JP2005219427A - Manufacturing method for barrier film and plasma cvd equipment used therefor - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a manufacturing method which enables manufacture with higher productivity of a barrier film having extremely high gas barrier properties and high transparency, being excellent in pliability and weather resistance and having the heat resistance and chemical resistance required for various post-processing suitabilities, and plasma CVD equipment used therefor. <P>SOLUTION: Using a first organic silicon compound having a bond of oxygen and silicon of an alkoxy group in a molecule and a second organic silicon compound having a carbon-silicon bond in a molecule as raw materials, an oxidized silicon carbide film (SiOC film) or an oxidized nitrided silicon carbide film (SiONC film) is formed on a base film by a plasma CVD method. An electrode making power on the occasion of the film formation is set to be higher than an electrode making allowable power on the occasion when the second organic silicon compound alone is used as the raw material. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to, for example, a method for producing a barrier film having a very high barrier property used as a packaging material for a food or medical product, a packaging material for an electronic device, or a substrate material, and a plasma CVD apparatus used therefor.

Conventionally, various materials have been developed and proposed as packaging materials having barrier properties against oxygen gas, water vapor, etc. and having good storage suitability for foods, pharmaceuticals, etc. A barrier film having a structure in which a coating layer of polyvinylidene chloride or ethylene vinyl alcohol copolymer is provided thereon has been proposed.
However, these barrier films have a problem in that the barrier property against oxygen and water vapor is not sufficient, and the barrier property is remarkably lowered particularly at the high temperature sterilization treatment. Furthermore, a barrier film provided with a polyvinylidene chloride coating layer generates toxic dioxins during incineration, and there is a concern about adverse environmental effects.

Therefore, in recent years, a barrier film having a structure in which a deposited film of an inorganic oxide such as silicon oxide or aluminum oxide is provided on a base film has been proposed. In addition, a lamination of a resin layer made of an epoxy resin or a mixture thereof and the above-described deposited film (Patent Document 1) has been proposed.
For example, as a method of manufacturing a barrier film provided with a silicon oxide film, a manufacturing method by plasma CVD (chemical vapor deposition) using 1,1,3,3 tetramethyldisiloxane (TMDSO) or the like as a raw material (Patent Document 2) )
JP-A-8-164595 JP-A-6-108255

  However, the above-described TMDSO, hexamethyldisiloxane (HMDSO), and the like have a carbon-silicon bond in the molecule, so that the decomposability is poor, and the manufactured barrier film has particularly insufficient gas barrier properties. This gas barrier property can be improved by increasing the input power during film formation. However, the load on the power supply and power cable is large, and the deterioration of the film-forming device is accelerated, and the damage to the base film due to the high discharge voltage during film formation is large, and the surface of the base film is smooth. There is a problem that the property is impaired or coloring occurs.

  The present invention has been made in view of such circumstances, has extremely high gas barrier properties, high transparency, excellent flexibility and weather resistance, and heat resistance necessary for various post-processing suitability. An object of the present invention is to provide a production method capable of producing a barrier film having good properties and chemical resistance with higher productivity, and a plasma CVD apparatus used therefor.

  In order to achieve such an object, the present invention provides a first organosilicon compound having a bond between oxygen and silicon of an alkoxy group in the molecule, and a second organosilicon having a carbon-silicon bond in the molecule. A compound is used as a raw material, and a power higher than an electrode charging allowable power when the second organic silicon compound is used as a raw material is applied to the electrode by a plasma CVD method to form a silicon oxide carbide film (SiOC film) or an oxidation A silicon nitride carbide film (SiONC film) was formed on the base film.

  In addition, the present invention uses a plasma CVD apparatus having a chamber composed of a plurality of continuous zones from the first zone to the nth zone (n is an integer of 2 or more). In a method for manufacturing a barrier film in which a silicon oxide is used as a raw material and a silicon oxycarbide film (SiOC film) or a silicon oxynitride carbide film (SiONC film) is laminated on a base film by a plasma CVD method, 1) In at least one of the zones, a first organosilicon compound having a bond between an oxygen of an alkoxy group and silicon in the molecule is used as a raw material, and in all other zones, a carbon-silicon bond is formed in the molecule In the nth zone from the zone after the zone using the second organosilicon compound having And configured so as to introduce a power higher than the electrode-on allowable power in said zone when only the second organic silicon compound as a raw material in all zones of the n zone from the first zone to the electrode.

As another aspect of the present invention, the silicon oxide carbide film (SiOC film) has an atomic composition ratio Si: O: C in the range of 100: 180 to 200: 40 to 80, and Si— in infrared absorption measurement. absorption peak by O-Si stretching vibration is in 1045~1060cm ^-1, absorption peaks due to Si-CH ₃ stretching vibration 1274 ± 8 cm ^-1, such as refractive index is in the range of 1.5 to 1.7 The configuration.
As another aspect of the present invention, the silicon oxynitride carbide film (SiONC film) has an atomic composition ratio Si: O: C: N in the range of 100: 130 to 180: 40 to 100: 100 to 150, The absorption peak due to Si—O and Si—N stretching vibration in the infrared absorption measurement is in the range of 830 to 1060 cm ⁻¹ , and the film density is in the range of 1.8 to 2.4 g / cm ³ ; did.

In another aspect of the present invention, the first organosilicon compound is a silane compound in which three or more of the silicon atom bonds are bonded to an oxygen atom or a hydrogen atom. The organosilicon compound is composed of at least one of tetramethoxysilane, tetraethoxysilane, trimethoxysilane, methyltrimethoxysilane, triethoxysilane, and ethyltriethoxysilane, and the first organic compound. The silicon compound was configured to be tetramethoxysilane.
As another aspect of the present invention, the second organosilicon compound is configured such that 50% or more of the bonds of silicon atoms are bonded to carbon atoms, and the second organosilicon compound Is configured to be at least one of tetramethylsilane, hexamethyldisilane, hexamethyldisiloxane, tetramethyldisiloxane, and hexamethyldisilazane.
As another aspect of the present invention, a configuration is adopted in which electric power about 1.1 to 2 times the electrode input allowable power is input to the electrode.

Further, the plasma CVD apparatus of the present invention includes a chamber having a lower electrode and an upper electrode on which a film-forming body is placed, a plasma generator connected to the lower electrode, and a source gas in the chamber. A raw material gas supply source for supply and a plurality of organosilicon compound supply sources capable of supplying an organosilicon compound at an arbitrary supply amount into the chamber are provided.
Further, the plasma CVD apparatus of the present invention includes a chamber composed of a plurality of continuous zones from the first zone to the nth zone (n is an integer of 2 or more), and the inside of the chamber is directed from the first zone to the nth zone. A transport means for transporting the film formation target, a coating drum and a lower electrode, which are upper electrodes disposed in each zone, and a power source for applying a voltage to the upper electrode and the lower electrode of each zone A source gas supply source for supplying a source gas to each zone, and a plurality of organosilicon compound supply sources capable of supplying an organosilicon compound to each zone at an arbitrary supply amount. .

According to the present invention, the plasma discharge voltage is reduced due to the presence of a decomposition product in which the first organosilicon compound is decomposed at the oxygen-silicon bond, compared to the case where the second organosilicon compound is used alone as a raw material, The electrode input voltage can be increased, and the silicon oxide carbide film (SiOC film) or silicon oxynitride carbide film (SiONC film) formed on the base film is dense and has an extremely high barrier property and is transparent. It is possible to produce a barrier film having high heat resistance and chemical resistance necessary for various post-processing suitability, high film formation speed and high barrier film productivity. It will be a thing. The manufactured barrier film is preferably used for applications that require extremely high gas barrier properties, heat resistance, chemical resistance, and weather resistance, such as packaging materials for foods and pharmaceuticals, packaging materials for electronic devices, and the like. Can do.
In addition, the CVD apparatus of the present invention can supply the first organosilicon compound and the second organosilicon compound at an arbitrary supply amount, and can control the electrode input voltage to an optimum one on the base film. It is possible to form a silicon oxycarbide film (SiOC film) or a silicon oxynitride carbide film (SiONC film) at a high film formation rate, whereby the productivity of the barrier film can be increased.

Next, embodiments of the present invention will be described with reference to the drawings.
FIG. 1 is a configuration diagram showing an example of a plasma CVD apparatus of the present invention. In FIG. 1, a plasma CVD apparatus 1 includes a chamber 2, a lower electrode 3, an upper electrode 4 constituting a parallel plate electrode disposed in the chamber 2, a plasma generator 5 connected to the lower electrode 3, An exhaust device 7 such as an oil rotary pump or a turbo molecular pump connected to the chamber 2 via an exhaust valve 6 and a gas inlet 8 for introducing the raw material gas into the chamber 2 are provided. The gas inlet 8 is connected to source gas supply sources 9a, 9b, and 9c, and is connected to organosilicon compound supply sources 9d and 9e via a monomer flow meter 10A and a vaporizer 10B.

  In the method for producing a barrier film of the present invention using such a plasma CVD apparatus 1, first, the base film P is mounted on the lower electrode 3 with the film formation surface on the upper side. Next, the inside of the chamber 2 is depressurized to a predetermined degree of vacuum by the exhaust device 7, and electric power having a predetermined frequency is input to the lower electrode 3. The source gas supplied from the source gas supply sources 9a, 9b and 9c and the source gas supplied from the organosilicon compound supply sources 9d and 9e via the monomer flow meter 10A and the vaporizer 10B are supplied to the gas inlet 8. Then, the inside of the chamber 2 is maintained at a predetermined pressure by controlling the degree of opening and closing of the exhaust valve 6 between the exhaust device 7 and the chamber 2. As a result, the introduced source gas is turned into plasma between the lower electrode 3 and the upper electrode 4 and adheres to the base film P to form a silicon oxide carbide film (SiOC film) or a silicon oxynitride carbide film (SiONC film). Is deposited.

In the present invention, the source gas supplied from the organosilicon compound supply sources 9d and 9e is a first organosilicon compound gas having a bond of oxygen and silicon of an alkoxy group in the molecule, and carbon in the molecule. Use at least a mixture with a second organosilicon compound gas having a silicon bond. Then, the lower electrode 3 is supplied with electric power higher than the electrode input allowable power at the time of film formation for the same film formation body (base film P) using only the second organosilicon compound gas as a raw material. The first organosilicon compound is easily decomposed at an oxygen-silicon bond, but the film-forming property is worse than that of the second organosilicon compound, and the decomposition product of the first organosilicon compound is plasma. The plasma discharge voltage decreases due to the presence in the atmosphere. Therefore, the power that can be input to the lower electrode 3 is higher than the electrode input allowable power when only the second organosilicon compound is used as a raw material, for example, about 1.1 to 2 times the electrode input allowable power Become. On the other hand, the second organosilicon compound is less decomposable than the first organosilicon compound, but plasma formation is promoted by the high input power as described above. Therefore, the film formation by the plasma formation of the first organosilicon compound gas and the second organosilicon compound gas becomes denser, and sufficient barrier properties (for example, the oxygen permeability is 0.5 cc / m ² / day). Hereinafter, a barrier film having a water vapor permeability of 0.5 g / m ² / day or less) is obtained. In addition, the deposition rate is increased and productivity is improved.
Although the plasma CVD apparatus 1 shown in FIG. 1 is a system for forming a film on a sheet-shaped base film, the plasma CVD apparatus of the present invention may be of a winding type.

  FIG. 2 is a block diagram showing another example of the plasma CVD apparatus of the present invention. In FIG. 2, a plasma CVD apparatus 11 includes a chamber 12 having three continuous film formation zones of a first film formation zone 12A, a second film formation zone 12B, and a third film formation zone 12C. A transport unit 13 including a feed roller 13a, a take-up roller 13b, and a guide roller 13c for transporting the base film P from the first film formation zone 12A to the third film formation zone 12C is provided. In each of the film formation zones 12A, 12B, and 12C, lower electrodes 14A, 14B, and 14C and coating drums 15A, 15B, and 15C that also serve as upper electrodes are disposed, and the lower electrodes and the coating drums (upper electrodes) are power sources. 16A, 16B, 16C are connected. Further, the chamber 12 is provided with an exhaust device 18 such as an oil rotary pump or a turbo molecular pump connected via an exhaust valve 17, and the film formation zones 12 A, 12 B and 12 C are connected via an exhaust valve 17. And an exhaust device 18 connected to each other and a gas inlet 19 for introducing the source gas into each film formation zone. Each gas inlet 19 is connected to source gas supply sources 20a, 20b, and 20c, and is connected to organosilicon compound supply sources 21a and 21b via a monomer flow meter 22 and a vaporizer 23.

  In the method for producing a barrier film of the present invention using such a plasma CVD apparatus 11, first, the base film P is placed in the plasma CVD apparatus 11 so that the film formation surface is outside the coating drums 15A, 15B, 15C. Attach to. Next, the inside of the chamber 12 is depressurized to a predetermined degree of vacuum by each exhaust device 18, and the lower electrodes 14A, 14B, 14C of the three film formation zones 12A, 12B, 12C and the coating drums (upper electrodes) 15A, 15B, Power having a predetermined frequency at 15C is supplied by the power supplies 16A, 16B, and 16C. Then, the raw material gas (for example, argon gas, helium gas, oxygen gas) supplied from the raw material gas supply sources 20a, 20b, and 20c and the organosilicon compound supply sources 21a and 21b are passed through the monomer flow meter 22 and the vaporizer 23. Source gas (first organosilicon compound gas and / or second organosilicon compound gas) is introduced from the gas inlet 19 for each film formation zone, and the exhaust device 18 and each film formation zone 12A. , 12B, 12C, the degree of opening / closing of the exhaust valve 17 is controlled to maintain the inside of each of the film formation zones 12A, 12B, 12C at a predetermined pressure. As a result, in the three film formation zones 12A, 12B, and 12C, the introduced source gas is converted into plasma between the lower electrodes 14A, 14B, and 14C and the coating drums (upper electrodes) 15A, 15B, and 15C. Then, film formation is sequentially performed on the transported base film P in each film formation zone from the first film formation zone 12A to the third film formation zone 12C, and a silicon oxide carbide film (SiOC film) or a silicon oxynitride carbide film (SiONC film) is formed.

  In the present invention as described above, in the second film formation zone 12B, the first organic silicon compound having a bond between an oxygen of an alkoxy group and silicon in the molecule is used as a raw material. In the film formation zone 12C, a second organosilicon compound having a carbon-silicon bond in the molecule is used as a raw material. Alternatively, in the first film formation zone 12A and the second film formation zone 12B, a first organosilicon compound having a bond of oxygen and silicon of an alkoxy group in the molecule is used as a raw material, and in the third film formation zone 12C A second organosilicon compound having a carbon-silicon bond in the molecule is used as a raw material. In the third film formation zone 12C, the same film formation body (base) using only the second organosilicon compound as a raw material in all the film formation zones of the first film formation zone 12A to the third film formation zone 12C. Power higher than the electrode charging allowable power in the third film formation zone 12C at the time of film formation on the material film P) is input between the lower electrode 14C and the coating drum (upper electrode) 15C by the power source 16C.

  Further, in the first film formation zone 12A, when a first organosilicon compound having a bond between an oxygen of an alkoxy group and silicon in the molecule is used as a raw material, the second film formation zone 12B and the third film formation zone 12C are used. , A second organosilicon compound having a carbon-silicon bond in the molecule is used as a raw material. In the second film formation zone 12B and the third film formation zone 12C, all the film formation zones of the first film formation zone 12A to the third film formation zone 12C are the same using only the second organosilicon compound as a raw material. The lower electrodes 14B and 14C are connected to the lower electrodes 14B and 14C by the power sources 16B and 16C with a power higher than the electrode input allowable power in the second film formation zone 12B and the third film formation zone 12C at the time of film formation on the film formation body (base film P) It is inserted between the coating drums (upper electrodes) 15B and 15C.

The first organosilicon compound is easily decomposed at an oxygen-silicon bond, but its film formability is poorer than that of the second organosilicon compound. Therefore, the decomposition product of the first organosilicon compound is a later component. It also moves to the film zone and exists in the plasma atmosphere. As a result, the plasma discharge voltage in the film formation zone after the film formation zone using the first organosilicon compound is lowered, and in this film formation zone, there is a gap between the lower electrode and the coating drum (upper electrode). The power that can be input to the electrode is higher than the allowable power input to the electrode when only the second organosilicon compound is used as a raw material (in the state where there is no decomposition product of the first organosilicon compound), for example, The electric power is about 1.1 to 2 times. On the other hand, the second organosilicon compound is less decomposable than the first organosilicon compound, but plasma formation is promoted by the high input power as described above. Therefore, the film formation by the plasma formation of the second organosilicon compound gas in the film formation zone after the film formation zone using the first organosilicon compound becomes denser, and sufficient barrier properties (for example, oxygen transmission) A barrier film having a rate of 0.5 cc / m ² / day or less and a water vapor transmission rate of 0.5 g / m ² / day or less) is obtained. In addition, the deposition rate is increased and productivity is improved.

  The plasma CVD apparatus 11 shown in FIG. 2 includes a chamber 12 having three consecutive film formation zones, a first film formation zone 12A, a second film formation zone 12B, and a third film formation zone 12C. However, there are no particular restrictions on the number, structure, etc. of the film formation zones.

The silicon oxide carbide film (SiOC film) formed by the present invention as described above has an atomic composition ratio Si: O: C in the range of 100: 180 to 200: 40 to 80, and is used in infrared absorption measurement. Si-O-Si stretching absorption peaks due to vibration 1045~1060cm ^-1, absorption peaks due to Si-CH ₃ stretching vibration is in 1274 ± 8 cm ^-1, the refractive index is within the range of 1.5 to 1.7 It is preferable. The silicon oxynitride carbide film (SiONC film) formed according to the present invention has an atomic composition ratio Si: O: C: N in the range of 100: 130 to 180: 40 to 100: 100 to 150, It is preferable that the absorption peak due to Si—O and Si—N stretching vibrations in the infrared absorption measurement is in the range of 830 to 1060 cm ⁻¹ and the film density is in the range of 1.8 to 2.4 g / cm ³ .

  Examples of the first organosilicon compound used in the present invention include a silane compound in which three or more of silicon atoms are bonded to an oxygen atom or a hydrogen atom. Specific examples include tetramethoxysilane, tetraethoxysilane, trimethoxysilane, methyltrimethoxysilane, triethoxysilane, ethyltriethoxysilane, and the like, and these are used alone or in combination of two or more. can do. Examples of the second organosilicon compound include those in which 50% or more of the silicon atoms are bonded to carbon atoms. Specific examples include tetramethylsilane, hexamethyldisilane, hexamethyldisiloxane, tetramethyldisiloxane, hexamethyldisilazane, etc., and these can be used alone or in combination of two or more. it can. In the present invention, oxygen gas, helium, or the like can be appropriately used as the source gas.

  Further, the base film used in the present invention is not particularly limited as long as it is a film capable of holding a silicon oxide film, and can be appropriately selected from the purpose of use of the barrier film and the like. Specifically, polyolefin resin such as polyethylene, polypropylene and polybutene as a base film; amorphous polyolefin resin such as cyclic polyolefin; (meth) acrylic resin; polyvinyl chloride resin; polystyrene resin; Saponified vinyl acetate copolymer; polyvinyl alcohol resin such as polyvinyl alcohol resin and ethylene-vinyl alcohol copolymer; polycarbonate resin; polyvinyl butyrate resin; polyarylate resin; ethylene-tetrafluoroethylene copolymer; Fluorocarbon resins such as fluorinated ethylene chloride, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, vinylidene fluoride, vinyl fluoride, perfluoro-perfluoropropylene-perfluorovinyl ether copolymer; polyvinyl acetate Fat; Acetal resin; Polyester resin such as polyethylene terephthalate (PET) and polyethylene 2,6-naphthalate (PEN); Polyamide resin such as nylon 6, nylon 12, copolymer nylon; Polyimide resin; Polyetherimide resin; A stretched (uniaxial or biaxial) or unstretched flexible transparent resin film such as a polyethersulfone resin; a polyethersulfone resin; a polyetheretherketone resin can be used. The thickness of the base film can be appropriately set within a range of 5 to 500 μm, preferably 10 to 100 μm. Moreover, at the time of film-forming, it is desirable to make the temperature of a base film into the range of -20 degreeC-100 degreeC, Preferably it is in the range of -10 degreeC-30 degreeC.

Next, an Example is shown and this invention is demonstrated further in detail.
[Example 1]
A sheet-like biaxially stretched polyester film (A4100 manufactured by Toyobo Co., Ltd., thickness 100 μm, size 21 cm × 21 cm) is prepared as a base film, and the lower part in the chamber of the plasma CVD apparatus configured as shown in FIG. The electrode was mounted with the substrate smooth surface on the upper side (film formation surface side). Next, the inside of the chamber was depressurized to an ultimate vacuum of 1 × 10 ⁻³ Pa by an exhaust device comprising an oil rotary pump and a turbo molecular pump.
Moreover, oxygen gas (manufactured by Taiyo Toyo Oxygen Co., Ltd. (purity 99.9999% or more)) and helium gas (manufactured by Taiyo Toyo Oxygen Co., Ltd. (purity 99.999% or more)) were prepared as source gases. . Furthermore, tetramethoxysilane (TMOS) (KBM-04 manufactured by Shin-Etsu Chemical Co., Ltd.) is used as the first organic silicon compound raw material, and hexamethyldisiloxane (HMDSO) (Toray Dow, Japan) is used as the second organic silicon compound raw material. Corning Silicone Co., Ltd. product SH200-0.65 cSt) was prepared.

Next, power having a frequency of 90 kHz (applied power 400 W) was applied to the parallel plate electrodes. Then, oxygen gas is introduced at a rate of 10 sccm and helium gas at 30 sccm from a gas inlet provided in the vicinity of the electrode, and at the same time, TMOS is vaporized and introduced at a monomer flow rate of 5 sccm, and HMDSO is vaporized at a monomer flow rate of 5 sccm. By controlling the degree of opening and closing of the exhaust valve between the chamber and the chamber, the pressure in the chamber was kept at 33 Pa, and a silicon oxide oxide film having a thickness of 100 nm was formed on the base film to obtain a barrier film. The deposition rate of this silicon oxide carbide film was 30 nm / min.
Note that sccm is an abbreviation for standard cubic centimeter per minute, and the same applies to the following examples and comparative examples.

As a result of measuring the components of the silicon oxide carbide film formed as described above under the following conditions, the number of O atoms was 185 and the number of C atoms was 70 with respect to the number of Si atoms. In addition, the refractive index of this silicon oxycarbide film was measured under the following conditions, and was 1.60. Furthermore, as a result of measurement under the following infrared absorption measurement conditions, the silicon oxide carbide film has an absorption peak due to Si—O—Si stretching vibration of 1050 cm ⁻¹ and an absorption peak due to Si—CH ₃ stretching vibration of 1274 cm ⁻¹ . It was confirmed that there was.

Component measurement method ESCA (ESCA LAB220i- manufactured by VG Scientific, UK)
XL). As an X-ray source, Ag-3d-5 / 2 peak intensity is 300
A monochrome AlX source with Kcps to 1 Mcps and a slit with a diameter of about 1 mm were used. The measurement was performed with the detector set on the normal of the sample surface used for the measurement, and appropriate charge correction was performed. For the analysis after the measurement, the software Eclipse version 2.1 attached to the above-mentioned ESCA apparatus is used, Si: 2p,
The measurement was performed using peaks corresponding to binding energies of C: 1s and O: 1s. At this time, the background of Shirley is removed for each peak,
Sensitivity coefficient correction of each element in the peak area (C = 0, Si = 0.817, O =
2.930) was performed to determine the atomic ratio.

Refractive index measurement method Using a spectrophotometer (UV-2450, manufactured by Shimadzu Corporation), the refractive index of the film was determined by utilizing optical interference.

Infrared absorption measuring method Fourier transform infrared spectrophotometer (JASCO Corporation Herschel FT) equipped with ATR (multiple reflection) measuring device (JASCO Corporation ATR-300 / H)
/ IR-610). The infrared absorption spectrum was measured using a germanium crystal as a prism at an incident angle of 45 degrees.

Moreover, about the barrier film produced as mentioned above, the oxygen transmission rate and the water vapor transmission rate were measured on condition of the following. As a result, the oxygen permeability is ^{0.03cc / m 2 / day · atm} , the water vapor transmission rate was 0.05g / m ² / day, it was confirmed with good barrier properties. Furthermore, after storing the barrier film in an environmental tester (humid heat oven) at 65 ° C. and a relative humidity of 90% RH for 500 hours, the oxygen transmission rate and the water vapor transmission rate were measured under the same conditions. was ^{02cc / m 2 / day · atm} , the water vapor transmission rate was 0.05g / m ² / day, it was confirmed that has a good heat resistance.

Measurement of oxygen permeability Using an oxygen gas permeability measuring device (OX-TRAN 2/20 manufactured by MOCON),
The temperature was 23 ° C., the humidity was 90% RH, and the measurement background difference was subtracted.
Measurement of water vapor transmission rate Using a water vapor transmission rate measurement device (PERMATRAN-W 3/31 manufactured by MOCON), temperature 37.8 ° C, humidity 100% RH, measurement background difference is subtracted, with independent zero measurement (Yes).

[Comparative Example 1]
Without using TMOS as a source gas, helium gas was introduced into the chamber from the gas inlet at 30 sccm, and at the same time, HMDSO was vaporized and introduced at a monomer flow rate of 5 sccm, and a parallel plate electrode having a power of 350 W having a frequency of 90 kHz ( A barrier film was obtained by forming a silicon oxide carbide film having a thickness of 100 nm on a base film in the same manner as in Example 1 except that the limit value of allowable input power was applied. The deposition rate of this silicon oxide carbide film was 20 nm / min, which was a lower value than that of Example 1.
The components of the silicon oxycarbide film formed as described above were measured under the same conditions as in Example 1. As a result, the number of O atoms was 110 and the number of C atoms was 125 with respect to the number of Si atoms of 100. Further, the refractive index of this silicon oxycarbide film was measured under the same conditions as in Example 1. As a result, it was 1.53. Further, as a result of infrared absorption measurement as in Example 1, the silicon oxide carbide film has an absorption peak due to Si—O—Si stretching vibration of 1040 cm ⁻¹ and an absorption peak due to Si—CH ₃ stretching vibration of 1274 cm. ^-1 was present.

Further, the oxygen permeability and water vapor permeability of the barrier film produced as described above were measured under the same conditions as in Example 1. As a result, the oxygen permeability was 1.8 cc / m ² / day · atm, the water vapor permeability was 2.0 g / m ² / day, and it was confirmed that the barrier property was greatly inferior to that of Example 1. It was.

[Example 2]
A roll-shaped biaxially stretched polyester film (A4100 manufactured by Toyobo Co., Ltd., thickness: 100 μm) was prepared as a base film, and three continuous film formation zones (first film formation zone) having a structure as shown in FIG. The substrate smooth surface was mounted as the outside of the coating drum (film formation surface side) in a chamber of a plasma CVD apparatus having (˜third film formation zone). Next, the inside of the chamber and each film formation zone were depressurized to an ultimate vacuum of 1 × 10 ⁻³ Pa by an exhaust device composed of an oil rotary pump and a mechanical booster pump.
Further, as source gases, oxygen gas (manufactured by Taiyo Toyo Oxygen Co., Ltd. (purity 99.9999% or more)), helium gas (manufactured by Taiyo Toyo Oxygen Co., Ltd. (purity 99.999% or more)), argon gas (Daiyo Toyo Oxygen Co., Ltd. (purity 99.999% or more)) was prepared. Furthermore, tetramethoxysilane (TMOS) (KBM-04 manufactured by Shin-Etsu Chemical Co., Ltd.) is used as the first organic silicon compound raw material, and hexamethyldisiloxane (HMDSO) (Toray Dow, Japan) is used as the first organic silicon compound raw material. Corning Silicone Co., Ltd. product SH200-0.65 cSt) was prepared.

Next, in the first film formation zone, a power having a frequency of 40 kHz (input power 12 kW (limit value of allowable input power)) is applied between the lower electrode and the coating drum (upper electrode), and the first gas is introduced from the gas inlet. In one zone, oxygen gas 3 slm, helium gas 1 slm, and argon gas 0.4 slm were introduced, and at the same time, HMDSO was vaporized at a monomer flow rate of 1 slm. Note that slm is an abbreviation for standard liter per minute, and the same applies to the following examples and comparative examples.
In the second film formation zone, power having a frequency of 40 kHz (applied power 12 kW (limit value of allowable input power)) is applied between the lower electrode and the coating drum (upper electrode), and the first gas is introduced from the gas inlet. Into two zones, oxygen gas 1 slm, helium gas 1 slm, and argon gas 0.4 slm were introduced, and at the same time, TMOS was vaporized at a monomer flow rate of 1 slm and introduced.

Further, in the third film formation zone 3, electric power having a frequency of 40 kHz (input power 15 kW (limit value of allowable input power)) is applied between the lower electrode and the coating drum (upper electrode), and the third gas is supplied from the gas inlet. Oxygen gas 3 slm, helium gas 1 slm, and argon gas 0.4 slm were introduced into the zone, and at the same time, HMDSO was vaporized at a monomer flow rate of 1 slm.
Each film formation is controlled by independently controlling the exhaust valve (shown by member number 17 in FIG. 2) between the exhaust device (shown by member number 18 in FIG. 2) and the chamber for each film formation zone. While maintaining the zone at 3 Pa, a silicon oxide film (thickness 60 nm) was formed while conveying the base film at a speed of 20 m / min to obtain a barrier film. The deposition rate of this silicon oxide carbide film was 200 nm / min.

The components of the silicon oxide carbide film formed as described above were measured under the same conditions as in Example 1. As a result, the number of O atoms was 180 and the number of C atoms was 75 with respect to the number of Si atoms of 100. Further, the refractive index of this silicon oxycarbide film was measured under the same conditions as in Example 1. As a result, it was 1.62. Furthermore, as a result of performing infrared absorption measurement in the same manner as in Example 1, the above silicon oxide carbide film has an absorption peak due to Si—O—Si stretching vibration of 1050 cm ⁻¹ and an absorption peak due to Si—CH ₃ stretching vibration of 1274 cm. ^-1 was present.
Further, the oxygen permeability and water vapor permeability of the barrier film produced as described above were measured under the same conditions as in Example 1. As a result, the oxygen permeability was 0.1 cc / m ² / day · atm, the water vapor permeability was 0.1 g / m ² / day, and it was confirmed that the film had good barrier properties. Furthermore, after storing the barrier film in an environmental tester (humid heat oven) at 65 ° C. and a relative humidity of 90% RH for 500 hours, the oxygen transmission rate and the water vapor transmission rate were measured under the same conditions. It was 1 cc / m ² / day · atm, the water vapor transmission rate was 0.1 g / m ² / day, and it was confirmed that the film had good heat resistance.

[Comparative Example 2]
In the third film formation zone using HMDSO as a source gas, the same power (input power 12 kW) as that of the first film formation zone using HMDSO as a source gas was applied in the same manner as in Example 2, A silicon oxide carbide film having a thickness of 60 nm was formed on the base film to obtain a barrier film. The deposition rate of this silicon oxycarbide film was 150 nm / min, a value lower than that of Example 2.
As a result of measuring the components of the silicon oxide carbide film formed as described above under the same conditions as in Example 1, the number of O atoms was 150 and the number of C atoms was 90 with respect to the number of Si atoms of 100. Further, the refractive index of this silicon oxycarbide film was measured under the same conditions as in Example 1, and as a result, it was 1.55. Furthermore, as a result of performing infrared absorption measurement in the same manner as in Example 1, the above silicon oxide carbide film has an absorption peak due to Si—O—Si stretching vibration of 1044 cm ⁻¹ and an absorption peak due to Si—CH ₃ stretching vibration of 1274 cm. ^-1 was present.

Further, the oxygen permeability and water vapor permeability of the barrier film produced as described above were measured under the same conditions as in Example 1. As a result, the oxygen permeability was 1 cc / m ² / day · atm, the water vapor permeability was 1.2 g / m ² / day, and it was confirmed that the barrier property was greatly inferior to that of Example 2.

[Comparative Example 3]
In all of the first film formation zone to the third film formation zone, a power having a frequency of 40 kHz (input power 12 kW (limit value of allowable input power)) is applied between the lower electrode and the coating drum (upper electrode), By introducing oxygen gas at 3 slm, helium gas at 1 slm, and argon gas at 0.4 slm from the gas inlet into the first zone, and simultaneously introducing HMDSO by vaporizing at a monomer flow rate of 1 slm, a thickness of 60 nm is formed on the base film. A barrier oxide film was obtained by forming a silicon oxide carbide film. The deposition rate of this silicon oxycarbide film was 160 nm / min, which was a lower value than that of Example 2.

The components of the silicon oxycarbide film formed as described above were measured under the same conditions as in Example 1. As a result, the number of O atoms was 130 and the number of C atoms was 105 with respect to the number of Si atoms of 100. Further, the refractive index of this silicon oxycarbide film was measured under the same conditions as in Example 1, and as a result, it was 1.55. Furthermore, as a result of performing infrared absorption measurement in the same manner as in Example 1, the above silicon oxide carbide film has an absorption peak due to Si—O—Si stretching vibration of 1044 cm ⁻¹ and an absorption peak due to Si—CH ₃ stretching vibration of 1274 cm. ^-1 was present.
Further, the oxygen permeability and water vapor permeability of the barrier film produced as described above were measured under the same conditions as in Example 1. As a result, the oxygen permeability was 3 cc / m ² / day · atm, the water vapor permeability was 2.2 g / m ² / day, and it was confirmed that the barrier property was greatly inferior to that of Example 2.

[Example 3]
Tetramethoxysilane (TMOS) (KBM-04 manufactured by Shin-Etsu Chemical Co., Ltd.) as the first organic silicon compound raw material, and hexamethyldisilazane ((CH ₃ ) ₃ SiNHSi (CH ₃ ) as the second organic silicon compound raw material ₃ ) (LS-7150 manufactured by Shin-Etsu Chemical Co., Ltd.) was used, and helium gas was introduced at 30 sccm (without using oxygen gas). At the same time, TMOS was supplied at a monomer flow rate of 5 sccm, and hexamethyldisilazane was supplied at a monomer flow rate of 5 sccm. A silicon oxynitride silicon carbide film having a thickness of 100 nm was formed on the base film in the same manner as in Example 1 except that each was vaporized and introduced to obtain a barrier film. The deposition rate of this silicon oxynitride carbide film was 30 nm / min.

The components of the silicon oxynitride carbide film formed as described above were measured under the same conditions as in Example 1. As a result, the number of Si atoms was 100, the number of O atoms was 150, the number of C atoms was 60, and the number of N atoms was 120. It was. Further, the film density of this silicon oxynitride carbide film was measured under the following conditions and found to be 2.1 g / cm ³ . Further, as a result of infrared absorption measurement as in Example 1, it was confirmed that the silicon oxynitride carbide film had an absorption peak due to Si—O and Si—N stretching vibrations at 860 cm ⁻¹ .

Measurement of film density Using a X-ray reflectivity measuring apparatus (ATX-E, manufactured by Rigaku Corporation), the film density was measured as follows. In other words, an X-ray generator of 18 kW is used as an X-ray source, a CuKα wavelength λ = 1.5405 mm by a Cu target, and a parabolic artificial multilayer mirror and Ge (220) monochrome crystal are used as a monochromator. did. As setting conditions, scan speed: 0.1000 ° / min, sampling width: 0.002 °,
Scanning range: set to 0 to 4.0000 °. The sample was mounted on the substrate holder with a magnet, and the 0 ° position was adjusted by the automatic alignment function of the device. Thereafter, the reflectance was measured under the above setting conditions. About the obtained reflectance measurement value, analysis software (RGXR) attached to the above-mentioned X-ray reflectance measuring apparatus
The analysis was performed under the conditions of fitting area: 0.4 ° to 4.0 °. At that time, as a fitting initial value, it was determined by component measurement (ESCA measurement),
The element ratio (Si: N: O: C) of the thin film was input. The film density was calculated by fitting the reflectance using the nonlinear least square method.

Further, the oxygen permeability and water vapor permeability of the barrier film produced as described above were measured under the same conditions as in Example 1. As a result, the oxygen permeability was 0.02 cc / m ² / day · atm, the water vapor permeability was 0.03 g / m ² / day, and it was confirmed that the film had good barrier properties. Furthermore, after storing the barrier film in an environmental tester (humid heat oven) at 65 ° C. and a relative humidity of 90% RH for 500 hours, the oxygen transmission rate and the water vapor transmission rate were measured under the same conditions. It was 02 cc / m ² / day · atm, the water vapor transmission rate was 0.03 g / m ² / day, and it was confirmed that the film had good heat resistance.

[Comparative Example 4]
A barrier film was obtained by forming a silicon oxynitride carbide film having a thickness of 100 nm on the base film in the same manner as in Example 3 except that TMOS was not used as the source gas. The deposition rate of this silicon oxynitride carbide film was 20 nm / min, which was a lower value than in Example 3.
The components of the silicon oxynitride carbide film formed as described above were measured under the same conditions as in Example 1. As a result, the number of Si atoms was 100, the number of O atoms was 150, the number of C atoms was 75, and the number of N atoms was 155. It was. Further, the film density of this silicon oxynitride carbide film was measured under the same conditions as in Example 3, and was 1.7. Further, infrared absorption measurement was performed in the same manner as in Example 1. As a result, the silicon oxynitride carbide film had an absorption peak due to Si—O and Si—N stretching vibration at 1024 cm ⁻¹ .
Further, the oxygen permeability and water vapor permeability of the barrier film produced as described above were measured under the same conditions as in Example 1. As a result, the oxygen permeability was ^2.5 cc / m ² / day · atm, the water vapor permeability was 2.1 g / m ² / day, and it was confirmed that the barrier property was greatly inferior to that of Example 3. It was.

[Example 4]
Tetramethoxysilane (TMOS) (KBM-04 manufactured by Shin-Etsu Chemical Co., Ltd.) as the first organic silicon compound raw material, and hexamethyldisilazane ((CH ₃ ) ₃ SiNHSi (CH ₃ ) as the second organic silicon compound raw material ₃ ) A silicon oxynitride carbide film (thickness: 60 nm) while carrying the substrate film at a speed of 20 m / min in the same manner as in Example 2 except that (LS-7150 manufactured by Shin-Etsu Chemical Co., Ltd.) was used. ) To obtain a barrier film. The deposition rate of this silicon oxynitride carbide film was 200 nm / min.
The components of the silicon oxynitride carbide film formed as described above were measured under the same conditions as in Example 1. As a result, the number of Si atoms was 100, the number of O atoms was 160, the number of C atoms was 80, and the number of N atoms was 140. It was. The film density of this silicon oxynitride carbide film was measured under the same conditions as in Example 3. As a result, it was 2.2 g / cm ³ . Further, as a result of infrared absorption measurement as in Example 1, it was confirmed that the silicon oxynitride carbide film had an absorption peak at 900 cm ⁻¹ due to Si—O and Si—N stretching vibrations.

Further, the oxygen permeability and water vapor permeability of the barrier film produced as described above were measured under the same conditions as in Example 1. As a result, the oxygen permeability was 0.1 cc / m ² / day · atm, the water vapor permeability was 0.1 g / m ² / day, and it was confirmed that the film had good barrier properties. Furthermore, after storing the barrier film in an environmental tester (humid heat oven) at 65 ° C. and a relative humidity of 90% RH for 500 hours, the oxygen transmission rate and the water vapor transmission rate were measured under the same conditions. It was 1 cc / m ² / day · atm, the water vapor transmission rate was 0.1 g / m ² / day, and it was confirmed that the film had good heat resistance.

[Comparative Example 5]
In the third film formation zone using hexamethyldisilazane as a source gas, the same power (input power 12 kW) as that in the first film formation zone using hexamethyldisilazane as a source gas was applied. 4, a silicon oxynitride carbide film having a thickness of 60 nm was formed on the base film to obtain a barrier film. The deposition rate of this silicon oxynitride carbide film was 170 nm / min, which was a lower value than in Example 4.
The components of the silicon oxynitride carbide film formed as described above were measured under the same conditions as in Example 1. As a result, the number of Si atoms was 100, the number of O atoms was 115, the number of C atoms was 115, and the number of N atoms was 95. It was. Further, the film density of this silicon oxynitride carbide film was measured under the same conditions as in Example 3, and was 1.7. Further, infrared absorption measurement was performed in the same manner as in Example 1. As a result, the silicon oxynitride carbide film had an absorption peak at 1030 cm ⁻¹ due to Si—O and Si—N stretching vibrations.

Further, the oxygen permeability and water vapor permeability of the barrier film produced as described above were measured under the same conditions as in Example 1. As a result, the oxygen permeability was 1.5 cc / m ² / day · atm, the water vapor permeability was 1.8 g / m ² / day, and it was confirmed that the barrier property was greatly inferior to that of Example 4. It was.

[Comparative Example 6]
In all of the first film formation zone to the third film formation zone, a power having a frequency of 40 kHz (input power 12 kW (limit value of allowable input power)) is applied between the lower electrode and the coating drum (upper electrode), By introducing oxygen gas 3 slm, helium gas 1 slm, argon gas 0.4 slm from the gas inlet into the first zone, and simultaneously introducing hexamethyldisilazane by vaporizing at a monomer flow rate of 1 slm, A barrier oxynitride carbide film having a thickness of 60 nm was formed on the substrate. The deposition rate of this silicon oxynitride carbide film was 150 nm / min, which was a lower value than that of Example 4.

The components of the silicon oxynitride carbide film formed as described above were measured under the same conditions as in Example 1. As a result, the number of Si atoms was 100, the number of O atoms was 95, the number of C atoms was 130, and the number of N atoms was 95. It was. Further, the film density of this silicon oxynitride carbide film was measured under the same conditions as in Example 3, and was 1.7. Further, infrared absorption measurement was performed in the same manner as in Example 1. As a result, the silicon oxynitride carbide film had an absorption peak due to Si—O and Si—N stretching vibration at 1024 cm ⁻¹ .
Further, the oxygen permeability and water vapor permeability of the barrier film produced as described above were measured under the same conditions as in Example 1. As a result, the oxygen permeability was ^2.5 cc / m ² / day · atm, the water vapor permeability was 2.2 g / m ² / day, and it was confirmed that the barrier property was greatly inferior to that of Example 4. It was.

[Example 5]
Methyltrimethoxysilane ((CH ₃ Si (OCH ₃ ) ₃ ) (KBM13 manufactured by Shin-Etsu Chemical Co., Ltd.) as the first organic silicon compound raw material and hexamethyldisiloxane (HMDSO) as the second organic silicon compound raw material (Toray Dow Corning Silicone SH200-0.65 cSt) was introduced at 30 sccm of helium gas (no oxygen gas was used). At the same time, methyltrimethoxysilane was used as the monomer flow rate of 5 sccm, and HMDSO was used as the monomer. A barrier film was obtained by forming a silicon oxide carbide film having a thickness of 100 nm on the base film in the same manner as in Example 1 except that each gas was introduced at a flow rate of 5 sccm. The speed was 30 nm / min.

As a result of measuring the components of the silicon oxycarbide film formed as described above under the same conditions as in Example 1, the number of O atoms was 185 and the number of C atoms was 75 with respect to the number of Si atoms of 100. Further, the refractive index of this silicon oxycarbide film was measured under the same conditions as in Example 1. As a result, it was 1.68. Furthermore, as a result of performing infrared absorption measurement in the same manner as in Example 1, the silicon oxide carbide film has an absorption peak due to Si—O—Si stretching vibration of 1053 cm ⁻¹ and an absorption peak due to Si—CH ₃ stretching vibration of 1274 cm. ^-1 confirmed.

Further, the oxygen permeability and water vapor permeability of the barrier film produced as described above were measured under the same conditions as in Example 1. As a result, the oxygen permeability is ^{0.07cc / m 2 / day · atm} , the water vapor transmission rate was 0.05g / m ² / day, it was confirmed with good barrier properties. Furthermore, after storing the barrier film in an environmental tester (humid heat oven) at 65 ° C. and a relative humidity of 90% RH for 500 hours, the oxygen transmission rate and the water vapor transmission rate were measured under the same conditions. It was 05 cc / m ² / day · atm, the water vapor transmission rate was 0.04 g / m ² / day, and it was confirmed that the film had good heat resistance.

[Comparative Example 7]
A barrier oxide film was obtained by forming a silicon oxide carbide film having a thickness of 100 nm on a base film in the same manner as in Example 5 except that methyltrimethoxysilane was not used as the source gas. The deposition rate of this silicon oxide carbide film was 20 nm / min, which was a lower value than that of Example 5.
The components of the silicon oxycarbide film formed as described above were measured under the same conditions as in Example 1. As a result, the number of O atoms was 120 and the number of C atoms was 105 with respect to the number of Si atoms of 100. Further, the refractive index of this silicon oxycarbide film was measured under the same conditions as in Example 1. As a result, it was 1.48. Furthermore, as a result of performing infrared absorption measurement in the same manner as in Example 1, the above silicon oxide carbide film has an absorption peak due to Si—O—Si stretching vibration of 1044 cm ⁻¹ and an absorption peak due to Si—CH ₃ stretching vibration of 1274 cm. ^-1 was present.

Further, the oxygen permeability and water vapor permeability of the barrier film produced as described above were measured under the same conditions as in Example 1. As a result, the oxygen permeability was 1.4 cc / m ² / day · atm, the water vapor permeability was 1.4 g / m ² / day, and it was confirmed that the barrier property was greatly inferior to that of Example 5. It was.

[Example 6]
Methyltrimethoxysilane ((CH ₃ Si (OCH ₃ ) ₃ ) (KBM13 manufactured by Shin-Etsu Chemical Co., Ltd.) as the first organic silicon compound raw material and hexamethyldisiloxane (HMDSO) as the second organic silicon compound raw material (Toray Dow Corning Silicone Co., Ltd. SH200-0.65 cSt) In the same manner as in Example 2, a silicon oxide film (thickness) was conveyed while transporting the base film at a speed of 20 m / min. 60 nm) to form a barrier film, and the deposition rate of this silicon oxide carbide film was 200 nm / min.

As a result of measuring the components of the silicon oxycarbide film formed as described above under the same conditions as in Example 1, the number of O atoms was 160 and the number of C atoms was 80 with respect to the number of Si atoms of 100. Further, the refractive index of this silicon oxycarbide film was measured under the same conditions as in Example 1. As a result, it was 1.63. Furthermore, as a result of performing infrared absorption measurement in the same manner as in Example 1, the silicon oxide carbide film has an absorption peak due to Si—O—Si stretching vibration of 1053 cm ⁻¹ and an absorption peak due to Si—CH ₃ stretching vibration of 1274 cm. ^-1 confirmed.
Further, the oxygen permeability and water vapor permeability of the barrier film produced as described above were measured under the same conditions as in Example 1. As a result, the oxygen permeability was 0.08 cc / m ² / day · atm, the water vapor permeability was 0.1 g / m ² / day, and it was confirmed that the film had good barrier properties. Furthermore, after storing the barrier film in an environmental tester (humid heat oven) at 65 ° C. and a relative humidity of 90% RH for 500 hours, the oxygen transmission rate and the water vapor transmission rate were measured under the same conditions. It was 08 cc / m ² / day · atm, the water vapor transmission rate was 0.09 g / m ² / day, and it was confirmed that the film had good heat resistance.

[Comparative Example 8]
In the third film formation zone using hexamethyldisiloxane (HMDSO) as a source gas, the same power (input power 12 kW) as that in the first film formation zone using HMDSO as a source gas was applied. In the same manner as in 6, a silicon oxide carbide film having a thickness of 60 nm was formed on the base film to obtain a barrier film. The deposition rate of this silicon oxycarbide film was 180 nm / min, a value lower than that of Example 6.

The components of the silicon oxide carbide film formed as described above were measured under the same conditions as in Example 1. As a result, the number of O atoms was 130 and the number of C atoms was 110 with respect to the number of Si atoms of 100. Further, the refractive index of this silicon oxycarbide film was measured under the same conditions as in Example 1, and as a result, it was 1.55. Furthermore, as a result of performing infrared absorption measurement in the same manner as in Example 1, the above silicon oxide carbide film has an absorption peak due to Si—O—Si stretching vibration of 1044 cm ⁻¹ and an absorption peak due to Si—CH ₃ stretching vibration of 1274 cm. ^-1 was present.
Further, the oxygen permeability and water vapor permeability of the barrier film produced as described above were measured under the same conditions as in Example 1. As a result, the oxygen transmission rate was 1.8 cc / m ² / day · atm, the water vapor transmission rate was 1.5 g / m ² / day, and it was confirmed that the barrier property was greatly inferior to Example 6. It was.

  It can be used for packaging materials such as foods and pharmaceuticals, and packaging materials such as electronic devices.

It is a block diagram which shows an example of the plasma CVD apparatus of this invention. It is a block diagram which shows the other example of the plasma CVD apparatus of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Plasma CVD apparatus 2 ... Chamber 3 ... Lower electrode 4 ... Upper electrode 5 ... Plasma generator 6 ... Exhaust valve 7 ... Exhaust apparatus 8 ... Gas inlet 9a, 9b, 9c ... Raw material gas supply source 9d, 9e ... Organosilicon Compound supply source 10A ... monomer flow meter 10B ... vaporizer 11 ... plasma CVD apparatus 12 ... chamber 12A ... first deposition zone 12B ... second deposition zone 12C ... third deposition zone 13 ... conveying means 14A, 14B, 14C ... Lower electrode 15A, 15B, 15C ... Upper electrode (coating drum)
16A, 16B, 16C ... Power supply 17 ... Exhaust valve 18 ... Exhaust device 19 ... Gas inlet 20a, 20b, 20c ... Source gas supply source 21a, 21b ... Organosilicon compound supply source 22 ... Monomer flow meter 23 ... Vaporizer P ... Base film

Claims (12)

  Using the first organosilicon compound having a bond of oxygen and silicon of an alkoxy group in the molecule and the second organosilicon compound having a carbon-silicon bond in the molecule as raw materials, the second CVD method is performed by plasma CVD. An electric power higher than the electrode input allowable power when only the organosilicon compound is used as a raw material is applied to the electrode, and the silicon oxide carbide film (SiOC film) or the silicon oxynitride carbide film (SiONC film) is formed on the base film. A method for producing a barrier film, comprising forming the barrier film. A plasma CVD apparatus having a chamber composed of a plurality of continuous zones from the first zone to the nth zone (n is an integer of 2 or more) is used, and plasma is generated from the organosilicon compound as a raw material in each zone in order from the first zone. In a method for producing a barrier film in which a silicon oxide carbide film (SiOC film) or a silicon oxynitride carbide film (SiONC film) is laminated on a base film by a CVD method,
In at least one zone from the first zone to the (n-1) zone, a first organosilicon compound having a bond between an oxygen of an alkoxy group and silicon in the molecule is used as a raw material, and in all other zones , Using a second organosilicon compound having a carbon-silicon bond in the molecule as a raw material,
In the zone to the nth zone after the zone using the first organosilicon compound as the raw material, the second organosilicon compound is used as the raw material in all the zones from the first zone to the nth zone. The manufacturing method of the barrier film characterized by supplying electric power higher than the electrode input allowable power in a zone to an electrode. The silicon oxide carbide film (SiOC film) has an atomic composition ratio Si: O: C in the range of 100: 180 to 200: 40 to 80, and an absorption peak due to Si—O—Si stretching vibration in infrared absorption measurement. There 1045~1060cm ^-1, absorption peaks due to Si-CH ₃ stretching vibration is in the 1274 ± 8 cm ^-1, according to claim 1, wherein the refractive index being in the range of 1.5 to 1.7 Item 3. A method for producing a barrier film according to Item 2. The silicon oxynitride carbide film (SiONC film) has an atomic composition ratio Si: O: C: N in the range of 100: 130 to 180: 40 to 100: 100 to 150, and Si—O in infrared absorption measurement. The absorption peak due to Si—N stretching vibration is in the range of 830 to 1060 cm ⁻¹ , and the film density is in the range of 1.8 to 2.4 g / cm ^3. The manufacturing method of the barrier film of description.   5. The silane compound according to claim 1, wherein the first organosilicon compound is a silane compound in which three or more of silicon atoms are bonded to an oxygen atom or a hydrogen atom. The manufacturing method of the barrier film of description.   6. The first organosilicon compound is one or more of tetramethoxysilane, tetraethoxysilane, trimethoxysilane, methyltrimethoxysilane, triethoxysilane, and ethyltriethoxysilane. The manufacturing method of the barrier film of description.   The method for producing a barrier film according to claim 6, wherein the first organosilicon compound is tetramethoxysilane.   The barrier film according to any one of claims 1 to 7, wherein the second organosilicon compound has 50% or more of carbon atoms bonded to carbon atoms. Manufacturing method.   9. The second organic silicon compound is one or more of tetramethylsilane, hexamethyldisilane, hexamethyldisiloxane, tetramethyldisiloxane, and hexamethyldisilazane. Barrier film manufacturing method.   The method for producing a barrier film according to any one of claims 1 to 9, wherein electric power of about 1.1 to 2 times the electrode input allowable power is input to the electrode.   A chamber having a lower electrode and an upper electrode for placing a film formation body therein, a plasma generator connected to the lower electrode, a source gas supply source for supplying source gas into the chamber, A plasma CVD apparatus comprising: a plurality of organosilicon compound supply sources capable of supplying an organosilicon compound in an arbitrary supply amount into the chamber.   A chamber composed of a plurality of continuous zones from the first zone to the nth zone (n is an integer of 2 or more), and for transporting the film formation object from the first zone to the nth zone in the chamber Conveying means, a coating drum and a lower electrode, which are upper electrodes disposed in each zone, a power source for applying a voltage to the upper electrode and the lower electrode in each zone, and supplying a source gas to each zone And a plurality of organosilicon compound supply sources capable of supplying an organosilicon compound to each zone at an arbitrary supply amount.

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