JPWO2015060234A1 - Film forming method and film forming apparatus - Google Patents

Abstract

The subject of this invention is providing the film-forming method which suppresses generation | occurrence | production of a wrinkle, maintaining the film characteristic of a functional film. The film forming method of the present invention has at least one set of the following steps (1) to (5). Step (1): Step of supplying a film forming gas to the facing space between the resin substrates to be opposed to each other (2): Step of forming an endless tunnel-like magnetic field swelled in the facing space (3): Opposing Step (4) of generating plasma in the space: Step of forming a thin film layer on the resin substrate by facing the resin substrate (5): Step of exhausting the film forming gas in the facing space

Description

  The present invention relates to a film forming method and a film forming apparatus. More specifically, the present invention relates to a film forming method and a film forming apparatus that suppress the generation of wrinkles while maintaining the film characteristics of a functional film.

  In recent years, various functional films in which a thin film layer is formed on a flexible resin substrate such as a plastic film or a sheet have been proposed because of lightness and cracking. For example, a gas barrier film on which a metal or metal oxide film is formed is used for packaging of articles that require blocking of water vapor, oxygen, etc., especially for packaging for preventing deterioration of food, industrial products, pharmaceuticals, etc. It is widely used and also used in electronic devices such as liquid crystal display elements, photoelectric conversion elements (solar cells), and organic electroluminescence elements (organic EL elements).

In order to improve productivity, such a functional film is manufactured by continuously forming a functional layer as a thin film on a resin base material while conveying a long resin base material. Yes.
For example, a method for producing a gas barrier layer using a vacuum process (see, for example, Patent Document 1), and a method for producing a gas barrier film having a density distribution in an arbitrary layer having an inclined structure in order to improve adhesion. (For example, refer to Patent Document 2), a method of forming a film using a film-forming roller having a magnetic field generator for forming a closed magnetic circuit in order to suppress film deposition in a vacuum chamber (for example, Patent Document 2) 3, etc.) are known.

  However, when the energy input to improve the gas barrier performance is increased, the resin base material loses heat and wrinkles are generated. Accordingly, the composition of the gas barrier layer formed on the resin base material is reduced. As a result, the desired gas barrier performance cannot be obtained, and the color of the normal part without wrinkles is different. As a result, the productivity (yield) is remarkably lowered.

JP 2009-196155 A Japanese Patent No. 4821610 Japanese Patent No. 4268195

  The present invention has been made in view of the above problems and situations, and a solution to the problem is a film forming method and a film forming apparatus capable of suppressing the generation of wrinkles while maintaining the film characteristics of the functional film. Is to provide.

  In order to solve the above problems, the present inventor, in the process of examining the cause of the above problems, etc., in the depth direction of the film by X-ray photoelectron spectroscopy measurement in a predetermined region of the resin substrate on which the thin film layer is formed. In the elemental composition distribution, the absolute value of the difference between the average values of the carbon component ratios in arbitrary portions of the thin film layer is less than 2% with respect to the average value of the carbon component ratios in the wrinkle free portions of the thin film layer By controlling, it discovered that it was possible to provide a film forming method and a film forming apparatus capable of suppressing the generation of wrinkles while maintaining the film characteristics of the functional film, and reached the present invention.

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

1. In a vacuum chamber, a resin base material is disposed oppositely, and a film forming method for forming a thin film layer on the resin base material,
At least one set of the following steps (1) to (5), and
When the electric power input in the set of steps is 1 kW or more per 1 m of the width of the resin base material, the inner area excluding the area of 10 cm from both widthwise ends of the resin base material on which the thin film layer is formed Three or more measurement points are provided at equal intervals along the width direction, and the carbon component at each measurement point in the element composition distribution in the depth direction of the film by X-ray photoelectron spectroscopy measurement at the measurement point. A film forming method, wherein an average value of ratios is calculated, and control is performed so that an absolute value of a difference between the maximum value and the minimum value is less than 2%.
Step (1): Step of supplying a film forming gas to the facing space between the resin bases arranged to face each other Step (2): Step of forming an endless tunnel-like magnetic field swelled in the facing space Step (3) Step of generating plasma in the facing space Step (4): Positioning the resin base material facing each other and forming a thin film layer on the resin base material Step (5): Exhausting the film forming gas in the facing space Process

  2. Before the step of forming the thin film layer, the method includes a step of heating the resin base material, and the temperature difference between the resin base material temperature immediately before film formation and the resin base material in the step of forming the thin film layer The film forming method according to item 1, wherein the temperature is 10 ° C. or lower.

  3. 3. The film forming method according to claim 1, wherein the surface temperature of each film forming roller is increased stepwise from the upstream side to the downstream side in the transport direction.

  4). The film forming method according to any one of Items 1 to 3, wherein the magnetic force of each film forming roller is increased stepwise from the upstream side to the downstream side in the transport direction.

  5. The film forming method according to any one of claims 1 to 4, wherein a surface temperature of the film forming roller is lowered from an axial end portion toward a central portion.

  6). 6. The film forming method according to any one of claims 1 to 5, wherein the magnetic force of the film forming roller is reduced from the axial end toward the center.

  7). The film forming method according to any one of claims 1 to 6, wherein a cross-sectional diameter of the film forming roller is smaller from an axially central portion toward an end portion.

8). In a vacuum chamber, a resin substrate is disposed oppositely, and a film forming apparatus for forming a thin film layer on the resin substrate,
Having at least one set of the following means (1) to (5), and
When the electric power input in the set of means is 1 kW or more per 1 m of the width of the resin base material, the inner area excluding the area of 10 cm from both widthwise ends of the resin base material on which the thin film layer is formed Three or more measurement points are provided at equal intervals along the width direction, and the carbon component at each measurement point in the element composition distribution in the depth direction of the film by X-ray photoelectron spectroscopy measurement at the measurement point. A film forming apparatus, wherein an average value of ratios is calculated and controlled so that an absolute value of a difference between a maximum value and a minimum value thereof is less than 2%.
Means (1): Supply port for supplying a film forming gas to the facing space between the resin bases arranged to face each other Means (2): Magnetic field generator for forming an endless tunnel-like magnetic field swelled in the facing space (3): Power source for generating plasma in the facing space Means (4): A pair of film forming rollers for forming a thin film layer on the resin substrate Means (5): Exhausting the film forming gas in the facing space exhaust port

  9. Before transporting the resin base material to the pair of film forming rollers, a heating device for heating the resin base material is provided, and the resin base material temperature immediately before film formation and the pair of film forming rollers are The film forming apparatus according to item 8, wherein a temperature difference with the resin base material in the step of forming a thin film layer is 10 ° C. or less.

  10. 10. The film forming apparatus according to item 8 or 9, wherein the surface temperature of each film forming roller is increased stepwise from the upstream side to the downstream side in the transport direction.

  11. Item 11. The film formation according to any one of Items 8 to 10, wherein the magnetic force of each of the film formation rollers increases stepwise from the upstream side to the downstream side in the transport direction. apparatus.

  12 The film forming apparatus according to any one of Items 8 to 11, wherein a surface temperature of the film forming roller decreases from an axial end to a center.

  13. 13. The film forming apparatus according to any one of items 8 to 12, wherein a magnetic force of the film forming roller decreases from an axial end to a center.

  14 14. The film forming apparatus according to any one of items 8 to 13, wherein a cross-sectional diameter of the film forming roller decreases from an axially central portion toward an end portion.

  By the above means of the present invention, it is possible to provide a film forming method and a film forming apparatus capable of suppressing the generation of wrinkles while maintaining the film characteristics of the functional film.

  The expression mechanism / action mechanism of the effect of the present invention is not clear, but is presumed as follows.

  The resin base material is a thin film and has characteristics such as flexibility, but on the other hand, it undergoes local heat shrinkage due to a sudden temperature change, and as a result, the composition change of the functional layer formed on the resin base material This causes a problem that the film characteristics are deteriorated. In particular, stress easily accumulates at the center in the width direction of the resin base material, and similarly induces a change in the composition of the functional layer.

  As a method for analyzing an arbitrary elemental composition distribution in the depth direction of the functional layer, a so-called XPS depth is used in combination with measurement by X-ray photoelectron spectroscopy (XPS) and rare gas ion sputtering. Profile measurement is known. In the XPS depth profile, the etching time corresponds to the distance from the functional layer surface.

FIG. 5A shows the measurement of the carbon component ratio in the gas barrier layer on the resin substrate without wrinkles using XPS depth profile measurement. On the other hand, FIG. 5B is a measurement of the carbon component ratio in the gas barrier layer on the wrinkled resin substrate. Note that “wrinkle” in the present invention means that the resin base material is bent or deformed when visually observed.
As can be seen from FIGS. 5A and 5B, the gas barrier layer on the resin substrate with wrinkles is considered to have a carbon component ratio changed and the surface of the gas barrier layer is uneven as a result. It is estimated that the gas barrier performance is also uneven. In addition, in the non-uniform site | part, the color tone with a normal part differs, and productivity has fallen for these reasons.

  In the present invention, three or more measurement points are provided at equal intervals along the width direction in a predetermined region of the resin base material on which the thin film layer is formed, and the film is measured by X-ray photoelectron spectroscopy measurement at the measurement points. By calculating the average value of the carbon component ratio at each measurement point in the element composition distribution in the depth direction, and controlling the absolute value of the difference between the maximum value and the minimum value to be less than 2%, It is considered that the generation of wrinkles could be suppressed while maintaining the film characteristics of the functional film.

1 is a schematic diagram showing a schematic configuration of a film forming apparatus according to a first embodiment. Sectional drawing which shows schematic structure of gas barrier film The schematic diagram which shows schematic structure of the film-forming apparatus which concerns on 2nd Embodiment. Schematic diagram showing an example of uniformity evaluation method for functional film Graph showing an example of the carbon distribution curve of the gas barrier layer Graph showing an example of the carbon distribution curve of the gas barrier layer

  In the film forming method and the film forming apparatus of the present invention, three or more measurement points are provided at equal intervals along the width direction in a predetermined region of the resin base material on which the thin film layer is formed. Of the elemental composition distribution in the depth direction of the film by the line photoelectron spectroscopy measurement, the average value of the carbon component ratio at each measurement point is calculated, and the absolute value of the difference between the maximum value and the minimum value is less than 2%. It controls so that it may become. This feature is a technical feature common to the inventions according to claims 1 to 14.

  As an embodiment of the present invention, from the viewpoint of suppressing local thermal shrinkage due to rapid thermal change, the method includes a step of heating the resin base material before the step of forming the thin film layer, The temperature difference between the material temperature and the resin base material in the step of forming the thin film layer is 10 ° C. or less, and the surface temperature of each film forming roller is increased stepwise from the upstream side to the downstream side in the transport direction. It is preferable to increase the magnetic force of each film forming roller stepwise from the upstream side to the downstream side in the transport direction.

  In addition, since wrinkles on the resin substrate are likely to occur at the center in the width direction, the surface temperature of the film forming roller is lowered from the end in the axial direction toward the center, and the magnetic force of the film forming roller is decreased at the end in the axial direction. It is preferable to decrease from the center toward the center, or to decrease the cross-sectional diameter of the film forming roller from the center in the axial direction toward the end.

  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, "-" showing a numerical range is used by the meaning containing the numerical value described before and behind that as a lower limit and an upper limit.

[First Embodiment]
≪Film formation method≫
The film forming method of the present invention is a film forming method in which a resin base material is arranged oppositely in a vacuum chamber, and a thin film layer is formed on the resin base material. At least one set of the following steps (1) to ( 5), and when the electric power input in the set of steps is 1 kW or more per 1 m of the resin substrate width, a region of 10 cm from both ends in the width direction of the resin substrate on which the thin film layer is formed Three or more measurement points are provided at equal intervals along the width direction in the removed inner region, and each of the element composition distributions in the depth direction of the film by X-ray photoelectron spectroscopy measurement at each measurement point is measured. An average value of the carbon component ratios at the points is calculated, and control is performed such that the absolute value of the difference between the maximum value and the minimum value is less than 2%.

Step (1): Step of supplying a film forming gas to the facing space between the resin substrates to be opposed to each other Step (2): Step of forming an endless tunnel-like magnetic field swelled in the facing space Step (3): Opposing Step of generating plasma in space Step (4): A step of disposing a resin substrate oppositely and forming a thin film layer on the resin substrate Step (5): A step of exhausting a film forming gas in the opposite space

  When the absolute value of the difference between the maximum and minimum average carbon component ratios at each measurement point is 2% or more, the water vapor transmission rate becomes non-uniform, which deviates from the product specifications and is a practical problem. There is.

  Specifically, the control method includes a step of heating the resin base material before the step of forming the thin film layer, the resin base material temperature immediately before the film formation, and the resin base in the step of forming the thin film layer. The temperature difference with the material is 10 ° C. or less. Thereby, rapid expansion of the resin base material due to heat can be reduced, and generation of wrinkles can be suppressed. As a result, it can suppress that a wrinkle part applies a heat locally, and it can suppress that a film quality changes, and the absolute value of the difference of the maximum value and minimum value among the average value of a carbon component ratio will be less than 2%.

  In the present invention, three or more measurement points provided along the width direction are provided on a long functional film from the viewpoint of increasing accuracy (for example, the longitudinal direction of the functional film). The average value of the carbon component ratios at these measurement points is calculated, and the absolute difference between the maximum value and the minimum value is calculated. The value is preferably less than 2%.

  Hereinafter, as a preferable aspect of the film forming method according to the present embodiment, a film forming method including a step of heating before the step of forming the thin film layer will be described.

(I) Step of supplying a film forming gas (step (1))
In the step of supplying the film forming gas, the film forming gas for the functional layer is supplied to the facing space between the resin bases arranged to face each other. For example, when a gas barrier layer made of silicon oxide is formed by oxidizing a silicon compound, a silicon compound gas (raw material gas) and an oxygen gas (reaction gas) are supplied as film forming gases. As the film forming gas to be supplied, a carrier gas can be used as necessary, and a plasma generating gas can be supplied to promote the generation of plasma. Examples of the carrier gas include noble gases such as helium, argon, neon, xenon, and krypton, nitrogen gas, and the like, and examples of the plasma generating gas include hydrogen.
In the present invention, the “opposite space” refers to a space between a pair of film forming rollers 21 and 22 described later (see FIG. 1). Further, “opposing arrangement” in the resin base material means that the resin base material surfaces on which the thin film layers are formed are arranged so as to face each other.

(Ii) Step of forming a magnetic field (step (2))
In the step of forming a magnetic field, a magnetic field in which magnetic lines of force swell is generated in the vicinity of a region facing the facing space on the peripheral surfaces of the film forming rollers 21 and 22. Thereby, the plasma is easily converged, so that the film formation efficiency of the functional layer can be improved.

(Iii) Step of generating plasma (step (3))
In the step of generating plasma, power is generated by supplying power to the film forming rollers 21 and 22 using a conventionally known power source. The plasma is generated along the magnetic field lines of the magnetic field generated in step (2). Therefore, electrons are confined in the discharge space by the electric field and magnetic field in the discharge space (opposing space), high-density plasma is generated, and the film formation rate is improved.

(Iv) Step of heating In the step of heating, the temperature difference between the resin substrate immediately before forming the thin film layer by the pair of film forming rollers 21 and 22 and the resin substrate in the step of forming the thin film layer is 10 Heat to below ℃. Thereby, it can suppress that a resin base material heat-shrinks locally by a rapid thermal change.

(V) Step of forming a thin film layer (step (4))
In the step of forming the thin film layer on the resin base material, the plasma of the supplied source gas is generated by the plasma formed in the facing space between the pair of film forming rollers 21 and 22, and the raw material components are formed on the resin base material. By depositing, a thin film of the functional layer is formed.

(Vi) Step of exhausting the film forming gas (step (5))
In the step of evacuating the deposition gas, the residual gas that has not been used to form the functional layer thin film on the resin base material is exhausted from the vacuum chamber.

  Then, the film-forming apparatus used for the film-forming method of this invention is demonstrated.

≪Film deposition system≫
The film forming apparatus of the present invention is a film forming apparatus for forming a thin film layer on a resin base material by arranging a resin base material facing each other in a vacuum chamber, and at least one set of the following means (1) to ( 5), and when the electric power input by the set of means is set to 1 kW or more per 1 m of the width of the resin substrate, an area of 10 cm from both widthwise ends of the resin substrate on which the thin film layer is formed Three or more measurement points are provided at equal intervals along the width direction in the removed inner region, and each of the element composition distributions in the depth direction of the film by X-ray photoelectron spectroscopy measurement at each measurement point is measured. An average value of the carbon component ratios at the points is calculated, and control is performed such that the absolute value of the difference between the maximum value and the minimum value is less than 2%.

Means (1): Supply port for supplying a film forming gas to the opposing space between the resin substrates to be opposed to each other Means (2): Magnetic field generator for forming an endless tunnel-like magnetic field swelled in the opposing space Means (3 ): Power source for generating plasma in the facing space Means (4): A pair of film forming rollers for forming a thin film layer on the resin substrate Means (5): Exhaust port for exhausting the film forming gas in the facing space

  Specifically, the control method includes a heating device that heats the resin base material before the resin base material is transported to the pair of film forming rollers. The temperature difference with the resin base material in the step of forming the thin film layer using the film forming roller is set to 10 ° C. or less.

More specifically, as the film forming apparatus, a counter roller type film forming apparatus using a plasma CVD method is used.
As shown in FIG. 1, the film forming apparatus A includes a pair of film forming rollers 21 and 22 (means (4)) in a vacuum chamber 10 and a magnetic field generation provided inside the pair of film forming rollers 21 and 22. At least one set of film-forming region 20 provided with apparatuses 23 and 24 (means (2)), power source 25 (means (3)), supply port 26 (means (1)) and exhaust port 27 (means (5)). Have.
A heating device 31 is disposed on the upstream side in the transport direction X of the pair of film forming rollers 21 and 22.
An original winding roller 41 is rotatably disposed on the upstream side in the transport direction X in the vacuum chamber 10, and a winding roller 42 is rotatably disposed on the downstream side in the transport direction X. A transport roller is appropriately disposed between the members (transport rollers 43 to 46).

The film forming apparatus A transports the long resin base material 1 by the film forming rollers 21 and 22 and the transport rollers 43 to 46 under reduced pressure, and the film forming rollers 21 and 22 are transferred onto the transported resin base material 1. Thus, the functional layer is continuously formed.
The long resin substrate 1 is a functional film substrate, and one or more functional layers may already be formed.

  In the vacuum chamber 10, the internal pressure is adjusted under reduced pressure by the vacuum pump 50 when the functional layer is formed. Note that “under reduced pressure” means that the pressure in the vacuum chamber 50 is in the range of 0.01 to 20 Pa.

The pair of film forming rollers 21 and 22 form a functional layer as a thin film on the resin substrate 1 by a plasma CVD method.
Connected to a pair of film forming rollers 21 and 22 arranged to face each other is a supply port 26 for supplying a film forming gas, an exhaust port 27 for evacuating the film forming gas, and a pair of film forming rollers 21 and 22. The power source 25 is disposed.
Each film-forming roller 21 and 22 is a roller which conveys the resin base material 1, and functions also as a pair of electrodes.

Each film forming roller 21 and 22 has a built-in magnetic field generator 23 and 24, respectively.
The magnetic field generators 23 and 24 are fixed in the film forming rollers 21 and 22 so as not to rotate due to the rotation of the film forming rollers 21 and 22.
As the magnetic field generators 23 and 24, normal permanent magnets can be used.

  The pair of film forming rollers 21 and 22 forms a discharge space between the pair of film forming rollers 21 and 22 when a voltage is applied by the power supply 25. When a film forming gas (raw material gas and reaction gas) is supplied into the discharge space through the supply port 26, plasma of the raw material gas is generated, and the raw material components are deposited on the resin substrate 1 facing the discharge space. Since the pair of film forming rollers 21 and 22 form a magnetic field by the built-in magnetic field generators 23 and 24, respectively, plasma is generated along the magnetic field lines of the magnetic field. That is, electrons are confined in the discharge space by the electric field and magnetic field in the discharge space, and high-density plasma is generated, so that the film formation rate is improved.

  Moreover, each film-forming roller 21 and 22 is opposingly arranged so that a rotating shaft may become parallel on the same plane, and conveys the resin base material 1 so that the surface in which a functional layer is formed opposes. Therefore, after a functional layer is formed on the resin base material 1 by the film forming roller 21 on the upstream side in the transport direction X, the functional layer is further formed on the resin base material 1 by the film forming roller 22 on the downstream side in the transport direction X. The film formation rate can be further improved.

The film forming rollers 21 and 22 preferably have the same diameter from the viewpoint of efficiently forming a thin film.
The diameters of the film forming rollers 21 and 22 are preferably in the range of 100 to 1000 mm in diameter φ from the viewpoint of optimization of discharge conditions, space reduction in the vacuum chamber 10 and the like, and in the range of 100 to 700 mm. More preferably, it is within.
When the diameter φ is 100 mm or more, a sufficiently large discharge space can be formed, and a reduction in productivity can be prevented. In addition, a sufficient layer thickness can be obtained by short-time discharge, and the amount of heat applied to the resin substrate 1 at the time of discharge can be suppressed, so that residual stress can be suppressed. If the diameter φ is 1000 mm or less, the uniformity of the discharge space can be maintained, which is practical in device design.

The power supply 25 supplies power to the pair of film forming rollers 21 and 22.
As the power source 25, a conventionally known power source can be used for plasma generation. However, an AC power source that can alternately reverse the polarities of the film forming rollers 21 and 22 improves the film forming rate. This is preferable.
The amount of power supplied from the power supply 25 to the pair of film forming rollers 21 and 22 is preferably in the range of 0.1 to 10 kW per 1 m of the width of the resin base material. If the width is 0.1 kW / m or more, the generation of particles can be suppressed. Moreover, if it is 10 kW / m width or less, the emitted heat amount can be suppressed and the generation | occurrence | production of the wrinkle of the resin base material 1 by a temperature rise can be suppressed. Moreover, when setting it as alternating current power supply, it is preferable that the frequency of alternating current exists in the range of 50 Hz-1 MHz.

The supply port 26 supplies a film forming gas for the functional layer to the discharge space formed between the film forming rollers 21 and 22.
The supply port 26 is equidistant from the film forming rollers 21 and 22 and disposed above the discharge space, and the exhaust port 27 is equidistant from the film forming rollers 21 and 22 and the bottom surface of the vacuum chamber 10. 11 is disposed in a lower region of the discharge space. Accordingly, the film forming gas supplied from the supply port 26 passes through the discharge space between the film forming rollers 21 and 22 and is discharged from the exhaust port 27.

The original winding roller 41 is also called an unwinder, and unwinds the roll body of the resin base material 1.
The transport rollers 43 to 46 are also called guide rollers, and the unwound resin base material 1 is transferred from the original winding roller 41 to the pair of film forming rollers 21 and 22, and from the pair of film forming rollers 21 and 22 to the take-up roller 42. Convey continuously.
The take-up roller 42 is also called a winder and takes up the resin base material 1 formed into a film.

  A conventionally well-known thing can be used as each roller, For example, the roller made from metal or an alloy can be used. A coat layer may be provided on each roller surface.

  As the heating device 31, the resin substrate 1 is a resin substrate 1 immediately before film formation, and the resin substrate 1 in a step of forming a thin film layer using a pair of film formation rollers 21 and 22 (described later). If it can heat so that a temperature difference may be 10 degrees C or less, it will not restrict | limit, Conventionally well-known things, such as a heater, can be used.

  After forming the functional layer, the film forming apparatus A having the above configuration reverses the rotation direction of each roller so that the transport direction X of the resin base material 1 is the reverse direction, and further forms other functional layers. it can.

≪Method for producing functional film≫
Next, a film forming method using the film forming apparatus A will be described.

  First, the roll body of the resin base material 1 is set on the original winding roller 41. A part of the resin base material 1 is unwound from the original winding roller 41, is laid over the transport rollers 43 to 46, the film forming rollers 21 and 22, and is wound up by the winding roller 42.

Thereafter, the vacuum pump 50 is evacuated to reduce the pressure in the vacuum chamber 10.
After sufficiently reducing the pressure in the vacuum chamber 10, the transport of the resin base material 1 is started by the transport rollers 43 to 46 and the film forming rollers 21 and 22.

The conveyance speed (also referred to as line speed) of the resin base material 1 can be appropriately adjusted according to the type of film forming gas, the pressure in the vacuum chamber 10 and the like.
Practically, the conveyance speed of the resin base material 1 is in the range of 0.25 to 100 m / min, and preferably in the range of 0.5 to 30 m / min. If it is 0.25 m / min or more, the resin substrate 1 can be prevented from wrinkling due to heat, and if it is 100 m / min or less, the thickness of the functional layer to be formed is within a desired range. It becomes easy.
From the viewpoint of improving productivity, the transport speed of the resin base material 1 is preferably 5 m / min or more, and more preferably 10 m / min or more.

As the resin substrate 1 starts to be transported, a film forming gas for the functional layer is supplied from the supply port 26 between the film forming rollers 21 and 22 and a voltage is applied to generate plasma. The film forming gas can be supplied together with a carrier gas for transporting the film forming gas, a plasma discharge gas, or the like, as necessary.
Next, before the resin base material 1 is conveyed to the film forming roller 21, it is heated by the heating device 31. Specifically, heating is performed so that the temperature difference between the resin base material 1 immediately before film formation and the resin base material 1 when forming the thin film layer using the film formation roller 21 is 10 ° C. or less.
The resin base material 1 is conveyed to the film forming roller 21 and the raw material components of the functional layer are deposited on the surface of the resin base material 1. The resin base material 1 is sequentially conveyed to the conveyance rollers 44 and 45, and the film-forming roller 22 further deposits the raw material components of the functional layer to form the functional layer as a thin film.
The resin base material 1 on which the functional layer is formed is conveyed by the conveying roller 46 and wound up by the winding roller 42.

In the case where a functional layer is further formed on the resin substrate 1 on which the functional layer has already been provided as described above, a film formation region 20 is further provided following the transport roller 46, and the functionalities are obtained in the same procedure. A layer can be formed.
Also when forming the functional layer by reversing the transport direction of the resin base material 1, the transport order by the transport rollers 43 to 46 and the film forming rollers 21 and 22 is reversed. After the deposition, the same procedure can be followed except that the deposition roller 21 is further deposited.

  The functional film that can be produced by the film forming apparatus A includes a gas barrier film in which a gas barrier layer is formed, an insulating film in which an insulating layer is formed, and a refractive index difference with respect to a substrate. For example, a reflective film in which a thin film is stacked is used. Among them, when the gas barrier layer has many film defects, a gas such as water and oxygen penetrates through the film defects, and the gas barrier performance is remarkably deteriorated. Suitable for production of gas barrier film.

  Hereinafter, a gas barrier film will be described as an example of a functional film.

≪Gas barrier film≫
As shown in FIG. 2, the gas barrier film F includes a resin base material 1 and a gas barrier layer 2 formed on the resin base material 1.

(Resin base material)
The resin base material 1 is a flexible substrate.
The resin base material 1 is preferably a highly transparent resin. When the transparency of the resin is high and the transparency of the resin substrate 1 is high, a highly transparent gas barrier film F can be obtained and can be preferably used for an electronic device such as an organic EL element.

Examples of the resin include methacrylic acid ester, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polycarbonate (PC), polyarylate, polystyrene (PS), aromatic polyamide, polyether ether ketone, polysulfone, polyether sulfone. , Polyimide (PI), polyetherimide and the like. Among these, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polycarbonate (PC) and the like are preferable from the viewpoint of cost and availability.
The resin substrate 1 may have a configuration in which two or more of the above resins are laminated.

  The resin base material 1 can be manufactured by a conventionally known general manufacturing method. For example, an unstretched resin base material 1 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 used as a material is dissolved in a solvent, cast onto an endless metal resin support, dried, and peeled to remove an unstretched film that is substantially amorphous and not oriented. It can be obtained as the substrate 1.

  The unstretched film can be stretched in the film transport (MD) direction or the transverse direction (TD: Transverse Direction) perpendicular to the transport direction, and the resulting stretched film can be used as the resin substrate 1. . Examples of the stretching method include known methods such as uniaxial stretching, tenter sequential biaxial stretching, tenter simultaneous biaxial stretching, and tubular simultaneous biaxial stretching. Although a draw ratio can be suitably selected according to resin used as a raw material, both the conveyance direction and the width direction are preferably in the range of 2 to 10 times.

  The resin substrate 1 may be the above-described unstretched film or a stretched film. A stretched film is preferable from the viewpoint of strength improvement and thermal expansion suppression. Since optical functions such as retardation of the resin substrate 1 can be adjusted by stretching, it is preferable to use a stretched film when adjustment is required.

In order to obtain dimensional stability, the resin base material 1 may be subjected to relaxation treatment, offline heat treatment, and the like.
The relaxation treatment is preferably carried out in the tenter that is heat-set in the stretching step and then in the tenter that extends in the width direction or until the winding after the tenter exits. The relaxation treatment is preferably performed at a treatment temperature in the range of 80 to 200 ° C, and more preferably in the range of 100 to 180 ° C.
The off-line heat treatment method is not particularly limited. For example, a method of transporting by a roller transport method using a plurality of roller groups, a method of transporting air by blowing air on a film, and the like (specifically, heated air from a plurality of slits) For example, a method of spraying the film on one or both sides of the film surface), a method of using radiant heat from an infrared heater or the like, a conveying method of hanging the film under its own weight and winding it down. Good dimensional stability can be obtained by lowering the conveyance tension of the heat treatment as much as possible to promote thermal shrinkage. As the treatment temperature, a temperature range of (Tg + 50) to (Tg + 150) ° C. is preferable. Here, Tg refers to the glass transition temperature of the resin substrate 1.

  The resin base material 1 preferably has a thickness in the range of 5 to 500 μm, and more preferably in the range of 25 to 250 μm.

In the resin base material 1, a clear hard coat layer may be formed on the surface in order to improve adhesion with the gas barrier layer 2 formed on the resin base material 1.
As the clear hard coat layer, a curable resin such as a thermosetting resin or an active energy ray curable resin curable resin can be used. Of these, active energy ray-curable resins are preferred because they are easy to mold.

  The thermosetting resin is not particularly limited, and examples thereof include various thermosetting resins such as epoxy resins, cyanate ester resins, phenol resins, bismaleimide-triazine resins, polyimide resins, acrylic resins, and vinylbenzyl resins. .

  Any epoxy resin may be used as long as it has an average of two or more epoxy groups per molecule. Specifically, it is a bisphenol A type epoxy resin, a biphenyl type epoxy resin, a biphenyl aralkyl type epoxy resin, or a naphthol type epoxy. Resin, naphthalene type epoxy resin, bisphenol F type epoxy resin, phosphorus-containing epoxy resin, bisphenol S type epoxy resin, aromatic glycidylamine type epoxy resin (specifically, tetraglycidyldiaminodiphenylmethane, triglycidyl-p-aminophenol, Diglycidyl toluidine, diglycidyl aniline, etc.), alicyclic epoxy resin, aliphatic chain epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, bisphenol A novolac epoxy resin , Epoxy resin having a butadiene structure, phenol aralkyl type epoxy resin, epoxy resin having a dicyclopentadiene structure, diglycidyl etherified product of bisphenol, diglycidyl etherified product of naphthalenediol, glycidyl etherified product of phenol, diglycidyl alcohol Examples include etherified products, alkyl-substituted products of these epoxy resins, halides, hydrogenated products, and the like. These may be used alone or in combination of two or more.

The active energy ray-curable resin is a resin that is cured through a crosslinking reaction or the like by irradiation with active rays such as ultraviolet rays and electron beams.
Typical examples of the active energy ray curable resin include an ultraviolet curable resin, an electron beam curable resin, and the like, and among these, an ultraviolet curable resin is preferable.

  Examples of the ultraviolet curable resin include an ultraviolet curable urethane acrylate resin, an ultraviolet curable polyester acrylate resin, an ultraviolet curable epoxy acrylate resin, an ultraviolet curable polyol acrylate resin, and an ultraviolet curable epoxy resin. Can do.

  The UV curable acrylic urethane resin generally has a hydroxyl group such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate and the like obtained by reacting a polyester polyol with an isocyanate monomer or a prepolymer. It can be easily obtained by reacting an acrylate monomer having For example, the resin described in JP-A-59-151110 can be used.

  Examples of the UV curable polyester acrylate resin include resins that are easily formed when 2-hydroxyethyl acrylate and 2-hydroxy acrylate monomers are generally reacted with polyester polyol. For example, a resin described in JP-A-59-151112 can be used.

  Specific examples of the ultraviolet curable epoxy acrylate resin include resins formed by reacting epoxy acrylate as an oligomer and adding a reactive diluent and a photoinitiator to the oligomer. The resin described in Japanese Patent No. 105738 can be used.

  Examples of ultraviolet curable polyol acrylate resins include polyfunctional acrylate resins. Here, the polyfunctional acrylate resin is a compound having two or more acryloyloxy groups or methacryloyloxy groups in the molecule.

  Examples of the monomer of the polyfunctional acrylate resin include ethylene glycol diacrylate, diethylene glycol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylolethane triacrylate, and tetramethylolmethane. Triacrylate, tetramethylolmethane tetraacrylate, pentaglycerol triacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, glycerin triacrylate, dipentaerythritol triacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate , Dipen Erythritol hexaacrylate, tris (acryloyloxyethyl) isocyanurate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, tetra Methylol methane trimethacrylate, tetramethylol methane tetramethacrylate, pentaglycerol trimethacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, glycerol trimethacrylate, dipentaerythritol trimethacrylate, dipentaerythritol te La methacrylate, dipentaerythritol penta methacrylate, dipentaerythritol hexa methacrylate. These compounds are used alone or in admixture of two or more. Moreover, oligomers, such as a dimer and a trimer of the said monomer, may be sufficient.

  Examples of commercially available UV-curable resins that can be used include ADEKA OPTMER KR / BY series: KR-400, KR-410, KR-550, KR-566, KR-567, BY-320B (above, Asahi) (Manufactured by Denka), Koeihard A-101-KK, A-101-WS, C-302, C-401-N, C-501, M-101, M-102, T-102, D-102, NS -101, FT-102Q8, MAG-1-P20, AG-106, M-101-C (manufactured by Guangei Chemical Co., Ltd.), Seika Beam PHC2210 (S), PHC X-9 (K-3), PHC2213, DP -10, DP-20, DP-30, P1000, P1100, P1200, P1300, P1400, P1500, P1600, SCR900 (above, Daiichi Seika Kogyo Co., Ltd.) ), KRM7033, KRM7039, KRM7130, KRM7131, UVECRYL29201, UVECRYL29202 (above, manufactured by Daicel UCB), RC-5015, RC-5016, RC-5020, RC-5031, RC-5100, RC-5102, RC- 5120, RC-5122, RC-5152, RC-5171, RC-5180, RC-5181 (above, manufactured by DIC), Aulex No. 340 clear (above, China Paint Co., Ltd.), Sun Rad H-601, RC-750, RC-700, RC-600, RC-500, RC-611, RC-612 (above, Sanyo Chemical Industries Co., Ltd.), SP -1509, SP-1507 (above, Showa Polymer Co., Ltd.), RCC-15C (Grace Japan Co., Ltd.), Aronix M-6100, M-8030, M-8060 (above, Toagosei Co., Ltd.), Purple UV -1700B (manufactured by Nippon Synthetic Chemical).

The ultraviolet curable resin is preferably used together with a photopolymerization initiator in order to accelerate curing.
As the photopolymerization initiator, a group of double salts of onium salts that release a Lewis acid that initiates cationic polymerization by light irradiation is particularly preferable.

As such an onium salt, it is particularly effective to use an aromatic onium salt as a cationic polymerization initiator, and in particular, those described in JP-A Nos. 50-151996, 50-158680, etc. Aromatic halonium salts, Group VIA aromatic onium salts described in JP-A-50-151997, JP-A-52-30899, JP-A-59-55420, JP-A-55-125105, etc. 8428, 56-149402, 57-192429, etc., aromatic diazonium salts described in JP-B-49-17040, US Pat. No. 4,139,655, etc. The thiopyrylium salts described are preferred. Moreover, an aluminum complex, a photodegradable silicon compound type | system | group polymerization initiator, etc. can be mentioned. The cationic polymerization initiator can be used in combination with a photosensitizer such as benzophenone, benzoin isopropyl ether, or thioxanthone.
It is preferable that the usage-amount of a photoinitiator exists in the range of 2-30 mass% with respect to ultraviolet curable resin.

In order for the clear hard coat layer to improve the adhesion to the resin base material 1, the surface of the resin base material 1 is irradiated with vacuum ultraviolet rays or surface-treated by corona discharge, and then the clear hard coat layer is applied with a coating liquid. It can be formed by curing.
As a coating method, a wet process such as a coating method using a gravure coater, a dip coater, a reverse coater, a wire bar coater, a die coater, or the like, or an inkjet method can be used.
The clear hard coat layer coating solution is suitably applied within a range of 0.1 to 40.0 μm as a wet film thickness, and preferably within a range of 0.5 to 30.0 μm. The layer thickness after drying is preferably in the range of 0.1 to 30.0 μm, more preferably in the range of 1 to 10 μm.

As the light source used for curing the ultraviolet curable resin, any light source that generates ultraviolet light can be used without limitation. For example, a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a carbon arc lamp, a metal halide lamp, a xenon lamp, or the like can be used. Although the irradiation conditions differ depending on each lamp, the irradiation amount of the active energy ray is preferably in the range of 5 to 100 mJ / cm ² , particularly preferably in the range of ^{20 to} 80 mJ / cm ² .

(Gas barrier layer)
The gas barrier layer 2 has gas barrier properties.
Specifically, the gas barrier layer 2 has a water vapor permeability (25 ± 0.5 ° C., relative humidity 90 ± 2% RH) measured by a method according to JIS K 7129: 1992 of 1 × 10 ^−2. It is preferable to exhibit gas barrier properties of g / (m ² · day) or less. Further, the oxygen permeability measured by a method according to JIS K 7126: 1987 is 1 × 10 ⁻³ ml / (m ² · day · atm) or less, and the water vapor permeability is 1 × 10 ⁻⁵ g / It is more preferable that the gas barrier property is (m ² · day) or less.

  The material of the gas barrier layer 2 may be any material that has a function of suppressing the ingress of gas such as water and oxygen that causes performance deterioration of the electronic device using the gas barrier film F. Examples of the material for the gas barrier layer 2 include inorganic silicon compounds such as silicon oxide, silicon oxynitride, silicon dioxide, and silicon nitride, and organic silicon compounds.

In particular, the gas barrier layer 2 is preferably formed by oxidizing or nitriding a gas in which an organosilicon compound is vaporized.
Examples of the organosilicon compound include hexamethyldisiloxane, 1,1,3,3-tetramethyldisiloxane, vinyltrimethylsilane, methyltrimethylsilane, hexamethyldisilane, methylsilane, dimethylsilane, trimethylsilane, diethylsilane, propyl Examples thereof include silane, phenylsilane, vinyltriethoxysilane, vinyltrimethoxysilane, tetramethoxysilane, tetraethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, and octamethylcyclotetrasiloxane. Among these, hexamethyldisiloxane and 1,1,3,3-tetramethyldisiloxane are preferable from the viewpoint of easy handling and obtaining excellent gas barrier properties.
These organosilicon compounds can be used individually by 1 type or in combination of 2 or more types.

For example, when hexamethyldisiloxane (organosilicon compound: HMDSO: (CH ₃ ) ₆ Si ₂ O) and oxygen (O ₂ ) are used as a film forming gas, the film is formed by a pair of film forming rollers 21 and 22. In the discharge region, the reaction shown in the following reaction formula occurs, and silicon dioxide is generated.

(CH ₃ ) ₆ Si ₂ O + 12O ₂ → 6CO ₂ + 9H ₂ O + 2SiO ₂

  In the above reaction, the amount of oxygen required to completely oxidize 1 mol of hexamethyldisiloxane is 12 mol. Here, when the gas flow rate of oxygen gas is controlled to a gas flow rate equal to or less than the number of moles of oxygen necessary for complete oxidation, and a non-complete reaction is performed, carbon atoms in hexamethyldisiloxane that have not been completely oxidized are obtained. And hydrogen atoms can be taken into the gas barrier layer 2. Thereby, the atomic composition ratio in the gas barrier layer 2 can be adjusted.

≪X-ray photoelectron spectroscopy≫
The composition distribution of each layer constituting the functional film is sequentially measured while exposing the inside of the sample by using X-ray photoelectron spectroscopy (XPS) and rare gas ion sputtering such as argon in combination. It can be created by so-called XPS depth profile measurement in which surface composition analysis is performed. 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 in this way, the etching time generally correlates with the distance (L) from the surface in the layer thickness direction, so that the etching rate employed in the XPS depth profile measurement is used. The value calculated from the relationship between the etching time and the etching time can be adopted as the “distance from the surface in the layer thickness direction”.
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 an etching rate (etching rate) is 0.05 nm / sec. It is preferable to be (SiO ₂ thermal oxide equivalent value).

[Second Embodiment]
Compared with the first embodiment, the second embodiment is a film forming method in which a resin base material is arranged oppositely in a vacuum chamber and a thin film layer is formed on the resin base material. The width of the resin base material on which the thin film layer is formed when the electric power input in the set of steps is 1 kW or more per 1 m of the resin base material width. Three or more measurement points are provided at equal intervals along the width direction in the inner region excluding the 10 cm region from both ends in the direction of the film, and in the depth direction of the film by X-ray photoelectron spectroscopy measurement at the measurement points The element composition distribution is common in that the average value of the carbon component ratio at each measurement point is calculated and controlled so that the absolute value of the difference between the maximum value and the minimum value is less than 2%. The main differences from the first embodiment are as follows. In the present embodiment, the same parts as those in the first embodiment are denoted by the same reference numerals.

  Specifically, as the control method in the present embodiment, (i) the surface temperature of each film forming roller is increased stepwise from the upstream side to the downstream side in the transport direction, and (ii) each film forming roller. (Iii) Decreasing the surface temperature of the film forming roller from the axial end to the center, (iv) Film forming The magnetic force of the roller is decreased from the axial end portion toward the central portion, or (v) the cross-sectional diameter of the film forming roller is decreased from the axial central portion toward the end portion.

According to the control method (i), the rapid expansion of the resin base material due to heat can be reduced, and the generation of wrinkles can be suppressed. As a result, it can suppress that a wrinkle part applies a heat locally, and it can suppress that a film quality changes, and the absolute value of the difference of the maximum value and minimum value among the average value of a carbon component ratio will be less than 2%.
The reason is that once the resin base material enters the plasma space and is heated, it becomes strong against heat, and no wrinkle is generated even if there is a temperature change of 20 ° C. or more.
In addition, it is preferable to raise the temperature by dividing into three or more stages until the predetermined temperature is reached.

According to the control method (ii), it is possible to increase the plasma intensity by improving the magnetic force, reduce the rapid expansion of the resin base material due to the heat generated therewith, and suppress the generation of wrinkles. As a result, it can suppress that a wrinkle part applies a heat locally, and it can suppress that a film quality changes, and the absolute value of the difference of the maximum value and minimum value among the average value of a carbon component ratio will be less than 2%.
In addition, it is preferable to divide | segment into three steps or more and to improve a magnetic force until it becomes a predetermined magnetic force.

  According to the control method (iii), when the resin base material is deformed by heat, the stress is concentrated most in the vicinity of the center of the width of the resin base material. Rapid expansion of the resin base material can be reduced, and generation of wrinkles can be suppressed. As a result, it can suppress that a wrinkle part applies a heat locally, and it can suppress that a film quality changes, and the absolute value of the difference of the maximum value and minimum value among the average value of a carbon component ratio will be less than 2%.

  According to the control method (iv), when the resin base material is deformed by heat, the stress is concentrated most in the vicinity of the center of the width of the resin base material. By reducing the temperature and lowering the temperature, rapid expansion of the resin base material due to heat can be reduced, and generation of wrinkles can be suppressed. As a result, it can suppress that a wrinkle part applies a heat locally, and it can suppress that a film quality changes, and the absolute value of the difference of the maximum value and minimum value among the average value of a carbon component ratio will be less than 2%.

  According to the control method (v), when the resin base material is deformed by heat, the stress is concentrated most in the vicinity of the center of the width of the resin base material. High tension can be achieved, and the occurrence of wrinkles can be suppressed even if the resin base material is suddenly expanded by heat. As a result, it can suppress that a wrinkle part applies a heat locally, and it can suppress that a film quality changes, and the absolute value of the difference of the maximum value and minimum value among the average value of a carbon component ratio will be less than 2%.

  Hereinafter, a counter roller type film forming apparatus using the plasma CVD method used in the present embodiment will be described.

  As shown in FIG. 3, the film forming apparatus B includes a pair of film forming rollers 210 and 220 in the vacuum chamber 10, magnetic field generators 23 and 24 provided inside the pair of film forming rollers 210 and 220, and a power supply 25. And at least one set of the film forming region 20 provided with the supply port 26 and the exhaust port 27.

  The surface temperatures of the film forming rollers 210 and 220 are increased stepwise from the upstream side in the transport direction X toward the downstream side with the Tg of the resin base material 1 as a limit. That is, the surface temperature of the film forming roller 220 is set to be higher than the surface temperature of the film forming roller 210.

  Instead of the surface temperature of the film forming rollers 210 and 220, the magnetic force of the film forming rollers 210 and 220 may be set to increase stepwise.

Further, for each of the film forming rollers 210 and 220, the surface temperature may be set lower from the axial end portion toward the center portion, or the magnetic force may be set lower.
Examples of the method of changing the surface temperatures of the film forming rollers 210 and 220 along the axial direction include a method of introducing induction coils different in the axial direction in the induction heating type jacket roller.
Examples of a method of changing the magnetic force of the film forming rollers 210 and 220 along the axial direction include a method of introducing permanent magnets having different magnetic forces in the axial direction into the film forming rollers 210 and 220.
The width direction of the resin substrate 1 and the axial direction of the film forming rollers 210 and 220 indicate the same direction.

  In addition, for the purpose of increasing the tensile strength from the center in the width direction toward the end of the resin base material 1, drum-shaped ones may be used as the film forming rollers 210 and 220. That is, the drum-shaped film forming rollers 210 and 220 have a diameter (cross-sectional diameter) that decreases when cut along the rotation direction from the center in the axial direction toward the end.

  Each aspect of the film forming rollers 210 and 220 described above can be used alone or in combination. Moreover, it is also possible to use together with the configuration (heating device) in the first embodiment.

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

≪Preparation of gas barrier laminated film≫
(1) Production of Gas Barrier Laminate Film 1 As a film deposition apparatus, a gas barrier multilayer film is used by using a plasma CVD apparatus having two sets of heating apparatus of film deposition apparatus A and film deposition region 20 of film deposition apparatus B. 1-13 were produced.

First, a biaxially stretched polyethylene naphthalate film (PEN film, thickness: 100 μm, width: 350 mm, manufactured by Teijin DuPont Films, Inc., trade name “Teonex Q65FA”) is used as a base material, and this is attached to the original winding roller. did.
Next, plasma is generated between the pair of film forming rollers, and a film forming gas (raw material gas: hexamethyldisiloxane (HMDSO) and reaction gas: oxygen gas (also functions as a discharge gas) is generated in this discharge region. The gas mixture is adjusted to be different in the width direction so that the supply amount ratio is width direction end region / width direction non-end region = 1.05 / 1, and a thin film is formed by plasma CVD. A gas barrier laminate film having a thickness of 600 nm in the width direction non-end region was obtained.
The film forming conditions were set as follows.

Deposition gas mixture ratio (hexamethyldisiloxane / oxygen): 1/10
Degree of vacuum in the vacuum chamber: 3Pa
Applied voltage from power supply for plasma generation: ± 1.0 kV
Frequency of power source for plasma generation: 70 kHz
Film transport speed: 0.5 m / min
Input power: 3 kW / m width film forming roller surface temperature: 30 ° C.
Magnetic force of film forming roller: shape of reference film forming roller (center diameter / end diameter): 1
Temperature of the substrate heated by the heating device before entering the film forming roller: 60 ° C

(2) Manufacture of gas barrier laminate film 2 In preparation of gas barrier laminate film 1, the same applies except that the temperature of the substrate heated by the heating device before entering the film forming roller was changed to 55 ° C. A gas barrier laminated film 2 was produced.

(3) Manufacture of gas barrier laminate film 3 In preparation of gas barrier laminate film 1, the same applies except that the temperature of the substrate heated by the heating device before entering the film forming roller was changed to 50 ° C. A gas barrier laminate film 3 was produced.

(4) Preparation of gas barrier laminate film 4 Gas barrier laminate film 4 was prepared in the same manner as in preparation of gas barrier laminate film 1 except that the film formation conditions were changed as follows.

Deposition gas mixture ratio (hexamethyldisiloxane / oxygen): 1/10
Degree of vacuum in the vacuum chamber: 3Pa
Applied voltage from power supply for plasma generation: ± 1.0 kV
Frequency of power source for plasma generation: 70 kHz
Film transport speed: 0.5 m / min
Input power: Surface temperature of 3 kW / m width film forming roller: (Upstream side) 0 ° C. → 20 ° C. → 40 ° C. → 50 ° C. (Downstream side)
Magnetic force of film forming roller: shape of reference film forming roller (center diameter / end diameter): 1
Temperature of the substrate heated by the heating device before entering the film forming roller: 25 ° C.

(5) Production of Gas Barrier Laminate Film 5 In production of the gas barrier laminate film 4, the surface temperature of the film forming roller is 5 ° C. → 30 ° C. → 50 ° C. → 70 ° C. from the upstream side to the downstream side in the transport direction. A gas barrier laminate film 5 was produced in the same manner except that the above was changed.

(6) Production of gas barrier laminate film 6 A gas barrier laminate film 6 was produced in the same manner as in the production of the gas barrier laminate film 1 except that the film formation conditions were changed as follows.

Deposition gas mixture ratio (hexamethyldisiloxane / oxygen): 1/10
Degree of vacuum in the vacuum chamber: 3Pa
Applied voltage from power supply for plasma generation: ± 1.0 kV
Frequency of power source for plasma generation: 70 kHz
Film transport speed: 0.5 m / min
Input power: 3 kW / m width film forming roller surface temperature: 30 ° C.
Magnetic force of film forming roller: (Upstream side) x 50% → x 85% → x 115% → x 150% (downstream side)
Deposition roller shape (center diameter / end diameter): 1
Temperature of the substrate heated by the heating device before entering the film forming roller: 25 ° C.

(7) Production of Gas Barrier Laminate Film 7 In production of the gas barrier laminate film 6, x75% → x100% → from the upstream side to the downstream side in the transport direction with respect to the magnetic force of the film forming roller. A gas barrier laminate film 7 was produced in the same manner except that x150% was changed to x200%.

(8) Production of Gas Barrier Laminate Film 8 Gas barrier laminate film 8 was produced in the same manner as in production of gas barrier laminate film 1 except that the film formation conditions were changed as follows.

Deposition gas mixture ratio (hexamethyldisiloxane / oxygen): 1/10
Degree of vacuum in the vacuum chamber: 3Pa
Applied voltage from power supply for plasma generation: ± 1.0 kV
Frequency of power source for plasma generation: 70 kHz
Film transport speed: 0.5 m / min
Input power: 3 kW / m width film forming roller surface temperature: 30 ° C.
Magnetic force of film forming roller: shape of reference film forming roller (center part diameter / end part diameter): 1.02
Temperature of substrate heated by heating device before entering film forming roller: 50 ° C

(9) Preparation of gas barrier laminate film 9 In preparation of the gas barrier laminate film 8, except that the film formation roller was changed to a film formation roller having a central part diameter / end part diameter of 1.05, A gas barrier laminate film 9 was produced.

(10) Production of Gas Barrier Laminate Film 10 Gas barrier laminate film 10 was produced in the same manner as in production of gas barrier laminate film 1 except that the film formation conditions were changed as follows.

Deposition gas mixture ratio (hexamethyldisiloxane / oxygen): 1/10
Degree of vacuum in the vacuum chamber: 3Pa
Applied voltage from power supply for plasma generation: ± 1.0 kV
Frequency of power source for plasma generation: 70 kHz
Film transport speed: 0.5 m / min
Input power: 0.5 kW / m width film forming roller surface temperature: 30 ° C.
Magnetic force of film forming roller: shape of reference film forming roller (center diameter / end diameter): 1
Temperature of the substrate heated by the heating device before entering the film forming roller: 25 ° C.

(11) Production of Gas Barrier Laminate Film 11 Gas barrier laminate film 11 was produced in the same manner as in production of gas barrier laminate film 1 except that the film formation conditions were changed as follows.

Deposition gas mixture ratio (hexamethyldisiloxane / oxygen): 1/10
Degree of vacuum in the vacuum chamber: 3Pa
Applied voltage from power supply for plasma generation: ± 1.0 kV
Frequency of power source for plasma generation: 70 kHz
Film transport speed: 0.5 m / min
Input power: 3 kW / m width film forming roller surface temperature: 30 ° C.
Magnetic force of film forming roller: shape of reference film forming roller (center diameter / end diameter): 1
Temperature of the substrate heated by the heating device before entering the film forming roller: 25 ° C.

(12) Production of Gas Barrier Laminate Film 12 Gas barrier laminate film 12 was produced in the same manner as in production of gas barrier laminate film 1 except that the film formation conditions were changed as follows.

Deposition gas mixture ratio (hexamethyldisiloxane / oxygen): 1/10
Degree of vacuum in the vacuum chamber: 3Pa
Applied voltage from power supply for plasma generation: ± 1.0 kV
Frequency of power source for plasma generation: 70 kHz
Film transport speed: 0.5 m / min
Input power: 3 kW / m width film forming roller surface temperature: 30 ° C.
Magnetic force of film forming roller: shape of reference film forming roller (center diameter / end diameter): 1
Temperature of the substrate heated by the heating device before entering the film forming roller: 40 ° C

≪Evaluation of gas barrier laminate film≫
(1) Evaluation of water vapor transmission rate (WVTR performance)
About each produced gas-barrier laminated | multilayer film, the water-vapor-permeation rate was computed with the following measuring methods.

(apparatus)
Vapor deposition device: JE-400, a vacuum vapor deposition device manufactured by JEOL Ltd.
Constant temperature and humidity oven: Yamato Humidic Chamber IG47M
(raw materials)
Metal that reacts with water and corrodes: Calcium (granular)
Water vapor-impermeable metal: Aluminum (φ3-5mm, granular)

(Preparation of water vapor barrier property evaluation cell)
Using a vacuum vapor deposition device (JEOL-made vacuum vapor deposition device JEE-400), mask the gas barrier laminated film sample other than the part to be vapor-deposited before applying the transparent conductive film (9 locations of 12 mm x 12 mm), and use metallic calcium Was evaporated. Thereafter, the mask was removed in a vacuum state, and aluminum was deposited from another metal deposition source on the entire surface of one side of the sheet. After aluminum sealing, the vacuum state is released, and immediately facing the aluminum sealing side through a UV-curable resin for sealing (made by Nagase ChemteX) on quartz glass with a thickness of 0.2 mm in a dry nitrogen gas atmosphere The cell for evaluation was produced by irradiating with ultraviolet rays.
The obtained sample with both sides sealed is stored at 60 ° C. and 90% RH under high temperature and high humidity, and moisture permeated into the cell from the corrosion amount of metallic calcium based on the method described in JP-A-2005-283561. The amount was calculated. From the obtained water content, it evaluated according to the following reference | standard.
The evaluation results are shown in Table 1.

A: Less than 1 × 10 ⁻² g / (m ² · day) ○: 1 × 10 ⁻² g / (m ² · day) or more and 1 × 10 ⁻¹ g / (m ² · day) or less ×: 1 × More than 10 ⁻¹ g / (m ² · day)

(2) Uniformity evaluation A method for evaluating the uniformity of each gas barrier laminate film obtained will be described with reference to FIG.
With respect to the obtained CVD film, the XPS depth profile was measured, and the average value of the carbon component ratio in the elemental composition in the depth direction of the film was calculated.
Specifically, in the region T excluding 10 cm from both ends of the substrate width direction Y, the product effective length in the transport direction X, 1 m from the front and rear ends, and the center, Five measurement points (symbols Ma, Mb, and Mc in FIG. 4 respectively) were provided at equal intervals in the width direction Y, and the average value of the carbon component ratio at each measurement point was measured. As the sputtering method, a rare gas ion sputtering method using argon (Ar ⁺ ) as an etching ion species was adopted, and the etching rate was set to 0.05 nm / sec (converted to a SiO ₂ thermal oxide film). Here, the product effective length refers to the length in the transport direction X of an area where various manufacturing conditions are stable.
Of the average value of the carbon component ratio at each measurement point, the absolute value of the difference between the maximum value and the minimum value was calculated and evaluated according to the following criteria.
The evaluation results are shown in Table 1.

◎: 0% or more and less than 1% ○: 1% or more and less than 2% △: 2% or more and less than 4% ×: 4% or more

  In Table 1, from the upstream side to the downstream side in the transport direction, the film forming roller No. 1 to film forming roller No. 1 4

(3) Summary As is clear from Table 1, the gas barrier laminate films 1-9 produced using the film forming apparatus of the present invention are more gas barrier than the gas barrier laminate films 10-12. It can be seen that the element composition distribution in the depth direction of the film is excellent and uniform. In particular, the gas barrier laminate film 10 is inferior in gas barrier properties because the input power is small, and in the gas barrier laminate films 11 and 12, the resin base material immediately before film formation and the resin in the step of forming a thin film layer are used. Since the temperature difference with the substrate was 10 ° C. or more, the carbon composition distribution was not uniform.

  From the above, three or more measurement points are provided at equal intervals along the width direction in the inner area excluding the 10 cm area from both widthwise ends of the resin base material on which the thin film layer is formed. Of the elemental composition distributions in the depth direction of the film measured by X-ray photoelectron spectroscopy, the average value of the carbon component ratio at each measurement point is calculated, and the absolute value of the difference between the maximum value and the minimum value is 2% It was confirmed that control to be less than the value was useful for suppressing the generation of wrinkles while maintaining the film characteristics of the functional film.

  INDUSTRIAL APPLICABILITY The present invention can be particularly suitably used for providing a film forming method and a film forming apparatus capable of suppressing the generation of wrinkles while maintaining the film characteristics of a functional film.

DESCRIPTION OF SYMBOLS 1 Resin base material 2 Gas barrier layer 10 Vacuum chamber 11 Bottom surface 20 Film-forming area | region 21, 22, 210, 220 Film-forming roller 23, 24 Magnetic field generator 25 Power supply 26 Supply port 27 Exhaust port 31 Heating device 41 Original winding roller 42 Winding rollers 43 to 46 Conveying roller 50 Vacuum pump A, B Film forming device F Gas barrier film Ma, Mb, Mc Measuring point T Area X Conveying direction Y Width direction

Claims (14)

In a vacuum chamber, a resin base material is disposed oppositely, and a film forming method for forming a thin film layer on the resin base material,
At least one set of the following steps (1) to (5), and
When the electric power input in the set of steps is 1 kW or more per 1 m of the width of the resin base material, the inner area excluding the area of 10 cm from both widthwise ends of the resin base material on which the thin film layer is formed Three or more measurement points are provided at equal intervals along the width direction, and the carbon component at each measurement point in the element composition distribution in the depth direction of the film by X-ray photoelectron spectroscopy measurement at the measurement point. A film forming method, wherein an average value of ratios is calculated, and control is performed so that an absolute value of a difference between the maximum value and the minimum value is less than 2%.
Step (1): Step of supplying a film forming gas to the facing space between the resin bases arranged to face each other Step (2): Step of forming an endless tunnel-like magnetic field swelled in the facing space Step (3) Step of generating plasma in the facing space Step (4): Positioning the resin base material facing each other and forming a thin film layer on the resin base material Step (5): Exhausting the film forming gas in the facing space Process   Before the step of forming the thin film layer, the method includes a step of heating the resin base material, and the temperature difference between the resin base material temperature immediately before film formation and the resin base material in the step of forming the thin film layer The film forming method according to claim 1, wherein the temperature is set to 10 ° C. or lower.   The film forming method according to claim 1, wherein the surface temperature of each of the film forming rollers is increased stepwise from the upstream side to the downstream side in the transport direction.   4. The film forming method according to claim 1, wherein the magnetic force of each of the film forming rollers is increased stepwise from the upstream side to the downstream side in the transport direction.   The film forming method according to any one of claims 1 to 4, wherein a surface temperature of the film forming roller is lowered from an axial end portion toward a central portion.   The film forming method according to any one of claims 1 to 5, wherein the magnetic force of the film forming roller is reduced from an axial end toward a center.   The film forming method according to any one of claims 1 to 6, wherein a cross-sectional diameter of the film forming roller is small from an axially central portion toward an end portion. In a vacuum chamber, a resin substrate is disposed oppositely, and a film forming apparatus for forming a thin film layer on the resin substrate,
Having at least one set of the following means (1) to (5), and
When the electric power input in the set of means is 1 kW or more per 1 m of the width of the resin base material, the inner area excluding the area of 10 cm from both widthwise ends of the resin base material on which the thin film layer is formed In addition, three or more measurement points are provided at equal intervals along the width direction, and each of the above-mentioned measurement values of the element composition distribution in the depth direction of the film by X-ray photoelectron spectroscopy measurement at the three or more measurement points is measured. A film forming apparatus, wherein an average value of carbon component ratios at points is calculated and controlled so that an absolute value of a difference between the maximum value and the minimum value thereof is less than 2%.
Means (1): Supply port for supplying a film forming gas to the facing space between the resin bases arranged to face each other Means (2): Magnetic field generator for forming an endless tunnel-like magnetic field swelled in the facing space (3): Power source for generating plasma in the facing space Means (4): A pair of film forming rollers for forming a thin film layer on the resin substrate Means (5): Exhausting the film forming gas in the facing space exhaust port   Before transporting the resin base material to the pair of film forming rollers, a heating device for heating the resin base material is provided, and the resin base material temperature immediately before film formation and the pair of film forming rollers are The film forming apparatus according to claim 8, wherein a temperature difference with the resin base material in the step of forming a thin film layer is 10 ° C. or less.   10. The film forming apparatus according to claim 8, wherein the surface temperature of each of the film forming rollers increases stepwise from the upstream side to the downstream side in the transport direction.   11. The film formation according to claim 8, wherein the magnetic force of each of the film formation rollers increases stepwise from the upstream side to the downstream side in the transport direction. apparatus.   The film forming apparatus according to any one of claims 8 to 11, wherein a surface temperature of the film forming roller decreases from an axial end portion toward a central portion.   The film forming apparatus according to any one of claims 8 to 12, wherein a magnetic force of the film forming roller decreases from an axial end portion toward a central portion.   The film forming apparatus according to any one of claims 8 to 13, wherein a cross-sectional diameter of the film forming roller decreases from an axially central portion toward an end portion.

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