilazane compound, Are preferable, and aprotic organic solvents are more preferable. Specifically, examples of the solvent include aprotic solvents; Examples of the solvent include hydrocarbon solvents such as aliphatic hydrocarbons, alicyclic hydrocarbons, and aromatic hydrocarbons, such as pentane, hexane, cyclohexane, toluene, xylene, solvesso and terpene; Halogenated hydrocarbon solvents such as methylene chloride and trichloroethane; Esters such as ethyl acetate and butyl acetate; Ketones such as acetone and methyl ethyl ketone; And ethers such as dibutyl ether, dioxane, tetrahydrofuran, mono- and polyalkylene glycol dialkyl ether (diglyme), and the like. These solvents may be used alone or in combination of two or more.

In the present invention, the solid content concentration of the nitrogen-containing silicon compound in the coating liquid (1) is not particularly limited and varies depending on the layer thickness and the time for which the coating liquid is used, Is preferably from 0.1 to 30 mass%, more preferably from 0.5 to 20 mass%, and still more preferably from 1 to 15 mass%.

In the present invention, the solid content concentration of the metal M compound in the coating liquid (2) is not particularly limited and varies depending on the thickness of the layer or the time for which the coating liquid is allowed to be used. Is preferably from 0.1 to 50 mass%, more preferably from 0.5 to 20 mass%, and still more preferably from 1 to 10 mass%.

In the present invention, the mixing molar ratio (coating liquid (1): coating liquid (2)) when mixing the coating liquid (1) and the coating liquid (2) And it is preferable to add the coating liquid 2 so that the metal M content is 1 to 100 mol% with respect to the Si atom in the coating liquid 1, for example, although it can not be said uniformly .

In the present invention, it is preferable to mix the coating liquid (1) and the coating liquid (2) in an inert gas atmosphere. In particular, when the alkoxide of the metal M is used for the coating liquid 2, the oxidation reaction of the alkoxide of the metal M by moisture or oxygen in the atmosphere is suppressed.

It is preferable that the coating liquid (1) and the coating liquid (2) are mixed while heating to 30 to 90 캜 from the viewpoint of controlling the reactivity.

In addition, the coating liquid for forming a functional film of the present invention preferably contains a catalyst in order to promote the modification. Such a catalyst is not particularly limited, and for example, those described in paragraph &quot; 0048 &quot; of Japanese Patent Laid-Open Publication No. 2013-022799 can be suitably employed.

In addition to the coating liquid as described above, the coating liquid prepared by the sol-gel method may be used for forming the functional film of the present invention, as described in Japanese Patent Application Laid-Open No. 2005-231039.

The coating liquid used when the functional film is formed by the sol-gel method contains the silicon compound and the compound of the metal M. [ The coating liquid may contain a sol-gel process catalyst, an acid, water, an organic solvent, a resin or the like. In the sol-gel method, a functional film is obtained by polycondensation using such a coating liquid.

[Method of applying functional liquid coating liquid]

As a method for applying the coating liquid for forming a functional film of the present invention, a conventionally well-known wet coating method may be employed. Specific examples thereof include spin coating, roll coating, flow coating, inkjet, spray coating, printing, dip coating, die coating, flexible coating, bar coating and gravure printing.

The coating thickness can be appropriately set in accordance with the purpose. For example, the coating thickness per one functional layer is preferably from 1 to 500 nm, more preferably from 5 to 300 nm, and further preferably from 10 to 200 nm after drying. When the film thickness is 1 nm or more, sufficient barrier property can be obtained. When the film thickness is 500 nm or less, stable coating property can be obtained at the time of layer formation, and high light transmittance can be realized.

It is preferable to dry the coating film after applying the coating solution. By drying the coating film, the organic solvent contained in the coating film can be removed. At this time, all the organic solvents contained in the coating film may be dried, but some of them may be left. Even when a part of the organic solvent is left, a suitable functional coating liquid for forming a film can be obtained. In addition, the remaining solvent can be removed later.

The drying temperature of the coating film varies depending on the substrate to be applied, but is preferably 50 to 200 ° C. For example, when a polyethylene terephthalate substrate having a glass transition temperature (Tg) of 70 DEG C is used as a substrate, the drying temperature is preferably set to 150 DEG C or less in consideration of deformation of the substrate due to heat and the like. The temperature can be set by using a hot plate, an oven, a furnace, or the like. The drying time is preferably set to a short time. For example, when the drying temperature is 150 ° C, it is preferable to set it within 30 minutes. The drying atmosphere may be any atmosphere such as a nitrogen atmosphere, an argon atmosphere, a vacuum atmosphere, and a reduced pressure atmosphere in which the oxygen concentration is controlled in an air atmosphere.

The coating film obtained by applying the coating liquid for forming a functional film of the present invention may include a step of removing moisture before or during the modification treatment. As a method of removing moisture, it is preferable to carry out dehumidification while maintaining a low humidity environment. Since the humidity in a low humidity environment varies with temperature, the relationship between temperature and humidity appears to be a preferable form according to the specification of the dew point temperature. The preferable dew point temperature is not more than 4 캜 (temperature 25 캜 / humidity 25%), more preferably not more than -5 캜 (temperature 25 캜 / humidity 10%) and the holding time is suitably set according to the film thickness of the functional film . Under the condition that the film thickness of the functional film is 1.0 占 퐉 or less, it is preferable that the dew point temperature is -5 占 폚 or less and the holding time is 1 minute or more. The lower limit of the dew point temperature is not particularly limited, but is usually -50 ° C or higher, preferably -40 ° C or higher. The removal of moisture before or during the reforming process is a preferred form from the viewpoint of promoting the dehydration reaction of the silanol functionalized membrane.

(Modification treatment of functional film)

After the above-mentioned coating liquid is applied, the functional film of the present invention can be formed by a modification treatment. The modifying treatment in the present invention refers to a reaction in which a silicon compound and an additive element compound are converted into a predetermined chemical composition and the gas barrier film when the functional film of the present invention is used as a gas barrier layer has gas barrier properties as a whole To form a directional thin film at a level that can contribute to the expression. For example, the modification treatment for forming the functional film of the present invention refers to a reaction in which the silicon compound and the compound of the metal M are converted into a chemical composition represented by the above-described chemical formula (1).

Such a modifying treatment is carried out by a known method, and specifically includes a heat treatment, a plasma treatment, an active energy ray irradiation treatment and the like. Among them, the treatment with active energy ray irradiation is preferable from the viewpoint that it is possible to modify at low temperature and the degree of freedom in selection of the base material species is high.

[Heat treatment]

Examples of the heat treatment method include a method in which a substrate is brought into contact with a heating element such as a heat block to heat the coating film by heat conduction, a method in which an environment in which a coating film is loaded by an external heater using resistance wires or the like is heated, And a method using light, but the present invention is not limited thereto. In the case of conducting the heat treatment, a method capable of maintaining the smoothness of the coating film may be appropriately selected.

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

[Plasma Treatment]

In the present invention, a known method can be used for the plasma treatment which can be used as the reforming treatment, but from the viewpoint of excellent gas barrier properties, a method of implanting plasma ions is preferable.

As the plasma ion implantation method, there are a method of (A) injecting ions existing in a plasma generated by using an external electric field into the surface portion of a coating film of a functional film, or (B) a method of injecting ions It is preferable to inject ions existing in the plasma generated only by the electric field by the high voltage pulse into the surface portion of the coating film of the functional film.

In the above method (A), it is preferable that the pressure (ion implantation pressure) during ion implantation is 0.01 to 1 Pa. When the pressure at the time of plasma ion implantation is in this range, it is possible to easily and efficiently inject ions uniformly and efficiently form a desired functional film.

In the method (B), there is no need to increase the decompression degree, the processing operation is simple, and the processing time can be greatly shortened. In addition, it is possible to uniformly treat the entire coating film, and ions in the plasma can be continuously injected into the surface portion of the coating film with high energy when a negative high voltage pulse is applied. In addition, by applying a negative high voltage pulse to the coating film without requiring any other means such as a radio frequency (hereinafter abbreviated as &quot; RF &quot;) or a high frequency power source such as a microwave, It is possible to uniformly form an ion-implanted layer having a good quality in the portion.

In both of the methods (A) and (B), it is preferable that the pulse width at the time of applying the negative high voltage pulse, that is, the ion implantation time is 1 to 15 μsec. When the pulse width is within this range, ions can be uniformly injected more efficiently and efficiently.

The applied voltage for generating the plasma is preferably -1 to -50 kV, more preferably -1 to -30 kV, particularly preferably -5 to -20 kV.

Examples of the ions to be implanted include rare-earth ions such as argon, helium, neon, krypton, and xenon; Ions such as fluorocarbon, hydrogen, nitrogen, oxygen, carbon dioxide, chlorine, fluorine, and sulfur; Ions of alkane-based gases such as methane, ethane, propane, butane, pentane, and hexane; Ions of alkene-based gases such as ethylene, propylene, butene, and pentene; Ions of alkadienic gases such as pentadiene and butadiene; Ions of alkyne-based gases such as acetylene and methyl acetylene; Ions of aromatic hydrocarbon gases such as benzene, toluene, xylene, indene, naphthalene, and phenanthrene; Ions of a cycloalkane-based gas such as cyclopropane, cyclohexane and the like; And ions of cycloalkane gas such as cyclopentene and cyclohexene.

The amount of ions to be implanted may be appropriately determined in accordance with the purpose of use (required gas barrier property, transparency, etc.) of the film to be formed.

[Active energy ray irradiation treatment]

As the active energy ray, for example, infrared rays, visible rays, ultraviolet rays, X rays, electron rays, alpha rays, beta rays, gamma rays and the like can be used, but electron beams or ultraviolet rays are preferable and ultraviolet rays are more preferable. Ozone or active oxygen atoms generated by ultraviolet rays (synonymous with ultraviolet light) have a high oxidizing ability and it is possible to form a silicon-containing film having high denseness and insulation at a low temperature.

Any ultraviolet ray generator that is generally used in the ultraviolet ray irradiation treatment can be used.

In the present invention, ultraviolet rays generally refer to electromagnetic waves having a wavelength of 10 to 400 nm. In the case of ultraviolet irradiation treatment other than vacuum ultraviolet rays (10 to 200 nm) to be described later, the ultraviolet rays preferably have a wavelength of 210 to 375 nm Use ultraviolet rays.

It is preferable to set the irradiation intensity and irradiation time within the range in which the base material carrying the silicon-containing film to be irradiated is not damaged.

Generally, when the substrate temperature during the ultraviolet ray irradiation treatment is 150 占 폚 or higher, the properties of the base material such as a plastic film or the like are deformed or the strength thereof is deteriorated. However, in the case of a film having high heat resistance such as polyimide or a substrate such as a metal, a modification treatment at a higher temperature is possible. Therefore, the substrate temperature at the time of irradiation with ultraviolet rays has no general upper limit, and can be suitably set by those skilled in the art depending on the type of the substrate. The atmosphere of the ultraviolet ray irradiation treatment is not particularly limited.

Examples of such means for generating ultraviolet rays include metal halide lamps, high pressure mercury lamps, low pressure mercury lamps, xenon arc lamps, carbon arc lamps, excimer lamps (172 nm, 222 nm, 308 nm single wavelength, for example, Manufactured by Nippon Kayaku Co., Ltd.), UV light laser, and the like, but there is no particular limitation. In addition, when irradiating the generated ultraviolet rays to the silicon-containing film, it is preferable to reflect the ultraviolet rays from the generation source onto the silicon-containing film after reflecting the ultraviolet rays from the generation source from the viewpoint of achieving efficiency improvement and uniform irradiation.

The ultraviolet ray irradiation may be suitably applied to the batch treatment and the continuous treatment, and may be suitably selected in accordance with the shape of the substrate to be used. For example, in the case of a batch process, a laminate having a silicon-containing film on its surface can be treated in an ultraviolet burning furnace having the ultraviolet ray generating source as described above. The ultraviolet firing furnace itself is generally known, and for example, an ultraviolet firing furnace manufactured by Epson Corporation may be used. When the laminate having the silicon-containing film on its surface is in the form of a long film, it can be cerammed by irradiating ultraviolet rays continuously in a drying zone provided with the ultraviolet ray generating source as described above while conveying it. The time required for ultraviolet irradiation varies depending on the composition and concentration of the substrate and the silicon-containing film to be used, but is generally 0.1 second to 10 minutes, preferably 0.5 second to 3 minutes.

(Vacuum ultraviolet irradiation treatment: excimer irradiation treatment)

In the present invention, the most preferable modification treatment method is a treatment by vacuum ultraviolet irradiation (excimer irradiation treatment). In the treatment by vacuum ultraviolet irradiation, light energy of 100 to 200 nm, which is larger than the interatomic bonding force in the polysilazane compound, is used, preferably light energy of 100 to 180 nm wavelength is used, The silicon oxide film is formed at relatively low temperature (about 200 DEG C or less) by advancing the oxidation reaction by active oxygen or ozone while directly cutting by the action of only the photon.

The source of radiation in the present invention is not limited to an excimer radiator (e.g., a Xe excimer lamp) having a maximum emission at about 172 nm, a low pressure mercury vapor lamp having a bright line at about 185 nm And medium pressure and high pressure mercury vapor lamps having wavelength components of 230 nm or less, and excimer lamps having a maximum emission at about 222 nm.

Among them, the Xe excimer lamp is excellent in luminous efficiency because it radiates ultraviolet rays having a short wavelength of 172 nm into a single wavelength. Since this light has a large absorption coefficient of oxygen, oxygen atom species of the radical and ozone can be generated at a high concentration with a minute amount of oxygen.

It is also known that light energy of 172 nm, which is short in wavelength, has a high ability to disassociate bonds of organic substances. The modification of the polysilazane layer can be realized in a short time by the active oxygen, high energy of ozone and ultraviolet radiation.

Since the excimer lamp has high efficiency of generating light, it can be lighted with a low power input. Further, since the light having a long wavelength, which is a factor of temperature rise by light, is not emitted but energy is irradiated in the ultraviolet region, that is, at a short wavelength, the surface temperature of the object to be analyzed is suppressed from rising. Therefore, it is suitable for a flexible film material such as PET which is considered to be easily affected by heat.

Oxygen is necessary for the reaction at the time of ultraviolet irradiation, but since the vacuum ultraviolet ray absorbs by oxygen, the efficiency in the ultraviolet ray irradiation step tends to be lowered. Therefore, the irradiation of the vacuum ultraviolet ray is preferably carried out in a state where the oxygen concentration and the water vapor concentration are as low as possible . Incidentally, the element ratio x of the silicon of the oxygen in the present invention of the functional film SiM _w O _x N _y C _z composition, but also the balance between the added amount of the compound of the above metal M, the oxygen concentration at the time of excimer irradiation For example, 50 vol. Ppm or less, whereas the values of the element ratios y and z of silicon and nitrogen tend to increase. However, even if the oxygen concentration is exceeded by 10,000 ppm by volume during the excimer irradiation, the value of x is not increased, and conversely, the excimer light is absorbed by the atmospheric oxygen, so that the irradiation efficiency may be lowered. Therefore, in the present invention, the oxygen concentration at the time of vacuum ultraviolet irradiation is preferably adjusted suitably in the range of 10 to 10,000 vol. Ppm (0.001 to 1%), preferably in the range of 20 to 5000 vol. Ppm (0.002 to 0.5% Is more preferable. In addition, the concentration of water vapor between the telephone processes is not particularly limited, and is preferably in the range of 1000 to 4000 ppm by volume.

As the gas satisfying the irradiation atmosphere used for vacuum ultraviolet irradiation, dry inert gas is preferable, and dry nitrogen gas is preferable from the viewpoint of cost. The adjustment of the oxygen concentration can be adjusted by measuring the flow rate of the oxygen gas and the inert gas introduced into the irradiation hood and changing the flow rate ratio.

Incidentally, the element ratio z for a carbon silicon in the functional film of the invention SiM _w O _x N _y C _z composition, but also the balance between the kind of the compound of the above metal M, a vacuum ultraviolet ray on the coating face The amount of energy to be irradiated tends to be reduced. Therefore, in the present invention, it is preferable that the irradiation energy amount of the vacuum ultraviolet ray on the coating film surface is appropriately adjusted in the range of 1 to 10 J / cm ² . If it is less than 1 J / cm ² , the reforming may be insufficient, and if it exceeds 10 J / cm ² , cracks may be caused by excessive reforming and thermal deformation of the substrate may occur. It is particularly preferable to adjust the thickness in the range of 1 to ^2.5 J / cm ² .

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

Further, in the present invention, when the functional film is formed by such a modifying treatment, by increasing the light amount of the excimer, the temperature at the time of modification, or the energy at the time of modification, the ratio of (I _{[ Si- H]} / I it is possible to reduce the value of _{[Si -O]),} may also be reduced by carrying out the modification of the value in the number of the example, oxygen or moisture _{environment, (I [Si -H] /} I [Si -O]) . Among them, it is preferable to control the oxygen concentration at the time of the reforming treatment.

{Use of functional film}

The functional film of the present invention is excellent in durability and bending resistance under high temperature and high humidity, and has various uses. For example, the functional film of the present invention can be used as a film having various functions such as a gas barrier layer, an electric insulating layer, a hard coating layer (upper layer of abrasion resistance), a foreign matter prevention layer, and a refractive index control layer.

&Lt; Use as gas barrier layer >

In the following description, a gas barrier film having a functional film when used as a gas barrier layer, which is an example of a functional film, is described, but the present invention is not limited thereto.

[Gas barrier film]

The gas barrier film according to the present invention has a substrate and at least one gas barrier layer on the substrate. The gas barrier film may further include other members. For example, the gas barrier film may be provided on the gas barrier layer, between the substrate and the gas barrier layer, or on the other surface of the substrate on which the gas barrier layer is not formed. Member. In the present invention, the other members are not particularly limited, and members used in conventional gas barrier films can be used in the same manner or properly modified. Specifically, an intermediate layer, a protective layer, a smoothing layer, an anchor coating layer, a bleed-out preventing layer, a decaying layer having moisture adsorbability, and an antistatic layer can be given.

Further, in the present invention, the gas barrier layer may be present as a single layer or may have a laminated structure of two or more layers. Further, in the present invention, the gas barrier layer may be formed on at least one surface of the substrate. For this reason, the gas barrier film of the present invention includes both a form in which the gas barrier layer is formed on one side of the substrate and a form in which the gas barrier layer is formed on both sides of the substrate.

(materials)

The gas barrier film according to the present invention is usually used as a substrate, a plastic film or a sheet is used, and a film or sheet containing a colorless transparent resin is preferably used. The plastic film to be used is not particularly limited in terms of the material and the thickness of the film so long as it can hold a gas barrier layer or the like, and can be appropriately selected depending on the intended use and the like.

Examples of the base material include polyacrylic acid esters, polymethacrylic acid esters, polyethylene terephthalate (PET), polybutylene terephthalate, polyethylene naphthalate (PEN), polycarbonate (PC), polyarylate, polyvinyl chloride Polypropylene (PP), cycloolefin polymer (COP), cycloolefin copolymer (COC), triacetate cellulose (TAC), styrene (PS), nylon (Ny), aromatic polyamide, A film of each resin such as polyether ether ketone, polysulfone, polyether sulfone, polyimide and polyether imide; a heat-resistant transparent film having a basic skeleton of silsesquioxane having an organic-inorganic hybrid structure (for example, Sila (Trade name, manufactured by Shin-Nittsu Sumitomo Chemical Co., Ltd.), and furthermore, the above-mentioned resin is laminated in two or more layers And the like.

(PET), polybutylene terephthalate, polyethylene naphthalate (PEN), polycarbonate (PC), polyimide and the like are preferably used from the viewpoints of cost and ease of accessibility, and optical transparency and small birefringence From the viewpoints of optical transparency, heat resistance, and adhesion with the gas barrier layer, TAC, COC, COP, PC, etc., which are produced by the flexible method in viewpoints of the basic structure, the silsesquioxane having an organic- A heat-resistant transparent film is preferably used.

On the other hand, for example, when a gas barrier film is used for an electronic device of a flexible display, the process temperature in the array fabrication process sometimes exceeds 200 deg. In the case of production by roll-to-roll, since a certain amount of tension is always applied to the substrate, when the substrate temperature is raised by placing the substrate at a high temperature and the substrate temperature exceeds the glass transition point, So that the base material is stretched due to the tensile force, which may cause damage to the gas barrier layer. Therefore, in such applications, it is preferable to use a heat-resistant material having a glass transition point of 150 캜 or higher as a substrate. That is, it is preferable to use a heat-resistant transparent film having polyimide, polyether imide and silsesquioxane having an organic-inorganic hybrid structure as a basic skeleton. However, since the heat-resistant resin represented by these is amorphous, the water absorption rate becomes larger than that of crystalline PET or PEN, and the dimensional change of the substrate due to humidity becomes larger, and the gas barrier layer may be damaged. However, even when these heat resistant materials are used as substrates, the formation of gas barrier layers on both sides can suppress dimensional changes due to absorption and desorption of the base film itself under harsh conditions of high temperature and high humidity, and suppress the damage to the gas barrier layer can do. Therefore, it is one of the more preferable forms to use a heat-resistant material as a base material and to form a gas barrier layer on both surfaces. Further, in order to reduce elongation and shrinkage of the substrate at a high temperature, a substrate containing glass fiber, cellulose or the like is also preferably used.

The substrate used in the present invention may be an unstretched film or a stretched film.

At least a substrate for forming the gas barrier layer according to the present invention may be subjected to various known processes for improving the adhesion such as corona discharge treatment, flame treatment, oxidation treatment or plasma treatment, lamination of a primer layer , And it is preferable to perform the above processes in combination as necessary.

The thickness of the 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 탆, preferably 10 to 200 탆. These base film may have a functional layer such as a transparent conductive layer, a primer layer or a hard coating layer. As for the functional layer, those described in paragraphs &quot; 0036 &quot; to &quot; 0038 &quot; of Japanese Patent Laid-Open Publication No. 2006-289627 can be preferably employed in addition to those described above.

Further, it is preferable that the substrate has a high surface smoothness. As the surface smoothness, it is preferable that the average surface roughness (Ra) is 2 nm or less. Although there is no particular lower limit, it is practically 0.01 nm or more. If necessary, both sides of the substrate, at least the side forming the gas barrier layer, may be polished to improve smoothness.

(Gas barrier layer)

The gas barrier film according to the present invention may contain at least one functional layer of the present invention as a gas barrier layer, and further preferably has another gas barrier layer from the viewpoint of further improving the gas barrier property.

Further, in the present invention, the other gas barrier layer is a gas barrier layer having a gas barrier property and a composition different from that of the above-mentioned functional film. Here, the "composition different from the functional film" means, for example, that the other gas barrier layer has the chemical composition represented by the chemical formula (1), and the values of w, x, y and z satisfy the following formulas (1) at the same time it satisfied, and also non-(I _{[Si -H]} of the absorption intensity derived from Si-H in the vicinity of 2200cm ^-1 to the absorption intensity derived from Si-O in the vicinity of 1050cm ^-1 were observed in the IR spectrum / I _{[ Si- O]} ) is 0.03 or less, it indicates that the composition is different from that of the functional film.

In the present invention, the other gas barrier layer can be formed by applying a coating liquid containing a silicon compound such as a polysilazane compound, and drying the applied coating film by application of energy. The other gas barrier layer formed by such a coating method is adjacent to the functional film according to the present invention so that the hydrolysis of the other gas barrier layer is suppressed and a synergistic effect capable of further improving the moisture resistance of the gas barrier film Is obtained. The detailed mechanism is unclear, but it can be presumed that the effect is caused by contacting with a metal M such as aluminum contained in the functional film. Alternatively, the functional film and the other gas barrier layer may be laminated in this order on the base material, the other gas barrier layer and the functional film may be laminated in this order on the base material. However, other gas barrier layers and functional films It is more preferable to laminate them in this order. Of course, another layer may be provided between the substrate and the functional film or other gas barrier layer according to the present invention.

In addition, other gas barrier layers formed by such a coating method may be formed by adding an additive element other than silicon.

Examples of the additive element include beryllium (Be), boron (B), magnesium (Mg), aluminum (Al), calcium (Ca), scandium (Sc), titanium (Ti), vanadium (Cr), Mn (Mn), Fe, Co, Ni, Cu, Zn, Ga, Ge, (Y), zirconium (Zr), niobium (Nb), molybdenum (Mo), technetium (Tc), ruthenium (Ru), rhodium (Rh), palladium (Pd) (Al), gadolinium (In), tin (Sn), barium (Ba), lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Gd), terbium (Tb), dispandium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), lutetium (Lu), hafnium (Hf) , Tungsten (W), rhenium (Re), osmium (Os), iridium (Ir), platinum (Pt), gold (Au), mercury (Hg), thallium (Tl) And the like.

Of these elements, boron, magnesium, aluminum, calcium, titanium, chromium, manganese, iron, cobalt, copper, (B), magnesium (Mg), aluminum (Al), calcium (Ca), zinc (Zn), gallium (Ga), zirconium (Fe), gallium (Ga), and indium (In) are more preferable, and boron (B), aluminum (Al), gallium (Ga), and indium (In) are more preferable. Group 13 elements such as boron (B), aluminum (Al), gallium (Ga), and indium (In) have trivalent valences and are insufficient in valence compared to tetravalent valences of silicon . By improving the flexibility, defects are restored, other gas barrier layers become dense films, and gas barrier properties are improved. Further, by increasing the flexibility, oxygen is supplied to the inside of the other gas barrier layer to become a gas barrier layer where oxidation progresses to the inside of the film, and the gas barrier layer becomes highly resistant to oxidation in the state where film formation is completed. The additional elements may be present singly or in the form of a mixture of two or more.

[Coating method]

In the present invention, the other gas barrier layer formed by the coating method may be formed by applying a coating liquid containing a silicon compound such as a polysilazane compound.

The silicon compound used for forming the other gas barrier layer according to the present invention is not particularly limited and may be a silicon compound containing nitrogen or a silicon compound containing no nitrogen, but is preferably a polysilazane compound. More specifically, a silicon compound containing nitrogen and a silicon compound containing no nitrogen, which are listed when forming the above-mentioned functional film, and a suitable form thereof, can be suitably used. Therefore, the description is omitted here.

The method of producing a coating liquid containing a silicon compound, the solvent to be used, the catalyst, the coating method, and the method of applying energy (modifying) when forming another gas barrier layer by a coating method are not limited to the above- Can be performed by the same operation as in the case of forming. It is preferable that the energy application is performed by vacuum ultraviolet irradiation. From the viewpoint of improving the efficiency of the ultraviolet irradiation process, the oxygen concentration at the time of irradiation with vacuum ultraviolet radiation is preferably 10 to 10,000 vol. Ppm, and more preferably 20 to 5000 vol. Ppm. From the viewpoint of considering the balance between modification and substrate deformation, the amount of irradiation energy of the vacuum ultraviolet ray on the coating film surface formed by applying the coating liquid for forming the other gas barrier layer is preferably 1 to 10 J / cm ² , And more preferably 1.5 to 8 J / cm ² .

When the above-mentioned other additive element is added and another gas barrier layer is formed by the coating method, the film thickness of the application, the drying temperature of application, the energy application (modification treatment) Shape and the like, and a corresponding description portion of the above-mentioned functional film is properly referred to.

When the other gas barrier layer is formed by the coating method, the solid content concentration of the silicon compound in the coating liquid is not particularly limited and varies depending on the layer thickness and the time for which the coating liquid is used, Is preferably from 0.1 to 30 mass%, more preferably from 0.5 to 20 mass%, and still more preferably from 1 to 15 mass%.

In the present invention, the thickness of the other gas barrier layer formed by the coating method is not particularly limited as long as the effect of the present invention is not impaired, but is preferably 1 to 500 nm, more preferably 5 to 300 nm, More preferably 10 to 200 nm.

[Vapor Deposition Method]

Other gas barrier layers according to the present invention can be formed by a gas phase film formation method such as a physical vapor deposition method, an atomic layer deposition method, or a chemical vapor deposition method in the same manner as the functional film other than the above-described coating method.

Further, in the present invention, defects of other gas barrier layers formed by the vapor phase deposition method can be efficiently repaired when the other gas barrier layers and the functional films are stacked in this order on the substrate, and the gas barrier properties The synergistic effect can be obtained, which is remarkably improved. This can be presumed to be the effect of the excimer light transmitted through the functional film directly modifying the interface itself (recombination of the structure by cleavage and recombination) of the other gas barrier layer / functional film when the functional film is subjected to the excimer reforming treatment.

From the viewpoint of the deposition rate and the processing area, it is preferable to apply the plasma CVD method such as the vacuum plasma CVD method or the atmospheric pressure plasma CVD method. In the present invention, at the time of forming another gas barrier layer, a film can be formed using the above-described CVD apparatus shown in Fig. 1 or the CVD apparatus shown in Fig. 2 (roll-to-roll vacuum film forming apparatus of opposite roll type) More preferably, the film is formed using a roll-to-roll vacuum film forming apparatus of an opposite roll type. More specifically, the film forming gas enumerated at the time of forming the above-described functional film can be appropriately selected. Description is omitted here.

In the present invention, the thickness of the other gas barrier layer formed by the above-mentioned preferable plasma CVD method is not particularly limited as long as the effect of the present invention is not impaired, but it is preferably 20 to 1000 nm, more preferably 50 And more preferably from 500 nm to 500 nm.

In the gas barrier film of the present invention, a layer having various functions can be further formed.

In the gas barrier film according to the present invention, a layer having various functions may be further formed. Examples of such a layer include, but are not limited to, an intermediate layer, a smoothing layer, or a bleed-out layer.

(Middle layer)

In the present invention, an intermediate layer may be further formed between the substrate of the gas barrier film and the gas barrier layer. The intermediate layer preferably has a function of improving adhesion between the substrate surface and the gas barrier layer. A commercially available support having an adhesive layer can also be preferably used.

(Smooth layer)

In the gas barrier film according to the present invention, the intermediate layer may be a smoothing layer. The smoothing layer used in the present invention is formed so as to planarize the roughened surface of the support on which protrusions or the like exist or to flatten the unevenness and pinholes generated in the gas barrier layer by the protrusions present in the base. This smoothing layer is basically made by curing a photosensitive material or a thermosetting material.

(Bleed-out preventing layer)

The gas barrier film according to the present invention may have a bleed-out preventing layer on the support surface opposite to the surface on which the gas barrier layer is formed. A bleed-out preventing layer can be formed. The bleed-out preventing layer is provided on the opposite side of the support having a smoothing layer for the purpose of suppressing the phenomenon that the unreacted oligomer or the like in the film substrate shifts to the surface and contaminates the contacting side when the film having the smoothing layer is heated . If the bleed-out preventing layer has this function, it may basically have the same structure as the smoothing layer.

[Electronic Devices]

In another aspect of the present invention, an electronic device having a gas barrier film of the present invention is provided.

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 oxides, sulfur oxides, ozone, etc.) in the air. Examples of the device include electronic devices such as an organic EL device, a liquid crystal display device (LCD), a thin film transistor, a touch panel, an electronic paper, and a solar cell (PV). From the viewpoint that the effect of the present invention can be obtained more efficiently, it is preferably used for an organic EL element or a solar cell, and is particularly preferably used for an organic EL element.

The gas barrier film of the present invention can also be used for film sealing of devices. That is, the device itself is used as a support, and the gas barrier film of the present invention is provided on the surface of the device. The device may be covered with a protective layer before installing the gas barrier film.

The gas barrier film of the present invention can also be used as a substrate for a device or as a film for sealing by a solid sealing method. The solid sealing method is a method in which a protective layer is formed on a device, and then an adhesive layer and a gas-barrier film are overlaid and cured. The adhesive is not particularly limited, but thermosetting epoxy resin, photo-curable acrylate resin and the like are exemplified.

(Organic EL device)

As an example of the organic EL device using the gas barrier film of the present invention, reference may be made to the disclosure of Japanese Patent Laid-Open No. 2007-30387 as appropriate.

(Liquid crystal display element)

The reflection type liquid crystal display device has a structure including a lower substrate, a reflective electrode, a lower alignment film, a liquid crystal layer, a lower alignment film, a transparent electrode, an upper substrate, a quarter wave plate, and a polarizing film in this order from below. The gas barrier film in the present invention can be used as the transparent electrode substrate and the upper substrate.

(Solar cell)

The gas barrier film of the present invention can also be used as a sealing film of a solar cell element. Here, it is preferable that the gas barrier film of the present invention be sealed so that the barrier layer is close to the solar cell element.

(Other)

As another application example of the gas barrier film of the present invention, for example, a thin film transistor described in Japanese Patent Application Laid-open No. 10-512104, Japanese Patent Laid-Open Publication No. 5-127822, Japanese Patent Application Laid-Open No. 2002-48913 An electronic paper described in Japanese Patent Application Laid-Open No. 2000-98326, and the like.

[Optical member]

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

(Circularly polarizing plate)

By using the gas barrier film of the present invention as a substrate, a? / 4 plate and a polarizing plate can be laminated to produce a circular polarizing plate. In this case, the angle formed by the slow axis of the? / 4 plate and the absorption axis of the polarizing plate is 45 占. It is preferable that such a polarizing plate is stretched in the direction of 45 DEG with respect to the longitudinal direction (MD). For example, those described in JP-A-2002-865554 can be suitably used.

&Lt; Use as electric insulating film &

The functional film of the present invention can be used as an electric insulating film.

As the electric insulating film, if the relative dielectric constant is large, the parasitic capacitance between the wirings increases due to the polarization of the insulating film, and the relative dielectric constant is preferably small in order to cause a delay in signal transmission and an increase in power consumption, It is preferable that the relative dielectric constant is in the range of 1.0 to 5.0. The functional film of the present invention has a dielectric constant in the range of 2.5 to 3.5, so that the functional film of the present invention is excellent in insulation performance and can be preferably used as an electric insulating film.

Although the insulating film as disclosed in Japanese Patent Laid-Open Publication No. 1474756 is usually formed at a high temperature of 850 캜, the functional film of the present invention can be formed at a low temperature (reforming treatment) of 100 캜 or lower And is excellent in durability under high temperature and high humidity and bending resistance. Therefore, it can be preferably used as an electric insulating film.

When the functional film of the present invention is used as an electric insulating film, the thickness is not particularly limited, but it is more preferably 10 to 1000 nm.

&Lt; Use as Hard Coating Layer >

The functional film of the present invention can be used as a hard coating layer (abrasion upper layer). Normally, the film as the hard coat layer tends to be fragile when the hardness is increased. However, since the functional film of the present invention is dense and has elasticity, it has a feature that it is not fragile while having scratch resistance.

The hard coat layer replacing the glass is preferably a pencil hardness test specified in JIS K5600-5-4 (ISO / DIN 15184) that exhibits a hardness of &quot; 5H &quot; or higher. If the cured film has the above hardness, it can be used as a hard coat layer. The functional film of the present invention can be suitably used as a hard coat layer because the pencil hardness is in the range of 6H to 9H though it depends on the forming method.

As described above, since the functional film of the present invention has high adhesion to the surface of the substrate and also has desired antistatic properties, optical characteristics and hardness, it can be preferably used as a hard coat layer serving also as an antistatic layer of the optical laminate.

When the functional film of the present invention is used as a hard coat layer, the thickness is not particularly limited, but it is more preferably 100 to 1000 nm.

As described above, the functional film of the present invention is excellent in durability and bending resistance under high temperature and high humidity, and can be used as a film having various functions. Of course, if only one layer of the functional layer of the present invention is present, the effect of the present invention can be exerted. However, when the functional film of the present invention is laminated to several layers, the effect of the present invention becomes more remarkable.

Example

The effects of the present invention will be described using the following examples and comparative examples. However, the technical scope of the present invention is not limited to the following embodiments. In the examples, "parts" or "%" are used, and "parts by weight" or "% by weight" are used unless otherwise specified. In the following operation, unless otherwise specified, the measurement of the operation and physical properties is performed at room temperature (20 to 25 DEG C) / relative humidity of 40 to 50%.

{Example 1}

A polyethylene naphthalate film substrate (thickness: 50 m) was provided on the thin film forming substrate 11 using the CVD apparatus 10 (parallel plate capacitively coupled type PECVD apparatus) shown in Fig. 1, (Functional film) having the composition shown in Table 1 was formed by supplying a hexamethyldisiloxane gas, a silane gas, an oxygen gas, an ammonia gas, and a trimethylaluminum gas, and adjusting the supply amount of each gas. Further, when adjusting the supply amount of the gases, in the form of increasing the value of _{I [Si -H] / I [} Si -O] , supply a lot of silane, and _{I [Si -H] / I [} Si -O] The oxygen gas was supplied in a large amount.

Specifically, the total flow rate of the hexamethyldisiloxane and the silane gas was set to 50 sccm, the flow rate of the helium gas was set to 50 sccm, the pressure in the chamber 12 was set to 10 Pa, the temperature of the thin film formation substrate 11 was set to 60 캜, The gas barrier layer was formed by adjusting the film forming time such that the RF power supply was 500 W and the RF power frequency was 13.56 MHz so that the film thickness became 150 nm and the gas barrier layer having the composition shown in Table 1 The gas barrier film sample No. 1 was prepared. 101 to 117 were produced.

&Lt; Measurement of element composition ratio of gas barrier layer >

According to the following apparatus and measurement conditions, the gas barrier film sample No. 1 was prepared. For the gas barrier layers 101 to 117, the composition profiles in the film thickness direction were analyzed, and the values of w, x, y, and z were determined. The results are shown in Table 1.

(XPS analysis condition)

Device: QUANTERASXM (manufactured by ULVAC-PY)

· X-ray source: monochromated Al-Kα

Measurement area: Si2p, C1s, N1s, O1s, M *

(M * is the optimum measurement area for the metal, for example in the case of boron: B1s; in the case of aluminum: Al2p; in the case of gallium: Ga3d or Ga2p; in case of indium: In3d; Case: Tl4f)

Sputter ion: Ar (2 keV)

Depth profile: After sputtering for 1 minute, the composition of the coating product was determined at an average value of 30 to 120 nm from the outermost surface of the gas barrier layer.

Quantitation: The background was determined by the Shirley method and quantified using the relative sensitivity coefficient method from the obtained peak area.

Data processing: MultiPak (manufactured by ULVAC-PY)

&Lt; Measurement of IR spectrum of gas barrier layer >

The gas barrier film sample No. 2 was prepared. 101 to 117, the respective IR spectra were measured.

Specifically, Nippon Bunko to whether or sikki manufactured using the ATR method using FT / IR-4200 in the manufacture, and Ge, after carrying out a correction to match the values obtained the IR spectrum obtained by a transmission method, each of the vicinity of 1050cm ^-1 The ratio (I _{[ Si- H]} / I _{[ Si- O]} ) of the absorption intensity derived from Si-H in the vicinity of 2200 cm ^-1 with respect to the absorption intensity derived from _Si- The results are shown in Table 1.

Further, when the gas barrier film sample was measured, the material other than the gas barrier layer serving as the target (for example, a base material or another layer to be described later) was used as the base and separately subjected to IR spectral measurement , And subtracting the measurement results from both sides, the influence of the lower limb was canceled.

Further, in the measurement results of element compositional ratio and the IR spectrum, chemical composition (formula represented by SiM _w O _x N _y C _z, M represents at least one member selected from the group consisting of the long form of the periodic table group 13 element , w, x, y and z are M, and the element ratio of the oxygen, nitrogen, and carbon, each of silicon, to a formula (1) have a satisfied) a to (4), and 1050cm ^-1 were observed in the vicinity of IR spectrum (I _{[ Si- H]} / I _{[ Si- O]} ) of the absorption intensity derived from Si-H in the vicinity of 2200 cm ^-1 with respect to the absorption intensity derived from _Si- And the other is a comparative example. When there are two or more gas barrier layers, at least one layer may be a functional film of the present invention, and the other is a comparative example. The same goes for the following.

&Quot; (3) &quot;

&Lt; Measurement of water permeability (WVTR) >

The gas barrier film sample No. 2 was prepared. (WVTR) at 40 占 폚 and 90% RH were measured using a film permeability evaluation device API-BA90 manufactured by NIPPON KABUSHIKI KAISHA. The results are shown in Table 1.

&Lt; Evaluation of deterioration treatment >

The gas barrier film sample No. 2 was prepared. 101 to 117 were subjected to the following two types of deterioration treatment tests, and the water permeability was measured in the same manner as in the measurement of the moisture permeability, and the results are shown in Table 1.

(High temperature and high humidity treatment test)

Each sample was allowed to stand in an environment of 95 ° C and 85% RH for 500 hours, and subjected to high temperature and high humidity treatment.

(Bending test)

Each sample was cut into a 10 cm square, wound in a 10 mm? Cylindrical column for 1 second so that the gas barrier layer side was inside, and then bent in a plane for 1 second to repeat the bending process 100,000 times.

As is clear from Table 1, the gas barrier film comprising the functional film of the present invention has a high gas barrier property and does not deteriorate gas barrier properties before and after storage under high temperature and high humidity conditions and before and after bending, It was found that gas barrier properties were exhibited even after storage under severe high temperature and high humidity condition of% RH, that is, durability and flexural resistance.

{Example 2}

The gas barrier film sample No. 2 including the gas barrier layer having the composition shown in Table 2 was produced by the following method. 201 to 213 were produced.

(Production of sample No. 201)

In accordance with the method described in Japanese Patent Application Laid-Open No. 63-191832, NAX-120 manufactured by AZ Electronic Materials Co., Ltd., which is a perhydro polysilazane solution under nitrogen atmosphere, was added with an Al content of 10 mol% Aluminum triisopropoxide was added and stirred at 80 캜 for 2 hours to obtain a coating liquid. The coating liquid was allowed to cool and then coated on a heat-resistant polyimide film &quot; UFIREX (registered trademark) -S &quot; (thickness: 50 mu m) manufactured by Ube Kosan Co., Ltd. under a nitrogen atmosphere so as to have a dry film thickness of 150 nm The substrate was heated at 350 캜 for 1 hour and then cooled at a rate of 5 캜 / min to form a gas Barrier Film Sample No. 201 was obtained.

(Production of sample No. 202)

The aluminum content was adjusted to 10 mol% with respect to the Si atoms in NAX-120 manufactured by AZ Electronic Materials Co., Ltd. as a perhydro polysilazane solution under nitrogen atmosphere in accordance with the method described in JP-A-11-105185 Aluminum triisopropoxide was added, and the mixture was stirred at 60 캜 for 3 hours to obtain a coating liquid. After the coating liquid was allowed to cool, a heat-resistant polyimide film &quot; UFIREX (registered trademark) -S &quot; (manufactured by Ube Kosan Co., Ltd.) having a thickness of 150 nm : 50 占 퐉), dried at room temperature for 10 minutes, then dried at 100 占 폚 for 3 minutes and further at 200 占 폚 for 3 minutes and further heated at 350 占 폚 for 1 hour and then at 5 占 폚 / min Deg.] C, and the gas barrier film sample No. 2 was dropped. 202.

(Preparation of sample No. 203)

NAX-120 manufactured by AZ Electronic Materials Co., Ltd., which is a perhydro polysilazane solution, was coated with a heat-resistant polyimide (manufactured by Ube Chemical Industries, Ltd.) so as to have a dry film thickness of 150 nm (Film thickness: 50 mu m), and dried at room temperature for 10 minutes. Thereafter, a vacuum ultraviolet ray of 172 nm was irradiated onto the hot plate at 80 캜 under a nitrogen atmosphere adjusted to an oxygen concentration of 0.01 to 0.1% so that the light amount was ² J / cm ² . 203 was obtained.

(Preparation of sample No. 204)

Aluminum ethylacetoacetate diisopropylate was added to NAX-120 manufactured by AZ Electronic Materials Co., Ltd. as a perhydro polysilazane solution so as to have an Al content of 10 mol% based on Si atoms, Lt; 0 &gt; C for 2 hours to obtain a coating liquid. After the coating liquid was allowed to cool, a heat-resistant polyimide film &quot; UFIREX (registered trademark) -S &quot; (manufactured by Ube Kosan Co., Ltd.) having a thickness of 150 nm : 50 mu m), and dried at room temperature for 10 minutes. Thereafter, a vacuum ultraviolet ray of 172 nm was irradiated onto the hot plate at 80 캜 under a nitrogen atmosphere adjusted to an oxygen concentration of 0.01 to 0.1% so that the light amount was ² J / cm ² . 204.

(Production of sample No. 205)

The sample No. 2 A coating liquid was prepared and applied in the same manner as in Example 204, and then plasma ion implantation treatment was performed in place of the vacuum ultraviolet ray treatment. 205.

Plasma ion implantation process

RF power source: manufactured by Nihon Den Sis Co., Ltd., type number &quot; RF &quot; 56000

· High-voltage pulse power source: "PV-3-HSHV-0835" manufactured by Guritase Corporation

Plasma ion implantation conditions

Plasma forming gas: Ar

Gas flow rate: 100 sccm

Duty ratio: 0.5%

Applied voltage: -6 kV

RF power: frequency 13.56 MHz, applied power 1000 W

· Chamber pressure: 0.2 Pa

Pulse width: 5 μsec

· Treatment time (ion implantation time): 200 seconds

(Production of sample No. 206)

Except that aluminum ethyl acetoacetate diisopropylate was added so as to have an Al content of 2 mol% with respect to Si atoms. In the same manner as in the production method of the gas barrier film sample No. 204, 206.

(Production of sample No. 207)

Except that aluminum ethyl acetoacetate diisopropylate was added so as to have an Al content of 1 mol% with respect to Si atoms. In the same manner as in the production method of the gas barrier film sample No. 204, 207 was obtained.

(Preparation of sample No. 208)

Except that aluminum ethylacetoacetate.diisopropylate was added so as to have an Al content of 90 mol% with respect to Si atoms. In the same manner as in the production method of the gas barrier film sample No. 204, 208 was obtained.

(Production of sample No. 209)

Except that aluminum ethyl acetoacetate diisopropylate was added so as to have an Al content of 110 mol% with respect to Si atoms. In the same manner as in the production method of the gas barrier film sample No. 204, 209 &lt; / RTI &gt;

(Production of sample No. 210)

Except that trimethoxyborane was added so as to have a B content of 10 mol% based on Si atoms instead of aluminum ethyl acetoacetate diisopropylate. In the same manner as in the production method of the gas barrier film sample No. 204, 210.

(Production of sample No. 211)

, Comprising 50 mol% of tetramethoxysilane, 10 mol% of tri-sec-butoxyaluminum, 35 mol% of 3-glycidoxypropyltrimethoxysilane, and 5 mol% of 3-aminopropyltriethoxysilane ] The coating liquid was applied onto a heat-resistant polyimide film "Uphirex (registered trademark) -S" (thickness: 50 μm) manufactured by Ube Kosan Co., Ltd. so that the film thickness after the modification treatment was 150 nm, Dried for one minute, and subjected to a heat treatment at 130 캜 for 30 minutes as a reforming treatment to obtain a gas barrier film sample No. 1. 211.

(Preparation of sample No. 212)

Except that triethoxy indium was used instead of tri-sec-butoxy aluminum. In the same manner as in the production method of the gas barrier film sample No. 211, 212.

(Production of sample No. 213)

Except that triethoxy thallium was used instead of tri-sec-butoxy aluminum. In the same manner as in the production method of the gas barrier film sample No. 211, 213 was obtained.

<Various Measurement and Evaluation>

The gas barrier film sample No. 2 obtained in the above was evaluated. The evaluation of the element composition ratio of the gas barrier layer, the measurement of the IR spectrum of the gas barrier layer, the measurement of the water permeability (WVTR), and the deterioration treatment were carried out in the same manner as in the measurement conditions of Example 1, The results are shown in Table 2.

As is clear from Table 2, the gas barrier film comprising the functional film of the present invention has a high gas barrier property, and does not deteriorate gas barrier properties before and after storage under high temperature and high humidity conditions and before and after bending, It was found that gas barrier properties were exhibited even after storage under severe high temperature and high humidity condition of% RH, that is, durability and flexural resistance.

{Example 3}

A 75 占 퐉 PET heat-resistant protective film was bonded to Zeonoa Film ZF-14 (thickness: 50 占 퐉) manufactured by Nippon Zeon Co., Ltd., which is a cycloolefin polymer, and a plasma CVD film deposition (Mixed gas of hexamethyldisiloxane (HMDSO) as a raw material gas and oxygen gas (also serving as a discharge gas) as a reaction gas) is supplied to the discharge region by discharging electric power by supplying electric power between opposing rolls by using the apparatus, And a thin film was formed by the plasma CVD method under the following conditions to form a first gas barrier layer having a thickness of 80 nm.

Film formation conditions:

· Mixing ratio of the film forming gas (hexamethyldisiloxane / oxygen): 100/1000 (unit: sccm (Standard Cubic Centimeter per Minute), 0 ° C, 1 atmospheric pressure]

Vacuum in the vacuum chamber: 1.5 Pa

Electric power applied from a plasma generating power source: 2 kW

· Frequency of power supply for plasma generation: 60 kHz

Film transport speed: 5 m / min

The following second gas barrier layer was laminated on the thus formed first gas barrier layer, and the gas barrier film sample No. 2 was laminated. 301 to 305 were produced. Also, WVTR of the first barrier layer was ^{5 × 10 -2 g / m 2} / day.

(Production of sample No. 301)

In accordance with the method described in Japanese Patent Application Laid-Open No. 63-191832, NAX-120 manufactured by AZ Electronic Materials Co., Ltd., which is a perhydro polysilazane solution under nitrogen atmosphere, was added with an Al content of 10 mol% Aluminum triisopropoxide was added and stirred at 80 캜 for 2 hours to obtain a coating liquid. After the coating solution was allowed to cool, the coating was applied on the first gas barrier layer obtained as described above so as to have a dry film thickness of 150 nm in a nitrogen atmosphere, followed by drying at 80 DEG C for 5 minutes under a nitrogen stream, For 3 hours to form a second gas barrier layer. 301 was obtained.

(Production of sample No. 302)

The aluminum content was adjusted to 10 mol% with respect to the Si atoms in NAX-120 manufactured by AZ Electronic Materials Co., Ltd. as a perhydro polysilazane solution under nitrogen atmosphere in accordance with the method described in JP-A-11-105185 Aluminum triisopropoxide was added, and the mixture was stirred at 60 캜 for 3 hours to obtain a coating liquid. After the coating liquid was allowed to cool, the first gas barrier layer obtained above was coated on the first gas barrier layer so as to have a dry film thickness of 150 nm in an atmosphere of 23 ° C and 50% RH, and then dried at room temperature for 10 minutes , And dried at 100 占 폚 for 3 minutes and at 200 占 폚 for 3 hours to form a second gas barrier layer. 302.

(Production of sample No. 303)

NAX-120 manufactured by AZ Electronic Materials Co., Ltd., which is a perhydro polysilazane solution, was coated on the first gas barrier layer obtained above in an atmosphere of 23 ° C and 50% RH so that the dried film thickness became 150 nm Followed by drying at room temperature for 10 minutes. Thereafter, a second gas barrier layer was formed by irradiating a vacuum ultraviolet ray of 172 nm with a light quantity of 2.1 J / cm ² on a hot plate at 80 캜 in a nitrogen atmosphere adjusted to an oxygen concentration of 0.01 to 0.1% Gas Barrier Film Sample No. 303 was obtained.

(Production of sample No. 304)

Aluminum ethylacetoacetate diisopropylate was added to NAX-120 manufactured by AZ Electronic Materials Co., Ltd. as a perhydro polysilazane solution so as to have an Al content of 10 mol% based on Si atoms, Lt; 0 &gt; C for 2 hours to obtain a coating liquid. After the coating liquid was allowed to cool, the first gas barrier layer obtained above was coated on the first gas barrier layer so as to have a dry film thickness of 150 nm in an atmosphere of 23 ° C. and 50% RH, followed by drying at room temperature for 10 minutes. Thereafter, a second gas barrier layer was formed by irradiating a vacuum ultraviolet ray of 172 nm with a light quantity of ² J / cm ² on a hot plate at 80 캜 in a nitrogen atmosphere adjusted to an oxygen concentration of 0.01 to 0.1% Barrier Film Sample No. 304 was obtained.

(Production of sample No. 305)

The sample No. 2 A coating liquid was prepared and applied in the same manner as in Example 304, and then plasma ion implantation treatment was performed in place of the vacuum ultraviolet ray treatment. 305 was obtained. In addition, the plasma ion implantation treatment is carried out in the same manner as in the above sample No. 1. 205 under the same conditions.

&Lt; Measurement of element composition ratio &

The gas barrier film sample No. 2 obtained in the above was evaluated. 301 to 305, element composition ratios of the first gas barrier layer and the second gas barrier layer were measured in the same manner as in the measurement of the element composition ratio in Example 1 described above. Results of the composition ratio of the first gas barrier layer is SiO _{1. 5} C _{0 . 5} . The results of each element composition ratio of the second gas barrier layer are shown in Table 3.

&Lt; Measurement of IR spectrum >

The gas barrier film sample No. 2 obtained in the above was evaluated. 301 to 305 were measured after the first gas barrier layer and the second gas barrier layer were laminated by the ATR method in the same manner as in the measurement of the IR spectrum performed in Example 1 described above, Almost the components of the second gas barrier layer were observed. The results are shown in Table 3.

&Lt; Measurement of water permeability (WVTR) >

The gas barrier film sample No. 2 obtained in the above was evaluated. 301 to 305, the moisture permeability (WVTR) of the barrier properties of the first barrier layer and the second barrier layer was measured in the same manner as in the measurement conditions of Example 1, and the results are shown in Table 3 . Further, the moisture permeability (WVTR) of the first gas barrier layer only was similarly measured, and the ^{5 × 10 - 2 (g /} m 2 / day) , respectively. The gas barrier film sample No. 2 obtained in the above was evaluated. 301 to 305 were used to fabricate an organic EL device as an electronic device in the following procedure.

&Lt; Fabrication of organic EL device >

(Formation of first electrode layer)

Each of the above-mentioned gas barrier film No. 1 to No. 4 produced in the above-mentioned manner. ITO (indium tin oxide) was formed on the layers 301 to 305 to a thickness of 150 nm by a sputtering method and heated at 120 DEG C for 10 minutes to form a transparent conductive film. This was patterned by photolithography to form a first electrode layer.

(Formation of hole transport layer)

The following coating liquid for forming a hole transport layer was applied on the first electrode layer formed above by an applicator under an environment of 25 캜 and a relative humidity of 50% RH, followed by drying and heating treatment under the following conditions, Thereby forming a hole transporting layer. Further, the coating liquid for forming the hole transport layer was applied so that the thickness of the hole transport layer after drying became 50 nm.

Before applying the coating liquid for forming a hole transport layer, a cleaning surface modification treatment of the gas-barrier film having the first electrode layer formed thereon was carried out by using a low pressure mercury lamp having a wavelength of 184.9 nm and irradiating the surface with an irradiation intensity of 15 mW / cm ² and a distance of 10 mm Respectively. The electrification elimination treatment was carried out by using the weak X-ray electricity.

&Lt; Coating liquid for forming hole transport layer >

A solution of polyethylene dioxythiophene polystyrene sulfonate (PEDOT / PSS, Bytron (registered trademark) P AI 4083 manufactured by Bayer Co.) diluted with pure water to 65 mass% and then diluted with methanol to 5 mass% was applied for forming a hole transport layer Solution.

&Lt; Conditions for drying and heat treatment >

After applying the coating liquid for forming the hole transporting layer, the solvent was blown off toward the film formation surface at a height of 100 mm, a discharge air velocity of 1 m / s, a wind velocity distribution of 5% and a temperature of 100 ° C, When the temperature was 150 DEG C, the heat treatment was conducted to form a hole transporting layer.

(Formation of light emitting layer)

The following coating liquid for forming a white light emitting layer was applied on the above-described hole transporting layer by an applicator under the following conditions, followed by drying and heating treatment under the following conditions to form a light emitting layer. The coating liquid for forming the white light emitting layer was applied so that the thickness of the light emitting layer after drying was 40 nm.

&Lt; Coating liquid for forming white light emitting layer &

1.0 g of a compound represented by the formula HA as a host material, 100 mg of a compound represented by the following formula (DA) as a dopant, 0.2 mg of a compound represented by the following formula DB as a dopant, 0.2 mg were dissolved in 100 g of toluene to prepare a coating liquid for forming a white light emitting layer.

[Chemical Formula 4]

<Coating Conditions>

The coating process was carried out at an application temperature of 25 캜 and a coating rate of 1 m / min in an atmosphere having a nitrogen gas concentration of 99% or more.

&Lt; Conditions for drying and heat treatment >

After applying the coating liquid for forming a white light emitting layer, the solvent was blown toward the film formation surface at a height of 100 mm, a discharge air speed of 1 m / s, a wind velocity distribution of 5% at a width of 60 ° C and a temperature of 60 ° C, A heat treatment was performed to form a light emitting layer.

(Formation of electron transport layer)

The following coating liquid for forming an electron transport layer was applied on the above-described light emitting layer by an applicator under the following conditions, and then dried and heat-treated under the following conditions to form an electron transport layer. The coating liquid for forming the electron transport layer was applied so that the thickness of the electron transport layer after drying was 30 nm.

<Coating Conditions>

In the application step, the application temperature of the coating solution for forming an electron transport layer was set to 25 캜 and the application speed was 1 m / min in an atmosphere having a nitrogen gas concentration of 99% or more.

&Lt; Coating liquid for forming electron transport layer >

The electron transport layer was prepared by dissolving the compound represented by the following formula (E-A) in 2,2,3,3-tetrafluoro-1-propanol to prepare a 0.5 mass% solution.

[Chemical Formula 5]

&Lt; Conditions for drying and heat treatment >

After the application liquid for forming the electron transport layer was applied, warm air was blown toward the film formation surface at a height of 100 mm, a discharge air velocity of 1 m / s, a wind speed distribution of 5% at a width of 60%, and a temperature of 60 캜, And heat treatment was performed at a temperature of 200 캜 to form an electron transporting layer.

(Formation of electron injection layer)

An electron injection layer was formed on the electron transport layer formed above. First, the substrate was placed in a decompression chamber, and the pressure was reduced to 5 × 10 ^-4 Pa. Cesium fluoride prepared in a tantalum deposition boat was heated in advance in a vacuum chamber to form an electron injection layer with a thickness of 3 nm.

(Formation of Second Electrode Layer)

A second electrode layer having a thickness of 100 nm was laminated on the electron injecting layer formed above under a vacuum of 5 10 ^-4 Pa by using a mask pattern using evaporation so as to have aluminum as the second electrode layer forming material and having extraction electrodes .

(Formation of Protective Layer)

Subsequently, SiO ₂ was laminated with a thickness of 200 nm by CVD to form a protective layer on the second electrode layer, except for the portions of the first electrode and the second electrode which were taken out.

Thus, the electronic device body 1 having the first electrode layer, the hole transporting layer, the light emitting layer, the electron transporting layer, the electron injecting layer, the second electrode layer, and the protective layer was produced.

[Sealing]

The gas barrier film sample No. 2 prepared in the above was prepared. 301 to 305 were used as the sealing members, respectively, and the obtained electronic element body was sealed using a sheet-shaped sealing material TB1655 manufactured by Three Bond Co., Ltd. to obtain a gas barrier film sample No. 1. Organic EL element sample No. &quot; 301 to 305 were produced.

&Lt; Evaluation of organic EL device >

The organic EL device sample No. 2 obtained in the above-mentioned example was used. 301 to 305 were evaluated for durability according to the following method. The results are shown in Table 3.

(Dark spot (DS) evaluation)

Each of the organic EL devices manufactured as described above was subjected to accelerated deterioration treatment for 10 hours under an environment of 95 캜 and 85% RH, a current of 1 mA / cm ² was applied to each organic EL device, and a luminescent image was photographed Dark spot was calculated as the area ratio (the incidence of DS). The results are shown in Table 3.

(Dark spot (DS) evaluation after deterioration treatment)

The following two kinds of deterioration treatment tests were performed on each of the organic EL devices manufactured as described above and the rate of occurrence of the dark spot DS after the deterioration treatment was evaluated in the same manner as the method for obtaining the DS incidence rate. The results are shown in Table 3.

[High temperature and high humidity treatment test]

Each of the organic EL device samples was allowed to stand in an environment of 95 ° C and 85% RH for 500 hours and then emitted by the same method as above to calculate the area ratio (DS generation rate) of the dark spots.

[Bending test]

Each organic EL element sample was wound in a 50 mm? Cylindrical cylinder for 1 second, and a flattening cycle of 1 second was repeated 100,000 times to carry out the accelerated deterioration treatment of the organic EL element. Thereafter, the area ratio of the dark spots (DS incidence rate).

As is clear from Table 3, the gas barrier film comprising the functional film of the present invention has a high gas barrier property, and the organic EL device using the organic EL device has a high occurrence rate of dark spots before and after storage under high temperature and high humidity conditions, That is, durability and flexural resistance.

{Example 4}

On the PET film substrate (thickness: 50 mu m), a first gas barrier layer was formed by the same method as in Example 3 described above. The following second gas barrier layer was laminated on the thus formed first gas barrier layer to form a gas barrier film sample No. 2. 401 to 405 were produced.

(Production of sample No. 401)

On the first gas barrier layer obtained above, the above-mentioned gas barrier film sample No. 2 was formed. A second gas barrier layer was formed in the same manner as in the production method of the gas barrier film sample No. 301, 401 was obtained.

(Production of sample No. 402)

On the first gas barrier layer obtained above, the above-mentioned gas barrier film sample No. 2 was formed. A second gas barrier layer was formed in the same manner as in the production method of the gas barrier film sample No. 302, 402 was obtained.

(Preparation of sample No. 403)

On the first gas barrier layer obtained above, the above-mentioned gas barrier film sample No. 2 was formed. A second gas barrier layer was formed in the same manner as in the production method of the gas barrier film sample No. 303, 403 was obtained.

(Production of sample No. 404)

On the first gas barrier layer obtained above, the above-mentioned gas barrier film sample No. 2 was formed. The second gas barrier layer was formed in the same manner as in the production method of the gas barrier film sample No. 304. 404.

(Production of sample No. 405)

On the first gas barrier layer obtained above, the above-mentioned gas barrier film sample No. 2 was formed. A second gas barrier layer was formed in the same manner as in the production method of the gas barrier film sample No. 305, 405 &lt; / RTI &gt;

(Production of sample No. 406)

NAX-120 manufactured by AZ Electronic Materials Co., Ltd., which is a perhydro polysilazane solution, was coated on a PET film substrate (thickness: 50 μm) so that the dry film thickness became 150 nm in an atmosphere of 23 ° C. and 50% RH Followed by drying at room temperature for 10 minutes. Thereafter, a first gas barrier layer was formed by irradiating a vacuum ultraviolet ray of 172 nm with a light amount of ⁶ J / cm ² on a hot plate at 80 캜 in a nitrogen atmosphere adjusted to an oxygen concentration of 0.01 to 0.1%.

Subsequently, aluminum ethylacetoacetate diisopropylate was added to NAX-120 manufactured by AZ Electronic Materials Co., Ltd. as a perhydro polysilazane solution in an atmosphere of nitrogen so as to have an Al content of 10 mol% based on Si atoms , And the mixture was stirred at 60 DEG C for 2 hours to obtain a coating liquid. After the coating liquid was allowed to cool, the first gas barrier layer obtained above was coated on the first gas barrier layer so as to have a dry film thickness of 150 nm in an atmosphere of 23 ° C. and 50% RH, followed by drying at room temperature for 10 minutes. Thereafter, a vacuum ultraviolet ray of 172 nm was irradiated onto the hot plate at 80 캜 in a nitrogen atmosphere adjusted to an oxygen concentration of 0.01 to 0.1% to obtain a light quantity of ² J / cm ² to form a second gas barrier layer, Barrier Film Sample No. 406 was obtained.

(Production of sample No. 407)

The sample No. 2 NAX-120 manufactured by AZ Electronic Materials Co., Ltd., which is a perhydro polysilazane solution, was applied to a first gas barrier layer similar to that of Example 406 so as to have a dry film thickness of 150 nm in an atmosphere of 23 ° C. and 50% RH Followed by drying at room temperature for 10 minutes. Thereafter, a vacuum ultraviolet ray of 172 nm was irradiated onto the hot plate at 80 캜 in a nitrogen atmosphere adjusted to an oxygen concentration of 0.01 to 0.1% to obtain a light quantity of ² J / cm ² to form a second gas barrier layer, Barrier Film Sample No. 407 &lt; / RTI &gt;

<Various measurements>

The gas barrier film sample No. 2 obtained in the above was evaluated. For 401 to 407, measurements of the moisture transmittance (WVTR) of the second gas barrier layer, the measurement of the IR spectra of the second gas barrier layer, and the barrier properties of the first and second barrier layers Was carried out in the same manner as in the measurement conditions of Example 1, and the results are shown in Table 4. &lt; tb &gt; &lt; TABLE &gt;

The gas barrier film sample No. 2 obtained in the above was evaluated. 401 to 407 were used to fabricate a solar cell as an electronic device in the following procedure.

&Lt; Fabrication of solar cell &

A transparent conductive film of indium tin oxide (ITO) was deposited as a first electrode layer (anode) to a thickness of 150 nm (sheet resistance: 12? / Square) on the substrate surface opposite to the gas barrier layer of each of the gas- And patterned to a width of 10 mm by using a normal photolithography method and wet etching to form a first electrode layer. The patterned first electrode layer was cleaned by ultrasonic cleaning with a surfactant and ultrapure water, ultrasonic cleaning with ultrapure water, followed by drying with nitrogen blow, and ultraviolet ozone cleaning was performed.

2.0% by mass of PEDOT-PSS (CLEVIOS (registered trademark) P VP AI 4083, manufactured by Heraeus Kabushiki Kaisha, conductivity: 1 x 10 ^-3 S / cm) containing a conductive polymer and polyanion was contained as the hole transport layer Was prepared and applied and dried using a blade coater in which the substrate was heated to 65 占 폚 so that the dry film thickness became about 30 nm. Thereafter, the film was subjected to heat treatment for 20 seconds with hot air at 120 DEG C to form a hole transport layer on the first electrode layer. Thereafter, it was taken into a glove box and worked under a nitrogen atmosphere.

First, in a nitrogen atmosphere, the device formed up to the hole transport layer was subjected to heat treatment at 120 DEG C for 3 minutes.

Subsequently, 0.8% by mass of the following compound A as a p-type organic semiconductor material and 1.6% by mass of a PC60BM (nanom (registered trademark) spectra E100H, manufactured by Frontier Carbon Kabushiki Kaisha) as an n-type organic semiconductor material were added to o- (P-type organic semiconductor material: n-type organic semiconductor material = 33: 67 (mass ratio)). (60 minutes) with heating while heating at 100 DEG C on a hot plate, and then the substrate was coated using a blade coater, which had been cooled to 40 DEG C, so as to have a dry film thickness of about 170 nm, and dried at 120 DEG C for 2 minutes, A photoelectric conversion layer was formed on the hole transport layer.

[Chemical Formula 6]

(7)

Subsequently, the compound B was dissolved in a mixed solvent of 1-butanol: hexafluoroisopropanol = 1: 1 in a concentration of 0.02% by mass to prepare a solution. This solution was applied and dried using a blade coater in which the substrate was heated to 65 占 폚 so that the dried film thickness became about 5 nm. Thereafter, heat treatment was performed for 2 minutes with hot air at 100 DEG C to form an electron transport layer on the photoelectric conversion layer.

Subsequently, the element having the electron transport layer formed thereon was placed in a vacuum evaporation apparatus. Then, the device was set so that the shadow mask having a width of 10 mm was orthogonal to the transparent electrode, and the inside of the vacuum evaporation apparatus was reduced to 10 ^-3 Pa or less, and silver was deposited to 100 nm at the deposition rate of 2 nm / Was formed on the electron transporting layer.

As a sealing member, a polyethylene terephthalate (PET) film (12 μm thick) was laminated on a 30 μm thick aluminum foil (manufactured by Toyo Aluminum Kabushiki Kaisha) with a dry lamination adhesive (two-component reaction type urethane adhesive) (Adhesive layer thickness: 1.5 占 퐉) was used and sealing was performed using a sheet-like sealant TB1655 manufactured by Three Bond Co., Ltd. to obtain a gas barrier film sample No. 1. Solar cell sample No. 401 to 407 corresponding to Fig. 401 to 407 were produced.

&Lt; Evaluation of solar cell &

The photovoltaic cell sample No. 2 obtained in the above was obtained. 401 to 407 were subjected to durability evaluation according to the following method.

(Measurement of short-circuit current density, open-circuit voltage, curve factor and photoelectric conversion efficiency)

Each manufactured type cell was irradiated with light of 100 mW / cm ² intensity using a solar simulator (AM1.5G filter), a mask having an effective area of 1 cm ² was superimposed on the light receiving unit, and the IV characteristic was evaluated. The density Jsc (mA / cm ² ), the open-circuit voltage Voc (V) and the curve factor FF were measured and the initial photoelectric conversion efficiency (%) was calculated by the following formula. The results are shown in Table 4.

&Quot; (4) &quot;

Thereafter, the power generation efficiency after the deterioration treatment was measured under the following conditions. The results are shown in Table 4.

[High temperature and high humidity treatment test]

Each of the solar cell samples was subjected to measurement of power generation efficiency after being left in an environment of 95 ° C and 85% RH for 500 hours.

[Bending test]

Each of the solar cell samples was subjected to an accelerated deterioration treatment for 10 hours under an environment of 95 DEG C and 85% RH, and then subjected to an accelerated deterioration treatment The efficiency was measured.

As apparent from Table 4, the gas barrier film comprising the functional film of the present invention has a high gas barrier property, and the solar cell using the same has high power generation efficiency before and after storage under high temperature and high humidity conditions, before and after bending, That is, durability and flexural resistance.

{Example 5}

<Fabrication of Functional Film as Semiconductor Insulating Film>

A solution of aluminum ethylacetoacetate diisopropylate in an amount of 10 mol% based on Si atoms in NAX-120 manufactured by AZ Electronic Materials Co., Ltd., a perhydro polysilazane solution, And the mixture was stirred at 60 占 폚 for 2 hours to obtain a coating liquid. After the coating liquid was allowed to cool, the coating was applied in an atmosphere of 23 ° C and 50% RH to a dry film thickness of 150 nm and dried at room temperature for 10 minutes. Thereafter, a vacuum ultraviolet ray of 172 nm was irradiated on the hot plate at 80 캜 in an atmosphere of nitrogen adjusted to an oxygen concentration of 0.01 to 0.1% so as to have a light quantity of 1 J / cm ² to form an insulating film. According to a conventional method, the relative dielectric constant was measured and found to be 3.1. In addition, as a result of the elemental composition, and IR spectrum measured in the same manner as the measurement conditions in Example 1, having a composition within the scope of the present invention, also in the IR spectrum of the present invention _{(I [Si -H] / I} [Si - _O] ) values were within the scope of the present invention. Thus, it has been found that the functional film of the present invention can be used as an insulating film of a semiconductor.

In addition, an insulating film which can not be obtained unless the temperature is as high as about 850 占 폚, as disclosed in Japanese Patent Laid-Open Publication No. 2012-174756, can be formed at a low temperature of 100 占 폚 or lower in the present invention.

{Example 6}

<Fabrication of Functional Film as Hard Coating Layer>

In a nitrogen atmosphere, in a NAX-120 manufactured by AZ Electronic Materials Co., Ltd., which is a perhydro polysilazane solution, aluminum ethylacetoacetate diisopropylate (manufactured by Nippon Polyurethane Industry Co., Ltd.) having an Al content of 10 mol% And the mixture was stirred at 60 占 폚 for 2 hours to obtain a coating liquid. After the coating liquid was allowed to cool, the coating was applied in an atmosphere of 23 ° C and 50% RH to a dry film thickness of 150 nm and dried at room temperature for 10 minutes. Thereafter, a vacuum ultraviolet ray of 172 nm was irradiated onto the hot plate at 80 캜 in a nitrogen atmosphere adjusted to an oxygen concentration of 0.01 to 0.1% to a light quantity of ^2.5 J / cm ² to form a hard coat layer. The pencil hardness was measured according to JIS K5600-5-4 (ISO / DIN 15184), and it was 9H. In addition, as a result of the elemental composition, and IR spectrum measured in the same manner as the measurement conditions in Example 1, having a composition within the scope of the present invention, also in the IR spectrum of the present invention _{(I [Si -H] / I} [Si - _O] ) values were within the scope of the present invention. Thus, it has been found that the functional film of the present invention can be used as a hard coat layer.

The present application is based on Japanese Patent Application No. 2013-210553 filed on October 7, 2013, the disclosure of which is incorporated by reference in its entirety.

Claims (8)

(1): &lt; EMI ID =
[Chemical Formula 1]

(Wherein M represents at least one member selected from the group consisting of Group 13 elements of the long form periodic table and w, x, y, and z are elemental ratios of M, oxygen, nitrogen, The following formulas (1) to (4)
[Equation 1]

Lt; / RTI &gt;
Comprises a chemical composition, expressed in, and also the IR spectrum observed in the vicinity of 1050cm ^-1 of Si-O in the absorption intensity derived from Si-H in the vicinity of 2200cm ^-1 to the absorption intensity derived from the ratio (I _{[Si-H ]} / I _[Si-O] ) is 0.03 or less. The method according to claim 1,
Wherein w, x, y and z satisfy the following expressions (6) to (9).
&Quot; (2) &quot;

3. The method according to claim 1 or 2,
Wherein w, x, y and z satisfy the following formula (5):
&Quot; (3) &quot;

Lt; / RTI &gt; 4. The method according to any one of claims 1 to 3,
Wherein M represents at least one kind selected from the group consisting of boron, aluminum, gallium, and indium. 5. The method according to any one of claims 1 to 4,
Wherein M is aluminum. 6. The method according to any one of claims 1 to 5,
Functional film, which is a gas barrier layer. A gas barrier film comprising a substrate and at least one layer of the gas barrier layer according to Claim 6 on the substrate. An electronic device having a gas barrier film according to claim 7.

Images