Silicon oxide film, material for gas barrier film, and method for producing silicon oxide film

Abstract

The present invention provides a silicon oxide film that exhibits high gas barrier properties even as a thin film. The silicon oxide film satisfies the following requirements (1) and (2): (1) a water vapor transmission rate (WVTR) of 9.0×10 ‑3 g / m 2 (2) The carbon concentration in the film measured by X-ray photoelectron spectroscopy (XPS) is 3.0 atom% or less.

Description

Technical Field

[0001] The present invention relates to a silicon oxide film useful as a gas barrier film, a material for a gas barrier film, and a method for producing a silicon oxide film using the material for a gas barrier film. Background Art

[0002] Gas barrier films that are imparted with gas barrier properties by forming a film on a plastic substrate or plastic film include those formed by physical film formation methods, CVD methods (Chemical Vapor Deposition methods), and the like. Examples of materials for such gas barrier films include oxides such as SiO2 and Al2O3, and nitrides such as SiN.

[0003] For example, Patent Document 1 proposes a barrier bag film that uses a mixture of hexamethyldisiloxane, 1,1,3,3-tetramethyldisiloxane, 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, and an inert gas such as oxygen and helium or argon as raw materials, and forms a SiO2 gas barrier layer by plasma-enhanced chemical vapor deposition (PECVD). However, the water vapor transmission rate (WVTR), an indicator of gas barrier performance, of this film is 0.2 to 0.6 g / m 2 · Oxygen permeability: 0.4~0.5cc / m 2 Such a high value means that the gas barrier performance is low.

[0004] In Patent Document 2, a polyethylene naphthalate (PEN) film having a SiO2 gas barrier layer formed thereon was produced by PECVD using tetraethoxysilane and oxygen as raw materials at a film forming pressure of less than 20 Pa. However, the film forming pressure was high and the WVTR was 1.7×10 -3 g / m 2 · The sky is large and cannot be said to have sufficient gas barrier properties.

[0005] Patent Document 3 describes a method for forming a low-dielectric-constant insulating film using an organosilane compound by PECVD. Although WVTR is not described, the high-frequency power source (RF power source) used during film formation is a relatively low 75 W, indicating that this method forms a low-density thin film. Therefore, it is presumed that the resulting film is not suitable for use as a gas barrier material.

[0006] Patent Document 4 discloses that a WVTR as low as 1.0×10 -5 ~2.9×10 -5 g / m 2However, since the organic thin film and the inorganic thin film must be formed through separate film forming processes, there is a problem that the number of manufacturing steps increases and the manufacturing cost of the gas barrier film rises.

[0007] Patent Document 5 describes that a single-layer film with a thickness of 800 nm obtained by forming an organosilane compound having a specific structure into a film by PECVD exhibits a WVTR of 2.1×10 -4 g / m 2 · Gas barrier film with such low value.

[0008] Prior art literature

[0009] Patent Literature

[0010] Patent Document 1: Japanese Patent No. 4139446

[0011] Patent Document 2: Japanese Patent Application Laid-Open No. 2016-176091

[0012] Patent Document 3: Japanese Patent No. 4863182

[0013] Patent Document 4: Japanese Patent No. 5394867

[0014] Patent Document 5: Japanese Patent No. 6007662 Summary of the Invention

[0015] Problems to be solved by the invention

[0016] In recent years, with the trend toward thinner gas barrier films, even thinner films are required to have high gas barrier properties. Generally speaking, the thinner the film thickness, the higher the WVTR. The present invention aims to provide a film having a WVTR of 10 even when the film thickness is less than 500 nm. - 3 g / m 2 A silicon oxide film having high gas barrier properties with a WVTR of less than one day, a material for a gas barrier film, and a method for producing a silicon oxide film using the material for a gas barrier film.

[0017] Solutions to the Problem

[0018] The present inventors have conducted intensive studies to solve the above problems and have found that the above problems can be solved by using a silicon oxide film or a gas barrier film material having specific characteristics, thereby completing the present invention.

[0019] That is, the present invention has the following aspects.

[0020] [1] A silicon oxide film that satisfies the following requirements (1) and (2):

[0021] (1) The water vapor transmission rate (WVTR) is 9.0×10 -3 g / m 2 ·Days or less;

[0022] (2) The carbon concentration in the film measured by X-ray photoelectron spectroscopy (XPS) is 3.0 atom% or less.

[0023] [2] The silicon oxide film according to [1] above, wherein

[0024] The water vapor transmission rate (WVTR) of the film with a thickness of less than 500 nm is 1.0×10 -6 ~9.0×10 -3 g / m 2 ·sky.

[0025] [3] A gas barrier film material for chemical vapor deposition, comprising an organosilane compound represented by the following formula (1).

[0026] [Chemical Formula 1]

[0027] R 1 n 、-Si——(OR 2 ) 4-n (1)

[0028] (R 1 represents an alkyl group having 1 to 20 carbon atoms or a hydrogen atom. n represents an integer of 1 to 3. When n is 2 or more, multiple R 1 are optionally the same or different, and both R 1 They are optionally bonded to each other to form an alkanediyl group. 2 represents an alkyl group having 1 to 10 carbon atoms. When n is 2 or less, multiple R 2 Optional: same or different.)

[0029] [4] The material for a gas barrier film according to [3] above, wherein

[0030] R 1 It is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.

[0031] [5] The material for a gas barrier film according to [3] or [4] above, wherein

[0032] R 2 It is an alkyl group having 1 to 3 carbon atoms.

[0033] [6] The material for a gas barrier film according to any one of [3] to [5] above, wherein

[0034] R 1is selected from a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a cyclopentyl group, a 1-methylbutyl group, a 2-methylbutyl group, a 3-methylbutyl group, a 1-ethylpropyl group, a 1,1-dimethylpropyl group, a 1,2-dimethylpropyl group, and a 2,2-dimethylpropyl group.

[0035] [7] The material for a gas barrier film according to any one of [3] to [6] above, wherein

[0036] The gas barrier film material is any of the following: dimethoxymethylsilane, trimethoxymethylsilane, ethyldimethoxysilane, ethyltrimethoxysilane, dimethoxypropylsilane, trimethoxypropylsilane, dimethoxyisopropylsilane, trimethoxyisopropylsilane, butyldimethoxysilane, butyltrimethoxysilane, isobutyldimethoxysilane, isobutyltrimethoxysilane, sec-butyldimethoxysilane, sec-butyltrimethoxysilane, tert-butyldimethoxysilane, tert-butyltrimethoxysilane, dimethoxypentylsilane, trimethoxypentylsilane, 1-methylbutyldimethoxysilane, 1- Methylbutyltrimethoxysilane, 2-methylbutyldimethoxysilane, 2-methylbutyltrimethoxysilane, 3-methylbutyldimethoxysilane, 3-methylbutyltrimethoxysilane, 1,1-dimethylpropyltrimethoxysilane, 1,1-dimethylpropyltrimethoxysilane, 1,2-dimethylpropyltrimethoxysilane, 1,2-dimethylpropyltrimethoxysilane, 2,2-dimethylpropyltrimethoxysilane, 2,2-dimethylpropyltrimethoxysilane, cyclopentyltrimethoxysilane, cyclopentyltrimethoxysilane, diethoxymethylsilane, triethoxymethylsilane, diethoxy Ethylsilane, triethoxyethylsilane, diethoxypropylsilane, triethoxypropylsilane, diethoxyisopropylsilane, triethoxyisopropylsilane, butyldiethoxysilane, butyltriethoxysilane, isobutyldiethoxysilane, isobutyltriethoxysilane, sec-butyldiethoxysilane, sec-butyltriethoxysilane, tert-butyldiethoxysilane, tert-butyltriethoxysilane, diethoxypentylsilane, triethoxypentylsilane, diethoxy-1-methylbutylsilane, triethoxy-1-methylbutylsilane, diethoxy-2-methylbutylsilane, triethoxy-2-methylbutyl Silane, diethoxy-3-methylbutylsilane, triethoxy-3-methylbutylsilane, diethoxy-1,1-dimethylpropylsilane, triethoxy-1,1-dimethylpropylsilane, diethoxy-1,2-dimethylpropylsilane, triethoxy-1,2-dimethylpropylsilane, diethoxy-2,2-dimethylpropylsilane, triethoxy-2,2-dimethylpropylsilane, cyclopentyldiethoxysilane, cyclopentyltriethoxysilane, dimethoxydimethylsilane, diethoxydimethylsilane, diethyldimethoxysilane, diethoxydiethylsilane, methoxytrimethylsilane.

[0037] [8] A method for producing a silicon oxide film, which is the method for producing a silicon oxide film according to [1] or [2] above, comprising:

[0038] The gas barrier film material described in any one of [3] to [7] is formed into a film by plasma enhanced chemical vapor deposition under the conditions of a film forming pressure of 0.01 Pa or more and less than 20 Pa.

[0039] [9] The method for manufacturing a silicon oxide film according to [8], comprising:

[0040] The film is formed by plasma enhanced chemical vapor deposition under the condition that the power of a high frequency power source (RF power source) is 100 W or more.

[0041]

[10] The method for manufacturing a silicon oxide film according to [8] or [9] above, comprising:

[0042] The power density of the high frequency power supply (RF power supply) is 0.1W / cm 2 The film was formed by plasma enhanced chemical vapor deposition under the above conditions.

[0043]

[11] A laminated film formed of the silicon oxide film according to [1] or [2] above and a substrate.

[0044]

[12] A gas barrier film formed of the silicon oxide film described in [1] or [2] above.

[0045]

[13] A gas barrier film formed from the laminated film according to

[11] above.

[0046] Effects of the Invention

[0047] The silicon oxide film of the present invention is suitable for gas barrier films, insulating films, semiconductor gate oxide films, protective films, etc. Among them, even if the film thickness is 500nm or less, it has a water vapor transmission rate (WVTR) of 9.0×10 -3 g / m 2 · The low value of less than 1 day makes it particularly suitable for gas barrier films. DETAILED DESCRIPTION

[0048] Hereinafter, the present invention will be described in detail.

[0049] Silicon oxide film

[0050] The water vapor transmission rate (WVTR) of the silicon oxide film of the present invention when the thickness is 500 nm or less, preferably 50 to 500 nm, more preferably 100 to 500 nm, and particularly preferably 200 to 500 nm is 9.0×10 -3 g / m 2Less than 1.0×10 -6 ~9.0×10 -3 g / m 2 ·days, more preferably 1.0×10 -6 ~9.0×10 -4 g / m 2 ·days, particularly preferably 1.0×10 -4 ~9.0×10 -4 g / m 2 ·sky.

[0051] Here, the water vapor transmission rate (WVTR) is measured by gas chromatography (GC method).

[0052] Furthermore, in the silicon oxide film of the present invention, the carbon concentration in the film measured by X-ray photoelectron spectroscopy (XPS) is 3.0 atom% or less, preferably 1.5 atom% or less, and particularly preferably 1.0 atom% or less.

[0053] In order to achieve high gas barrier performance, the thickness of the silicon oxide film is preferably 10 nm or more, more preferably 50 nm to 1000 nm, and particularly preferably 100 nm to 1000 nm.

[0054] It should be noted that the gas barrier film in the present invention refers to the film that does not permeate gases such as oxygen, nitrogen, carbon dioxide, and water vapor. The gas barrier performance is evaluated using the water vapor transmission rate (WVTR) because it is a commonly used measurement indicator in the field of materials.

[0055] The silicon oxide film in the present invention may be formed as a stacked film consisting of a silicon oxide film and a substrate.

[0056] Examples of the substrate include polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polycarbonate (PC), polyamide (PA), polyimide (PI), cycloolefin polymer (COP), polyethylene (PE), polypropylene (PP), polystyrene (PS), polyvinyl chloride (PVC), polyvinyl alcohol (PVA), cellulose triacetate (TAC), polyethersulfone (PES), cycloolefin copolymer (COC), polyacrylonitrile (PAN), ethylene-vinyl alcohol copolymer (EVOH), ABS resin, methacrylic resin, epoxy resin, Polyesters, modified polyphenylene ethers, polyacetals, polybutylene terephthalate, polyacrylates, polyarylates, polysulfones, polyamide-imides, polyether-imides, polyphenylene sulfides, polyether-ether-ketones, and fluororesins are preferred. Among them, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polycarbonate (PC), polyamide (PA), polyimide (PI), cycloolefin polymer (COP), polystyrene (PS), polyvinyl chloride (PVC), polyvinyl alcohol (PVA), cellulose triacetate (TAC), polyether-sulfone (PES), methacrylic resins, and epoxy resins are preferred. Polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polycarbonate (PC), polyamide (PA), polyimide (PI), and cycloolefin polymer (COP) are particularly preferred.

[0057] The visible light transmittance of the laminated film is preferably 80% or more, more preferably 85% or more, and particularly preferably 88% or more.

[0058] Here, the visible light transmittance is a value measured based on the average transmittance (including the substrate) at a wavelength of 380 to 780 nm using a spectrophotometer (U-4100, manufactured by Hitachi High-Technologies Co., Ltd.) The average transmittance of the substrate is also a value measured using the same device.

[0059] The surface roughness (Ra) of the laminated film is preferably 10 nm or less, more preferably 5.0 nm or less, and particularly preferably 3.0 nm or less. Here, the surface roughness (Ra) is measured using an atomic force microscope.

[0060] The film thickness of the laminate film (total thickness of the silicon oxide film and the substrate) is preferably 10 μm or more, more preferably 50 μm to 2000 μm, and particularly preferably 100 μm to 1000 μm. The preferred thickness of the silicon oxide film in the laminate film is as described above.

[0061] Gas barrier film materials

[0062] The gas barrier film material is a silicon oxide film material for chemical vapor deposition, formed of an organosilane compound represented by the following formula (1) (also referred to as organosilane compound (1)).

[0063] [Chemical Formula 2]

[0064] R 1 n -Si——(OR 2 ) 4-n (1)

[0065] In formula (1), R 1 represents an alkyl group having 1 to 20 carbon atoms or a hydrogen atom. n represents an integer of 1 to 3. When n is 2 or more, multiple R 1 are optionally the same or different, and both R 1 They are optionally bonded to each other to form an alkanediyl group. 2 represents an alkyl group having 1 to 10 carbon atoms. When n is 2 or less, multiple R 2 Optional same or different.

[0066] As R in formula (1) 1 The alkyl group having 1 to 20 carbon atoms may have any structure including linear, branched, and cyclic. 1 In the case of two R 1 The case where the alkyl groups are bonded to each other to form an alkanediyl group is also included in the scope of the present invention. As the alkyl group having 1 to 20 carbon atoms, an alkyl group having 1 to 10 carbon atoms is preferred, an alkyl group having 1 to 5 carbon atoms is further preferred, and an alkyl group having 1 to 4 carbon atoms is particularly preferred, from the viewpoint of obtaining high gas barrier properties, high vapor pressure, and suitability for gasification. 1 They may be the same or different from each other.

[0067] As R in an alkyl group having 1 to 20 carbon atoms 1 Examples thereof include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1-ethylpropyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 2,2-dimethylpropyl, cyclopentyl, hexyl, cyclohexyl, octyl, nonyl, decyl, and eicosyl.

[0068] Two R's 1 They may be bonded to each other to form an alkanediyl group. Examples of the alkanediyl group include propane-1,3-diyl, butane-1,4-diyl, pentane-1,4-diyl, pentane-1,5-diyl, hexane-2,5-diyl, hexane-1,6-diyl, and heptane-1,7-diyl.

[0069] From the viewpoint of easy availability of raw materials and high vapor pressure of the gas barrier film material represented by formula (1), R 1 , preferably methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1-ethylpropyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 2,2-dimethylpropyl, hexyl, octyl, or nonyl, particularly preferably methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1-ethylpropyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, or 2,2-dimethylpropyl.

[0070] As R 2 The alkyl group having 1 to 10 carbon atoms in the group includes a methyl group, an ethyl group, a propyl group, an isopropyl group, a cyclopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a 1-methylbutyl group, a 2-methylbutyl group, a 3-methylbutyl group, a 1-ethylpropyl group, a 1,1-dimethylpropyl group, a 1,2-dimethylpropyl group, a 2,2-dimethylpropyl group, etc. Among them, from the viewpoint of easy availability of raw materials, a methyl group, an ethyl group, a propyl group, or an isopropyl group is preferred, and a methyl group or an ethyl group is more preferred.

[0071] n represents an integer of 1 to 3.

[0072] Specific examples of the organosilane compound represented by formula (1) include the following organosilane compounds.

[0073] Dimethoxymethylsilane, trimethoxymethylsilane, ethyldimethoxysilane, ethyltrimethoxysilane, dimethoxypropylsilane, trimethoxypropylsilane, dimethoxyisopropylsilane, trimethoxyisopropylsilane, butyldimethoxysilane, butyltrimethoxysilane, isobutyldimethoxysilane, isobutyltrimethoxysilane, sec-butyldimethoxysilane, sec-butyltrimethoxysilane, tert-butyldimethoxysilane, tert-butyltrimethoxysilane, dimethoxypentylsilane, trimethoxypentylsilane, 1-methylbutyldimethoxysilane, 1-methylbutyltrimethoxysilane, 2-methylbutyldimethoxysilane silane, 2-methylbutyltrimethoxysilane, 3-methylbutyldimethoxysilane, 3-methylbutyltrimethoxysilane, 1-ethylpropyldimethoxysilane, 1-ethylpropyltrimethoxysilane, 1,1-dimethylpropyldimethoxysilane, 1,1-dimethylpropyltrimethoxysilane, 1,2-dimethylpropyldimethoxysilane, 1,2-dimethylpropyltrimethoxysilane, 2,2-dimethylpropyltrimethoxysilane, 2,2-dimethylpropyltrimethoxysilane, cyclopentyldimethoxysilane, cyclopentyltrimethoxysilane, cyclohexyldimethoxysilane, cyclohexyltrimethoxysilane,

[0074] Diethoxysilane, trimethoxysilane, diethoxymethylsilane, triethoxymethylsilane, diethoxyethylsilane, triethoxyethylsilane, diethoxypropylsilane, triethoxypropylsilane, diethoxyisopropylsilane, triethoxyisopropylsilane, butyldiethoxysilane, butyltriethoxysilane, isobutyldiethoxysilane, isobutyltriethoxysilane, sec-butyldiethoxysilane, sec-butyltriethoxysilane, tert-butyldiethoxysilane, tert-butyltriethoxysilane, diethoxypentylsilane, triethoxypentylsilane, 1-methylbutyldiethoxysilane, 1-methylbutyltriethoxysilane, 2- Methylbutyldiethoxysilane, 2-methylbutyltriethoxysilane, 3-methylbutyldiethoxysilane, 3-methylbutyltriethoxysilane, 1-ethylpropyldiethoxysilane, 1-ethylpropyltriethoxysilane, 1,1-dimethylpropyldiethoxysilane, 1,1-dimethylpropyltriethoxysilane, 1,2-dimethylpropyldiethoxysilane, 1,2-dimethylpropyltriethoxysilane, 2,2-dimethylpropyldiethoxysilane, 2,2-dimethylpropyltriethoxysilane, cyclopentyldiethoxysilane, cyclopentyltriethoxysilane, cyclohexyldiethoxysilane, cyclohexyltriethoxysilane,

[0075] Tripropoxysilane, methyltripropoxysilane, ethyltripropoxysilane, tripropoxypropylsilane, tripropoxyisopropylsilane, butyltripropoxysilane, isobutyltripropoxysilane, sec-butyltripropoxysilane, tert-butyltripropoxysilane, pentyltriisopropoxysilane, 1-methylbutyltriisopropoxysilane, 2-methylbutyltriisopropoxysilane, 3-methylbutyltriisopropoxysilane, 1-ethylpropyltriisopropoxysilane, 1,1-dimethylpropyltriisopropoxysilane, 1,2-dimethylpropyltriisopropoxysilane, 2,2-dimethylpropyltriisopropoxysilane, cyclopentyltriisopropoxysilane,

[0076] Methoxydimethylsilane, dimethoxydimethylsilane, ethoxydimethylsilane, diethoxydimethylsilane, dimethylpropoxysilane, dimethyldipropoxysilane, dimethylisopropoxysilane, dimethyldiisopropoxysilane, diethylmethoxysilane, diethyldimethoxysilane, ethoxydiethylsilane, diethoxydiethylsilane, diethylpropoxysilane, diethyldipropoxysilane, diethylisopropoxysilane, diethyldiisopropoxysilane, diisopropylmethoxysilane, diisopropyldimethoxysilane, diisopropylethoxysilane, diisopropyldiethoxysilane, diisopropylpropoxysilane, diisopropyldipropoxysilane, diisopropylisopropoxysilane, diisopropyldiisopropoxysilane, di-sec-butylmethoxysilane , di-sec-butyldimethoxysilane, di-sec-butylethoxysilane, di-sec-butyldiethoxysilane, di-sec-butylpropoxysilane, di-sec-butyldipropoxysilane, di-sec-butylisopropoxysilane, di-sec-butyldiisopropoxysilane, di-tert-butylmethoxysilane, di-tert-butyldimethoxysilane, di-tert-butylethoxysilane, di-tert-butyldiethoxysilane, di-tert-butylpropoxysilane, di-tert-butyldipropoxysilane, di-tert-butylisopropoxysilane, di-tert-butyldiisopropoxysilane, methoxytrimethylsilane, ethoxytrimethylsilane, triethylmethoxysilane, ethoxytriethylsilane, 1,1-dimethoxy-1-silacyclopentane, 1,1-diethoxy-1-silacyclopentane, 1,1-dimethoxy-1-silacyclopentane, etc.

[0077] Among the above, the organosilane compound represented by formula (1) is preferably the following organosilane compound because it becomes a material for a gas barrier film having a high vapor pressure or a low WVTR.

[0078] Dimethoxymethylsilane, trimethoxymethylsilane, ethyldimethoxysilane, ethyltrimethoxysilane, dimethoxypropylsilane, trimethoxypropylsilane, dimethoxyisopropylsilane, trimethoxyisopropylsilane, butyldimethoxysilane, butyltrimethoxysilane, isobutyldimethoxysilane, isobutyltrimethoxysilane, sec-butyldimethoxysilane, sec-butyltrimethoxysilane, tert-butyldimethoxysilane, tert-butyltrimethoxysilane, 1-methylbutyldimethoxysilane, 1-methyl butyltrimethoxysilane, 2-methylbutyldimethoxysilane, 2-methylbutyltrimethoxysilane, 3-methylbutyldimethoxysilane, 3-methylbutyltrimethoxysilane, 1,1-dimethylpropyltrimethoxysilane, 1,1-dimethylpropyltrimethoxysilane, 1,2-dimethylpropyltrimethoxysilane, 1,2-dimethylpropyltrimethoxysilane, 2,2-dimethylpropyltrimethoxysilane, 2,2-dimethylpropyltrimethoxysilane, trimethoxycyclopentylsilane,

[0079] Diethoxymethylsilane, triethoxymethylsilane, ethyldiethoxysilane, ethyltriethoxysilane, diethoxypropylsilane, triethoxypropylsilane, diethoxyisopropylsilane, triethoxyisopropylsilane, butyldiethoxysilane, butyltriethoxysilane, isobutyldiethoxysilane, isobutyltriethoxysilane, sec-butyldiethoxysilane, sec-butyltriethoxysilane, tert-butyldiethoxysilane, tert-butyltriethoxysilane, 1-methylbutyldiethoxysilane, 1-methyl 1,2-Dimethylpropyldiethoxysilane, 1,2-Dimethylpropyltriethoxysilane, 2,2-Dimethylpropyldiethoxysilane, 2,2-Dimethylpropyltriethoxysilane, 1,2-Dimethylpropyltriethoxysilane, 1,1-Dimethylpropyltriethoxysilane, 1,1-Dimethylpropyltriethoxysilane, 1,2 ...

[0080] dimethoxymethylsilane, dimethoxydimethylsilane, diethoxydimethylsilane, diethyldimethoxysilane, diethoxydiethylsilane, diethyldipropoxysilane, diisopropyldimethoxysilane, diisopropyldiethoxysilane, di-sec-butyldimethoxysilane, di-sec-butyldiethoxysilane, di-tert-butyldimethoxysilane, or di-tert-butyldiethoxysilane,

[0081] Dimethoxymethylsilane, trimethoxymethylsilane, ethyltrimethoxysilane, trimethoxypropylsilane, isopropyltrimethoxysilane, butyltrimethoxysilane, isobutyltrimethoxysilane, sec-butyltrimethoxysilane, tert-butyldimethoxysilane, tert-butyltrimethoxysilane, 1-methylbutyltrimethoxysilane, 1,1-dimethylpropyltrimethoxysilane, 1,2-dimethylpropyltrimethoxysilane,

[0082] diethoxymethylsilane, triethoxymethylsilane, ethyltriethoxysilane, triethoxypropylsilane, triethoxyisopropylsilane, butyltriethoxysilane, isobutyltriethoxysilane, sec-butyltriethoxysilane, tert-butyldiethoxysilane, tert-butyltriethoxysilane, 1-methylbutyltriethoxysilane, 1,1-dimethylpropyltriethoxysilane, 1,2-dimethylpropyltriethoxysilane, dimethoxymethylsilane, dimethoxydimethylsilane, diethoxydimethylsilane, diethyldimethoxysilane, or diethoxydiethylsilane.

[0083] A method for obtaining the organosilane compound represented by formula (1) as a material for a gas barrier film will be described.

[0084] The organosilane compound represented by formula (1) can be directly used as a commercial product, or it can be used after being appropriately purified, or an organosilane compound obtained by appropriate synthesis can be used. These organosilane compounds can be synthesized by a method in which an alcohol and / or a metal alkoxide is allowed to act on an alkylhalosilane compound (Synthesis Method 1. For example, the method described in K. Lin, R. J. Wiles, CB Kelly, G. H. M. Davies, G. A. Molander, ACS Catalysis, 2017, Vol. 7, pp. 5129-5133), or a method in which an alkyl magnesium halide or an alkyl lithium is allowed to act on an alkoxysilane (Synthesis Method 2. For example, the method described in S. Masaoka, T. Banno, M. Ishikawa, Journal of Organometallic Chemistry, 2006, Vol. 691, pp. 182-192). The organosilane compound obtained by synthesis can also be purified by a general method such as recrystallization, distillation, and column chromatography and then used for film formation.

[0085] [Chemical Formula 3]

[0086]

[0087] [Chemical Formula 4]

[0088]

[0089] (Where R 1 、R 2 and n represents R in formula (1) 1 、R 2 and n have the same meaning.)

[0090] <Method for producing silicon oxide film>

[0091] The silicon oxide film of the present invention is produced by forming the gas barrier film material by plasma enhanced chemical vapor deposition at a film forming pressure (gauge pressure, the same unless otherwise specified) of 0.01 Pa to less than 20 Pa.

[0092] In addition, in the method for producing a silicon oxide film, as described below, a silicon oxide film is produced on a substrate, and therefore a stacked film can also be produced at the same time.

[0093] When a silicon oxide film is produced, a film is formed by plasma enhanced chemical vapor deposition (PECVD). In this case, oxygen must be supplied in addition to the organosilane compound (1). Specifically, when a gas barrier film is produced by PECVD using the organosilane compound (1) and oxygen as raw materials, the organosilane compound (1) is vaporized and supplied to a film forming chamber provided with a film forming substrate. As a method for vaporization, there are, for example, a method in which the organosilane compound (1) is added to a heated constant temperature bath and vaporized by reducing the pressure using a vacuum pump or the like; a method in which the organosilane compound (1) is added to a heated constant temperature bath and a carrier gas such as helium, neon, argon, krypton, xenon or nitrogen is blown into the bath to vaporize; or a method in which the organosilane compound (1) is supplied directly or as a solution to a vaporizer, heated, and vaporized in the vaporizer (liquid jet method).

[0094] Examples of the solvent used in the case of forming a solution include 1,2-dimethoxyethane, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, diethylene glycol dimethyl ether, and diethylene glycol dimethyl ether. Ethers such as alkane, tetrahydrofuran, and cyclopentyl methyl ether, and hydrocarbons such as hexane, cyclohexane, methylcyclohexane, ethylcyclohexane, heptane, octane, nonane, decane, benzene, toluene, ethylbenzene, and xylene. These solvents may be used alone or in combination of two or more in any proportion.

[0095] In this way, the organosilane compound (1) and oxygen supplied to the film forming chamber react with the plasma generated in the film forming chamber to form a gas barrier film on the film forming substrate. Film formation can be performed using plasma alone, but it can also be combined with light irradiation, heating of the film forming substrate, etc.

[0096] The plasma generation source is not particularly limited, and examples thereof include capacitively coupled plasma, inductively coupled plasma, helicon wave plasma, surface wave plasma, and electron cyclotron resonance plasma.

[0097] As the film-forming apparatus for producing the silicon oxide film, any chemical vapor deposition apparatus commonly used by those skilled in the art may be used, and examples thereof include batch-type, single-wafer, and roll-to-roll systems.

[0098] The pressure in the film forming chamber must be within the range of 0.01 Pa to less than 20 Pa, and is preferably 0.1 Pa to less than 15 Pa from the viewpoint of low WVTR of the obtained gas barrier film and ease of vacuum control.

[0099] The power of the high-frequency power source (RF power source) is preferably 100 W or more, and more preferably 200 W to 1500 W from the viewpoint of low WVTR of the obtained gas barrier film.

[0100] The power density of the applied voltage for plasma discharge is preferably 0.1 W / cm 2 From the viewpoint of low WVTR of the obtained gas barrier film, it is more preferably 2.0 W / cm 2 ~100W / cm 2 .

[0101] The temperature of the film-forming substrate during film formation is not particularly limited, but is equal to or lower than the heat-resistant temperature of the film-forming substrate, and is preferably in the range of 0°C to 300°C.

[0102] The type of film-forming substrate is not particularly limited, and examples thereof include polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polycarbonate (PC), polyamide (PA), polyimide (PI), cycloolefin polymer (COP), polyethylene (PE), polypropylene (PP), polystyrene (PS), polyvinyl chloride (PVC), polyvinyl alcohol (PVA), cellulose triacetate (TAC), polyethersulfone (PES), cycloolefin copolymer (COC), polyacrylonitrile (PAN), ethylene-vinyl alcohol copolymer (EVOH), ABS resin, methacrylic resin, epoxy resin, modified polyphenylene ether, polyacetal, polybutylene terephthalate, polyacrylate, polyarylate, polysulfone, polyamideimide, polyetherimide, polyphenylene sulfide, polyetheretherketone, fluororesin, etc.

[0103] When the supply flow rate of the organosilane compound (1) supplied during film formation is X and the supply flow rate of oxygen is Y, the ratio of oxygen to the organosilane compound (1) (Y / X) is preferably 1 or more, more preferably 5-100.

[0104] Example

[0105] Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto.

[0106] A gas barrier film was formed on a substrate using a conventional CVD device that forms films using a volume-coupled PECVD method. The film-forming substrates used were a 125 μm thick polyethylene naphthalate (PEN) film (visible light transmittance of 88.3% and a surface roughness Ra of 0.71 nm) and a 125 μm thick polyethylene terephthalate (PET) film (visible light transmittance of 89.3% and a surface roughness Ra of 1.17 nm). As raw gas, organic silane compounds, oxygen, and argon gas vaporized in a thermostatic bath were used. Furthermore, a high-frequency power supply with a frequency of 13.56 MHz was used as the power source.

[0107] The thickness of the film after film formation was estimated by taking a cross-sectional image of the film using a field emission scanning electron microscope (manufactured by JEOL Ltd., FE-SEM) JSM-7600F.

[0108] The water vapor transmission rate (WVTR), which is an indicator of gas barrier performance, was measured by gas chromatography (GC method) using a moisture transmission rate measuring apparatus (GTR3000 series, manufactured by GTR Tech).

[0109] The film composition (including carbon concentration) of the gas barrier film was analyzed using an X-ray photoelectron spectroscopy analyzer (manufactured by ULVAC PHI, Inc., XPS) PHI5000 VersaProbeII.

[0110] For the analysis of the synthesized organosilane compound (1), 1 H-NMR (proton nuclear magnetic resonance spectroscopy), 13 C-NMR (carbon 13 nuclear magnetic resonance spectroscopy) and 29 Si-NMR (silicon 29 nuclear magnetic resonance spectroscopy) measurements were performed using a Bruker-Avance DPX-400 nuclear magnetic resonance spectrometer, using deuterated chloroform as the solvent. IR (infrared absorption) spectroscopy was performed using a Horiba FT-720 spectrophotometer and a DuraSamplIRII (reflection type) from SensIR Technologies. Mass spectrometry was performed using a gas chromatograph-type mass spectrometer (Shimadzu Corporation, GCMS-QP2010 model) with a DB-5MS from Agilent Technologies as the capillary column.

[0111] (Example 1) Film formation using tert-butyltriethoxysilane

[0112] A silicon oxide film was formed on a PEN film using tert-butyltriethoxysilane synthesized with reference to the method described in K. Lin, R. J. Wiles, C. B. Kelly, G. H. M. Davies, G. A. Molander, AC Catalysis, 2017, Vol. 7, pp. 5129-5133, along with oxygen, by PECVD. The tert-butyltriethoxysilane supply flow rate was set to 80 sccm, the oxygen supply flow rate was set to 2100 sccm, the film formation chamber pressure was set to 8 Pa, and the power of the high-frequency power supply (RF power supply) with a power frequency of 13.56 MHz was set to 1000 W. The film was formed for 14 minutes. In addition, the ratio of the oxygen supply flow rate to the tert-butyltriethoxysilane supply flow rate (Y / X) was 26.3.

[0113] The thickness of the obtained silicon oxide film was 800 nm. The film composition was Si = 33 atom%, O = 67 atom%, and the carbon concentration was less than 1.0 atm%. The WVTR was 2.0×10 -4 g / m 2 ·sky.

[0114] The visible light transmittance of the laminated film composed of the silicon oxide film and the PEN film was 88.2%, and the surface roughness (Ra) was 0.68 nm.

[0115] A silicon oxide film was formed on a PEN film using tert-butyltriethoxysilane along with oxygen by PECVD. The tert-butyltriethoxysilane supply flow rate was set to 80 sccm, the oxygen supply flow rate was set to 2100 sccm, the film deposition chamber pressure was set to 8 Pa, and the power of the high-frequency power supply (RF power supply) at a frequency of 13.56 MHz was set to 1000 W. The film deposition was carried out for 7 minutes. The ratio of the oxygen supply flow rate to the tert-butyltriethoxysilane supply flow rate (Y / X) was 26.3.

[0116] The thickness of the obtained silicon oxide film was 400 nm. The WVTR was 4.3×10 -4 g / m 2 The visible light transmittance of the laminated film composed of the silicon oxide film and the PEN film was 88.5%.

[0117] When tert-butyltriethoxysilane is used together with oxygen to form a film by PECVD, even a thin silicon oxide film with a thickness of 400 nm shows a WVTR of 10 -3 g / m 2 10 below the Heaven level -4 g / m 2 ·Sky grade, suitable for use as gas barrier film.

[0118] (Example 2) Film formation using tert-butyltriethoxysilane

[0119] A silicon oxide film was formed on a PET film by PECVD using tert-butyltriethoxysilane obtained in the same manner as in Example 1, along with oxygen. The tert-butyltriethoxysilane supply flow rate was set to 80 sccm, the oxygen supply flow rate was set to 2100 sccm, the film deposition chamber pressure was set to 8 Pa, and the power of the high-frequency power supply (RF power supply) with a power frequency of 13.56 MHz was set to 1000 W. The film deposition was performed for 8 minutes. The ratio of the oxygen supply flow rate to the tert-butyltriethoxysilane supply flow rate (Y / X) was 26.3.

[0120] The thickness of the obtained silicon oxide film was 500 nm. The WVTR was 3.9×10 -3 g / m 2The visible light transmittance of the laminated film composed of the silicon oxide film and the PET film was 91.0%.

[0121] When tert-butyltriethoxysilane is used together with oxygen to form a film by PECVD, even a thin silicon oxide film with a thickness of 500 nm shows a WVTR of 10 -3 g / m 2 ·Sky grade, suitable for use as gas barrier film.

[0122] (Example 3) Film formation using isopropyltrimethoxysilane

[0123] Isopropyltrimethoxysilane, synthesized using the method described in K. Lin, R. J. Wiles, C. B. Kelly, G. H. M. Davies, G. A. Molander, AC Catalysis, 2017, Vol. 7, pp. 5129-5133, was used with oxygen to form a silicon oxide film on a PEN film by PECVD. The supply flow rate of isopropyltrimethoxysilane was set to 80 sccm, the supply flow rate of oxygen was set to 2100 sccm, the film formation chamber pressure was set to 8 Pa, and the power of the high-frequency power supply (RF power supply) with a power frequency of 13.56 MHz was set to 1000 W. The film was formed for 11 minutes. In addition, the ratio of the supply flow rate of oxygen to the supply flow rate of isopropyltrimethoxysilane (Y / X) was 26.3.

[0124] The thickness of the obtained silicon oxide film was 800 nm. The film composition was Si = 33 atom%, O = 67 atom%, and the carbon concentration was less than 1.0 atm%. The WVTR was 2.0×10 -4 g / m 2 ·sky.

[0125] The visible light transmittance of the laminated film composed of the silicon oxide film and the PEN film was 88.2%, and the surface roughness (Ra) was 0.67 nm.

[0126] A silicon oxide film was formed on a PEN film using isopropyltrimethoxysilane along with oxygen by PECVD. The isopropyltrimethoxysilane supply flow rate was set to 80 sccm, the oxygen supply flow rate was set to 2100 sccm, the film deposition chamber pressure was set to 8 Pa, and the power of the high-frequency power supply (RF power supply) at a frequency of 13.56 MHz was set to 1000 W. The film deposition was performed for 3 minutes. The ratio of the oxygen supply flow rate to the isopropyltrimethoxysilane supply flow rate (Y / X) was 26.3.

[0127] The thickness of the obtained silicon oxide film was 200 nm. The WVTR was 6.9×10 -4 g / m 2The visible light transmittance of the laminated film composed of the silicon oxide film and the PEN film was 88.4%.

[0128] When isopropyltrimethoxysilane is used together with oxygen to form a film by PECVD, even a thin silicon oxide film with a thickness of 200 nm shows a WVTR of 10 -3 g / m 2 10 below the Heaven level -4 g / m 2 ·Sky grade, suitable for use as gas barrier film.

[0129] (Synthesis Example 1) Synthesis of (1,2-dimethylpropyl)trimethoxysilane

[0130] A 500 mL three-necked flask equipped with a magnetic stirrer, a condenser coil, a dropping funnel, and a three-way stopcock was purged with argon and charged with 136 g (4.26 mol) of dehydrated methanol, 422 g (4.17 mol) of triethylamine, and 1800 mL of diethyl ether. While cooling the reaction vessel in an ice bath, 275 g (1.34 mol) of trichloro-1,2-dimethylpropylsilane, synthesized according to a documented method (MG Voronkov, NG Romanova, LG Smirnova, Chemicke Listy pro Vedu a Prumysl, Vol. 52, pp. 640-653, 1958), was added dropwise from the dropping funnel over 3.5 hours. The mixture was then stirred at room temperature for 16 hours. The reaction mixture was filtered through a Buchner funnel to remove solid impurities. The filtrate was concentrated using a rotary evaporator, hexane was added, and the mixture was washed three times with water. The organic layer was dried over anhydrous magnesium sulfate, filtered, and concentrated again using a rotary evaporator. The resulting mixture was distilled under reduced pressure (boiling point 79°C / 3.3 kPa) to obtain 226 g (yield 87.7%) of (1,2-dimethylpropyl)trimethoxysilane as a colorless, transparent liquid.

[0131] Mass spectrum (EI, 70 eV) m / z (%) 177 ([M-CH3] + , 1.1), 121(Si(OMe)3 + , 100). 1 H-NMR (400MHz, CDCl3) δ (ppm) 0.83 ~ 0.90 (m, 1H), 0.92 ~ 1.00 (m, 9H), 1.78 ~ 1.90 (m, 1H), 3.58 (s, 9H). 13 C-NMR (100MHz, CDCl3) δ (ppm) 10.01, 20.57, 22.09, 23.53, 28.76, 50.65. 29Si-NMR (80MHz, CDCl3) δ (ppm)-43.7.IR (thin film, cm -1 )2956,2945,2875,2841,1466,1387,1375,1365,1230,1190,1082,910,793,727.

[0132] (Example 4) Film Formation Using (1,2-Dimethylpropyl)trimethoxysilane

[0133] A silicon oxide film was formed on a PEN film using (1,2-dimethylpropyl)trimethoxysilane obtained in Synthesis Example 1, along with oxygen, by PECVD. The (1,2-dimethylpropyl)trimethoxysilane supply flow rate was 80 sccm, and the oxygen supply flow rate was 2100 sccm. The film deposition chamber pressure was set to 8 Pa, and the power of the high-frequency power supply (RF power supply) at a frequency of 13.56 MHz was set to 1000 W. The film deposition was performed for 11 minutes. The ratio of the oxygen flow rate to the (1,2-dimethylpropyl)trimethoxysilane flow rate (Y / X) was 26.3.

[0134] The thickness of the obtained silicon oxide film was 800 nm. The film composition was Si = 33 atom%, O = 67 atom%, and the carbon concentration was less than 1.0 atm%. The WVTR was 2.0×10 -4 g / m 2 ·sky.

[0135] The visible light transmittance of the laminated film composed of the silicon oxide film and the PEN film was 88.1%, and the surface roughness (Ra) was 0.62 nm.

[0136] A silicon oxide film was formed on a PEN film using (1,2-dimethylpropyl)trimethoxysilane obtained in Synthesis Example 1, along with oxygen, by PECVD. The (1,2-dimethylpropyl)trimethoxysilane supply flow rate was 80 sccm, and the oxygen supply flow rate was 2100 sccm. The film deposition chamber pressure was set to 8 Pa, and the power of the high-frequency power supply (RF power supply) at a frequency of 13.56 MHz was set to 1000 W. The film deposition was performed for 3 minutes. The ratio of the oxygen flow rate to the (1,2-dimethylpropyl)trimethoxysilane flow rate (Y / X) was 26.3.

[0137] The thickness of the obtained silicon oxide film was 250 nm. The WVTR was 7.2×10 -4 g / m 2 The visible light transmittance of the laminated film composed of the silicon oxide film and the PEN film was 88.2%.

[0138] When (1,2-dimethylpropyl)trimethoxysilane is used together with oxygen to form a film by PECVD, even a thin silicon oxide film with a thickness of 250 nm shows a WVTR of 10 -3 g / m 2 10 below the Heaven level -4 g / m 2 ·Sky grade, suitable for use as gas barrier film.

[0139] (Example 5) Film formation using tert-butyltrimethoxysilane

[0140] A silicon oxide film was formed on a PEN film using tert-butyltrimethoxysilane synthesized using the method described in K. Lin, R. J. Wiles, C. B. Kelly, G. H. M. Davies, G. A. Molander, AC Catalysis, 2017, Vol. 7, pp. 5129-5133, along with oxygen, by PECVD. The tert-butyltrimethoxysilane supply flow rate was set to 80 sccm, the oxygen supply flow rate was set to 2100 sccm, the film formation chamber pressure was set to 8 Pa, and the power of the high-frequency power supply (RF power supply) with a power frequency of 13.56 MHz was set to 1000 W. The film was formed for 14 minutes. In addition, the ratio of the oxygen supply flow rate to the tert-butyltrimethoxysilane supply flow rate (Y / X) was 26.3.

[0141] The thickness of the obtained silicon oxide film was 800 nm. The WVTR was 4.1×10 -4 g / m 2 The film composition is Si = 35 atom%, O = 65 atom%, and the carbon concentration is less than 1.0 atm%.

[0142] The visible light transmittance of the laminated film composed of the silicon oxide film and the PEN film was 88.1%, and the surface roughness (Ra) was 0.70 nm.

[0143] A silicon oxide film was formed on a PEN film using tert-butyltrimethoxysilane along with oxygen by PECVD. The tert-butyltrimethoxysilane supply flow rate was set to 80 sccm, the oxygen supply flow rate was set to 2100 sccm, the film deposition chamber pressure was set to 8 Pa, and the power of the high-frequency power supply (RF power supply) at a frequency of 13.56 MHz was set to 1000 W. The film deposition was carried out for 4 minutes. The ratio of the oxygen supply flow rate to the tert-butyltrimethoxysilane supply flow rate (Y / X) was 26.3.

[0144] The thickness of the obtained silicon oxide film was 250 nm. The WVTR was 8.5×10 -4 g / m 2The visible light transmittance of the laminated film composed of the silicon oxide film and the PEN film was 88.2%.

[0145] When tert-butyltrimethoxysilane is used together with oxygen to form a film by PECVD, even a thin silicon oxide film with a thickness of 250nm can achieve a WVTR as low as 10 -3 g / m 2 10 below the Heaven level -4 g / m 2 ·Sky grade, suitable for use as gas barrier film.

[0146] (Example 6) Film formation using dimethoxydimethylsilane

[0147] A silicon oxide film was formed on a PEN film using dimethoxydimethylsilane along with oxygen by PECVD. The dimethoxydimethylsilane supply flow rate was set to 80 sccm, the oxygen supply flow rate was set to 2100 sccm, the film deposition chamber pressure was set to 8 Pa, and the power of the high-frequency power supply (RF power supply) at a frequency of 13.56 MHz was set to 1000 W. The film deposition was performed for 8 minutes. The ratio of the oxygen supply flow rate to the dimethoxydimethylsilane supply flow rate (Y / X) was 26.3.

[0148] The thickness of the obtained silicon oxide was 800 nm. The WVTR was 7.3×10 -4 g / m 2 The film composition was Si = 36 atom%, O = 64 atom%, and the carbon concentration was less than 1.0 atm%.

[0149] The visible light transmittance of the laminated film composed of the silicon oxide film and the PEN film was 88.5%, and the surface roughness (Ra) was 0.70 nm.

[0150] A silicon oxide film was formed on a PEN film using dimethoxydimethylsilane along with oxygen by PECVD. The dimethoxydimethylsilane supply flow rate was set to 80 sccm, the oxygen supply flow rate was set to 2100 sccm, the film deposition chamber pressure was set to 8 Pa, and the power of the high-frequency power supply (RF power supply) at a frequency of 13.56 MHz was set to 1000 W. The film deposition was performed for 2 minutes. The ratio of the oxygen supply flow rate to the dimethoxydimethylsilane supply flow rate (Y / X) was 26.3.

[0151] The thickness of the obtained silicon oxide film was 200 nm. The WVTR was 2.0×10 -3 g / m 2 The visible light transmittance of the laminated film composed of the silicon oxide film and the PEN film was 88.3%.

[0152] When dimethoxydimethylsilane is used together with oxygen to form a film by PECVD, even a thin silicon oxide film with a thickness of 200 nm shows a WVTR of 10. -3 g / m 2 ·Sky grade, suitable for use as gas barrier film.

[0153] (Comparative Example 1) Film Formation Using Hexamethyldisiloxane

[0154] Hexamethyldisiloxane was used together with oxygen to form a film on a PEN film by PECVD. The supply flow rate of hexamethyldisiloxane was set to 80 sccm, the supply flow rate of oxygen was set to 2100 sccm, the pressure in the film forming chamber was set to 6 Pa, and the power of the high-frequency power supply (RF power supply) with a power frequency of 13.56 MHz was set to 1000 W. The film was formed for 7 minutes. In addition, the ratio of the supply flow rate of oxygen to the supply flow rate of hexamethyldisiloxane (Y / X) was 26.3. The thickness of the obtained film was 800 nm. The WVTR was 2.8×10 -3 g / m 2 Day, showing high values.

[0155] Hexamethyldisiloxane was used together with oxygen to form a film on a PEN film using the PECVD method. The hexamethyldisiloxane supply flow rate was set to 80 sccm, the oxygen supply flow rate was set to 2100 sccm, the film deposition chamber pressure was set to 6 Pa, and the power of the high-frequency power supply (RF power supply) with a power frequency of 13.56 MHz was set to 1000 W. The film deposition was carried out for 2 minutes. The ratio of the oxygen supply flow rate to the hexamethyldisiloxane supply flow rate (Y / X) was 26.3.

[0156] The thickness of the obtained film was 200 nm. The WVTR was 2.4×10 -2 g / m 2 Day, showing high values.

[0157] The silicon oxide film produced using the organosilane compound represented by formula (1) of the present invention has a WVTR of 10 even if the thickness is 500 nm or less. -3 g / m 2 · It has high gas barrier properties below the day level, making it suitable for use as a gas barrier film.

[0158] For silane compounds outside the range of the organosilane compounds represented by formula (1) of the present invention, when formed into films, the WVTR is higher than 10 when the film thickness is 500 nm or less, as compared with the comparative examples. -3 g / m 2 · Sky grade, low gas barrier property, not suitable for gas barrier film.

Claims

1. A laminated film comprising a silicon oxide film and a substrate, wherein the silicon oxide film satisfies the following requirements (1) and (2): (1) When the film thickness is less than 500 nm, the water vapor transmission rate (WVTR) is 1.0 × 10 -6 ~9.0×10 -4 g / m 2 ·sky; (2) The carbon concentration in the film measured by X-ray photoelectron spectroscopy (XPS) is 1.5 atom% or less, The silicon oxide film is formed by forming the following gas barrier film material by plasma enhanced chemical vapor deposition under the conditions of a film forming pressure of 0.01 Pa or more and less than 20 Pa and a high-frequency power supply power of 100 W or more, wherein the gas barrier film material is any material selected from the following: Trimethoxyisopropylsilane, tert-butyltrimethoxysilane, tert-butyltriethoxysilane, 1,2-dimethylpropyltrimethoxysilane.

2. The laminated film according to claim 1, wherein The water vapor transmission rate (WVTR) of the silicon oxide film when the film thickness is less than 500 nm is 1.0×10 -4 ~9.0×10 -4 g / m 2 ·sky.

3. The laminated film according to claim 1 or 2, wherein The gas barrier film material is any material selected from the following: Trimethoxyisopropylsilane, tert-butyltrimethoxysilane, 1,2-dimethylpropyltrimethoxysilane.

4. A method for manufacturing a silicon oxide film, wherein the silicon oxide film is the silicon oxide film according to claim 1 or 2, the method comprising: The following gas barrier film material for chemical vapor deposition is formed into a film by plasma enhanced chemical vapor deposition under the conditions of a film forming pressure of 0.01 Pa or more and less than 20 Pa and a high-frequency power supply power of 100 W or more, wherein the gas barrier film material is any material selected from the following: Trimethoxyisopropylsilane, tert-butyltrimethoxysilane, tert-butyltriethoxysilane, 1,2-dimethylpropyltrimethoxysilane.

5. The method for manufacturing a silicon oxide film according to claim 4, comprising: The film is formed by plasma enhanced chemical vapor deposition under the condition that the power of the high frequency power supply is 200 to 1500W.

6. The method for manufacturing a silicon oxide film according to claim 4 or 5, comprising: The power density of the high frequency power supply is 0.1W / cm 2 The film was formed by plasma enhanced chemical vapor deposition under the above conditions. A gas barrier film formed of the laminated film according to claim 1 or 2.

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