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

Abstract

To provide a silicon oxide film that exhibits excellent gas barrier properties even as a thin film.SOLUTION: The silicon oxide film is characterized by satisfying the following conditions (1) and (2). (1) The water vapor transmission rate (WVTR) at a film thickness of 500 nm or less is at most 9.0×10-3 g / m2 day. (2) The carbon concentration in the film as measured by X-ray photoelectron spectroscopy (XPS) is at most 3.0 atom%.SELECTED DRAWING: None

Description

[Technical Field]

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

[0002] Gas barrier films that provide gas barrier properties by being deposited on plastic substrates or plastic films include those deposited by physical deposition methods and those deposited by CVD (Chemical Vapor Deposition). The composition of these gas barrier films includes oxides such as SiO2 and Al2O3, and nitrides such as SiN. For example, Patent Document 1 proposes a barrier bag film in which an SiO2 gas barrier layer is formed by plasma-enhanced chemical vapor deposition (PECVD) using a mixed gas of hexamethyldisiloxane, 1,1,3,3-tetramethyldisiloxane, 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, oxygen, and an inert gas such as helium or argon as raw materials. However, the film has a water vapor transmission rate (WVTR) of 0.2 to 0.6 g / m², which is an indicator of gas barrier performance. 2 ·day, oxygen permeability is 0.4~0.5cc / m 2 The value for 'day' is high, meaning the gas barrier performance is low.

[0003] Patent Document 2 describes the production of polyethylene naphthalate (PEN) film with an SiO2 gas barrier layer formed at a deposition pressure of 20 Pa or less by PECVD using tetraethoxysilane and oxygen as raw materials. However, the deposition pressure is high, and the WVTR is 1.7 × 10⁻⁶. -3 g / m 2 • The gas barrier properties were still not sufficient.

[0004] In addition, Patent Document 3 describes a method of forming a low dielectric constant insulating film by using an organic silane compound and the PECVD method. Although WVTR is not described, since the power of the high-frequency power source (RF power source) during film formation is as low as 75 W and it is a method of forming a low-density thin film, it is presumed that the formed film is not a film suitable for a gas barrier material.

[0005] In Patent Document 4, by using a laminated film of an organic thin film - an inorganic thin film, WVTR is 1.0×10 -5 ~2.9×10 -5 g / m 2 ·day, which is a very low film, is described. However, since it is necessary to form the organic thin film and the inorganic thin film in individual film formation processes, there is a problem that the number of manufacturing processes increases and the manufacturing cost of the gas barrier film increases.

[0006] In Patent Document 5, by forming a specific organic silane compound having a specific structure by the PECVD method, a single-layer film with a film thickness of 800 nm and a gas barrier film showing a WVTR of 2.1×10 -4 g / m 2 ·day is described.

Prior Art Documents

Patent Documents

[0007]

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

Patent Document 5

Summary of the Invention

Problems to be Solved by the Invention

[0008] In recent years, with the thinning of gas barrier films, higher gas barrier properties are required even for thinner films. Generally, when the film thickness becomes thinner, WVTR tends to increase. The present invention provides a film with a film thickness of 500 nm or less and a WVTR of 10 -3 g / m 2The objective is to provide a silicon oxide film having high gas barrier properties exhibiting a WVTR of less than one day, a material for gas barrier films, and a method for manufacturing a silicon oxide film using the gas barrier film material. [Means for solving the problem]

[0009] As a result of diligent research to solve the above problems, the inventors of the present invention have found that the above problems can be solved by using silicon oxide films and gas barrier film materials having specific properties, and have completed the present invention.

[0010] In other words, the present invention consists of the following configuration. [1] A silicon oxide film characterized by satisfying the following requirements (1) to (2). (1) Water vapor transmission rate (WVTR) at film thickness of 500 nm or less is 9.0 × 10 -3 g / m 2 ·day or less (2) The carbon concentration in the film measured by X-ray photoelectron spectroscopy (XPS) is 3.0 atom% or less. [2] The water vapor transmission rate (WVTR) at a film thickness of 500 nm or less is 1.0 × 10⁻⁶ -6 ~9.0×10 -3 g / m 2 • A silicon oxide film as described in [1]. [3] Formula (1)

[0011] [Formula 1]

[0012] (In the formula, R 1 R represents an alkyl group or hydrogen atom having 1 to 20 carbon atoms. n represents an integer from 1 to 3. If n is 2 or greater, multiple Rs are used. 1 The two Rs may be the same or different, and also, the two Rs may be different. 1 They may bond to each other to form an alkanediyl group. 2 This represents an alkyl group having 1 to 10 carbon atoms. If n is 2 or less, multiple R 2A gas barrier film material for chemical vapor deposition, comprising an organosilane compound represented by (which may be the same or different in form). [4] R 1 The gas barrier film material described in [3] is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. [5] R 2 However, the gas barrier film material is an alkyl group having 1 to 3 carbon atoms as described in [3] or [4]. [6] R 1 A gas barrier film material according to any one of [3] to [5], wherein the group consists of a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, an s-butyl group, a t-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. [7] The materials for gas barrier films include dimethoxymethylsilane, trimethoxymethylsilane, ethyldimethoxysilane, ethyltrimethoxysilane, dimethoxypropylsilane, trimethoxypropylsilane, dimethoxyisopropylsilane, trimethoxyisopropylsilane, butyldimethoxysilane, butyltrimethoxysilane, isobutyldimethoxysilane, isobutyltrimethoxysilane, s-butyldimethoxysilane, s-butyltrimethoxysilane, t-butyldimethoxysilane, t-butyltrimethoxysilane, dimethoxypentylsilane, trimethoxypentylsilane, 1-methylbutyldimethoxysilane, 1-methylbutyltrimethoxysilane, 2-methylbutyl Dimethyl dimethoxysilane, 2-methylbutyltrimethoxysilane, 3-methylbutyldimethoxysilane, 3-methylbutyltrimethoxysilane, 1,1-dimethylpropyldimethoxysilane, 1,1-dimethylpropyltrimethoxysilane, 1,2-dimethylpropyldimethoxysilane, 1,2-dimethylpropyltrimethoxysilane, 2,2-dimethylpropyldimethoxysilane, 2,2-dimethylpropyltrimethoxysilane, cyclopentyldimethoxysilane, cyclopentyltrimethoxysilane, diethoxymethylsilane, triethoxymethylsilane, diethoxyethylsilane, triethoxyethylsilane, diethoxypropylsilane, triethoxypropylsilane Diethoxyisopropylsilane, Triethoxyisopropylsilane, Butyldiethoxysilane, Butyltriethoxysilane, Isobutyldiethoxysilane, Isobutyltriethoxysilane, s-Butyldiethoxysilane, s-Butyltriethoxysilane, t-Butyldiethoxysilane, t-Butyltriethoxysilane, Diethoxypentylsilane, Triethoxypentylsilane, Diethoxy-1-methylbutylsilane, Triethoxy-1-methylbutylsilane, Diethoxy-2-methylbutylsilane, Triethoxy-2-methylbutylsilane, Diethoxy-3-methylbutylsilane, Triethoxy-3-methylbutylsilane A gas barrier film material according to any one of [3] to [6], which is one of butylsilane, 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, or methoxytrimethylsilane. [8] A method for producing a silicon oxide film according to [1] or [2], wherein a gas barrier film material according to any one of [3] to [7] is deposited by plasma-excited chemical vapor deposition under conditions of a deposition pressure of 0.01 Pa or more and less than 20 Pa. [9] A method for producing a silicon oxide film as described in [8], wherein the film is formed by plasma-excited chemical vapor deposition under the condition that the power of the high-frequency power supply (RF power supply) is 100W or more.

[10] The power density of the high-frequency power supply (RF power supply) is 0.1 W / cm². 2 A method for producing a silicon oxide film according to [8] or [9], wherein the film is formed by plasma-excited chemical vapor deposition under the above conditions.

[11] A laminated film comprising the silicon oxide film described in [1] or [2] and a substrate.

[12] A gas barrier film comprising a silicon oxide film as described in [1] or [2].

[13] A gas barrier film comprising the laminated film described in

[11] .

[0013] The present invention will be described in detail below.

[0014] First, let's discuss silicon oxide films.

[0015] The silicon oxide film of the present invention is a silicon oxide film that satisfies the following requirements (1) to (2). (1) Water vapor transmission rate (WVTR) at film thickness of 500 nm or less is 9.0 × 10 -3 g / m 2 ·day or less (2) The carbon concentration in the film measured by X-ray photoelectron spectroscopy (XPS) is 3.0 atom% or less. The silicon oxide film has a water vapor transmission rate (WVTR) of 9.0 × 10⁻¹⁰ at a film thickness of 500 nm or less. -3 g / m 2 • Less than or equal to 1.0 × 10 days, preferably 1.0 × 10 -6 ~9.0×10 -3 g / m 2 • day, more preferably 1.0 × 10 -6 ~9.0×10 -4 g / m 2 • day, particularly preferably 1.0 × 10 -4 ~9.0×10 -4 g / m 2 It is a day.

[0016] Here, the water vapor transmission rate (WVTR) was measured using gas chromatography (GC).

[0017] The silicon dioxide has a carbon concentration in the film measured by X-ray photoelectron spectroscopy (XPS) of 3.0 atom% or less, preferably 1.5 atom% or less, and particularly preferably 1.0 atom% or less.

[0018] Furthermore, the thickness of the silicon oxide film is preferably 10 nm or more in order to achieve high gas barrier performance, more preferably 50 nm to 1000 nm, and particularly preferably 100 nm to 1000 nm.

[0019] It can also be a multilayer film consisting of a silicon oxide film and a substrate.

[0020] Examples of substrates 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), triacetylcellulose (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, and polyamide. Examples include imides, polyetherimides, polyphenylene sulfides, polyetheretherketones, and fluororesins, among which polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polycarbonate (PC), polyamide (PA), polyimide (PI), cycloolefin polymer (COP), polystyrene (PS), polyvinyl chloride (PVC), polyvinyl alcohol (PVA), triacetylcellulose (TAC), polyethersulfone (PES), methacrylic resin, and epoxy resin are preferred, with polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polycarbonate (PC), polyamide (PA), polyimide (PI), and cycloolefin polymer (COP) being particularly preferred.

[0021] The laminated film preferably has a visible light transmittance of 80% or more, more preferably 85% or more, and particularly preferably 88% or more.

[0022] Here, visible light transmittance is measured using a spectrophotometer (Hitachi High-Technologies Corporation U-4100) as the average transmittance (including the substrate) at wavelengths of 380 to 780 nm. The average transmittance of the substrate was also measured using the same device.

[0023] The laminated film preferably has a surface roughness (Ra) of 10 nm or less, more preferably 5.0 nm or less, and particularly preferably 3.0 nm or less.

[0024] Here, surface roughness (Ra) is measured using an atomic force microscope.

[0025] The thickness of the laminated film is preferably 10 μm or more, more preferably 50 μm to 2000 μm, and particularly preferably 100 μm to 1000 μm.

[0026] Next, we will explain materials for gas barrier films.

[0027] The material for the gas barrier film is given by formula (1)

[0028] [chemical 2]

[0029] (In the formula, R 1 R represents an alkyl group or hydrogen atom having 1 to 20 carbon atoms. n represents an integer from 1 to 3. If n is 2 or greater, multiple Rs are used. 1 The two Rs may be the same or different, and also, the two Rs may be different. 1 They may bond to each other to form an alkanediyl group. 2 This represents an alkyl group having 1 to 10 carbon atoms. If n is 2 or less, multiple R 2 These may be the same or different in phase.) This is a gas barrier film material for chemical vapor deposition consisting of an organosilane compound represented by ).

[0030] R in equation (1) 1 R is an alkyl group having 1 to 20 carbon atoms or a hydrogen atom, and the alkyl group having 1 to 20 carbon atoms may have a linear, branched, or cyclic structure. In addition, there may be multiple R atoms in the molecule.1 If there are two R 1 Alkyl groups formed by the bonding of carbon atoms to each other are also included within the scope of the present invention. As alkyl groups having 1 to 20 carbon atoms, alkyl groups having 1 to 10 carbon atoms are preferred because they provide high gas barrier properties and have a high vapor pressure, making them suitable for vaporization. Alkyl groups having 1 to 5 carbon atoms are even more preferred, and alkyl groups having 1 to 4 carbon atoms are particularly preferred.

[0031] Also, multiple R 1 They may be the same or different.

[0032] R in alkyl groups having 1 to 20 carbon atoms 1 Examples of these groups include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, s-butyl group, t-butyl group, pentyl group, 1-methylbutyl group, 2-methylbutyl group, 3-methylbutyl group, 1-ethylpropyl group, 1,1-dimethylpropyl group, 1,2-dimethylpropyl group, 2,2-dimethylpropyl group, cyclopentyl group, hexyl group, cyclohexyl group, octyl group, nonyl group, decyl group, and eicosyl group.

[0033] Two R's 1 These groups may bond to each other to form an alkanediyl group, and examples of such alkanediyl groups include propane-1,3-diyl group, butane-1,4-diyl group, pentane-1,4-diyl group, pentane-1,5-diyl group, hexane-2,5-diyl group, hexane-1,6-diyl group, heptane-1,7-diyl group, and the like.

[0034] Because the raw materials are readily available and the vapor pressure of the gas barrier film material shown in equation (1) is high, R 1Preferably, the group is a methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, s-butyl group, t-butyl group, pentyl group, 1-methylbutyl group, 2-methylbutyl group, 3-methylbutyl group, 1-ethylpropyl group, 1,1-dimethylpropyl group, 1,2-dimethylpropyl group, 2,2-dimethylpropyl group, hexyl group, octyl group, or nonyl group, and particularly preferably a methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, s-butyl group, t-butyl group, pentyl group, 1-methylbutyl group, 2-methylbutyl group, 3-methylbutyl group, 1-ethylpropyl group, 1,1-dimethylpropyl group, 1,2-dimethylpropyl group, or 2,2-dimethylpropyl group.

[0035] R 2 Examples of C1-C10 alkyl groups in this compound include methyl, ethyl, propyl, isopropyl, cyclopropyl, butyl, isobutyl, s-butyl, t-butyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1-ethylpropyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, and 2,2-dimethylpropyl. Among these, methyl, ethyl, propyl, or isopropyl groups are preferred due to their ease of raw material availability, with methyl or ethyl groups being even more preferred.

[0036] n represents an integer between 1 and 3.

[0037] Specific examples of organosilane compounds represented by formula (1) include: Dimethoxymethylsilane, trimethoxymethylsilane, ethyldimethoxysilane, ethyltrimethoxysilane, dimethoxypropylsilane, trimethoxypropylsilane, dimethoxyisopropylsilane, trimethoxyisopropylsilane, butyldimethoxysilane, butyltrimethoxysilane, isobutyldimethoxysilane, isobutyltrimethoxysilane, s-butyldimethoxysilane, s-butyltrimethoxysilane, t-butyldimethoxysilane, t-butyltrimethoxysilane, dimethoxypentylsilane, trimethoxypentylsilane, 1-methylbutyldimethoxysilane, 1-methylbutyltrimethoxysilane, 2-methylbutyldimethoxysilane Toxysilane, 2-methylbutyltrimethoxysilane, 3-methylbutyldimethoxysilane, 3-methylbutyltrimethoxysilane, 1-ethylpropyldimethoxysilane, 1-ethylpropyltrimethoxysilane, 1,1-dimethylpropyldimethoxysilane, 1,1-dimethylpropyltrimethoxysilane, 1,2-dimethylpropyldimethoxysilane, 1,2-dimethylpropyltrimethoxysilane, 2,2-dimethylpropyldimethoxysilane, 2,2-dimethylpropyltrimethoxysilane, cyclopentyldimethoxysilane, cyclopentyltrimethoxysilane, cyclohexyldimethoxysilane, cyclohexyltrimethoxysilane, Diethoxysilane, trimethoxysilane, diethoxymethylsilane, triethoxymethylsilane, diethoxyethylsilane, triethoxyethylsilane, diethoxypropylsilane, triethoxypropylsilane, diethoxyisopropylsilane, triethoxyisopropylsilane, butyldiethoxysilane, butyltriethoxysilane, isobutyldiethoxysilane, isobutyltriethoxysilane, s-butyldiethoxysilane, s-butyltriethoxysilane, t-butyldiethoxysilane, t-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, Tripropoxysilane, methyltripropoxysilane, ethyltripropoxysilane, tripropoxypropylsilane, tripropoxyisopropylsilane, butyltripropoxysilane, isobutyltripropoxysilane, s-butyltripropoxysilane, t-butyltripropoxysilane, pentyltriisopropoxysilane, 1-methylbutyltriisopropoxysilane, 2-methylbutyltriisopropoxysilane, 3-methylbutyltriisopropoxysilane, 1-ethylpropyltriisopropoxysilane, 1,1-dimethylpropyltriisopropoxysilane, 1,2-dimethylpropyltriisopropoxysilane, 2,2-dimethylpropyltriisopropoxysilane, cyclopentyltri Isopropoxysilane, Methoxydimethylsilane, dimethoxydimethylsilane, ethoxydimethylsilane, diethoxydimethylsilane, dimethylpropoxysilane, dimethyldipropoxysilane, dimethylisopropoxysilane, dimethyldiisopropoxysilane, diethylmethoxysilane, diethyldimethoxysilane, ethoxydiethylsilane, diethoxydiethylsilane, diethylpropoxysilane, diethyldipropoxysilane, diethylisopropoxysilane, diethyldiisopropoxysilane, diisopropylmethoxysilane, diisopropyldimethoxysilane, diisopropylethoxysilane, diisopropyldiethoxysilane, diisopropylpropoxysilane, diisopropyldipropoxysilane, diisopropylisopropoxysilane, diisopropyldiisopropoxysilane, diisopropyldiisopropoxysilane, di-s-butylmethoxysilane, di-s-butyl Di-dimethoxylan, di-s-butylethooxylan, di-s-butyldiethooxylan, di-s-butylpropoxysilane, di-s-butyldipropoxysilane, di-s-butylisopropoxysilane, di-s-butyldiisopropoxysilane, di-t-butylmethooxylan, di-t-butyldimethooxylan, di-t-butylethooxylan, di-t-butyldiethooxylan, di-t-butylpropoxy Examples include silane, di-t-butyldipropoxysilane, di-t-butylisopropoxysilane, di-t-butyldiisopropoxysilane, methoxytrimethylsilane, ethoxytrimethylsilane, triethylmethoxysilane, ethoxytriethylsilane, 1,1-dimethoxy-1-silacyclopentane, 1,1-diethoxy-1-silacyclopentane, and 1,1-dimethoxy-1-silacyclopentane, etc. Among these, dimethoxymethylsilane, trimethoxymethylsilane, ethyldimethoxysilane, ethyltrimethoxysilane, dimethoxypropylsilane, trimethoxypropylsilane, dimethoxyisopropylsilane, trimethoxyisopropylsilane, butyldimethoxysilane, butyltrimethoxysilane, isobutyldimethoxysilane, isobutyltrimethoxysilane, s-butyldimethoxysilane, s-butyltrimethoxysilane, t-butyldimethoxysilane, t-butyltrimethoxysilane Silane, 1-methylbutyldimethoxysilane, 1-methylbutyltrimethoxysilane, 2-methylbutyldimethoxysilane, 2-methylbutyltrimethoxysilane, 3-methylbutyldimethoxysilane, 3-methylbutyltrimethoxysilane, 1,1-dimethylpropyldimethoxysilane, 1,1-dimethylpropyltrimethoxysilane, 1,2-dimethylpropyldimethoxysilane, 1,2-dimethylpropyltrimethoxysilane, 2,2-dimethylpropyldimethoxysilane, 2,2-dimethylpropyltrimethoxysilane, trimethoxycyclopentylsilane, Diethoxymethylsilane, triethoxymethylsilane, ethyldiethoxysilane, ethyltriethoxysilane, diethoxypropylsilane, triethoxypropylsilane, diethoxyisopropylsilane, triethoxyisopropylsilane, butyldiethoxysilane, butyltriethoxysilane, isobutyldiethoxysilane, isobutyltriethoxysilane, s-butyldiethoxysilane, s-butyltriethoxysilane, t-butyldiethoxysilane, t-butyltriethoxysilane, 1-methylbutyldiethoxysilane 1-methylbutyltriethoxysilane, 2-methylbutyldiethoxysilane, 2-methylbutyltriethoxysilane, 3-methylbutyldiethoxysilane, 3-methylbutyltriethoxysilane, 1,1-dimethylpropyldiethoxysilane, 1,1-dimethylpropyltriethoxysilane, 1,2-dimethylpropyldiethoxysilane, 1,2-dimethylpropyltriethoxysilane, 2,2-dimethylpropyldiethoxysilane, 2,2-dimethylpropyltriethoxysilane, triethoxycyclopentylsilane, Dimethoxymethylsilane, dimethoxydimethylsilane, diethoxydimethylsilane, diethyldimethoxysilane, diethoxydiethylsilane, diethyldipropoxysilane, diisopropyldimethoxylane, diisopropyldiethoxylane, di-s-butyldimethoxylane, di-s-butyldiethoxylane, di-t-butyldimethoxylane, or di-t-butyldiethoxylane are preferred. Dimethoxymethylsilane, trimethoxymethylsilane, ethyltrimethoxysilane, trimethoxypropylsilane, isopropyltrimethoxysilane, butyltrimethoxysilane, isobutyltrimethoxysilane, s-butyltrimethoxysilane, t-butyldimethoxysilane, t-butyltrimethoxysilane, 1-methylbutyltrimethoxysilane, 1,1-dimethylpropyltrimethoxysilane, 1,2-dimethylpropyltrimethoxysilane, Diethoxymethylsilane, triethoxymethylsilane, ethyltriethoxysilane, triethoxypropylsilane, triethoxyisopropylsilane, butyltriethoxysilane, isobutyltriethoxysilane, s-butyltriethoxysilane, t-butyldiethoxysilane, t-butyltriethoxysilane, 1-methylbutyltriethoxysilane, 1,1-dimethylpropyltriethoxysilane, 1,2-dimethylpropyltriethoxysilane, dimethoxymethylsilane, dimethoxydimethylsilane, diethoxydimethylsilane, diethyldimethoxysilane, or diethoxydiethylsilane are more preferred.

[0038] This section describes how to obtain the organosilane compound, which is a gas barrier film material represented by formula (1).

[0039] The organosilane compounds used as gas barrier film materials, represented by formula (1), may be purchased commercially and used as is, or they may be purified as appropriate, or they may be synthesized as appropriate. These gas barrier film materials can be synthesized by reacting alkylhalosilane compounds with alcohols and / or metal alkoxides (Synthesis Method 1. For example, the method described in K. Lin, RJ Wiles, CB Kelly, GHMDavies, GA Molander, ACS Catalysis, 2017, Vol. 7, pp. 5129-5133), or by reacting alkoxysilanes with alkylalkylmagnesium halides or alkyllithium (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 gas barrier film materials obtained by synthesis can also be purified by general methods such as recrystallization, distillation, and column chromatography and used for film formation.

[0040] [C3]

[0041] [C4]

[0042] (In the formula, R 1 , R 2 And n are R in equation (1). 1 , R 2 (And it represents the same meaning as n.) Finally, the method for producing the silicon oxide film of the present invention will be described.

[0043] The silicon oxide film of the present invention is manufactured by depositing the above-mentioned gas barrier film material by plasma-excited chemical vapor deposition under conditions of a deposition pressure of 0.01 Pa or more and less than 20 Pa.

[0044] Furthermore, in the method for manufacturing silicon oxide films, since the silicon oxide film is manufactured on the substrate as described below, a multilayer film can also be manufactured at the same time.

[0045] When manufacturing silicon oxide films, it is essential to use plasma-excited chemical vapor deposition (PECVD) to deposit the film, supplying oxygen in addition to the organic silane compound (1). Specifically, when manufacturing a gas barrier film using the PECVD method with organic silane compound (1) and oxygen as raw materials, the organic silane compound (1) is vaporized and supplied to the deposition chamber where the deposition substrate is installed. Methods of vaporization include, for example, placing the organic silane compound (1) in a heated constant-temperature bath and vaporizing it by reducing the pressure using a vacuum pump, placing the organic silane compound (1) in a heated constant-temperature bath and vaporizing it by blowing in a carrier gas such as helium, neon, argon, krypton, xenon, or nitrogen, or sending the organic silane compound (1) as is or as a solution to a vaporizer and heating it to vaporize it in the vaporizer (liquid injection method). Examples of solvents that can be used in solution include ethers such as 1,2-dimethoxyethane, diglyme, triglyceride, dioxane, tetrahydrofuran, and cyclopentyl methyl ether, and hydrocarbons such as hexane, cyclohexane, methylcyclohexane, ethylcyclohexane, heptane, octane, nonane, decane, benzene, toluene, ethylbenzene, and xylene. These can be used individually or mixed in any ratio.

[0046] In this manner, the organic silane compound (1) and oxygen supplied to the deposition chamber react with the plasma generated within the chamber, forming a gas barrier film on the deposition substrate. While deposition can proceed with plasma alone, light irradiation or heating of the deposition substrate may also be used in combination.

[0047] There are no particular limitations on the source of the plasma, and examples include capacitively coupled plasma, inductively coupled plasma, helicon wave plasma, surface wave plasma, and electron cyclotron resonance plasma.

[0048] For the production of silicon oxide films, any chemical vapor deposition apparatus commonly used by those skilled in the art may be used, such as batch type, single-wafer type, or roll-to-roll type.

[0049] The pressure in the deposition chamber must be in the range of 0.01 Pa or more and less than 20 Pa, and is preferably 0.1 Pa or more and less than 15 Pa, given the low WVTR of the resulting gas barrier film and the ease of controlling the vacuum level.

[0050] The power of the high-frequency power supply (RF power supply) is preferably 100W or more, and more preferably 200W to 1500W, given the low WVTR of the resulting gas barrier film.

[0051] The power density applied to the electrodes for plasma discharge is 0.1 W / cm². 2 It is preferable that the above is true, and the resulting gas barrier film has a low WVTR of 2.0 W / cm². 2 ~100W / cm 2 That is even more preferable.

[0052] There are no particular limitations on the temperature of the substrate used for film deposition during film formation, but it is preferably below the heat resistance temperature of the substrate and within the range of 0°C to 300°C.

[0053] There are no particular limitations on the types of substrates used for film formation. Examples 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), triacetylcellulose (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, polyamide-imide, polyetherimide, polyphenylene sulfide, polyetheretherketone, and fluororesins.

[0054] If X is the supply flow rate of the organic silane compound (1) supplied during film formation and Y is the supply flow rate of oxygen, the ratio of oxygen to the organic silane compound (1) Y / X is preferably 1 or more, and more preferably 5 to 100. [Effects of the Invention]

[0055] The silicon oxide film of the present invention is suitable for gas barrier films, insulating films, semiconductor gate oxide films, protective films, etc., and is particularly suitable for gas barrier films because it has a low WVTR even below 500 nm. [Examples]

[0056] The present invention will be described in more detail below with reference to examples, but the present invention is not limited thereto.

[0057] A gas barrier film was deposited on a substrate using a general CVD apparatus employing the capacitively coupled PECVD method. The substrates used for film deposition were a 125 μm thick polyethylene naphthalate (PEN) film (visible light transmittance 88.3%, surface roughness Ra 0.71 nm) and a 125 μm thick polyethylene terephthalate (PET) film (visible light transmittance 89.3%, surface roughness Ra 1.17 nm). Organic silane compounds, oxygen gas, and argon gas, vaporized in a constant temperature bath, were used as raw material gases. Furthermore, a high-frequency power supply with a frequency of 13.56 MHz was used.

[0058] The thickness of the deposited film was estimated by taking cross-sectional images of the film using a JEOL JSM-7600F field emission scanning electron microscope (FE-SEM).

[0059] The water vapor transmission rate (WVTR), an indicator of gas barrier performance, was measured using gas chromatography (GC method) with a GTR3000 series moisture transmission rate measuring instrument manufactured by GTR Tech.

[0060] The film composition of the gas barrier membrane was analyzed using an ULVAC-PHI X-ray photoelectron spectroscopy (XPS) system, PHI5000 VersaProbeII.

[0061] Analysis of the synthesized organosilane compound (1) was performed. 1 H-NMR (Proton Nuclear Magnetic Resonance Spectrum), 13 13C-NMR (carbon-13 nuclear magnetic resonance spectrum) and 29 Si-NMR (silicon-29 nuclear magnetic resonance spectroscopy) measurements were performed using a Bruker-Avance DPX-400 nuclear magnetic resonance spectrometer with deuterated chloroform as the solvent. IR (infrared absorption) spectra were measured using a Horiba FT-720 spectrophotometer with SensIRtechnologies' DuraSamplIRII (reflection type). Mass spectra were measured using a Shimadzu GCMS-QP2010 gas chromatography-type mass spectrometry instrument. An analytical instrument was used, and the capillary column was the DB-5MS from Agilent Technologies, Inc.

[0062] (Example 1) Film formation using t-butyltriethoxysilane A silicon oxide film was deposited on a PEN film using t-butyltriethoxysilane synthesized based on the method described in K. Lin, RJ Wiles, CB Kelly, GHMDavies, and GA Molander, ACS Catalysis, 2017, Vol. 7, pp. 5129-5133, with oxygen by PECVD. The t-butyltriethoxysilane supply flow rate was 80 sccm, the oxygen supply flow rate was 2100 sccm, the deposition chamber pressure was 8 Pa, and the power of the high-frequency power supply (RF power supply) with a power frequency of 13.56 MHz was 1000 W, and the film was deposited for 14 minutes. The oxygen supply flow rate ratio Y / X to the t-butyltriethoxysilane supply flow rate was 26.3.

[0063] The obtained silicon oxide film had a thickness of 800 nm. The film composition was Si=33 atom%, O=67 atom%, and the carbon concentration was less than 1.0 atm%. The WVTR value was 2.0 × 10⁻⁶. -4 g / m 2 It was a day.

[0064] The visible light transmittance of the laminated film consisting of a silicon oxide film and a PEN film was 88.2%. The surface roughness (Ra) was 0.68 nm.

[0065] A silicon oxide film was deposited on a PEN film using t-butyltriethoxysilane and oxygen via the PECVD method. The t-butyltriethoxysilane supply flow rate was 80 sccm, the oxygen supply flow rate was 2100 sccm, the deposition chamber pressure was 8 Pa, and the power of the high-frequency power supply (RF power supply) with a power frequency of 13.56 MHz was 1000 W. Deposition was carried out for 7 minutes. The oxygen supply flow rate ratio Y / X to the t-butyltriethoxysilane supply flow rate was 26.3.

[0066] The obtained silicon oxide film had a thickness of 400 nm. The WVTR value was 4.3 × 10⁻⁶. -4 g / m 2 The visible light transmittance of the laminated film consisting of a silicon oxide film and a PEN film was 88.5%.

[0067] When t-butyltriethoxysilane is used to form a film with oxygen by PECVD, even a thin silicon oxide film of 400 nm has a WVTR of 10 -3 g / m 2 • Daily order below 10 -4 g / m 2 It exhibits a day-order timescale and is suitable as a gas barrier film.

[0068] (Example 2) Film formation using t-butyltriethoxysilane Using t-butyltriethoxysilane obtained in the same manner as in Example 1, a silicon oxide film was deposited on a PET film by PECVD with oxygen. The t-butyltriethoxysilane supply flow rate was 80 sccm, the oxygen supply flow rate was 2100 sccm, the deposition chamber pressure was 8 Pa, and the power of the high-frequency power supply (RF power supply) with a power frequency of 13.56 MHz was 1000 W, and the film was deposited for 8 minutes. The oxygen supply flow rate ratio Y / X to the t-butyltriethoxysilane supply flow rate was 26.3.

[0069] The obtained silicon oxide film had a thickness of 500 nm. The WVTR value was 3.9 × 10⁻⁶. -3 g / m 2 The visible light transmittance of the laminated film consisting of a silicon oxide film and a PET film was 91.0%.

[0070] When t-butyltriethoxysilane is used to form a film with oxygen by PECVD, even a thin silicon oxide film of 500 nm has a WVTR of 10 -3 g / m 2 It exhibits a day-order timescale and is suitable as a gas barrier film.

[0071] (Example 3) Film formation using isopropyltrimethoxysilane A silicon oxide film was deposited on a PEN film using isopropyltrimethoxysilane synthesized based on the method described in K. Lin, RJ Wiles, CB Kelly, GHMDavies, and GA Molander, ACS Catalysis, 2017, Vol. 7, pp. 5129-5133, along with oxygen, by PECVD. The isopropyltrimethoxysilane supply flow rate was 80 sccm, the oxygen supply flow rate was 2100 sccm, the deposition chamber pressure was 8 Pa, and the power of the high-frequency power supply (RF power supply) with a power frequency of 13.56 MHz was 1000 W, and the film was deposited for 11 minutes. The oxygen supply flow rate ratio Y / X to the isopropyltrimethoxysilane supply flow rate was 26.3.

[0072] The obtained silicon oxide film had a thickness of 800 nm. The film composition was Si=33 atom%, O=67 atom%, and the carbon concentration was less than 1.0 atm%. The WVTR value was 2.0 × 10⁻⁶. -4 g / m 2 It was a day.

[0073] The visible light transmittance of the laminated film consisting of a silicon oxide film and a PEN film was 88.2%. The surface roughness (Ra) was 0.67 nm.

[0074] A silicon oxide film was deposited on a PEN film using isopropyltrimethoxysilane and oxygen via the PECVD method. The deposition process was performed for 3 minutes with an isopropyltrimethoxysilane supply flow rate of 80 sccm, an oxygen supply flow rate of 2100 sccm, a deposition chamber pressure of 8 Pa, and a high-frequency power supply (RF power supply) of 13.56 MHz at a power frequency of 1000 W. The oxygen supply flow rate ratio (Y / X) to the isopropyltrimethoxysilane supply flow rate was 26.3.

[0075] The obtained silicon oxide film had a thickness of 200 nm. The WVTR value was 6.9 × 10⁻⁶. -4 g / m 2 It was a day.

[0076] The visible light transmittance of the laminated film consisting of a silicon oxide film and a PEN film was 88.4%.

[0077] When isopropyltrimethoxysilane is used to form a film with oxygen by the PECVD method, even with a thin silicon oxide film thickness of 200 nm, the WVTR is 10 -3 g / m 2 • Daily order below 10 -4 g / m 2 It exhibits a day-order timescale and is suitable as a gas barrier film.

[0078] (Synthesis Example 1) Synthesis of (1,2-dimethylpropyl)trimethoxysilane A 500 mL three-necked flask equipped with a magnetic stirring bar, a Liebig condenser, a dropping funnel, and a three-way stopcock was purged with argon, and 136 g (4.26 mol) of anhydrous methanol, 422 g (4.17 mol) of triethylamine, and 1800 mL of diethyl ether were placed inside. While cooling the reaction vessel in an ice bath, 275 g (1.34 mol) of trichloro-1,2-dimethylpropylsilane, synthesized according to the literature description (MGVoronkov, NGR Romanova, LGSmirnova, Chemicke Listy pro Vedu a Prumysl, Vol. 52, pp. 640-653, 1958), was added dropwise from the dropping funnel over 3.5 hours, and the mixture was stirred at room temperature for a further 16 hours. The reaction mixture was filtered through a Buchner funnel to separate 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 subjected to vacuum distillation (boiling point 79°C / 3.3kPa) to obtain 226 g of (1,2-dimethylpropyl)trimethoxysilane as a colorless, clear liquid (yield 87.7%).

[0079] 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 to 0.90 (m, 1H), 0.92 to 1.00 (m, 9H), 1.78 to 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. 29 Si-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.

[0080] (Example 4) Film formation using (1,2-dimethylpropyl)trimethoxysilane Using the (1,2-dimethylpropyl)trimethoxysilane obtained in Synthesis Example 1, a silicon oxide film was formed on a PEN film by PECVD method together with oxygen. The supply flow rate of (1,2-dimethylpropyl)trimethoxysilane was 80 sccm, the oxygen supply flow rate was 2100 sccm, the pressure in the film formation chamber was 8 Pa, and the power of a high-frequency power source (RF power source) with a power supply frequency of 13.56 MHz was 1000 W, and film formation was carried out for 11 minutes. Also, the flow rate ratio Y / X of oxygen to the flow rate of (1,2-dimethylpropyl)trimethoxysilane was 26.3.

[0081] The film thickness of the obtained silicon oxide film was 800 nm. The composition of the film was Si = 33 atom%, O = 67 atom%, and the carbon concentration was less than 1.0 atm%. The WVTR value was 2.0×10 -4 g / m 2 ·day.

[0082] The visible light transmittance of the laminated film composed of the silicon oxide film and the PEN film was 88.1%. The surface roughness (Ra) was 0.62 nm.

[0083] Using the (1,2-dimethylpropyl)trimethoxysilane obtained in Synthesis Example 1, a silicon oxide film was formed on a PEN film by PECVD method together with oxygen. The supply flow rate of (1,2-dimethylpropyl)trimethoxysilane was 80 sccm, the oxygen supply flow rate was 2100 sccm, the pressure in the film formation chamber was 8 Pa, and the power of a high-frequency power source (RF power source) with a power supply frequency of 13.56 MHz was 1000 W, and film formation was carried out for 3 minutes. Also, the flow rate ratio Y / X of oxygen to the flow rate of (1,2-dimethylpropyl)trimethoxysilane was 26.3.

[0084] The film thickness of the obtained silicon oxide film was 250 nm. The WVTR value was 7.2×10 -4 g / m 2 ·day.

[0085] The visible light transmittance of the laminated film composed of the silicon oxide film and the PEN film was 88.2%.

[0086] When a film is formed by the PECVD method using (1,2-dimethylpropyl)trimethoxysilane together with oxygen, even if the thickness of the silicon oxide film is as thin as 250 nm, the WVTR is 10 -3 g / m 2 ·day or less of the order of 10 -4 g / m 2 ·day order, indicating suitability as a gas barrier film.

[0087] (Example 5) Film formation using t-butyltrimethoxysilane A silicon oxide film was formed on a PEN film by the PECVD method using t-butyltrimethoxysilane synthesized by referring to the method described in K. Lin, R. J. Wiles, C. B. Kelly, G. H. M. Davies, G. A. Molander, ACS Catalysis, 2017, Vol. 7, pp. 5129-5133, together with oxygen. The supply flow rate of t-butyltrimethoxysilane was 80 sccm, the oxygen supply flow rate was 2100 sccm, the pressure in the film formation chamber was 8 Pa, and the power of a high-frequency power supply (RF power supply) with a power frequency of 13.56 MHz was 1000 W, and film formation was carried out for 14 minutes. Also, the supply flow rate ratio Y / X of oxygen to the supply flow rate of t-butyltrimethoxysilane was 26.3.

[0088] The thickness of the obtained silicon oxide film was 800 nm. The WVTR value was 4.1×10 -4 g / m 2 ·day. The composition of the film was Si = 35 atom% and O = 65 atom%, and the carbon concentration was less than 1.0 atm%.

[0089] The visible light transmittance of the laminated film composed of the silicon oxide film and the PEN film was 88.1%. The surface roughness (Ra) was 0.70 nm.

[0090] ​A silicon oxide film was deposited on a PEN film using t-butyltrimethoxysilane and oxygen via PECVD. The deposition process was performed for 4 minutes with a t-butyltrimethoxysilane supply flow rate of 80 sccm, an oxygen supply flow rate of 2100 sccm, a deposition chamber pressure of 8 Pa, and a high-frequency power supply (RF power supply) of 13.56 MHz at a power frequency of 1000 W. The oxygen supply flow rate ratio (Y / X) to the t-butyltrimethoxysilane supply flow rate was 26.3.

[0091] The obtained silicon oxide film had a thickness of 250 nm. The WVTR value was 8.5 × 10⁻⁶. -4 g / m 2 It was a day.

[0092] The visible light transmittance of the laminated film consisting of a silicon oxide film and a PEN film was 88.2%.

[0093] When t-butyltrimethoxysilane is used to form a film with oxygen by PECVD, even a thin silicon oxide film with a thickness of 250 nm has a WVTR of 10. -3 g / m 2 • Daily order below 10 -4 g / m 2 Its temperature is low, on the order of days, making it suitable as a gas barrier film.

[0094] (Example 6) Film formation using dimethoxydimethylsilane A silicon oxide film was deposited on a PEN film using dimethoxydimethylsilane (manufactured by Tokyo Chemical Industry Co., Ltd.) and oxygen via the PECVD method. The dimethoxydimethylsilane supply flow rate was 80 sccm, the oxygen supply flow rate was 2100 sccm, the pressure in the deposition chamber was 8 Pa, and the power of the high-frequency power supply (RF power supply) with a power frequency of 13.56 MHz was 1000 W, and the film was deposited for 8 minutes. The ratio of the oxygen supply flow rate to the dimethoxydimethylsilane supply flow rate, Y / X, was 26.3.

[0095] The resulting silicon dioxide film thickness was 800 nm. The WVTR value was 7.3 × 10⁻⁶. -4 g / m 2The test period was 1 day. The film composition was Si=36atom%, O=64atom%, and the carbon concentration was less than 1.0atm%.

[0096] The visible light transmittance of the laminated film consisting of a silicon oxide film and a PEN film was 88.5%. The surface roughness (Ra) was 0.70 nm.

[0097] A silicon oxide film was deposited on a PEN film using dimethoxydimethylsilane (manufactured by Tokyo Chemical Industry Co., Ltd.) and oxygen via the PECVD method. The dimethoxydimethylsilane supply flow rate was 80 sccm, the oxygen supply flow rate was 2100 sccm, the pressure in the deposition chamber was 8 Pa, and the power of the high-frequency power supply (RF power supply) with a power frequency of 13.56 MHz was 1000 W, and the film was deposited for 2 minutes. The ratio of the oxygen supply flow rate to the dimethoxydimethylsilane supply flow rate, Y / X, was 26.3.

[0098] The obtained silicon oxide film had a thickness of 200 nm. The WVTR value was 2.0 × 10⁻⁶. -3 g / m 2 It was a day.

[0099] The visible light transmittance of the laminated film consisting of a silicon oxide film and a PEN film was 88.3%.

[0100] When dimethoxydimethylsilane is used to form a film with oxygen by the PECVD method, even with a thin silicon oxide film thickness of 200 nm, the WVTR is 10 -3 g / m 2 It exhibits a day-order timescale and is suitable as a gas barrier film.

[0101] (Comparative Example 1) Film formation using hexamethyldisiloxane Hexamethyldisiloxane was used to deposit a film on a PEN film with oxygen using the PECVD method. The hexamethyldisiloxane supply flow rate was 80 sccm, the oxygen supply flow rate was 2100 sccm, the pressure in the deposition chamber was 6 Pa, and the power of the high-frequency power supply (RF power supply) with a power frequency of 13.56 MHz was 1000 W, and the film deposition was carried out for 7 minutes. The ratio of the oxygen supply flow rate to the hexamethyldisiloxane supply flow rate, Y / X, was 26.3.

[0102] The thickness of the obtained film was 800 nm. The WVTR value was 2.8 × 10⁻⁶. -3 g / m 2 It was a day, and showed a high value.

[0103] Hexamethyldisiloxane was used to deposit a film on a PEN film with oxygen using the PECVD method. The hexamethyldisiloxane supply flow rate was 80 sccm, the oxygen supply flow rate was 2100 sccm, the pressure in the deposition chamber was 6 Pa, and the power of the high-frequency power supply (RF power supply) with a power frequency of 13.56 MHz was 1000 W, and the film was deposited for 2 minutes. The ratio of the oxygen supply flow rate to the hexamethyldisiloxane supply flow rate, Y / X, was 26.3.

[0104] The thickness of the obtained film was 200 nm. The WVTR value was 2.4 × 10⁻⁶. -2 g / m 2 It was a day, and showed a high value.

[0105] The silicon oxide film produced using the organosilane compound represented by formula (1) of the present invention has a WVTR of 10 even at a film thickness of 500 nm or less. -3 g / m 2 Because it possesses high gas barrier properties of less than one day, it is suitable as a gas barrier film.

[0106] For silane compounds outside the range of organic silane compounds represented by formula (1) of the present invention, compared to the comparative example, when a film is formed, the WVTR is 10 when the film thickness is 500 nm or less. -3 g / m 2 • It is more expensive than day-order material, has low gas barrier properties, and is not suitable for gas barrier films.

Claims

1. A silicon oxide film characterized by satisfying the following requirements (1) and (2): (1) Water vapor transmission rate (WVTR) of 9.0 × 10 for films with a thickness of 500 nm or less -3 g / m 2 ·day or less (2) The carbon concentration in the film measured by X-ray photoelectron spectroscopy (XPS) is 3.0 atom% or less.

2. Water vapor transmission rate (WVTR) of 1.0×10 for films with a thickness of 500 nm or less -6 ~9.0×10 -3 g / m 2 2. The silicon oxide film according to claim 1, wherein the silicon oxide film is 0.1-day.

3. Formula (1) [Formula 1] (In the formula, 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 may be the same or different, and two R 1 may be 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 may be the same or different.) A gas barrier film material for chemical vapor deposition, comprising an organosilane compound represented by the following formula:

4. R 1 4. The gas barrier film material according to claim 3, wherein is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.

5. R 2 5. The gas barrier film material according to claim 3, wherein is an alkyl group having 1 to 3 carbon atoms.

6. R 1 is selected from the group consisting of a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a s-butyl group, a t-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.

7. The gas barrier film material is dimethoxymethylsilane, trimethoxymethylsilane, ethyldimethoxysilane, ethyltrimethoxysilane, dimethoxypropylsilane, trimethoxypropylsilane, dimethoxyisopropylsilane, trimethoxyisopropylsilane, butyldimethoxysilane, butyltrimethoxysilane, isobutyldimethoxysilane, isobutyltrimethoxysilane, s-butyldimethoxysilane, s-butyltrimethoxysilane, t-butyldimethoxysilane, t-butyltrimethoxysilane, dimethoxypentylsilane, trimethoxypentylsilane, 1-methylbutyldimethoxysilane, 1-methylbutyltrimethoxysilane, 2-methylbutyldimethoxysilane, 2-methylbutyltrimethoxysilane, 3-methylbutyldimethoxysilane, 3-methylbutyltrimethoxysilane, 1,1-dimethylpropyldimethoxysilane, 1,1-dimethylpropyltrimethoxysilane, 1,2-dimethylpropyldimethoxysilane, 1,2-dimethylpropyl Trimethoxysilane, 2,2-dimethylpropyldimethoxysilane, 2,2-dimethylpropyltrimethoxysilane, cyclopentyldimethoxysilane, cyclopentyltrimethoxysilane, diethoxymethylsilane, triethoxymethylsilane, diethoxyethylsilane, triethoxyethylsilane, diethoxypropylsilane, triethoxypropylsilane, diethoxyisopropylsilane, triethoxyisopropylsilane, butyldiethoxysilane, butyltriethoxysilane, isobutyldiethoxysilane, isobutyltriethoxysilane, s-butyldiethoxysilane, s-butyltriethoxysilane, t-butyldiethoxysilane, t-butyltriethoxysilane, diethoxypentylsilane, triethoxypentylsilane, diethoxy-1-methylbutylsilane, triethoxy 7. The gas barrier film material according to claim 3, wherein the compound is any one of cyclopentyl-1-methylbutylsilane, diethoxy-2-methylbutylsilane, triethoxy-2-methylbutylsilane, 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, and methoxytrimethylsilane.

8. 8. The method for producing a silicon oxide film according to claim 1, wherein the gas barrier film material according to any one of claims 3 to 7 is deposited by plasma enhanced chemical vapor deposition under a deposition pressure of 0.01 Pa or more and less than 20 Pa.

9. 9. The method for producing a silicon oxide film according to claim 8, wherein the film is formed by plasma-excited chemical vapor deposition under conditions where the power of a high frequency power source (RF power source) is 100 W or more.

10. The power density of the high frequency power source (RF power source) is 0.1W / cm 2 10. The method for producing a silicon oxide film according to claim 8, wherein the film is formed by plasma-excited chemical vapor deposition under the above conditions.

11. A laminated film comprising the silicon oxide film according to claim 1 or 2 and a substrate.

12. 3. A gas barrier film comprising the silicon oxide film according to claim 1.

13. A gas barrier film comprising the laminate film according to claim 11.