JPWO2015025783A1 - Gas barrier film manufacturing apparatus and gas barrier film manufacturing method - Google Patents

Abstract

Prevents quality degradation of gas barrier film. The roller CVD apparatus 20 is disposed so as to form a discharge space H between a vacuum chamber 200 having a pair of opposed inner wall surfaces, and faces the wound resin substrate 2 via the discharge space H. Film forming rollers 31, 32, magnetic field generators 34, 35 for generating a magnetic field on the peripheral surfaces of the film forming rollers 31, 32, a plasma generating power source 33 for discharging the discharge space H, and the discharge space H A gas supply port 36 that is disposed above and supplies a film forming gas to the discharge space H; a gas discharge port 37 that is disposed in a lower region of the discharge space H and discharges the gas in the discharge space H to the outside of the vacuum chamber 200; The covering member that is exposed without contacting the resin base material 2 on the peripheral surfaces of the film forming rollers 31 and 32 and that covers the exposed region R adjacent to the contact region with the resin base material 2 in the circumferential direction. 38.

Description

  The present invention relates to a gas barrier film manufacturing apparatus and a gas barrier film manufacturing method. More specifically, an apparatus for manufacturing a transparent gas barrier film having excellent flexibility, used for gas blocking of electronic devices such as liquid crystals, organic electroluminescence (organic EL), solar cells, and electronic paper, and manufacturing of a gas barrier film Regarding the method.

  In recent years, in the electronic device field, in addition to demands for weight reduction and size increase, long-term reliability and a high degree of freedom in shape, and the ability to display curved surfaces have been added. Instead of difficult glass substrates, resin substrates such as transparent plastics are beginning to be adopted.

  However, a resin base material such as a transparent plastic has a problem that gas barrier properties are inferior to a glass base material. It has been found that when a base material with poor gas barrier properties is used, water vapor or oxygen penetrates and, for example, the function in the electronic device is deteriorated.

  Therefore, it is generally known that a layer having gas barrier properties (hereinafter referred to as a gas barrier layer) is formed on a resin substrate, and these laminates are used as a gas barrier film. For example, gas barrier films used for packaging materials and liquid crystal display elements that require gas barrier properties are known in which silicon oxide is vapor-deposited on a resin substrate, and in which aluminum oxide is vapor-deposited. Yes.

  By the way, an inter-roller discharge plasma chemical vapor deposition method (hereinafter also referred to as a roller CVD method) to which a magnetic field is applied has been proposed as a method for forming a gas barrier layer that can achieve both high gas barrier properties and high productivity. (For example, refer to Patent Document 1). In this film forming method, a belt-shaped resin base material is conveyed while being wound around each of a pair of rollers (film forming rollers), and plasma discharge is performed while supplying a film forming gas between the rollers to form a resin base material on the resin base material. In addition, a gas barrier layer is formed by vapor phase growth.

  FIG. 8 shows a film forming apparatus (hereinafter referred to as a roller CVD apparatus) 100 to which the roller CVD method is applied. As shown in this figure, in the roller CVD apparatus 100, along the transport direction X of the resin base material K, the feed roller 101, the transport roller 102, the film forming roller 103, the transport rollers 104 and 105, the film forming roller 106, the transport A roller 107 and a take-up roller 108 are arranged in this order, and the resin base material K is transported in the transport direction X while applying a predetermined tension to the resin base material K sent from the feed roller 101. ing.

  Among these, the pair of film forming rollers 103 and 106 are arranged close to each other with their peripheral surfaces facing each other, and are connected to the plasma generation power source 110 so as to function as a pair of counter electrodes, respectively. Thus, plasma can be generated by discharging into a space 109 (also referred to as a discharge space) between the film forming roller 103 and the film forming roller 106. Magnetic field generators 111 and 112 are provided inside the film forming roller 103 and the film forming roller 106, respectively, and are fixed so as to follow the rotation of the film forming rollers 103 and 106 and do not rotate themselves.

Further, in the vicinity of the film forming rollers 103 and 106, a gas supply port 113 for supplying a film forming gas (raw material gas or the like) into the discharge space 109 at a predetermined speed and a vacuum pump 116 are connected to the gas from the discharge space 109. The gas discharge port 114 for discharging the gas and the gas supplied from the gas supply port 113 and the film forming material formed due to the gas pass through the discharge space 109 and then the gas. It is discharged from the discharge port 114.
Of the components of the roller CVD apparatus 100 described above, at least the film forming rollers 103 and 106, the gas supply port 113, the plasma generation power source 110, and the magnetic field generation apparatuses 111 and 112 are the vacuum chamber 120. Is placed inside.

  In the roller CVD apparatus 100 as described above, a plasma discharge is generated between the pair of film forming rollers 103 and 106 while supplying a film forming gas (such as a raw material gas) into the discharge space 109. A film forming gas (raw material gas or the like) is decomposed by plasma, and a gas barrier layer is formed on the surface of the resin base material K on the film forming roller 103 and the surface of the resin base material K on the film forming roller 106 by a roller CVD method. It is formed. At this time, the film formation efficiency of the gas barrier layer is improved by the magnetic field generated by the magnetic field generators 111 and 112, and the concentration gradient of each element component such as carbon atoms continuously changes in the gas barrier layer. Adhesion, flexibility and gas barrier properties are improved.

  However, in the roller CVD apparatus 100 as described above, the film forming material to be discharged from the gas discharge port 114 through the discharge space 109 between the film forming rollers 103 and 106 diffuses into the vacuum chamber 120. Such a film forming material adheres and accumulates on the film forming rollers 103 and 106. When the film forming material adheres to and accumulates on the film forming roller, for example, the dielectric constant of the electrode changes when the film forming roller and the resin base material K are integrally regarded as electrodes, and plasma is generated. Therefore, the concentration gradient of each element component in the gas barrier layer cannot be provided as designed, and the gas barrier property of the gas barrier film is lowered. Such a problem becomes prominent when film formation is performed continuously, and becomes particularly remarkable in the region of the end portion of the resin base material that is fed from the feed roller 101 and formed into a film.

JP 2010-260347 A

  The present invention has been made in view of the above-described problems and situations, and a solution to the problem is to provide a gas barrier film manufacturing apparatus and a gas barrier film manufacturing method capable of preventing deterioration of the quality of the gas barrier film. It is to be.

  In order to solve the above problems, the present inventors have found that the problems of the present invention can be solved by preventing adhesion / deposition of the film forming material to the film forming roller in the process of examining the cause of the above problems, etc. The present invention has been reached.

  That is, the said subject which concerns on this invention is solved by the following means.

1. A vacuum chamber having at least a pair of inner wall surfaces facing each other;
A pair of resin bases that are arranged to extend between the pair of inner wall surfaces so as to form a facing space with each other and that are wound while being conveyed are opposed to each other through the facing space. A film forming roller;
A magnetic field generating member that is provided inside each film forming roller and generates a swelled magnetic field in the vicinity of a region facing the facing space of the peripheral surface of the film forming roller,
A plasma generating power source connected to the pair of film forming rollers and generating plasma by causing discharge in the facing space;
A gas supply port that is disposed on one of the upper side and the lower side of the opposing space and supplies a film forming gas to the opposing space;
A gas exhaust port disposed on the other of the upper side and the lower side of the opposing space, for exhausting the gas in the opposing space to the outside of the vacuum chamber;
With
In a gas barrier film manufacturing apparatus for forming a gas barrier layer on one surface of the resin substrate by plasma chemical vapor deposition while discharging between the film forming rollers to which a magnetic field is applied,
Of the peripheral surface of the film forming roller, it is exposed without contacting the resin base material, and covers an exposed region adjacent to the contact region with the resin base material in the circumferential direction of the film forming roller. An apparatus for producing a gas barrier film comprising a covering member.
2. The covering member is
2. The apparatus for producing a gas barrier film according to claim 1, wherein the gas barrier film manufacturing apparatus is formed so as to be curved along a peripheral surface of the film forming roller in a circumferential direction of the film forming roller.
3. 3. The gas barrier film manufacturing apparatus according to claim 1, wherein at least a surface opposite to the film forming roller of the surface of the covering member is roughened.
4). The apparatus for producing a gas barrier film according to any one of claims 1 to 3, further comprising a temperature control unit that maintains the covering member at a predetermined temperature.
5). The covering member is
The apparatus for producing a gas barrier film according to any one of claims 1 to 4, wherein the apparatus is disposed at a position away from the exposed region by 0.1 to 100 mm.
6). The covering member is
6. The apparatus for producing a gas barrier film according to claim 5, wherein the apparatus is disposed at a position separated from the exposed region by 0.1 to 50 mm.
7). The covering member is
7. The apparatus for producing a gas barrier film according to claim 6, wherein the apparatus is disposed at a position separated from the exposed region by 0.1 to 25 mm.
8). The covering member is
The gas barrier film manufacturing apparatus according to any one of claims 1 to 7, wherein the gas barrier film manufacturing apparatus is detachably attached to the gas barrier film manufacturing apparatus.
9. Standing up from the bottom surface of the vacuum chamber to the bottom of each film forming roller so that the resin base material is interposed between the film forming rollers, and in cooperation with the pair of inner wall surfaces of the vacuum chamber The apparatus for producing a gas barrier film according to any one of claims 1 to 8, further comprising a partition wall that surrounds a space from an opposing space to the gas discharge port.
10. The pair of film forming rollers disposed outside the space between the pair of inner wall surfaces of the vacuum chamber and including the facing space and surrounded by the partition wall and the resin base material. A supply port for supplying non-reactive gas is provided on the side of each roller including
The apparatus for producing a gas barrier film according to any one of claims 1 to 9, wherein a non-reactive gas is supplied from the supply port so as not to impair the exhaust capability of the production apparatus.
11. A gas barrier film manufacturing method using the gas barrier film manufacturing apparatus according to any one of Items 1 to 10,
The film-forming gas supplied from the gas supply port to the facing space is a film-forming gas containing an organosilicon compound,
Forming a gas barrier layer containing carbon atoms, silicon atoms and oxygen atoms on one surface of the resin substrate by plasma chemical vapor deposition while discharging between the film forming rollers to which a magnetic field is applied. A method for producing a gas barrier film.

  By the above means of the present invention, it is possible to prevent the quality of the gas barrier film from being deteriorated.

  Although the expression mechanism or action mechanism of the effect of the present invention is not clarified, the present inventors infer as follows.

  That is, since the covering member covers the exposed area on the peripheral surface of the film forming roller, it is considered that the film forming material diffused in the vacuum chamber is prevented from adhering and depositing on the film forming roller. Therefore, it is considered that the concentration gradient of each element component in the gas barrier layer can be provided as designed, and the quality deterioration of the gas barrier film can be prevented.

It is a schematic diagram which shows the structure of a gas barrier film. It is a schematic diagram which shows the structure of a gas barrier film. It is a schematic diagram which shows a roller CVD apparatus. It is a graph which shows an example of the silicon distribution curve of the gas barrier layer of this invention, an oxygen distribution curve, and a carbon distribution curve. It is a graph which shows an example of the silicon distribution curve, oxygen distribution curve, and carbon distribution curve of the gas barrier layer of a comparative example. It is a schematic diagram of the electronic device provided with the gas barrier film. It is a figure which shows the modification of a coating | coated member. It is a figure which shows the modification of a coating | coated member. It is a figure which shows the modification of a coating | coated member. It is a schematic diagram which shows the roller CVD apparatus provided with the partition. It is a schematic diagram which shows the conventional roller CVD apparatus.

DESCRIPTION OF SYMBOLS 1 Gas barrier film 2 Resin base material 4 Gas barrier layer 31, 32 Film-forming roller 33 Power source for plasma generation 34, 35 Magnetic field generator 36 Gas supply port 37 Gas discharge port 38 Cover member 39 Partition 200 Vacuum chamber 375 Temperature control unit H Discharge space

  An apparatus for producing a gas barrier film of the present invention includes a vacuum chamber having at least a pair of inner wall surfaces facing each other, and an extended space between the pair of inner wall surfaces so as to form an opposing space therebetween. A pair of film-forming rollers that are disposed and conveyed while being opposed to each other through the facing space; and provided inside each film-forming roller, of the peripheral surfaces of the film-forming rollers Near the region facing the facing space, a magnetic field generating member that generates a swelled magnetic field, a plasma generation power source that is connected to the pair of film forming rollers and discharges the facing space to generate plasma, and A gas supply port that is disposed on one of the upper and lower sides of the facing space and supplies a film forming gas containing an organosilicon compound to the facing space, and is disposed on the other of the upper and lower sides of the facing space. A gas exhaust port for exhausting the gas in the facing space to the outside of the vacuum chamber, and one of the resin substrates is formed by plasma chemical vapor deposition while discharging between the film forming rollers to which a magnetic field is applied. In a gas barrier film manufacturing apparatus for forming a gas barrier layer containing carbon atoms, silicon atoms, and oxygen atoms on the surface, the peripheral surface of the film forming roller is exposed without contacting the resin substrate. And a covering member that covers an exposed region adjacent to the contact region with the resin base material in the circumferential direction of the film forming roller. This feature is a technical feature common to the inventions according to claims 1 to 9.

  As an embodiment of the present invention, from the viewpoint of the effect of the present invention, the covering member is formed to be curved along the peripheral surface of the film forming roller in the circumferential direction of the film forming roller. preferable. Moreover, it is preferable that at least the surface on the opposite side of the film forming roller of the surface of the covering member is roughened. Moreover, it is preferable that the manufacturing apparatus of a gas barrier film is provided with the temperature control part which maintains the said coating | coated member at predetermined temperature. Moreover, it is preferable that the said covering member is arrange | positioned by 0.1-100 mm from the said exposed area, Preferably it is 0.1-50 mm, More preferably, it is arrange | positioned only 0.1-25 mm. Moreover, it is preferable that the said covering member is provided with respect to the manufacturing apparatus of the said gas barrier film so that attachment or detachment is possible.

The “gas barrier property” as used in the present invention is a water vapor permeability (temperature: 60 ± 0.5 ° C., relative humidity (RH): 90 ± 2%) measured by a method according to JIS K 7129-1992. ) Is 3 × 10 ⁻³ g / (m ² · 24 h) or less, and the oxygen permeability measured by a method according to JIS K 7126-1987 is 1 × 10 ⁻³ mL / m ² · 24 h · atm or less. It means that.

  In the present invention, “vacuum ultraviolet light”, “vacuum ultraviolet light”, “VUV”, and “VUV light” specifically mean light having a wavelength of 100 to 200 nm.

  Hereinafter, the present invention, its components, and modes and modes for carrying out the present invention will be described in detail. In addition, in this application, "-" is used in the meaning which includes the numerical value described before and behind that as a lower limit and an upper limit.

《Basic structure of gas barrier film》
1A and 1B are schematic cross-sectional views showing an example of the basic configuration of the gas barrier film of the present invention.

  As shown to FIG. 1A and FIG. 1B, the gas barrier film 1 of this invention is the resin base material 2 as a support body, the smoothing layer 3 formed in the one surface of the said resin base material 2, and between rollers. A gas barrier layer 4 formed on the smoothing layer 3 by a discharge plasma chemical vapor deposition method (FIG. 1A). Further, a second gas barrier layer 5 formed by subjecting a polysilazane coating film to vacuum ultraviolet irradiation (VUV) treatment is disposed on the gas barrier layer 4 as required (FIG. 1B).

[1] Smoothing layer 3
In the gas barrier film 1 of the present invention, among the surfaces of the resin base material 2, the surface on which the gas barrier layer 4 is formed has a surface free energy dispersion component of 30 to 40 mN / in an environment of 23 ° C. and 50% RH. The smoothing layer 3 within the range of m is formed. In particular, the dispersion component of the surface free energy is preferably in the range of 33 to 38 mN / m because adhesion and gas barrier properties are improved.

  Forming the smoothing layer 3 having the dispersion component of the surface free energy on the surface on which the gas barrier layer 4 is formed, and forming the gas barrier layer 4 by the inter-roller discharge plasma chemical vapor deposition method to which a magnetic field is applied. As a result, many carbon atom components can be oriented in a portion close to the resin substrate 2, and as a result, the adhesion between the resin substrate 2 and the gas barrier layer 4 is improved, and the gas barrier property is also improved.

  When the surface free energy dispersion component in the smoothing layer 3 is 30 to 40 mN / m or more, a surface having good wettability with the gas barrier layer 4 by the inter-roller discharge plasma chemical vapor deposition method can be obtained. The carbon atom component in the peripheral part of the base material 2 can be controlled to a predetermined condition, and as a result, excellent adhesion and barrier properties can be realized. On the other hand, when the dispersion component of the surface free energy is less than 30 mN / m or greater than 40 mN / m, the carbon atom component around the resin base material 2 decreases, and as a result, the adhesion and barrier properties deteriorate. .

The dispersion component γSD value of the surface free energy is measured by the following method.
Measure the contact angle between the surface of the smoothing layer 3 produced and three solvents, water, nitromethane, and diiodomethane as standard liquids, using an automatic contact angle measuring device CA-V (manufactured by Kyowa Interface Chemical Co., Ltd.). Then, the γSH value was calculated based on the following formula, and the dispersion component γSD and the hydrogen bond component γSH value (mN / m) of the surface free energy of the smoothing layer 3 were obtained. In addition, the contact angle was 3 μl of the solvent dropped on the surface of the smoothing layer 3 in an environment of 23 ° C. and 50% RH, and a value 100 ms after the landing was used.

γL · (1 + cos θ) / 2 = (γSD · γLD) ^1/2 + (γSP · γLP) ^1/2 + (γSH · γLH) ^1/2
Where
γL: surface tension of liquid θ: contact angle between liquid and solid γSD, γSP, γSH: dispersion of solid surface free energy, polarity, hydrogen bonding component γLD, γLP, γLH: dispersion of surface free energy of liquid, polarity, hydrogen Binding component γL = γLD + γLP + γLH,
γS = γSD + γSP + γSH

As the surface free energy (γSD, γSP, γSH) of the three components of the standard liquid, the surface free energy of the solid surface can be obtained by solving the ternary simultaneous equations from the respective contact angle values using the following values. Each component value (γsd, γsp, γsh) was determined.
[Water (29.1, 1.3, 42.4), Nitromethane (18.3, 17.7, 0), Diiodomethane (46.8, 4.0, 0)]

  The smoothing layer 3 is not particularly limited as long as it has the above surface free energy, but contains a resin having a radical reactive unsaturated bond, inorganic particles, a photoinitiator, a solvent, and a reactive diluent. Further, it is preferable that the reactive diluent is contained in an amount of 0.1 to 10% by mass as the content ratio in the smoothing layer 3. In the smoothing layer 3, the composition ratio of the resin having a radical reactive unsaturated bond, the inorganic particles, the photoinitiator, the solvent, and the reactive diluent, and the structure and size of each constituent material are appropriately adjusted. Therefore, it is preferable from the viewpoint of adjusting to a desired surface free energy.

<1.1> Resin having a radical-reactive unsaturated bond Examples of resins applicable to the smoothing layer 3 include epoxy resins, acrylic resins, urethane resins, polyester resins, silicone resins, and ethylene vinyl. Examples thereof include acetate (EVA) resin. By using these, the light transmittance of the resin composition can be further enhanced. In particular, among the above resin group, a photocurable or thermosetting resin type having a radical-reactive unsaturated bond is preferable, among them, from the viewpoint of productivity, obtained film hardness, smoothness, transparency, etc. In particular, an ultraviolet curable resin is preferable.

  As the ultraviolet curable resin, any resin that can be cured by ultraviolet irradiation to form a transparent resin composition can be used without limitation. From the viewpoint of the hardness, smoothness, and transparency of the resulting smoothing layer 3. It is preferable to use acrylic resin, urethane resin, polyester resin, and the like.

  Examples of the acrylic resin composition include acrylate compounds having a radical reactive unsaturated bond, mercapto compounds having an acrylate compound and a thiol group, epoxy acrylate, urethane acrylate, polyester acrylate, polyether acrylate, polyethylene glycol acrylate, glycerol methacrylate, and the like. What dissolved the polyfunctional acrylate monomer etc. are mentioned. Moreover, it is also possible to use it as a mixture which mixed the above resin compositions in arbitrary ratios, and resin containing the reactive monomer which has one or more photopolymerizable unsaturated bonds in a molecule | numerator If there is no restriction in particular.

  Preferable specific examples include UV curable resin Unidic V-4025 A-BPEF (fluorene-containing acrylate: manufactured by Shin-Nakamura Chemical Co., Ltd.) manufactured by DIC Corporation, and LCH1559 (manufactured by Toyochem: hybrid hard coat agent containing silica). However, it is not limited to these. Among these, LCH1559 containing inorganic particles is preferable.

  As a photoinitiator, well-known things, such as Irgacure 184 (made by BASF Japan), can be used, and it can be used by 1 type, or 2 or more types of combination.

<1.2> Reactive Diluent The reactive diluent applicable to the smoothing layer 3 is a monofunctional reactive monomer having one acryloyl group or one methacryloyl group per molecule, and is originally a highly viscous oligomer. In this embodiment, it also serves to adjust the surface free energy dispersion component.

  Thus, since the reactive diluent has a role of adjusting the dispersion component of the surface free energy, it preferably has a polar group or a hydrophobic group. Examples of the polar group include an epoxy group, an ethylene oxide group, a carbonyl group, a hydroxy group, a carboxy group, a phosphate group, and a primary, secondary, or tertiary amino group. The hydrophobic group includes a methylene group. , Isobonyl groups, penteniol groups, and the like. By combining both structures, the surface free energy can be appropriately adjusted by adjusting the addition amount.

  The addition amount of the reactive diluent is 0.1 to 10% by mass as the mass ratio with respect to the smoothing layer 3 from the viewpoint of the obtained surface free energy dispersion component, formation of a cured coating film, surface hardness, and the like. Is preferred. More preferably, it is 1-5 mass%.

  Within the range of 0.1 to 10% by mass, an appropriate surface free energy dispersion component can be obtained on the surface of the smoothing layer 3, and sufficient adhesion and gas barrier properties with the gas barrier layer 4 can be obtained. preferable. In addition, sufficient smoothness and hardness can be obtained, and it is preferable that the roller contact when performing the inter-roller discharge plasma chemical vapor deposition method is not damaged.

  Specific examples of preferable reactive diluents include fluorine oligomers manufactured by AGC Seimi Chemical Co., Ltd .: Surflon S-651, hydroxyethyl methacrylate, FA-512M (dicyclopentenyloxyethyl methacrylate (manufactured by Hitachi Chemical Co., Ltd.)), Phosphoric acid acrylate: Light acrylate P-1A (Kyoeisha Chemical Co., Ltd.), GMA (Light ester G glycidyl methacrylate (Kyoeisha Chemical Co., Ltd.)), and isobonyl methacrylate: Light ester IB-X (Kyoeisha Chemical) However, it is not limited to these.

<1.3> Inorganic particles Examples of inorganic particles applicable to the smoothing layer 3 include silica fine particles such as dry silica and wet silica, titanium oxide, zirconium oxide, zinc oxide, tin oxide, cerium oxide, antimony oxide, and indium tin. Examples include metal oxide fine particles such as mixed oxide and antimony tin mixed oxide, and organic fine particles such as acrylic and styrene. In particular, silica fine particles in the range of 10 to 50 nm are dispersed in an organic solvent from the viewpoint of transparency and hardness. The dispersed nano-dispersed silica particles are preferable.

  In addition, the inorganic particles are preferably blended in the range of 5 to 50 parts by weight, particularly in the range of 10 to 40 parts by weight, with respect to 100 parts by weight of the curable resin constituting the smoothing layer 3. Is preferred. The addition amount is also appropriately determined according to the arithmetic average roughness described later.

<1.4> Method for Forming Smoothing Layer 3 The smoothing layer 3 is a composition (smooth) using the above-described resin having a radical-reactive unsaturated bond, inorganic particles, a photoinitiator, a solvent, and a reactive diluent. For example, doctor blade method, spin coating method, dipping method, table coating method, spray method, applicator method, curtain coating method, die coating method, ink jet method, dispenser method, etc., if necessary It can be formed by adding a curing agent and curing the resin composition by heating or ultraviolet irradiation.

  As a method of curing the ultraviolet curable resin by irradiating with ultraviolet rays, an ultra-high pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc, a metal halide lamp, etc. are used. The irradiation can be performed by irradiating ultraviolet rays in a wavelength region in the range of ˜400 nm or irradiating an electron beam in a wavelength region of 100 nm or less emitted from a scanning or curtain type electron beam accelerator.

  The thickness of the smoothing layer 3 is not particularly limited, but is preferably in the range of 0.1 to 10 μm, and particularly preferably in the range of 0.5 to 5 μm. Further, the smoothing layer 3 may be composed of two or more layers.

  If necessary, additives such as an antioxidant, a plasticizer, another matting agent, and a thermoplastic resin can be added to the smoothing layer 3. Moreover, there is no restriction | limiting in particular as a solvent used when forming the smoothing layer 3 using the coating liquid for smoothing layer formation which melt | dissolved or disperse | distributed resin in the solvent, Well-known alcohol solvent, aromatic carbonization It can be used by appropriately selecting from conventionally known organic solvents such as hydrogen solvents, ether solvents, ketone solvents, ester solvents and the like. Among these, MEK (methyl ethyl ketone) can be preferably used.

<1.5> Arithmetic average roughness Ra of the surface of the smoothing layer 3
The smoothing layer 3 preferably has a surface arithmetic average roughness Ra value in the range of 0.5 to 2.0 nm, more preferably in the range of 0.8 to 1.5 nm.

  If the arithmetic average roughness Ra of the smoothing layer 3 is in the range of 0.5 to 2.0 nm, the surface of the smoothing layer 3 has an appropriate roughness, and due to friction with the roller, the gas barrier layer 4 is stable, and the gas barrier layer 4 can be formed with high accuracy by the inter-roller discharge plasma chemical vapor deposition method. Therefore, the uniform gas barrier layer 4 can be formed.

The arithmetic average roughness Ra of the surface of the smoothing layer 3 can be measured by the following method.
<Method of measuring surface arithmetic average roughness Ra; AFM measurement>
The arithmetic average roughness Ra is calculated from an uneven sectional curve continuously measured with an AFM (Atomic Force Microscope), for example, DI3100 manufactured by Digital Instruments, with a detector having a stylus having a minimum tip radius, and the minimum tip Measurement is made many times in a section whose measuring direction is several tens of μm with a radius stylus, and it is obtained as roughness relating to the amplitude of fine irregularities.

[2] Gas barrier layer 4
The gas barrier layer 4 is formed on the surface of the smoothing layer 3 by an inter-roller discharge plasma chemical vapor deposition method to which a magnetic field is applied.

  The gas barrier layer 4 in the present invention uses a raw material gas containing an organosilicon compound and a reaction gas as a film forming gas, and contains carbon atoms, silicon atoms, and oxygen atoms as constituent elements. It is a more preferable embodiment that all the conditions of the carbon atom distribution profile defined by “)” to “Condition (4)” are satisfied.

  “Condition (1)” When the carbon atom ratio of the gas barrier layer 4 is within a distance range of 89% of the layer thickness in the vertical direction from the surface of the gas barrier layer 4 in the layer thickness direction, it corresponds to the distance from the surface. Change continuously.

  “Condition (2)” The maximum value of the carbon atom ratio of the gas barrier layer 4 is less than 20 at% within the distance range from the surface of the gas barrier layer 4 to 89% of the layer thickness in the vertical direction from the surface of the gas barrier layer 4. is there.

  “Condition (3)” The carbon atom ratio of the gas barrier layer 4 is within a distance range of 90 to 95% of the layer thickness in the vertical direction from the surface of the gas barrier layer 4 in the layer thickness direction (adjacent to the resin base material 2). Within a distance range of 5 to 10% from the surface to be continuously increased.

  “Condition (4)” The maximum value of the carbon atom ratio of the gas barrier layer 4 is within a distance range of 90 to 95% of the layer thickness in the vertical direction from the surface of the gas barrier layer 4 in the layer thickness direction (resin substrate 2) within a distance range of 5 to 10% in the vertical direction from the surface adjacent to 2).

  The average value of the carbon atom content ratio and the carbon atom distribution profile in the gas barrier layer 4 can be obtained by measurement of an XPS depth profile described later.

Hereinafter, details of the gas barrier layer 4 will be further described.
<2.1> Carbon Atom Profile in Gas Barrier Layer 4 The gas barrier layer 4 contains carbon atoms, silicon atoms, and oxygen atoms as constituent elements, and the distance from the surface in the layer thickness direction of the gas barrier layer 4 and silicon In the carbon distribution curve showing the relationship with the ratio of the amount of carbon atoms to the total amount of atoms, oxygen atoms and carbon atoms (carbon atom ratio), the carbon atom content profile has the above-mentioned “condition (1)” to “condition ( It is preferable that all the conditions of “4)” are satisfied from the viewpoint of obtaining the gas barrier film 1 having further excellent flexibility (flexibility) and adhesion.

  In addition, it is a preferable embodiment that the carbon atom ratio has a configuration in which the carbon atom ratio continuously changes with a concentration gradient in a specific region of the gas barrier layer 4 from the viewpoint of achieving both gas barrier properties and flexibility.

  In the gas barrier layer 4 having such a carbon atom distribution profile, it is preferable that the carbon distribution curve in the layer has at least one extreme value. Furthermore, it is more preferable to have at least two extreme values, and it is particularly preferable to have at least three extreme values. When the carbon distribution curve does not have an extreme value, the gas barrier property when the obtained gas barrier film 1 is bent is insufficient. Further, in the case of having at least two or three extreme values as described above, the gas in the thickness direction of the gas barrier layer 4 with respect to one extreme value and the extreme value adjacent to the extreme value included in the carbon distribution curve. The absolute value of the difference in distance from the surface of the barrier layer 4 is preferably 200 nm or less, and more preferably 100 nm or less.

  In addition, in this embodiment, an extreme value means the maximum value or the minimum value of the atomic ratio of each element.

(2.1.1) Local maximum value and local minimum value In this embodiment, the local maximum value means that the value of the atomic ratio of the element changes from increasing to decreasing when the distance from the surface of the gas barrier layer 4 is changed. And the atomic ratio of the element at a position where the distance from the surface in the thickness direction of the gas barrier layer 4 from the point to the surface of the gas barrier layer 4 is further changed by 20 nm than the value of the atomic ratio of the element at that point. The point where the value decreases by 3 at% or more.

  Furthermore, in this embodiment, the minimum value is a point where the value of the atomic ratio of the element changes from decreasing to increasing when the distance from the surface of the gas barrier layer 4 is changed, and the atomic ratio of the element at that point The atomic ratio value of the element at a position where the distance from the surface of the gas barrier layer 4 in the layer thickness direction of the gas barrier layer 4 from the above point is further changed by 20 nm is increased by 3 at% or more. Say.

  In the gas barrier layer 4, (1) the maximum value of the carbon atom ratio within a distance range of 89% in the vertical direction from the surface (the surface opposite to the surface in contact with the resin base material 2) is less than 20 at%. And (3) the maximum value of the carbon atom ratio within the distance range of 90 to 95% in the vertical direction (within the distance range of 5 to 10% from the surface adjacent to the resin base material 2) is 20 at. % Or more is a preferred embodiment.

(2.1.2) Continuous change in concentration gradient In the present invention, the gas barrier layer 4 has (2) a carbon atom ratio having a concentration gradient within a distance range of 89% in the vertical direction from the surface. And (4) in the range of 90 to 95% in the vertical direction from the surface, in other words, perpendicular to the surface portion from the surface adjacent to the resin base material 2. It is a preferable embodiment that the carbon atom ratio in the range of 5 to 10% in the direction of the layer thickness continuously increases in the direction.

In the present embodiment, “the concentration gradient of the carbon atom ratio continuously changes” means that the carbon distribution ratio in the carbon distribution curve does not include a portion where the carbon atom ratio changes discontinuously. In the relationship between the distance (x, unit: nm) from the surface in the layer thickness direction of the gas barrier layer 4 calculated from the speed and the etching time, and the carbon atomic ratio (C, unit: at%), the following formula ( It means that the condition represented by F1) is satisfied.
Formula (F1)
(DC / dx) ≦ 0.5

<2.2> Each element profile in the gas barrier layer 4 The gas barrier layer 4 is characterized by containing carbon atoms, silicon atoms and oxygen atoms as constituent elements, and the ratio, maximum value and minimum value of each atom. A preferred embodiment for the value is described below.

(2.2.1) Relationship between maximum value and minimum value of carbon atom ratio In gas barrier layer 4, the absolute value of the difference between the maximum value and the minimum value of carbon atom ratio in the carbon distribution curve is 5 at% or more. preferable. In such a gas barrier layer 4, the absolute value of the difference between the maximum value and the minimum value of the carbon atom ratio is more preferably 6 at% or more, and particularly preferably 7 at% or more. By setting the absolute value of the difference between the maximum value and the minimum value of the carbon atom ratio to 5 at% or more, the gas barrier property when the produced gas barrier film 1 is bent is sufficient.

(2.2.2) Relationship between the maximum value and the minimum value of the oxygen atomic ratio In the gas barrier layer 4, the absolute value of the difference between the maximum value and the minimum value in the oxygen distribution curve is preferably 5 at% or more. % Or more is more preferable, and 7 at% or more is particularly preferable. When the absolute value is 5 at% or more, the gas barrier property when the obtained gas barrier film 1 is bent is sufficient.

(2.2.3) Relationship between maximum value and minimum value of silicon atom ratio In gas barrier layer 4, the absolute value of the difference between the maximum value and the minimum value in the silicon distribution curve is preferably less than 5 at%. % Is more preferable, and it is particularly preferable that it is less than 3 at%. If the absolute value is less than 5 at%, the gas barrier film 1 obtained has sufficient gas barrier properties and mechanical strength.

(2.2.4) Ratio of the total amount of oxygen atoms + carbon atoms In the gas barrier layer 4, the distance from the surface of the layer in the layer thickness direction and the oxygen relative to the total amount of silicon atoms, oxygen atoms and carbon atoms In an oxygen-carbon total distribution curve (also referred to as an oxygen-carbon distribution curve) showing a relationship with a ratio of the total amount of atoms and carbon atoms (referred to as an atomic ratio of oxygen-carbon total), the oxygen-carbon total The absolute value of the difference between the maximum value and the minimum value of the atomic ratio is preferably less than 5 at%, more preferably less than 4 at%, and particularly preferably less than 3 at%. When the absolute value is less than 5 at%, the gas barrier film 1 to be obtained has a sufficient gas barrier property.

  In the above description regarding the carbon atom distribution profile (silicon distribution curve, oxygen distribution curve and carbon distribution curve; see FIGS. 3 and 4 to be described later), “the total amount of silicon atoms, oxygen atoms and carbon atoms” means silicon. The total number of atoms, oxygen atoms and carbon atoms is meant, and “amount of carbon atoms” means the number of carbon atoms. The same applies to “amount of silicon atoms” and “amount of oxygen atoms” for the silicon distribution curve and the oxygen-carbon distribution curve. Moreover, at% means the atomic number ratio of each atom when the total atom number of a silicon atom, an oxygen atom, and a carbon atom is 100 at%.

<2.3> About elemental composition distribution analysis (depth profile) in the layer thickness direction by XPS Silicon distribution curve, oxygen distribution curve, and carbon distribution curve, and oxygen-carbon total distribution curve in the layer thickness direction of the gas barrier layer 4 Is a so-called XPS depth profile measurement that uses Xray Photoelectron Spectroscopy (XPS) measurement and rare gas ion sputtering such as argon to perform surface composition analysis sequentially while exposing the inside of the sample. Can be created. A distribution curve obtained by such XPS depth profile measurement can be created, for example, with the vertical axis as the atomic ratio (unit: at%) of each element and the horizontal axis as the etching time (sputtering time). In the element distribution curve with the horizontal axis as the etching time, the etching time is generally correlated with the distance from the surface of the gas barrier layer 4 in the layer thickness direction of the gas barrier layer 4. “Distance from the surface of the gas barrier layer 4 in the thickness direction of the barrier layer 4” as a distance from the surface of the gas barrier layer 4 calculated from the relationship between the etching rate and the etching time employed in the XPS depth profile measurement. Can be adopted. In addition, as a sputtering method employed for such XPS depth profile measurement, a rare gas ion sputtering method using argon (Ar ⁺ ) as an etching ion species is employed, and the etching rate (etching rate) is 0.05 nm / It is preferable to set to sec (SiO ₂ thermal oxide film conversion value).

  In the present invention, the gas barrier layer 4 is formed in the layer surface direction (parallel to the surface of the gas barrier layer 4) from the viewpoint of forming a gas barrier layer 4 that is uniform over the entire layer surface and has excellent gas barrier properties. In the same direction) is preferably substantially uniform. The gas barrier layer 4 is substantially uniform in the layer surface direction means that the oxygen distribution curve, the carbon distribution curve, and the carbon distribution curve at any two measurement points on the surface of the gas barrier layer 4 by XPS depth profile measurement. When an oxygen-carbon total distribution curve is created, the number of extreme values of the carbon distribution curve obtained at any two measurement points is the same, and the atomic ratio of carbon in each carbon distribution curve is the same. The absolute value of the difference between the maximum value and the minimum value is the same or within 5 at%.

  The gas barrier film 1 of the present invention preferably includes at least one gas barrier layer 4 that satisfies all of the above-mentioned “condition (1)” to “condition (4)”. Two or more layers may be provided. Further, when two or more such gas barrier layers 4 are provided, the materials of the plurality of gas barrier layers 4 may be the same or different. Further, when two or more such gas barrier layers 4 are provided, such a gas barrier layer 4 may be formed on one surface of the resin base material 2, It may be formed on the surface. Moreover, as such a plurality of gas barrier layers 4, a gas barrier layer 4 that does not necessarily have a gas barrier property may be included.

  Further, in the silicon distribution curve, the oxygen distribution curve, and the carbon distribution curve, the silicon atom ratio, the oxygen atom ratio, and the carbon atom ratio are within a distance range from the surface of the gas barrier layer 4 to 89% of the layer thickness. In the gas barrier layer 4, the maximum value of the silicon atom ratio relative to the total amount of silicon atoms, oxygen atoms and carbon atoms is preferably in the range of 19 to 40 at%, and preferably in the range of 25 to 35 at%. More preferred. Further, the maximum value of the oxygen atom ratio relative to the total amount of silicon atoms, oxygen atoms and carbon atoms in the gas barrier layer 4 is preferably in the range of 33 to 67 at%, and is preferably in the range of 41 to 62 at%. More preferred. Furthermore, the maximum value of the carbon atom ratio with respect to the total amount of silicon atoms, oxygen atoms and carbon atoms in the gas barrier layer 4 is preferably in the range of 1 to 19 at%, and is preferably in the range of 3 to 19 at%. More preferred.

<2.4> Thickness of Gas Barrier Layer 4 The thickness of the gas barrier layer 4 is preferably in the range of 5 to 3000 nm, more preferably in the range of 10 to 2000 nm, and 100 to 1000 nm. It is particularly preferable that it is within the range. When the thickness of the gas barrier layer 4 is within the above range, the gas barrier properties such as oxygen gas barrier property and water vapor barrier property are excellent, and the gas barrier property is not deteriorated by bending.

  Moreover, when the gas barrier film 1 is provided with the several gas barrier layer 4, the total value of the thickness of those gas barrier layers 4 is the range of 10-10000 nm normally, and is the range of 10-5000 nm. It is more preferable, it is more preferable that it is the range of 100-3000 nm, and it is especially preferable that it is the range of 200-2000 nm. When the total thickness of the gas barrier layer 4 is within the above range, gas barrier properties such as oxygen gas barrier properties and water vapor barrier properties are sufficient, and the gas barrier properties tend not to decrease due to bending.

<2.5> Formation Method of Gas Barrier Layer 4 The gas barrier layer 4 is formed on the surface of the smoothing layer 3 on the resin substrate 2 by an inter-roller discharge plasma chemical vapor deposition method to which a magnetic field is applied.

  More specifically, the gas barrier layer 4 in the present invention uses a discharge plasma treatment apparatus between rollers to which a magnetic field is applied, conveys the resin base material 2 while being wound around a pair of film forming rollers, and between the pair of film forming rollers. A film forming gas is supplied while applying a magnetic field to perform plasma discharge, and the film is formed by a plasma chemical vapor deposition method. Thus, when discharging while applying a magnetic field between a pair of film forming rollers, it is preferable to reverse the polarity between the pair of film forming rollers alternately. Further, as a film forming gas used in such a plasma chemical vapor deposition method, a raw material gas containing an organosilicon compound and a reactive gas are used, and the content of the reactive gas in the film forming gas is set in the film forming gas. The total amount of the organosilicon compound is preferably less than the theoretical amount necessary for complete reaction. Moreover, in the gas barrier film 1 of this invention, it is preferable that the gas barrier layer 4 is a layer formed by the continuous film-forming process.

  In order to form a gas barrier layer in which the carbon atomic ratio has a concentration gradient and continuously changes in the layer, an inter-roller discharge plasma chemical vapor deposition method using a magnetic field is used.

  In the discharge plasma chemical vapor deposition method between rollers to which a magnetic field is applied (hereinafter, also simply referred to as “roller CVD method”), formation is performed while applying a magnetic field between a plurality of film forming rollers when generating plasma. It is preferable to generate a plasma discharge in the discharge space, and in the present invention, a pair of film forming rollers is used, and the resin base material 2 is conveyed while being wound around each of the pair of film forming rollers. It is preferable to generate plasma by discharging in a state where a magnetic field is applied between the rollers. In this way, a pair of film forming rollers are used, and the resin base material 2 is conveyed while being wound around the pair of film forming rollers, and plasma discharge is performed between the pair of film forming rollers, thereby forming a resin base material. It becomes possible to form the gas barrier layer 4 in which the distance between the film 2 and the film forming roller changes so that the carbon atom ratio has a concentration gradient and continuously changes in the layer.

  In addition, while forming a film on the surface portion of the resin substrate 2 existing on one film forming roller at the time of film formation, the film is also formed on the surface portion of the resin substrate 2 existing on the other film forming roller at the same time. In addition to being able to efficiently produce a thin film, the film formation rate can be doubled, and since a film having the same structure can be formed, it is possible to at least double the extreme value in the carbon distribution curve, It becomes possible to efficiently form a layer satisfying all of the above “condition (1)” to “condition (4)”.

  From the viewpoint of productivity, it is preferable to form the gas barrier layer 4 on the surface of the resin base material 2 by a roll-to-roll method.

  An apparatus that can be used when manufacturing the gas barrier film 1 by such a plasma chemical vapor deposition method is not particularly limited, but includes a film forming roller including at least a pair of magnetic field applying apparatuses, a plasma, and the like. It is preferable that the apparatus includes a power source and is configured to be capable of discharging between a pair of film forming rollers. For example, when the manufacturing apparatus shown in FIG. The gas barrier film 1 can be produced by a roll-to-roll method using the growth method.

  Hereinafter, the manufacturing apparatus of the gas barrier film 1 will be described in more detail with reference to FIG. In addition, the resin base material 2 in the following description means the resin base material which has the smoothing layer 3 on the surface.

FIG. 2 is a schematic diagram illustrating an example of an inter-roller discharge plasma CVD apparatus (hereinafter also referred to as a roller CVD apparatus 20) to which a magnetic field is applied.
The roller CVD apparatus 20 is a gas barrier film manufacturing apparatus according to the present invention. As shown in FIG. 2, the long strip-shaped resin substrate 2 having a predetermined width is conveyed by a plurality of rollers in the conveyance direction X. However, the gas barrier film 1 is manufactured by forming the gas barrier layer 4 on the resin substrate 2 by the CVD method.

  The roller CVD apparatus 20 includes a box-shaped vacuum chamber 200. The vacuum chamber 200 is connected to a vacuum pump 370 so that the internal pressure is appropriately adjusted. Moreover, the vacuum chamber 200 in the present embodiment has two pairs of inner wall surfaces facing each other.

  Inside the vacuum chamber 200, a delivery roller (original winding roller) 25 around which the resin base material 2 is wound is rotatably disposed on the upstream side in the transport direction X, and the resin is disposed on the downstream side in the transport direction X. A winding roller 26 for winding the substrate 2 is rotatably disposed. In the present embodiment, the feed roller 25 and the take-up roller 26 are a pair of inner wall surfaces facing each other (not shown in FIG. Between the inner wall surfaces of the first and second inner walls). The winding roller 26 is connected to a driving source (not shown) such as a motor for rotating the winding roller 26. As the winding roller 26, a known roller can be appropriately used as long as the resin base material 2 on which the gas barrier layer 4 is formed can be wound. As the delivery roller 25, a known roller can be used as appropriate.

  Between the delivery roller 25 and the take-up roller 26, the transport roller 21, the film formation roller 31, the transport rollers 22 and 23, the film formation roller 32, the transport roller from the upstream side to the downstream side in the transport direction X. 24 are arranged in this order. The transport rollers 21 to 24 and the film forming rollers 31 and 32 are rotatably arranged in a state of extending substantially horizontally between the pair of inner wall surfaces in the vacuum chamber 200, respectively. The resin base material 2 is transported in the transport direction X while applying a predetermined tension to 2.

Among these, as the transport rollers 21 to 24, known rollers can be appropriately selected and used.
In addition, the pair of film forming rollers 31 and 32 is disposed so as to form an opposing space (hereinafter also referred to as a discharge space H) between them, and is a resin base wound around itself while being conveyed. The material 2 is made to oppose through the discharge space H. The pair of film forming rollers 31 and 32 are respectively connected to a plasma generating power source 33 and function as a pair of counter electrodes. The plasma generating power source 33 can generate a plasma by causing electric discharge to discharge the discharge space H between the film forming roller 31 and the film forming roller 32. As such a plasma generation power source 33, a power source of a known plasma generation apparatus can be used as appropriate. However, from the viewpoint of performing the roller CVD method more efficiently, the polarities of the film forming rollers 31 and 32 are alternately set. It is preferable to use one that can be reversed (such as an AC power supply). Moreover, as such a plasma generating power source 33, it becomes possible to carry out the roller CVD method more efficiently, so that the applied power can be in the range of 100 W to 10 kW, and the AC frequency is 50 Hz. It is more preferable that it can be in the range of ˜500 kHz.

  In addition, when using the film-forming rollers 31 and 32 also as an electrode in this way, the material and design should just be changed suitably. As the film forming rollers 31 and 32 that can be used as electrodes, known rollers can be used as appropriate. However, as the film forming rollers 31 and 32, those having the same diameter are preferably used from the viewpoint of forming a thin film more efficiently. The diameters of the film forming rollers 31 and 32 are preferably in the range of 100 to 1000 mmφ, particularly in the range of 100 to 700 mmφ, from the viewpoint of discharge conditions, the space of the vacuum chamber 200 described later, and the like. If the diameter is 100 mmφ or more, the plasma discharge space H will not be reduced, so there is no decrease in productivity, and it is possible to avoid that the total heat of plasma discharge is applied to the film in a short time, and the residual stress is less likely to increase. . On the other hand, if it is 1000 mmφ or less, it is preferable because practicality can be maintained in terms of device design including uniformity of the plasma discharge space H and the like.

  The pair of film forming rollers 31 and 32 as described above are preferably arranged such that the central axes are substantially parallel to each other. By arranging a pair of film forming rollers (film forming roller 31 and film forming roller 32) in this way, the film forming rate can be doubled and a film having the same structure can be formed. The extreme value can be at least doubled.

  A magnetic field generator 34 and a magnetic field generator 35 are provided inside the film forming roller 31 and the film forming roller 32, respectively, and are fixed so as to follow the rotation of the film forming rollers 31 and 32 and do not rotate themselves. It is in the state. These magnetic field generators 34 and 35 have no lines of magnetic force between the magnetic field generator 34 provided on one film forming roller 31 and the magnetic field generator 35 provided on the other film forming roller 32, The magnetic poles are preferably arranged so that each magnetic field generator 34, 35 forms a substantially closed magnetic circuit. By providing such magnetic field generators 34 and 35, it is possible to generate a magnetic field in which magnetic lines of force swell in the vicinity of the region facing the discharge space H in the peripheral surfaces of the film forming rollers 31 and 32. Since the plasma is easily converged on the exit portion, this is excellent in that the film formation efficiency of the gas barrier layer 4 can be improved.

Further, these magnetic field generators 34 and 35 are provided with racetrack-shaped magnetic poles that are long in the axial direction of the film forming rollers 31 and 32, respectively. It is preferable that one magnetic field generator 34 and the other magnetic field generator 35 are arranged so that the opposite magnetic poles have the same polarity. By providing the magnetic field generators 34 and 35, the magnetic field generators 34 and 35 are formed such that the magnetic field lines do not straddle the magnetic field generators 34 and 35 on the opposing film forming rollers 31 and 32 side. A racetrack-like magnetic field can be easily formed in the vicinity of the roller surface facing the discharge space H along the axial direction of 31 and 32, and the plasma can be converged on the magnetic field. It is excellent in that the gas barrier layer 4 as a vapor deposition film can be efficiently formed on the surface of the resin base material 2 wound along.
In addition, as such magnetic field generators 34 and 35, well-known magnetic field generators, such as a permanent magnet and an electromagnet, can be used suitably, for example.

  Further, in the vicinity of the film forming rollers 31 and 32, a gas supply port 36 for supplying a film forming gas containing an organosilicon compound to the discharge space H at a predetermined speed and a gas in the discharge space H connected to the vacuum pump 370. In addition, a gas discharge port 37 for discharging a film forming material formed due to the gas to the outside of the vacuum chamber 200 is provided. In the present embodiment, the gas supply port 36 is disposed at an equal distance from the film forming rollers 31 and 32 and above the discharge space H, and the gas discharge port 37 is formed by the film forming rollers 31 and 32. At the same distance from the bottom surface 201 of the vacuum chamber 200 and in the lower region of the discharge space H. Thereby, the gas supplied from the gas supply port 36 passes through the discharge space H between the film forming rollers 31 and 32 and is discharged from the gas discharge port 37.

  A covering member 38 that covers the exposed region R of the film forming rollers 31 and 32 is disposed in the vicinity of the film forming rollers 31 and 32. Here, the exposed region R is exposed without contacting the resin base material 2 on the peripheral surfaces of the film forming rollers 31 and 32, and the film forming roller with respect to the contact region with the resin base material 2. 31 and 32 are adjacent regions in the circumferential direction.

  The covering member 38 extends substantially horizontally between the pair of inner wall surfaces in the vacuum chamber 200, and the film forming rollers 31, 32 in the circumferential direction of the film forming rollers 31, 32. It is curved and formed in a round bracket shape so as to follow the peripheral surface.

  The covering member 38 is preferably disposed away from the exposed region R by 0.1 to 100 mm, more preferably disposed from the exposed region R by 0.1 to 50 mm. Preferably, it is spaced from the exposed region R by 0.1 to 25 mm.

Further, the covering member 38 in the present embodiment is detachably attached to the pair of inner wall surfaces in the vacuum chamber 200.
The covering member 38 is formed of a material that does not affect the film formation, and at least the surface on the opposite side of the film forming rollers 31 and 32 of the surface of the covering member 38 is roughened. Here, examples of materials that do not affect the film formation include metal materials such as stainless steel, copper, and aluminum that have been subjected to insulation treatment, and non-materials such as SiO ₂ , Al ₂ O ₃ , B ₂ O ₃ , CaO, and MgO. Examples thereof include synthetic resin materials such as metal materials, polyether ether ketone, polyphenylene sulfide, polyimide, polyamide, and polytetrafluoroethylene. Further, that the covering member 38 is roughened means that the arithmetic average roughness (center average roughness) defined by JIS B0601-1994 is 1 μm or more. In order to roughen the covering member 38 in this way, for example, sandblasting or polishing can be used.

  A temperature control unit 375 for maintaining the covering member 38 at a predetermined temperature is connected to the covering member 38. The temperature control unit 375 is configured to easily attach the film forming material to the surface of the covering member 38 by maintaining the temperature of the covering member 38 at a predetermined temperature. The temperature controller 375 may control the temperature of the covering member 38 by heat conduction or by radiation. Further, instead of connecting the temperature control unit 375 to the covering member 38, a potential control unit that controls the potential of the covering member 38 may be connected. This potential control unit controls the potential of the covering member 38 to make it easy to attach the film forming material to the covering member 38.

  In the roller CVD apparatus 20 as described above, plasma discharge is performed while applying a magnetic field between the pair of film forming rollers 31 and 32 while supplying a film forming gas (such as a source gas) into the discharge space H. By generating, the film forming gas (raw material gas or the like) is decomposed by the plasma, and the surface of the resin base material 2 on the film forming roller 31 and the surface of the resin base material 2 on the film forming roller 32 by the roller CVD method. Then, the gas barrier layer 4 is formed. At this time, since the covering member 38 covers the exposed region R on the peripheral surface of the film forming rollers 31 and 32, the film forming material diffused in the vacuum chamber 200 adheres and accumulates on the film forming rollers 31 and 32. Is prevented. Further, since the covering member 38 is formed to be curved along the peripheral surface of the film forming rollers 31 and 32 in the circumferential direction of the film forming rollers 31 and 32, the film forming material diffused into the vacuum chamber 200 is formed. Adhering and depositing on the film forming rollers 31 and 32 is reliably prevented. Further, since the surface of the covering member 38 opposite to the film forming rollers 31 and 32 is roughened, the film forming material diffused into the vacuum chamber 200 is opposite to the film forming rollers 31 and 32 of the covering member 38. As a result, the film forming material diffused in the vacuum chamber 200 is more reliably prevented from adhering and depositing on the film forming rollers 31 and 32. Further, since the temperature control unit 375 maintains the covering member 38 at a predetermined temperature, the film forming material is more easily attached to the covering member 38. As a result, the film forming material diffused in the vacuum chamber 200 is formed on the film forming roller 31. It is more reliably prevented from adhering to and depositing on 32. Further, since the covering member 38 is arranged 0.1 to 100 mm, preferably 0.1 to 50 mm, particularly preferably 0.1 to 25 mm away from the exposed region R of the film forming rollers 31 and 32, the vacuum is applied. The film forming material diffused in the chamber 200 is more reliably prevented from adhering to and depositing on the film forming rollers 31 and 32.

  On the other hand, at this time, the feeding roller 25, the winding roller 26, and the film forming roller 31 transport the resin base material 2 in the transport direction X, so that the region of the resin base material 2 on which the gas barrier layer 4 is formed becomes the winding roller. 26, a new region of the resin base material 2 in which the gas barrier layer 4 is not formed is fed from the feed roller 25 and conveyed onto the film forming rollers 31 and 32. As a result, the gas barrier layer 4 is formed on the surface of the resin base material 2 by a continuous film-to-roll film forming process. The type of source gas, the power of the plasma generating power source 33, the strength of the magnetic field generators 34 and 35, the pressure in the vacuum chamber, the diameters of the film forming rollers 31 and 32, the conveyance speed of the resin base material 2, etc. are appropriately selected. Can be adjusted.

(2.5.1) Source gas The source gas constituting the film forming gas for forming the gas barrier layer 4 is preferably an organosilicon compound containing at least silicon.

  Examples of the organosilicon compound applicable to the present invention include hexamethyldisiloxane, 1,1,3,3-tetramethyldisiloxane, vinyltrimethylsilane, methyltrimethylsilane, hexamethyldisilane, methylsilane, dimethylsilane, and trimethyl. Examples thereof include silane, diethylsilane, propylsilane, phenylsilane, vinyltriethoxysilane, vinyltrimethoxysilane, tetramethoxysilane, tetraethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, and octamethylcyclotetrasiloxane. Among these organosilicon compounds, hexamethyldisiloxane and 1,1,3,3-tetramethyldisiloxane are preferable from the viewpoints of handling in film formation and gas barrier properties of the obtained gas barrier layer 4. Moreover, these organosilicon compounds can be used individually by 1 type or in combination of 2 or more types.

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

  As the film forming gas, a carrier gas may be used as necessary to supply the source gas into the vacuum chamber 200. Further, as the film forming gas, a discharge gas may be used as necessary in order to generate plasma discharge. As such carrier gas and discharge gas, known ones can be used as appropriate, and for example, a rare gas such as helium, argon, neon, xenon, or hydrogen gas can be used.

  When such a film-forming gas contains a raw material gas and a reactive gas, the ratio of the raw material gas and the reactive gas is a theoretically required reactive gas for completely reacting the raw material gas and the reactive gas. It is preferable that the ratio of the reaction gas is not excessively increased rather than the ratio of the amount. If the ratio of the reaction gas is excessively increased, it is difficult to obtain the target gas barrier layer 4 in the present invention. Therefore, in order to obtain the desired performance as a barrier film, it is preferable that the total amount of the organosilicon compound in the film-forming gas be less than the theoretical oxygen amount necessary for complete oxidation.

As a representative example, a system of hexamethyldisiloxane (organosilicon compound: HMDSO: (CH ₃ ) ₆ Si ₂ O :) as a raw material gas and oxygen (O ₂ ) as a reaction gas will be described below.

A film-forming gas containing hexamethyldisiloxane (HMDSO, (CH ₃ ) ₆ Si ₂ O) as a source gas and oxygen (O ₂ ) as a reaction gas is reacted by a roller CVD method to form silicon-oxygen. When forming a thin film of the type, a reaction represented by the following reaction formula (1) occurs by the film forming gas, and a thin film made of silicon dioxide SiO ₂ is formed.

Reaction Formula (1) (CH ₃ ) 6Si ₂ O + 12O ₂ → 6CO ₂ + 9H ₂ O + 2SiO ₂
In such a reaction, the amount of oxygen required to completely oxidize 1 mol of hexamethyldisiloxane is 12 mol. Therefore, when the film forming gas contains 12 moles or more of oxygen with respect to 1 mole of hexamethyldisiloxane and is completely reacted, a uniform silicon dioxide film is formed. The ratio is controlled to a flow rate equal to or less than the raw material ratio of the complete reaction, which is the theoretical ratio, and the incomplete reaction is performed. That is, it is necessary to set the amount of oxygen to less than 12 moles of the stoichiometric ratio with respect to 1 mole of hexamethyldisiloxane.

  In the actual reaction in the vacuum chamber 200 of the roller CVD apparatus 20, the raw material hexamethyldisiloxane and the reaction gas, oxygen, are supplied from the gas supply unit to the film formation region to form a film. Even if the molar amount (flow rate) of oxygen is 12 times the molar amount (flow rate) of hexamethyldisiloxane as a raw material, the reaction cannot actually proceed completely. It is considered that the reaction is completed only when the oxygen content is supplied in a large excess compared to the stoichiometric ratio. For example, in order to obtain silicon oxide by complete oxidation by a CVD method, the molar amount (flow rate) of oxygen may be about 20 times or more the molar amount (flow rate) of hexamethyldisiloxane as a raw material. Therefore, the molar amount (flow rate) of oxygen with respect to the molar amount (flow rate) of the raw material hexamethyldisiloxane is preferably an amount of 12 times or less (more preferably 10 times or less) which is the stoichiometric ratio. . By containing hexamethyldisiloxane and oxygen in such a ratio, carbon atoms and hydrogen atoms in hexamethyldisiloxane that have not been completely oxidized are taken into the gas barrier layer 4, and the desired gas barrier layer 4. Can be formed, and the obtained gas barrier film 1 can exhibit excellent barrier properties and bending resistance. If the molar amount (flow rate) of oxygen relative to the molar amount (flow rate) of hexamethyldisiloxane in the film forming gas is too small, unoxidized carbon atoms and hydrogen atoms are excessively taken into the gas barrier layer 4. It will be. In this case, the transparency of the barrier film is lowered, and the gas barrier film 1 is used for a flexible substrate for an electronic device such as an organic EL device or an organic thin film solar cell that requires transparency. It becomes impossible. From such a viewpoint, the lower limit of the molar amount (flow rate) of oxygen relative to the molar amount (flow rate) of hexamethyldisiloxane in the film forming gas is more than 0.1 times the molar amount (flow rate) of hexamethyldisiloxane. Preferably, the amount is more than 0.5 times.

(2.5.2) Degree of vacuum The pressure (degree of vacuum) in the vacuum chamber 200 can be appropriately adjusted according to the type of the source gas, but is preferably in the range of 0.5 Pa to 100 Pa.

(2.5.3) Other Roller Film Formation Conditions In the roller CVD method using the roller CVD apparatus 20 or the like as shown in FIG. 2, plasma is discharged in order to discharge between the film formation roller 31 and the film formation roller 32. The power applied to the electrode drum (installed in the film forming roller 31 and the film forming roller 32 in FIG. 2) connected to the generating power source 33 is the type of source gas, the pressure in the vacuum chamber 200, and the like. Although it can adjust suitably according to this and it cannot generally say, it is preferable to set it as the range of 0.1-10 kW. If the applied power is in such a range, no generation of particles (illegal particles) is observed, and the amount of heat generated during film formation is within the control range. There is no thermal deformation of the base material 2, performance deterioration due to heat, and generation of wrinkles during film formation. In addition, it is possible to prevent problems such as damage to the film forming roller due to generation of a large current discharge between the bare film forming rollers 31 and 32 due to melting of the resin base material 2 by heat.

  Although the conveyance speed (line speed) of the resin base material 2 can be suitably adjusted according to the kind of source gas, the pressure in a vacuum chamber, etc., it is preferable to set it as the range of 0.25-100 m / min. More preferably, it is in the range of 0.5 to 20 m / min. If the line speed is within the above range, wrinkles due to the heat of the resin base material 2 hardly occur, and the thickness of the formed gas barrier layer 4 can be sufficiently controlled.

(2.5.4) Element profile in gas barrier layer 4 formed by roller CVD method An example of each element profile in the thickness direction of the layer according to the XPS depth profile of gas barrier layer 4 formed as described above As shown in FIG.

  FIG. 3 is a graph showing an example of the silicon distribution curve, oxygen distribution curve, and carbon distribution curve of the gas barrier layer 4.

  In FIG. 3, symbols A to D represent A as a carbon distribution curve, B as a silicon distribution curve, C as an oxygen distribution curve, and D as an oxygen-carbon distribution curve. As shown in FIG. 3, the gas barrier layer has a maximum carbon atom ratio within a distance range of 89% vertically from the surface and less than 20 at%, and a distance of 89% vertically from the surface. It can be seen that the carbon atom ratio within the range has a concentration gradient and a structure in which the concentration changes continuously (corresponding to the above-mentioned “condition (1)” and “condition (2)”). ).

  In addition, the gas barrier layer 4 has a carbon atom ratio within a distance range of 90 to 95% in the vertical direction (within a distance range of 5 to 10% in the vertical direction from the surface adjacent to the resin base material 2) with respect to the surface. It can be seen that the maximum value of is 20 at% or more and the carbon atom ratio continuously increases (corresponding to the above-mentioned “condition (3)” and “condition (4)”). ).

FIG. 4 is a graph showing an example of a carbon distribution curve, a silicon distribution curve, and an oxygen distribution curve of a gas barrier layer of a comparative example. In the gas barrier layer formed by a flat electrode (horizontal transport) type discharge plasma CVD method, A carbon atom distribution curve A, a silicon atom distribution curve B, an oxygen atom distribution curve C, and an oxygen-carbon distribution curve D are shown.
As shown in this figure, it can be seen that the gas barrier layer of the comparative example has a configuration in which a continuous change in the concentration gradient of the carbon atom component does not occur.

[3] Resin substrate 2
Here, the resin base material 2 constituting the gas barrier film 1 will be described. The resin base material 2 is not particularly limited as long as it is formed of an organic material capable of holding the gas barrier layer 4 having the above gas barrier properties.

  Examples of the resin substrate 2 applicable to the present invention include methacrylic acid ester, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polycarbonate (PC), polyarylate, polystyrene (PS), aromatic polyamide, poly Examples of the resin film include ether ether ketone, polysulfone, polyether sulfone, polyimide, and polyetherimide, and a laminated film formed by laminating two or more layers of the above resins. In view of cost and availability, resin films such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), and polycarbonate (PC) are preferably used.

  The thickness of the resin base material 2 is preferably in the range of 5 to 500 μm, more preferably in the range of 25 to 250 μm.

  Moreover, it is preferable that the resin base material 2 in this invention is transparent. When the resin base material 2 is transparent and the layer formed on the resin base material 2 is also transparent, it becomes a transparent gas barrier film 1 and is used as a transparent substrate for electronic devices (for example, organic EL). It is also possible.

  Moreover, the resin base material 2 using the said resin etc. may be an unstretched film, and may be a stretched film. A stretched film is preferable from the viewpoint of strength improvement and thermal expansion suppression. Moreover, a phase difference etc. can also be adjusted by extending | stretching.

  The resin substrate 2 in the present invention can be produced by a conventionally known general film forming method. For example, an unstretched resin base material 2 that is substantially amorphous and not oriented can be produced by melting a resin as a material with an extruder, extruding it with an annular die or a T-die, and quenching. In addition, the resin as a material is dissolved in a solvent, cast on an endless metal resin support, dried, and peeled to form an unstretched film that is substantially amorphous and not oriented. The resin base material 2 can also be manufactured.

  The flow of the resin base material 2 (vertical axis, MD) is applied to the unstretched resin base material 2 by a known method such as uniaxial stretching, tenter sequential biaxial stretching, tenter simultaneous biaxial stretching, and tubular simultaneous biaxial stretching. ) Direction or a direction perpendicular to the flow direction of the resin base material 2 (horizontal axis, TD), can be used to produce a stretched resin base material. The draw ratio in this case can be appropriately selected according to the resin that is the raw material of the resin substrate 2, but is preferably in the range of 2 to 10 times in the MD direction and the TD direction, respectively.

  Moreover, the resin base material 2 in this invention may perform a relaxation | loosening process and off-line heat processing at the point of dimensional stability. The relaxation treatment is preferably carried out in the process from the heat setting during the stretching film forming step in the above-described film forming method to the winding after the tenter is drawn out in the TD direction. The relaxation treatment is preferably performed at a treatment temperature in the range of 80 to 200 ° C, and more preferably at a treatment temperature in the range of 100 to 180 ° C. Although it does not specifically limit as a method of off-line heat processing, For example, the method of conveying by the roller conveyance method by a several roller group, the air conveyance which blows and blows air to a film, etc. (one side of a film surface heated air from several slits) Or a method of spraying on both surfaces), a method of using radiant heat by an infrared heater or the like, a conveying method of hanging a film under its own weight and winding it down. The conveyance tension of the heat treatment is made as low as possible to promote thermal shrinkage, whereby the resin base material 2 with good dimensional stability is obtained. As the treatment temperature, a temperature range of (Tg + 50) to (Tg + 150) ° C. is preferable. Tg here refers to the glass transition temperature of the resin substrate 2.

The resin base material 2 in the present invention can be applied with an undercoat layer coating solution inline on one or both sides in the course of film formation. In the present invention, such undercoating during the film forming process is referred to as in-line undercoating. Examples of resins used in the undercoat layer coating solution useful in the present invention include polyester resins, acrylic-modified polyester resins, polyurethane resins, acrylic resins, vinyl resins, vinylidene chloride resins, polyethyleneimine vinylidene resins, polyethyleneimine resins, and polyvinyl alcohol resins. , Modified polyvinyl alcohol resin, gelatin and the like, and any of them can be preferably used. A conventionally well-known additive can also be added to these undercoat layers. The undercoat layer can be formed using a known coating method such as roller coating, gravure coating, knife coating, dip coating, or spray coating. The coating amount of the undercoat layer is preferably in the range of 0.01 to ² g / m ² (dry state).

[4] Second gas barrier layer 5
In the gas barrier film 1 of the present invention, a polysilazane-containing liquid is applied and dried on the gas barrier layer 4 by a wet application method, and the formed coating film is irradiated with vacuum ultraviolet light (VUV light) having a wavelength of 200 nm or less. Then, it is preferable to form the second gas barrier layer 5 by subjecting the formed coating film to a modification treatment.

  By forming the second gas barrier layer 5 on the gas barrier layer 4, a second defect constituted by polysilazane imparted from above on the minute defect portion generated when the gas barrier layer 4 that has already been formed is formed. It is preferable from the viewpoint of being able to be filled with the gas barrier layer components, efficiently preventing gas purging, and further improving gas barrier properties and flexibility.

  The thickness of the second gas barrier layer 5 is preferably in the range of 1 to 500 nm, more preferably in the range of 10 to 300 nm. If the thickness of the second gas barrier layer 5 is 1 nm or more, desired gas barrier performance can be exhibited. If the thickness is 500 nm or less, film quality deterioration such as generation of cracks in a dense silicon oxynitride film Can be prevented.

<4.1> Polysilazane The polysilazane in the present invention is a polymer having a silicon-nitrogen bond in the molecular structure, and is a polymer that is a precursor of silicon oxynitride. The polysilazane to be applied is not particularly limited, A compound having a structure represented by the following general formula (1) is preferable.

上記一般式（１）において、Ｒ^１、Ｒ^２及びＲ^３は、各々水素原子、アルキル基、アルケニル基、シクロアルキル基、アリール基、アルキルシリル基、アルキルアミノ基、又はアルコキシ基を表す。

In the general formula (1), R ¹ , R ² and R ³ each represent a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, an alkylsilyl group, an alkylamino group, or an alkoxy group.

In the present invention, from the viewpoint of compactness as the obtained second gas barrier layer 5, perhydropolysilazane in which all of R ¹ , R ² and R ³ are composed of hydrogen atoms is particularly preferable.

  Perhydropolysilazane is presumed to have a linear structure and a ring structure centered on a 6-membered ring and an 8-membered ring. Its molecular weight is about 600 to 2000 in terms of number average molecular weight (Mn) (gel Polystyrene conversion by permeation chromatography), which is a liquid or solid substance.

  Polysilazane is commercially available in the form of a solution dissolved in an organic solvent, and a commercially available product can be used as it is as a polysilazane-containing coating solution. Examples of the commercially available polysilazane solution include NN120-20, NAX120-20, and NL120-20 manufactured by AZ Electronic Materials Co., Ltd.

  The second gas barrier layer 5 is formed by applying and drying a coating liquid containing polysilazane on the gas barrier layer 4 formed by the inter-roller discharge plasma CVD method to which a magnetic field is applied, and then irradiating with vacuum ultraviolet rays. be able to.

  As an organic solvent for preparing a coating liquid containing polysilazane, it is preferable to avoid using an alcohol or water-containing one that easily reacts with polysilazane. Examples of applicable organic solvents include hydrocarbon solvents such as aliphatic hydrocarbons, alicyclic hydrocarbons, and aromatic hydrocarbons, ethers such as halogenated hydrocarbon solvents, aliphatic ethers, and alicyclic ethers. Specific examples include hydrocarbons such as pentane, hexane, cyclohexane, toluene, xylene, solvesso and turben, halogen hydrocarbons such as methylene chloride and trichloroethane, and ethers such as dibutyl ether, dioxane and tetrahydrofuran. These organic solvents may be selected according to purposes such as the solubility of polysilazane and the evaporation rate of the organic solvent, and a plurality of organic solvents may be mixed.

  The concentration of polysilazane in the second gas barrier layer-forming coating solution containing polysilazane varies depending on the layer thickness of the second gas barrier layer 5 and the pot life of the coating solution, but is preferably 0.2 to 35 masses. %.

  In order to promote the modification to silicon oxynitride, the second gas barrier layer forming coating solution contains an amine catalyst, a Pt compound such as Pt acetylacetonate, a Pd compound such as propionic acid Pd, Rh acetylacetonate, etc. A metal catalyst such as an Rh compound can also be added. In the present invention, it is particularly preferable to use an amine catalyst. Specific amine catalysts include N, N-diethylethanolamine, N, N-dimethylethanolamine, triethanolamine, triethylamine, 3-morpholinopropylamine, N, N, N ′, N′-tetramethyl-1 , 3-diaminopropane, N, N, N ′, N′-tetramethyl-1,6-diaminohexane and the like.

  The amount of these catalysts added to the polysilazane is preferably in the range of 0.1 to 10% by mass, and in the range of 0.2 to 5% by mass with respect to the total mass of the second gas barrier layer forming coating solution. It is more preferable that it is in the range of 0.5 to 2% by mass. By setting the addition amount of the catalyst within the range specified above, it is possible to avoid excessive silanol formation due to rapid progress of the reaction, decrease in film density, increase in film defects, and the like.

  Any appropriate wet coating method may be employed as a method for applying the second gas barrier layer forming coating solution containing polysilazane. Specific examples include a roller coating method, a flow coating method, an ink jet method, a spray coating method, a printing method, a dip coating method, a casting film forming method, a bar coating method, and a gravure printing method.

  The thickness of the coating film can be appropriately set according to the purpose. For example, the thickness of the coating film is preferably in the range of 50 nm to 2 μm as the thickness after drying, more preferably in the range of 70 nm to 1.5 μm, and in the range of 100 nm to 1 μm. Is more preferable.

<4.2> Excimer Treatment The second gas barrier layer 5 is a step of irradiating a layer containing polysilazane with vacuum ultraviolet (VUV), and at least a part of the polysilazane is modified into silicon oxynitride.

Here, perhydropolysilazane will be described as an example of the presumed mechanism in which the coating film containing polysilazane is modified in the vacuum ultraviolet irradiation step and becomes a specific composition of SiO _x N _y .

Perhydropolysilazane can be represented by a composition of “— (SiH ₂ —NH) _n —”. In the case of SiO _x N _y , x = 0 and y = 1. An external oxygen source is required for x> 0,
(I) oxygen and moisture contained in the polysilazane coating solution,
(Ii) oxygen and moisture taken into the coating film from the atmosphere of the coating and drying process,
(Iii) oxygen, moisture, ozone, singlet oxygen taken into the coating film from the atmosphere in the vacuum ultraviolet irradiation process,
(Iv) Oxygen and moisture moving into the coating film as outgas from the substrate side by heat applied in the vacuum ultraviolet irradiation process,
(V) When the vacuum ultraviolet ray irradiation step is performed in a non-oxidizing atmosphere, when moving from the non-oxidizing atmosphere to the oxidizing atmosphere, oxygen and moisture taken into the coating film from the atmosphere,
Etc. become oxygen sources.

  On the other hand, for y, the condition under which nitriding proceeds rather than the oxidation of Si is considered to be very special, so basically 1 is the upper limit.

  Also, from the relationship of Si, O, and N bond, x and y are basically in the range of 2x + 3y ≦ 4. In the state of y = 0 where the oxidation has progressed completely, the coating film contains silanol groups, and there are cases where 2 <x <2.5.

  The reaction mechanism presumed to produce silicon oxynitride and further silicon oxide from perhydropolysilazane in the vacuum ultraviolet irradiation step will be described below.

(1) Dehydrogenation and associated Si—N bond formation Si—H bonds and N—H bonds in perhydropolysilazane are relatively easily cleaved by excitation by vacuum ultraviolet irradiation, etc., and in an inert atmosphere, Si— It is considered that they are recombined as N (a dangling bond of Si may be formed). That is, the cured as SiN _y composition without oxidizing. In this case, the polymer main chain is not broken. The breaking of Si—H bonds and N—H bonds is promoted by the presence of a catalyst and heating. The cut H is released out of the membrane as H ₂ .

(2) Formation of Si—O—Si bond by hydrolysis and dehydration condensation The Si—N bond in perhydropolysilazane is hydrolyzed by water, and the polymer main chain is cleaved to form Si—OH. Two Si—OHs are dehydrated and condensed to form Si—O—Si bonds and harden. This is a reaction that occurs in the air, but during vacuum ultraviolet irradiation in an inert atmosphere, it is considered that water vapor generated as outgas from the resin base material 2 by the heat of irradiation becomes the main moisture source. When the water becomes excessive, Si—OH that cannot be dehydrated and condensed remains, and a cured film having a low gas barrier property represented by a composition of SiO _2.1 to SiO _2.3 is obtained.

(3) Direct oxidation by singlet oxygen, formation of Si-O-Si bond When a suitable amount of oxygen is present in the atmosphere during irradiation with vacuum ultraviolet rays, singlet oxygen having a very strong oxidizing power is formed. H or N in perhydropolysilazane is replaced with O to form a Si—O—Si bond and is cured. It is considered that recombination of the bond may occur due to cleavage of the polymer main chain.

(4) Oxidation with Si-N bond cleavage by vacuum ultraviolet irradiation and excitation Since the energy of vacuum ultraviolet light is higher than the bond energy of Si-N in perhydropolysilazane, the Si-N bond is broken and oxygen is surrounded by oxygen. When an oxygen source such as ozone or water is present, it is considered that the substrate is oxidized to form a Si—O—Si bond or a Si—O—N bond. It is considered that recombination of the bond may occur due to the cleavage of the polymer main chain.

  Adjustment of the composition of the silicon oxynitride of the layer subjected to vacuum ultraviolet irradiation on the layer containing polysilazane can be performed by appropriately controlling the oxidation state by appropriately combining the oxidation mechanisms (1) to (4) described above. .

In vacuum ultraviolet irradiation step, it is preferable that the illuminance of the vacuum ultraviolet rays in the coated film surface for receiving polysilazane coating film is in the range of 30~200mW / cm ^2, in a range of 50~160mW / cm ² More preferred. If it is 30 mW / cm ² or more, there is no concern about the reduction of the reforming efficiency, and if it is 200 mW / cm ² or less, the coating film is not ablated and the substrate is not damaged.

Irradiation energy amount of the VUV in the polysilazane coating film surface is preferably in the range of 200~10000mJ / cm ^2, and more preferably in a range of 500~5000mJ / cm ^2. If it is 200 mJ / cm ² or more, the modification can be sufficiently performed, and if it is 10000 mJ / cm ² or less, it is not excessively reformed, and cracking and thermal deformation of the resin substrate 2 can be prevented. it can.

  As the vacuum ultraviolet light source, a rare gas excimer lamp is preferably used. Atoms of noble gases such as Xe, Kr, Ar, and Ne are called inert gases because they are not chemically bonded to form molecules.

However, excited atoms of rare gases that have gained energy by discharge or the like can form molecules by combining with other atoms. When the rare gas is xenon,
e + Xe → Xe ^*
Xe ^* + 2Xe → Xe ₂ ^* + Xe
Xe ₂ ^* → Xe + Xe + hν (172 nm)
Thus, when the excited excimer molecule Xe ₂ ^* transitions to the ground state, excimer light of 172 nm is emitted.

  A feature of the excimer lamp is that the radiation is concentrated on one wavelength, and since only the necessary light is not emitted, the efficiency is high. Further, since no extra light is emitted, the temperature of the object can be kept low. Furthermore, since no time is required for starting and restarting, instantaneous lighting and blinking are possible.

  In order to obtain excimer light emission, a method using dielectric barrier discharge is known. Dielectric barrier discharge is a gas space created by placing a gas space between both electrodes via a dielectric such as transparent quartz and applying a high frequency high voltage of several tens of kHz to the electrode. It is a discharge called a thin micro discharge. When the micro discharge streamer reaches the tube wall (derivative), electric charges accumulate on the dielectric surface, and the micro discharge disappears.

  This micro discharge spreads over the entire tube wall, and is a discharge that is repeatedly generated and disappeared. For this reason, flickering of light that can be confirmed with the naked eye occurs. Moreover, since a very high temperature streamer reaches a pipe wall directly locally, there is a possibility that deterioration of the pipe wall is accelerated.

  As a method for efficiently obtaining excimer light emission, electrodeless electric field discharge is possible in addition to dielectric barrier discharge. Electrodeless electric field discharge by capacitive coupling, also called RF discharge. The lamp and electrodes and their arrangement may be basically the same as those of dielectric barrier discharge, but the high frequency applied between the two electrodes is lit at several MHz. Since the electrodeless field discharge can provide a spatially and temporally uniform discharge in this way, a long-life lamp without flickering can be obtained.

  In the case of dielectric barrier discharge, since micro discharge occurs only between the electrodes, the outer electrode covers the entire outer surface and transmits light to extract light to the outside in order to cause discharge in the entire discharge space. Must be a thing.

  For this reason, an electrode in which a fine metal wire is formed in a net shape is used. Since this electrode uses as thin a line as possible so as not to block light, it is easily damaged by ozone generated by vacuum ultraviolet light in an oxygen atmosphere. In order to prevent this, it is necessary to provide an atmosphere of an inert gas such as nitrogen around the lamp, that is, the inside of the irradiation apparatus, and provide a synthetic quartz window to extract the irradiation light. Synthetic quartz windows are not only expensive consumables, but also cause light loss.

  Since the double cylindrical lamp has an outer diameter of about 25 mm, the difference in distance to the irradiation surface cannot be ignored between the position directly below the lamp axis and the side surface of the lamp, resulting in a large difference in illuminance. Therefore, even if the lamps are closely arranged, a uniform illuminance distribution cannot be obtained. If the irradiation device is provided with a synthetic quartz window, the distance in the oxygen atmosphere can be made uniform, and a uniform illuminance distribution can be obtained.

  When electrodeless field discharge is used, it is not necessary to make the external electrodes mesh. The glow discharge spreads over the entire discharge space simply by providing an external electrode on a part of the lamp outer surface. As the external electrode, an electrode that also serves as a light reflector made of an aluminum block is usually used on the back of the lamp. However, since the outer diameter of the lamp is as large as in the case of the dielectric barrier discharge, synthetic quartz is required to obtain a uniform illuminance distribution.

  The biggest feature of the capillary excimer lamp is its simple structure. The quartz tube is closed at both ends, and only gas for excimer light emission is sealed inside.

  The outer diameter of the tube of the thin tube lamp is about 6 nm to 12 mm, and if it is too thick, a high voltage is required for starting.

  As the form of discharge, both dielectric barrier discharge and electrodeless field discharge can be used. The electrode may have a flat surface in contact with the lamp, but if the shape is matched to the curved surface of the lamp, the lamp can be firmly fixed, and the discharge is more stable when the electrode is in close contact with the lamp. Also, if the curved surface is made into a mirror surface with aluminum, it also becomes a light reflector.

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

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

  Therefore, compared with low-pressure mercury lamps with wavelengths of 185 nm and 254 nm and plasma cleaning, it is possible to shorten the process time associated with high throughput, reduce the equipment area, and irradiate organic materials and plastic substrates that are easily damaged by heat. .

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

  Oxygen is required for the reaction at the time of ultraviolet irradiation, but since vacuum ultraviolet rays are absorbed by oxygen, the efficiency in the ultraviolet irradiation process tends to decrease. It is preferable to carry out in a low state. That is, the oxygen concentration at the time of vacuum ultraviolet irradiation is preferably in the range of 10 to 10,000 ppm, more preferably in the range of 50 to 5000 ppm, and still more preferably in the range of 1000 to 4500 ppm.

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

[5] Each functional layer In the gas barrier film 1 of the present invention, each functional layer can be provided as necessary in addition to the above-described constituent layers.

<5.1> Overcoat layer An overcoat layer may be formed on the second gas barrier layer 5 for the purpose of further improving the flexibility. The organic material used for forming the overcoat layer is preferably an organic resin such as an organic monomer, oligomer or polymer, or an organic-inorganic composite resin layer using a siloxane or silsesquioxane monomer, oligomer or polymer having an organic group. Can be used. These organic resins or organic-inorganic composite resins preferably have a polymerizable group or a crosslinkable group, contain these organic resins or organic-inorganic composite resins, and contain a polymerization initiator, a crosslinking agent, etc. as necessary. It is preferable to apply a light irradiation treatment or a heat treatment to the layer formed from the organic resin composition coating solution to be cured.

[6] Electronic Device The gas barrier film 1 of the present invention is preferably provided as a film for an electronic device.

  Examples of the electronic device include an organic electroluminescence panel (organic EL panel), an organic electroluminescence element (organic EL element), an organic photoelectric conversion element, and a liquid crystal display element.

<6.1> Organic EL Panel as Electronic Device The gas barrier film 1 having the configuration shown in FIGS. 1A and 1B is used as a sealing film for sealing solar cells, liquid crystal display elements, organic EL elements, and the like, for example. be able to.

  An example of the organic EL panel P which is an electronic device using the gas barrier film 1 as a sealing film is shown in FIG.

  As shown in FIG. 5, the organic EL panel P is formed on the gas barrier film 1, the transparent electrode 6 such as ITO formed on the gas barrier film 1, and the transparent electrode 6. And an organic EL element 7 that is a main body of the electronic device, and a counter film 9 disposed via an adhesive layer 8 so as to cover the organic EL element 7. The transparent electrode 6 may form part of the organic EL element 7.

  A transparent electrode 6 and an organic EL element 7 are formed on the surfaces of the gas barrier film 1 on the gas barrier layer 4 side and the second gas barrier layer 5 side.

  In the organic EL panel P, the organic EL element 7 is suitably sealed so as not to be exposed to water vapor, and the organic EL element 7 is not easily deteriorated. Therefore, the organic EL panel P can be used for a long time. It becomes possible, and the lifetime of the organic EL panel P is extended.

  The counter film 9 may be a gas barrier film 1 in addition to a metal film such as an aluminum foil. When the gas barrier film 1 is used as the facing film 9, the surface side on which the gas barrier layer 4 is formed may be attached to the organic EL element 7 with the adhesive layer 8.

  As described above, according to the present embodiment, since the covering member 38 covers the exposed region R on the peripheral surface of the film forming rollers 31 and 32, the film forming material diffused in the vacuum chamber 200 adheres to the film forming rollers 31 and 32. -It can prevent that it accumulates. Therefore, the concentration gradient of each element component in the gas barrier layer 4 can be provided as designed, and the deterioration of the quality of the gas barrier film 1 can be prevented.

  Further, since the covering member 38 is formed to be curved along the peripheral surface of the film forming rollers 31 and 32 in the circumferential direction of the film forming rollers 31 and 32, the film forming material diffused into the vacuum chamber 200 is formed. It is possible to reliably prevent adhesion and deposition on the film forming rollers 31 and 32.

  Further, since the surface of the covering member 38 opposite to the film forming rollers 31 and 32 is roughened, the film forming material diffused into the vacuum chamber 200 is opposite to the film forming rollers 31 and 32 of the covering member 38. It becomes easy to adhere to the surface. Therefore, the film forming material diffused in the vacuum chamber 200 can be more reliably prevented from adhering to and depositing on the film forming rollers 31 and 32.

  Further, since the temperature control unit 375 maintains the covering member 38 at a predetermined temperature, the film forming material can be more easily attached to the covering member 38. Therefore, the film forming material diffused in the vacuum chamber 200 can be more reliably prevented from adhering to and depositing on the film forming rollers 31 and 32.

  Further, since the covering member 38 is arranged 0.1 to 100 mm, preferably 0.1 to 50 mm, particularly preferably 0.1 to 25 mm away from the exposed region R of the film forming rollers 31 and 32, the vacuum is applied. It is possible to more reliably prevent the film forming material diffused in the chamber 200 from adhering to and depositing on the film forming rollers 31 and 32.

  Further, since the covering member 38 is detachably attached to the inner wall surface of the vacuum chamber 200, when a large amount of film forming material adheres to the covering member 38, the covering member 38 is exchanged and is again formed. Can be easily adhered. Therefore, the film forming material diffused in the vacuum chamber 200 can be more reliably prevented from adhering to and depositing on the film forming rollers 31 and 32.

  In addition, about the detailed structure of each component of the gas barrier film 1 and roller CVD apparatus 20 in said embodiment, of course, it can change suitably in the range which does not deviate from the meaning of this invention.

  For example, although the roller CVD apparatus 20 has been described as transporting the resin base material 2 in the X direction in FIG. 2, it may be transported in the opposite direction. Moreover, although it demonstrated as a pair of film-forming rollers 31 and 32 conveying the same resin base material 2, it is good also as conveying separate resin base materials 2. FIG.

  In addition, the roller CVD apparatus 20 has been described as having the gas discharge port 37 on the bottom surface 201 of the vacuum chamber 200, but may be provided at a position other than the bottom surface. In addition, the roller CVD apparatus 20 has been described as having the gas supply port 36 above the discharge space H and the gas discharge port 37 below, but has the gas supply port 36 below and the gas discharge port 37 above. It's also good.

  Further, although the covering member 38 has been described as a shape curved in a parenthesis, the shape may be, for example, as shown in FIGS. 6A to 6C as long as the exposed region R of the film forming rollers 31 and 32 is covered. Here, the covering member 38 shown in FIG. 6A has a shape bent in an L shape when viewed from the axial direction of the film forming rollers 31 and 32. Moreover, the covering member 38 shown in FIG. 6B has a shape bent in a turtle shell shape when viewed from the axial direction of the film forming rollers 31 and 32. Further, the covering member 38 shown in FIG. 6C has a linear shape when viewed from the axial direction of the film forming rollers 31 and 32.

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto.

[Production of Roller CVD Equipment (1)]
As an example of the apparatus for producing a gas barrier film according to the present invention, a roller CVD apparatus (1) similar to the roller CVD apparatus 20 in the above embodiment was produced.
Specifically, in this roller CVD apparatus (1), a covering member similar to that in the above embodiment is provided.

[Production of Roller CVD Equipment (2)]
As a comparative example of the gas barrier film production apparatus according to the present invention, a roller CVD apparatus (2) similar to the conventional one was produced.
Specifically, in this roller CVD apparatus (2), the same covering member as in the above embodiment is not provided.

[Production of gas barrier film]
Using the above roller CVD apparatuses (1) and (2), a gas barrier layer having a thickness of 300 nm is formed on a 3000 m long resin substrate (manufactured by Kimoto Co., Ltd., KB film (G1SBF)) under the following film forming conditions. Then, a film was formed to form a gas barrier film.

<Film formation conditions>
Source gas: hexamethyldisiloxane (organosilicon compound: HMDSO: (CH ₃ ) ₆ Si ₂ O)
・ Raw gas supply: 50 sccm (Standard Cubic Centimeter per Minute)
・ Supply amount of oxygen gas (O ₂ ): 500 sccm
・ Degree of vacuum in the vacuum chamber: 3Pa
・ Applied power from the power source for plasma generation: 0.8 kW
・ Power supply frequency for plasma generation: 80 kHz
-Film transport speed: 1.5 m / min

[Evaluation of gas barrier film]
The gas barrier film formed by each roller CVD apparatus (1), (2) was evaluated as follows.

<Evaluation of gas barrier properties>
According to the following measuring method, the permeated water amount of each gas barrier film was measured.

  First, from each gas barrier film, a 10 m area on the front side (the side on which the gas barrier layer was first formed), an intermediate area, and a 10 m area on the end side were cut out and used as sample materials.

  Using a vacuum vapor deposition device JEE-400 (manufactured by JEOL Ltd.), the surface of each sample material of each gas barrier film is 12 mm × 12 mm in size through a mask so that the vapor deposition film thickness is 80 nm. (Metal that corrodes by reacting with moisture) was deposited.

  Thereafter, the mask was removed in a vacuum state, and metal aluminum (φ3 to 5 mm, granular, water vapor impermeable metal) was vapor-deposited on the entire surface of one side of the sheet, and temporarily sealed.

  Next, the vacuum state was released, and it was quickly transferred to a dry nitrogen gas atmosphere. And after bonding quartz glass with a thickness of 0.2 mm to the metallic aluminum vapor-deposited surface of the gas barrier film temporarily sealed as described above via an ultraviolet curable resin (manufactured by Nagase ChemteX Corporation), ultraviolet rays are bonded. Was applied to cure the ultraviolet curable resin, which was then sealed to prepare a sample for evaluating water vapor barrier properties.

  The obtained sample was stored for 100 hours in a constant temperature and humidity oven (Yamato Humidic Chamber IG47M) adjusted to a high temperature and high humidity of 60 ° C. and 90% RH, and stored based on the method described in JP-A-2005-283561. The amount of moisture permeated into the sample was calculated from the amount of corrosion of the metallic calcium before and after.

  Then, the evaluation value of the permeated water amount in the sample in the region on the leading side (the side on which the gas barrier layer was first formed) in each gas barrier film was set to the reference value “1”. Moreover, the value of the ratio of the permeated water amount in the samples in the intermediate region and the tail region in each gas barrier film to the permeated water amount in the head region was calculated and used as an evaluation value. Each evaluation value was as shown in Table 1 below.

  In addition, in order to confirm that there is no permeation of water vapor from other than the gas barrier film surface (such as quartz glass surface), a comparative sample using a quartz glass plate having a thickness of 0.2 mm instead of the gas barrier film sample was prepared. Then, when it was stored in a constant temperature and humidity oven adjusted to a high temperature and high humidity condition of 60 ° C. and 90% RH, it was confirmed that no metallic calcium corrosion occurred even after 1000 hours.

<Evaluation of composition of gas barrier layer>
From each gas barrier film, a 10 m area on the front side (the side on which the gas barrier layer was first formed), an intermediate area, and a 10 m area on the end side were cut out and used as samples.

Using an X-ray photoelectron spectrometer (manufactured by Thermo Fisher Scientific, model name “VG Theta Probe”), XPS depth profiles were measured for samples in each region of each gas barrier film. At the time of measurement, the irradiation X-ray of the X-ray photoelectron spectrometer was set to single crystal spectroscopy AlKα, and the X-ray spot shape and size were set to an 800 × 400 μm ellipse. The etching ion species was set to argon (Ar ⁺ ), the etching rate was set to 0.05 nm / sec in terms of SiO ₂ thermal oxide film, and the etching interval was set to 10 nm in terms of SiO ₂ .

  Then, the evaluation value of the carbon element ratio (absolute value of the difference between the maximum value and the minimum value) in the sample of the region on the top side (the side on which the gas barrier layer was first formed) in each gas barrier film The value was “1”. In addition, the ratio of the carbon element ratio (absolute value of the difference between the maximum value and the minimum value) in the sample in the intermediate region and the end region of each gas barrier film to the carbon element ratio in the start region Was calculated as an evaluation value. Each evaluation value was as shown in Table 1 above.

  As is clear from Table 1 above, the roller CVD apparatus as an example of the present invention, that is, the roller CVD apparatus (1) provided with the covering member, is more gas than the roller CVD apparatus (2) of the comparative example. It can be seen that the degree of decrease in the gas barrier property is small in the region on the front side, the region on the middle side and the region on the end side of the barrier film, and the degree of change in the carbon element ratio in the XPS depth profile is small. From this, it can be seen that in the roller CVD apparatus (1), even if the gas barrier film is continuously produced, the quality deterioration of the gas barrier film can be prevented.

  By the way, the film forming material diffused in the vacuum chamber 200, which is the object of the above embodiment, is prevented from adhering and depositing on the film forming rollers 31 and 32, and each element component in the gas barrier layer 4 is prevented from being deposited. In order to further promote the purpose of preventing the deterioration of the quality of the gas barrier film 1 by making it possible to provide a concentration gradient as designed, for example, between the film forming rollers 31 and 32 as shown in FIG. It is erected from the bottom surface 201 of the vacuum chamber 200 to below the film forming rollers 31 and 32 so that the resin base material 2 is interposed, and cooperates with a pair of inner wall surfaces of the vacuum chamber 201 to face each other (discharge space). A partition wall 39 surrounding the space from H to the gas discharge port 37 can be provided.

  That is, as shown in FIG. 7, a partition wall 39 is disposed along the gas discharge port 37 on the side of the gas discharge port 37. The partition wall 39 is erected from the bottom surface 201 of the vacuum chamber 200 to at least below the film forming rollers 31 and 32 so that the resin base material 2 is interposed between the film forming rollers 31 and 32. 200 is configured so as to surround the space from the discharge space H to the gas discharge port 37 in cooperation with the pair of inner wall surfaces (front and rear inner wall surfaces not shown in FIG. 7).

  More specifically, the partition wall 39 is provided to rise from the bottom surface 201 of the vacuum chamber 200 to below the film forming rollers 31 and 32, and to bend from the upper end of the rising portion 390. A bent portion 391 that extends in a direction away from the outlet 37 and faces a partial region of the resin base material 2, and a support that stands from the bottom surface of the vacuum chamber 200 and supports the tip of the bent portion 391 from below. Part 392.

  Among these, the bent portion 391 preferably has a length of 5 cm or more, more preferably a length of 20 cm or more, in a plane perpendicular to the axial direction of the film forming rollers 31 and 32 (for example, the paper surface of FIG. 7). Particularly preferably, it has a length of 45 cm or more. In addition, in this vertical surface, it is preferable that the bending part 391 opposes the resin base material 2 over the full length. Further, the bent portion 391 is preferably disposed away from the resin base material 2 by 0.1 to 100 mm, more preferably from the resin base material 2 by 0.1 to 50 mm. Particularly preferably, the resin substrate 2 is arranged at a distance of 0.1 to 25 mm.

The partition wall 39 is detachably provided on the bottom surface of the vacuum chamber 200. The partition wall 39 is preferably made of a material that does not affect the film formation, and the surface on the gas discharge port 37 side is preferably roughened. Here, examples of materials that do not affect the film formation include metal materials such as stainless steel, copper, and aluminum that have been subjected to insulation treatment, and non-materials such as SiO ₂ , Al ₂ O ₃ , B ₂ O ₃ , CaO, and MgO. Examples thereof include synthetic resin materials such as metal materials, polyether ether ketone, polyphenylene sulfide, polyimide, polyamide, and polytetrafluoroethylene. Further, the roughening of the partition walls 39 means that the arithmetic average roughness (center average roughness) defined by JIS B0601-1994 is 1 μm or more. In order to roughen the partition wall 39 in this way, for example, sandblasting or polishing can be used.

  The partition wall 39 is connected to a temperature control unit 395 that maintains the partition wall 39 at a predetermined temperature. The temperature control unit 395 makes it easy for the film forming material to adhere to the surface of the partition wall 39 by maintaining the temperature of the partition wall 39 at a predetermined temperature. Note that the temperature control unit 395 may control the temperature of the partition wall 39 by heat conduction or by radiation. Further, instead of the temperature control unit 395 being connected to the partition wall 39, a potential control unit for controlling the potential of the partition wall 39 may be connected. This potential control unit controls the potential of the partition wall 39 so that the film forming material is easily attached to the partition wall 39.

  As described above, when the partition wall 39 is provided, the pair of inner wall surfaces of the vacuum chamber 200 (the pair of inner wall surfaces extending the film forming rollers 31 and 32 between) and the partition wall 39 cooperate to discharge. Since the space from the space H to the gas discharge port 37 is surrounded, the film forming material to be discharged from the gas discharge port 37 may go around from below the film forming rollers 31 and 32 and diffuse into the vacuum chamber 200. Is prevented. Further, the partition wall 39 is provided with a bent portion 391 provided so as to be bent from the upper end of the rising portion 390 and extending in a direction away from the gas discharge port 37 and facing a partial region of the resin base material 2. Therefore, it is difficult for the film forming material to pass between the partition wall 39 and the film forming rollers 31 and 32 as compared with the case where the bent portion 391 is not provided. In addition, the bent portion 391 has a length of 5 cm or more, preferably 20 cm or more, particularly preferably 45 cm or more in the plane perpendicular to the axial direction of the film forming rollers 31 and 32, and is 0.1 to 100 mm from the resin substrate 2; Preferably, the film-forming material is more difficult to pass between the partition wall 39 and the film-forming rollers 31 and 32 because the distance is preferably 0.1 to 50 mm, particularly preferably 0.1 to 25 mm. Further, the surface of the partition wall 39 on the gas discharge port 37 side is roughened, and the temperature control unit 395 maintains the partition wall 39 at a predetermined temperature, so that the film forming material is likely to adhere to the partition wall 39, It becomes more difficult for the film forming material to pass between the partition wall 39 and the film forming rollers 31 and 32.

  Although not shown in the drawings, the internal space of the vacuum chamber 200 shown in FIGS. 2 and 7 is disposed outside the space surrounded by the partition wall 38, the resin base material 2 and the like, including the plasma discharge space H. Provided with a supply port (not shown) for supplying a non-reactive gas on the side of each roller, that is, on the side of the feed roller 25, the take-up roller 26, the transport rollers 21, 24, and the film forming rollers 31, 32, It is possible to supply the non-reactive gas from the supply port so as not to impair the exhaust capability of the vacuum pump 370.

  If comprised in this way, it will become difficult to flow into the side of each roller, such as the film-forming rollers 31 and 32, by the loose flow of the non-reactive gas supplied from the supply port.

  There is a possibility of use in fields such as gas blocking of electronic devices such as liquid crystals, organic electroluminescence (organic EL), solar cells, and electronic paper.

Claims (11)

A vacuum chamber having at least a pair of inner wall surfaces facing each other;
A pair of resin bases that are arranged to extend between the pair of inner wall surfaces so as to form a facing space with each other and that are wound while being conveyed are opposed to each other through the facing space. A film forming roller;
A magnetic field generating member that is provided inside each film forming roller and generates a swelled magnetic field in the vicinity of a region facing the facing space of the peripheral surface of the film forming roller,
A plasma generating power source connected to the pair of film forming rollers and generating plasma by causing discharge in the facing space;
A gas supply port that is disposed on one of the upper side and the lower side of the opposing space and supplies a film forming gas to the opposing space;
A gas exhaust port disposed on the other of the upper side and the lower side of the opposing space, for exhausting the gas in the opposing space to the outside of the vacuum chamber;
With
In a gas barrier film manufacturing apparatus for forming a gas barrier layer on one surface of the resin substrate by plasma chemical vapor deposition while discharging between the film forming rollers to which a magnetic field is applied,
Of the peripheral surface of the film forming roller, it is exposed without contacting the resin base material, and covers an exposed region adjacent to the contact region with the resin base material in the circumferential direction of the film forming roller. An apparatus for producing a gas barrier film comprising a covering member. The covering member is
2. The gas barrier film manufacturing apparatus according to claim 1, wherein the gas barrier film is formed so as to be curved along a circumferential surface of the film forming roller in a circumferential direction of the film forming roller.   The apparatus for producing a gas barrier film according to claim 1, wherein at least a surface of the covering member opposite to the film forming roller is roughened.   The apparatus for producing a gas barrier film according to any one of claims 1 to 3, further comprising a temperature control unit that maintains the covering member at a predetermined temperature. The covering member is
The apparatus for producing a gas barrier film according to any one of claims 1 to 4, wherein the apparatus is disposed at a position separated from the exposed region by 0.1 to 100 mm. The covering member is
The apparatus for producing a gas barrier film according to claim 5, wherein the apparatus is disposed at a position separated from the exposed region by 0.1 to 50 mm. The covering member is
The apparatus for producing a gas barrier film according to claim 6, wherein the apparatus is disposed at a position separated from the exposed region by 0.1 to 25 mm. The covering member is
The apparatus for producing a gas barrier film according to any one of claims 1 to 7, wherein the apparatus is detachable from the apparatus for producing the gas barrier film.   Standing up from the bottom surface of the vacuum chamber to the bottom of each film forming roller so that the resin base material is interposed between the film forming rollers, and in cooperation with the pair of inner wall surfaces of the vacuum chamber The apparatus for producing a gas barrier film according to any one of claims 1 to 8, further comprising a partition wall surrounding a space from the facing space to the gas discharge port. The pair of film forming rollers disposed outside the space between the pair of inner wall surfaces of the vacuum chamber and including the facing space and surrounded by the partition wall and the resin base material. A supply port for supplying non-reactive gas is provided on the side of each roller including
The non-reactive gas of the grade which does not impair the exhaust capability of the said manufacturing apparatus is supplied from the said supply port, The manufacturing apparatus of the gas barrier film as described in any one of Claims 1-9 characterized by the above-mentioned. A gas barrier film manufacturing method using the gas barrier film manufacturing apparatus according to any one of claims 1 to 10,
The film-forming gas supplied from the gas supply port to the facing space is a film-forming gas containing an organosilicon compound,
Forming a gas barrier layer containing carbon atoms, silicon atoms and oxygen atoms on one surface of the resin substrate by plasma chemical vapor deposition while discharging between the film forming rollers to which a magnetic field is applied. A method for producing a gas barrier film.

Images