JP5836235B2 - Functional film - Google Patents

Description

  The present invention relates to a functional film such as a gas barrier film formed by forming an inorganic layer on a substrate.

Various functional films such as gas barrier films, protective films, optical films such as optical filters and antireflection films, etc. in various devices such as optical elements, display devices such as liquid crystal displays and organic EL displays, semiconductor devices, thin film solar cells, etc. (Functional sheet) is used.
As an example of such a functional film, a plastic film such as a polyethylene terephthalate (PET) film is used as a substrate, and an inorganic layer (a layer made of an inorganic compound) that exhibits a desired function is formed thereon. It has the composition which becomes.

  For example, in the case of a gas barrier film, a gas barrier film is known in which an inorganic layer made of silicon oxide or silicon nitride that exhibits gas barrier properties is formed on the surface of a plastic film.

In a gas barrier film in which an inorganic layer is formed on such a substrate, if there is a crack or the like in the inorganic layer that expresses the target function, moisture will permeate from here. Decreases.
On the other hand, it is known that by applying an appropriate internal stress to the inorganic layer, the inorganic layer is prevented from being damaged and good gas barrier properties are secured.

For example, Patent Document 1 discloses that when a gas barrier film formed by vapor-depositing a glass thin film (silicon oxide thin film) on a base film is produced, the deposition rate is reduced to 3 to 10 liters / sec. A method for producing a gas barrier film that gives a residual compressive stress of 280 to 480 MPa is described.
In Patent Document 1, the glass thin film has a residual compressive stress of 280 to 480 MPa, thereby preventing breakage of the glass thin film, improving productivity and quality, and maintaining gas barrier properties.

Patent Document 2 describes a gas barrier film that has a barrier layer made of an inorganic oxide on a base film, and the barrier layer is a thin film having a residual compressive stress of 100 MPa to 3 GPa.
In Patent Document 2, since the barrier layer made of an inorganic oxide has a residual compressive stress of 100 MPa to 3 GPa, a gas barrier film that can maintain a good gas barrier property for a long period of time and further ensure transparency is obtained. It is supposed to be done.

JP 2000-71378 A JP 2000-280395 A

As shown in Patent Document 1 and Patent Document 2, in the gas barrier film having an inorganic layer made of an inorganic oxide such as silicon oxide, when the film is bent by increasing the residual compressive stress of the inorganic layer, When pulled, the inorganic layer can be prevented from being cracked and the gas barrier property is lowered.
However, these gas barrier films stabilize a higher performance gas barrier film, for example, a high performance gas barrier film having a water vapor transmission rate of less than 1 × 10 ⁻³ [g / (m ² · day)]. It is difficult to obtain.

  An object of the present invention is a functional film formed by forming an inorganic layer on the surface of a plastic film or the like as a substrate (or support), and has high performance such as high gas barrier properties, and also has good performance. The object is to provide a functional film having flexibility.

In order to solve the above problems, the functional film of the present invention is formed into a flexible sheet-like film on at least one surface made of an organic compound and a surface of the substrate made of an organic compound. An inorganic layer made of silicon nitride,
And the residual compressive stress of an inorganic layer is 200-4000 MPa,
Further, in the Fourier transform infrared absorption spectrum of the inorganic layer, Si-N bonds of the peak located at 800~900cm ^-1, Si-H bonds of the peak located 2100～2200Cm ^-1, and, 3300～3400Cm ^-1 The N—H bond peak located in the region satisfies “0.02 <SiH / SiN <0.14” and “0.005 <NH / SiN <0.09”. Provide a protective film.

In such a functional film of the present invention, it is preferable that the substrate is formed by forming an organic layer as a base of the inorganic layer on the surface of the plastic film.
Moreover, it is preferable to have an organic layer in the outermost surface.
Furthermore, it is preferable to have a plurality of combinations of an inorganic layer and an organic layer serving as a base for the inorganic layer.

  According to the present invention, a high-performance functional film having high performance such as high gas barrier properties and good flexibility can be obtained.

(A)-(C) are figures which show notionally an example of the gas barrier film using the functional film of this invention. It is a figure which shows notionally an example of the film-forming apparatus which manufactures the gas barrier film shown in FIG. It is a graph which shows the result of Example 2 of this invention.

  Hereinafter, the functional film of the present invention will be described in detail based on a preferred embodiment shown in the accompanying drawings.

FIG. 1A conceptually shows an example of a gas barrier film using the functional film of the present invention.
A gas barrier film 10 shown in FIG. 1A is obtained by forming an inorganic layer (inorganic film) 14 made of silicon nitride on a substrate 12 made of a plastic film.

Here, the inorganic layer 14 of the gas barrier film 10 has a residual compressive stress of 200 to 4000 MPa, and further, Si located at 800 to 900 cm ⁻¹ in a Fourier transform infrared absorption spectrum (hereinafter referred to as FT-IR). -N bond of the peak, SiH bond peak located at 2100～2200Cm ^-1, and the peak intensity ratio of N-H bond located 3300～3400Cm ^-1 is, 0.02 <SiH / SiN < 0.14 and 0.005 <NH / SiN <0.09 are satisfied.
This will be described in detail later.

In addition, the functional film of this invention is not limited to a gas barrier film.
That is, the present invention can be used in various known functional films such as various protective films, various optical films such as an optical filter and an antireflection film, and the like. However, as will be described later, according to the present invention, damages such as foreign matter such as dust on the surface of the substrate 12 and cracks (cracks) of the inorganic layer 14 due to irregularities such as the surface roughness of the substrate 12 are suitably applied. Can be suppressed. Therefore, the functional film of the present invention is suitably used for a gas barrier film in which performance deterioration due to damage to the inorganic layer 14 is large.

In the gas barrier film of the present invention, the substrate 12 is a flexible sheet, and at least one surface is made of an organic compound. If the board | substrate 12 satisfy | fills this condition, various well-known sheet-like materials can be utilized.
Preferably, the long and flexible sheet-like substrate 12 (substrate 24 (substrate 24 ()) is formed so that the inorganic layer 14 (and the organic layer 28) can be formed by roll-to-roll described later. The support 26) is used, that is, in the present invention, the so-called web-like substrate 12 is preferably used.

  As the substrate 12, specifically, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyethylene, polypropylene, polystyrene, polyamide, polyvinyl chloride, polycarbonate, polyacrylonitrile, polyimide, polyacrylate, polymethacrylate, etc., A plastic film made of various plastics (polymer material / resin material) is preferably exemplified.

In the present invention, various functions such as a protective layer, an adhesive layer, a light reflection layer, an antireflection layer, a light shielding layer, a planarization layer, a buffer layer, and a stress relaxation layer are provided on the surface of such a plastic film. A layer (film) made of an organic compound to be obtained may be used as the support 26 (substrate).
Furthermore, in the present invention, such a plastic film is used as a support (support 26), and an organic layer (organic layer 28) serving as a base layer for the inorganic layer 14 is formed on the support. (Substrate 24) can also be suitably used. A substrate obtained by forming an organic layer on this support will be described in detail later.

In the gas barrier film 10 of the present invention, the surface roughness of the substrate 12 is not limited.
Here, as will be described later, in terms of preventing cracking of the inorganic layer 14, the surface of the substrate 12 is smoother, including irregularities on the surface of the substrate itself and irregularities caused by foreign matter attached to the substrate surface. However, this is advantageous in terms of gas barrier properties. On the other hand, the substrate 12 having no foreign matter such as dust and having high surface smoothness is more expensive.
On the other hand, the gas barrier film 10 of the present invention can prevent the inorganic layer 14 from cracking due to the unevenness of the substrate surface even when the substrate 12 having a high surface roughness is used. Therefore, according to the present invention, a high-performance gas barrier film 10 can be obtained even when a general inexpensive substrate 12 that has not been subjected to particularly high-level smoothing treatment or cleaning is used.

In the gas barrier film 10, an inorganic layer 14 is formed on the substrate 12.
The inorganic layer 14 is a film made of silicon nitride (a film containing silicon nitride as a main component), and the gas barrier film 10 mainly exhibits gas barrier properties. That is, the inorganic layer 14 mainly expresses the intended function in the functional film of the present invention.

  Here, in the gas barrier film 10 (functional film) of the present invention, the inorganic layer 14 has a residual compressive stress of 200 to 4000 MPa.

Further, in the gas barrier film 10 of the present invention, the inorganic layer 14 has an Si—N bond peak (absorption due to Si—N stretching vibration) located at 800 to 900 cm ⁻¹ in FT-IR (Fourier transform infrared absorption spectrum). Peak (peak intensity)), Si—H bond peak located at 2100-2200 cm ⁻¹ (absorption peak due to Si—H stretching vibration), and N—H bond peak located at 3300-3400 cm ^−1. (Absorption peak due to stretching vibration of NH) has a predetermined intensity ratio.
Specifically, SiH / SiN, which is the intensity ratio between the Si—N bond peak and the Si—H bond peak, is 0.02 <SiH / SiN <0.14, and the Si—N bond peak NH / SiN, which is the intensity ratio with the peak of the N—H bond, satisfies 0.005 <NH / SiN <0.09.

  Since the gas barrier film 10 of the present invention has such a configuration, the inorganic layer 14 is cracked due to foreign matters such as dust attached to the surface of the substrate 12 and unevenness of the substrate surface such as the surface roughness of the substrate 12. In this way, a high-performance gas barrier film that prevents damage such as the above and secures sufficient flexibility (softness) as a film is realized.

As described above, in the gas barrier film formed by forming an inorganic layer made of silicon oxide or the like on the surface of the plastic film, the inorganic layer when bent or pulled by increasing the internal stress of the inorganic layer. It is known that the gas barrier property can be prevented from lowering by preventing cracks and the like.
However, with inorganic oxides such as silicon oxide, it is difficult to form a dense film. For example, a high water vapor transmission rate is less than 1 × 10 ⁻³ [g / (m ² · day)]. It is difficult to obtain a high performance gas barrier film.

In contrast, if silicon nitride is used, a very dense film can be formed, and a high-performance gas barrier film can be formed.
However, even if the inorganic layer 14 is made of silicon nitride, a high gas barrier property cannot be obtained if the inorganic layer 14 has cracks or cracks. In particular, in the case of a high-performance gas barrier film having a water vapor transmission rate of less than 1 × 10 ⁻³ [g / (m ² · day)], moisture that penetrates from here is a major problem even with extremely fine cracks and cracks. That is, in order to obtain the target performance, it becomes a big obstacle.

However, fine cracks and the like are often formed in the inorganic layer 14 made of silicon nitride.
The present inventor has intensively studied the cause of this fine crack. As a result, the film formation surface (formation surface) of the inorganic layer 14 includes unevenness caused by foreign matters such as dust attached to the surface of the substrate 12 and unevenness of the surface of the substrate 12 itself (surface roughness of the substrate 12). It was found that unevenness was the cause.
That is, if the film-forming surface of the inorganic layer 14 has irregularities, a force that pushes the inorganic layer 14 outwardly acts on the convex portions. As a result, the inorganic layer 14 is cracked starting from this convex portion, and fine cracks are generated in the inorganic layer 14.

  As a result of further investigation, the present inventor has found that the residual compressive stress (hereinafter simply referred to as compressive stress) of the inorganic layer 14 is 200 to 200 in the gas barrier film 10 (functional film) having the inorganic layer 14 made of silicon nitride. By setting the pressure to 4000 MPa, it is possible to prevent the generation of fine cracks and cracks in the inorganic layer 14 due to the unevenness of the surface of the substrate 12, and to prevent the spread of these even if fine cracks or cracks occur. I found it.

Naturally, the compressive stress of the inorganic layer 14 is also influenced by the components contained in the inorganic layer 14 (hydrogen (hydrogen compound) inevitably mixed in), but the influence of the amount of hydrogen is significant.
Moreover, as long as the gas barrier film 10 is a film, it is preferable to have good flexibility. However. If the flexibility of the inorganic layer 14 is low, when the gas barrier film is bent, the inorganic layer 14 is cracked and the gas barrier property is lowered.
Here, if the amount of hydrogen in the film of the inorganic layer 14 made of silicon nitride increases, a dense film cannot be formed and sufficient gas barrier properties cannot be obtained. However, the flexibility of the inorganic layer 14 can be ensured by containing a certain amount of hydrogen.

  As a result of further investigations, the present inventor has further investigated SiH, which is an intensity ratio between the Si—N bond peak and the Si—H bond peak in FT-IR of the inorganic layer 14 made of silicon nitride. / SiN is 0.02 <SiH / SiN <0.14, and NH / SiN which is the intensity ratio of the Si—N bond peak to the N—H bond peak is 0.005 <NH / SiN <0. 0.09 provides a dense inorganic layer 14 having excellent gas barrier properties, and the compressive stress of the inorganic layer 14 can be suitably within the above range, and the flexibility of the inorganic layer 14, that is, the gas barrier film 10 It was found that the flexibility can be secured.

That is, according to the present invention having such a configuration, the water vapor transmission rate is less than 1 × 10 ⁻³ [g / (m ² · day)], and the gas barrier property is high and sufficient. A high-performance gas barrier film 10 that also ensures flexibility can be obtained.

As described above, in the gas barrier film 10 of the present invention, the compressive stress of the inorganic layer 14 is 200 to 4000 MPa.
When the compressive stress of the inorganic layer 14 is less than 200 MPa, the effect of preventing the cracking of the inorganic layer 14 due to the unevenness of the substrate surface described above cannot be sufficiently obtained, and sufficient flexibility of the inorganic layer 14 cannot be ensured. Inconvenience arises.
When the compressive stress of the inorganic layer 14 exceeds 4000 MPa, the compressive stress is too high, causing the inorganic layer 14 to crack or peel off, and the gas barrier film 10 has increased curl.

  Considering the above points, the compressive stress of the inorganic layer 14 is preferably 500 to 3000 MPa.

Moreover, SiH / SiN which is an intensity ratio of the Si—N bond peak located at 800 to 900 cm ⁻¹ and the Si—H bond peak located at 2100 to 2200 cm ⁻¹ in FT-IR is less than 0.02. , and / or, is less than NH / SiN 0.005 is the intensity ratio between the peak of NH bond located SiN bond peaks and 3300～3400Cm ^-1 located 800～900Cm ^-1, The amount of hydrogen in the inorganic layer 14 is insufficient, so that the flexibility of the inorganic layer 14 cannot be ensured and the inorganic layer 14 is broken due to bending of the gas barrier film or the like.

  Conversely, when SiH / SiN, which is the intensity ratio between the Si—N bond peak and the Si—H bond peak in FT-IR, exceeds 0.14 and / or the Si—N bond peak and N— When NH / SiN, which is the intensity ratio with respect to the peak of H bond, exceeds 0.09, the amount of hydrogen in the inorganic layer 14 is too large, resulting in low film density and insufficient gas barrier properties. Inconvenience arises.

Considering the above points, it is preferable that SiH / SiN is 0.03 <SiH / SiN <0.11.
Further, NH / SiN is preferably 0.01 <NH / SiN <0.05.

In the present invention, the thickness of the inorganic layer 14 is preferably 15 to 200 nm.
If the thickness of the inorganic layer 14 is 15 nm or less, it may be difficult to obtain a desired gas barrier property stably. Silicon nitride is hard and brittle. For this reason, if the thickness of the inorganic layer 14 exceeds 200 nm, it tends to naturally cause cracks, cracks, peeling, etc., and it may be difficult to stably obtain the desired gas barrier properties (target performance). .
In consideration of such points, the thickness of the inorganic layer 14 is more preferably 15 to 100 nm, and particularly preferably 20 to 75 nm.

A gas barrier film 10 shown in FIG. 1A uses a plastic film such as PET as a substrate 12.
However, the present invention is not limited to this, and various substrates can be used as long as they are flexible and one surface is made of an organic compound.

  For example, a sheet-like material having an organic layer 28 on the surface of the support 26 is preferably used as the substrate 24 as in the gas barrier film 20 shown in FIG.

  As the support 26, a plastic film similar to that of the substrate 12 described above is preferably exemplified. Further, a metal film or the like can be used as long as it has necessary flexibility.

The organic layer 28 is a layer made of an organic compound (a layer (film) containing an organic compound as a main component), and is basically formed by crosslinking (polymerizing) monomers and / or oligomers.
The organic layer 28 formed on the surface of the support 26, that is, the organic layer 28 that is the lower layer of the inorganic layer 14 functions as a base layer for properly forming the inorganic layer 14.
By having such an organic layer 28, the surface of the organic layer 28 can be flattened by embedding irregularities on the surface of the support 26, foreign matters attached to the surface of the support 26, and the like. By flattening the surface of the organic layer, areas where the inorganic compound that becomes the inorganic layer 14 is difficult to deposit, such as irregularities on the surface of the support 26 and shadows of foreign matter, are eliminated, and the entire surface of the organic layer 28 is appropriately formed. The inorganic layer 14 can be formed.

In addition, the inorganic layer 14 made of silicon nitride is hard and brittle, and thus is easily damaged by an impact received from the outside.
Therefore, the gas barrier film 20 shown in FIG. 1 (B) has the organic layer 28 also in the uppermost layer as a protective layer which protects the inorganic layer 14 as a preferable aspect. By having such an uppermost organic layer 28, the gas barrier film 20 can prevent the inorganic layer 14 from being damaged and can stably exhibit the target gas barrier property.

Further, the gas barrier film of the present invention may have a plurality of combinations of the inorganic layer 14 and the organic layer 28 which is the base of the inorganic layer 14 as in the gas barrier film 30 shown in FIG. (In the gas barrier film 30 shown in FIG. 1C, there are two combinations of organic layers / inorganic layers).
In other words, in the present invention, a substrate having a plurality of combinations of the underlying organic layer 28 and the inorganic layer 14 on the support 26 and having an organic layer formed thereon is used as a substrate. The inorganic layer 14 may be formed thereon, and more preferably, the organic layer 28 may be formed thereon as a protective layer.
By having a plurality of combinations of the underlying organic layer 28 and the inorganic layer 14, a gas barrier film having higher gas barrier properties can be obtained.

In addition, when the gas barrier film of this invention has the some inorganic layer 14, at least 1 inorganic layer 14 should just satisfy the conditions of the said compression stress and the peak ratio of FT-IR. However, in the present invention, preferably, all the inorganic layers 14 satisfy the conditions of the compressive stress and the peak ratio of FT-IR.
Moreover, when the gas barrier film of this invention has the some inorganic layer 14, the thickness of each inorganic layer 14 may be the same or different.

In the case where the gas barrier film of the present invention has a plurality of organic layers 28, the material for forming each organic layer 28 may be the same or different, but considering the productivity, all the organic layers 28 are the same. It is preferable to form a film with a material.
Furthermore, when the gas barrier film of the present invention has a plurality of organic layers 28, the thickness of each organic layer 28 may be the same or different.

The thickness of the organic layer 28 is preferably 0.5 to 5 μm.
By setting the thickness of the organic layer 28 to 0.5 μm or more, unevenness on the surface of the support 26 (deposition surface of the inorganic layer 14) and foreign matters attached to the surface of the support 26 are suitably embedded. The surface of the organic layer 28 can be flattened. Moreover, if it is the uppermost organic layer 28, the function as a protective layer of the inorganic layer 14 can fully be acquired.
Further, by setting the thickness of the organic layer 28 to 5 μm or less, it is possible to suitably suppress the occurrence of problems such as cracks in the organic layer 28 and curling of the gas barrier film 10 due to the organic layer 28 being too thick. be able to.
Considering the above points, the thickness of the organic layer 28 is more preferably 1 to 3 μm.

As described above, the organic layer 28 is a layer made of an organic compound, and is basically obtained by crosslinking (polymerizing) monomers and / or oligomers.
The material for forming the organic layer 28 is not limited, and various known organic compounds (resins / polymer compounds) can be used.
Specifically, polyester, acrylic resin, methacrylic resin, methacrylic acid-maleic acid copolymer, polystyrene, transparent fluororesin, polyimide, fluorinated polyimide, polyamide, polyamideimide, polyetherimide, cellulose acylate, polyurethane, poly Ether ether ketone, polycarbonate, alicyclic polyolefin, polyarylate, polyether sulfone, polysulfone, fluorene ring modified polycarbonate, alicyclic modified polycarbonate, fluorene ring modified polyester, acryloyl compound, thermoplastic resin, or polysiloxane, etc. An organosilicon compound is preferably exemplified.

Among these, the organic layer 28 composed of a radical polymerizable compound and / or a polymer of a cationic polymerizable compound having an ether group as a functional group is preferable from the viewpoint of excellent Tg and strength.
In particular, in addition to the above Tg and strength, acrylic resin and methacrylic resin mainly composed of acrylate and / or methacrylate monomer or oligomer polymer in terms of low refractive index and excellent optical properties are organic layers. 28 is preferably exemplified.
Among them, in particular, dipropylene glycol di (meth) acrylate (DPGDA), trimethylolpropane tri (meth) acrylate (TMPTA), dipentaerythritol hexa (meth) acrylate (DPHA), etc. Acrylic resins and methacrylic resins mainly composed of a polymer of acrylate and / or methacrylate monomers or oligomers are preferably exemplified.

Such an organic layer 28 may be formed (formed) by a known method.
For example, a coating material containing an organic solvent, an organic compound that becomes the organic layer 28, a surfactant, and the like is prepared, and this coating material is applied, dried, and then cross-linked.

In the gas barrier film 10 of the present invention, the inorganic layer 14 is preferably formed by plasma CVD using silane gas, ammonia gas and hydrogen gas (or further nitrogen gas) as a source gas (film formation gas / process gas) ( Form.
During the formation of the inorganic layer 14 by plasma CVD, a bias electric field applied to the substrate 12, the amount of hydrogen gas introduced (hydrogen dilution amount), the amount of silane gas and ammonia gas supplied (supply amount ratio), and the substrate temperature By adjusting at least one of (film formation temperature), the compressive stress of the inorganic layer 14 to be formed can be controlled.
Further, by adjusting the supply amount of hydrogen gas and / or the supply amount of silane gas and ammonia gas, SiH which is an intensity ratio between the Si—N bond peak and the Si—H bond peak in FT-IR. / SiN and NH / SiN which is the intensity ratio of the Si—N bond peak and the N—H bond peak can be controlled.

Film formation of the inorganic layer 14 made of silicon nitride by plasma CVD is performed by a known method by controlling the above conditions so that the compressive stress of the inorganic layer 14 and the peak intensity ratio of FT-IR fall within the predetermined range. Just do it.
Here, the inorganic layer 14 is preferably formed by using a roll-to-roll (hereinafter referred to as RtoR). RtoR is an inorganic layer 14 formed by feeding a substrate from a roll formed by winding a long substrate (web-shaped substrate) 12 and transporting the substrate in the longitudinal direction. This is a manufacturing method in which the substrate is again wound into a roll.
By using such RtoR, it becomes possible to manufacture the gas barrier film 10 with high production efficiency.

FIG. 2 conceptually shows an example of a film forming apparatus for forming the inorganic layer 14 by RtoR.
A film forming apparatus 50 shown in FIG. 2 basically includes a vacuum chamber 60, an unwind chamber 62 and a film forming chamber 64 in the vacuum chamber 60, and a drum 68.
In FIG. 2, a part of the shower electrode 80 disposed in the film forming chamber 64 is shown in cross section. In addition to the illustrated members, the film forming apparatus 50 is a known apparatus that forms a film by a vapor deposition method while conveying a long film forming material such as a pair of conveying rollers, a guide member, and various sensors. You may have the various members provided in.

In the film forming apparatus 50, the substrate roll R formed by winding the substrate 12 (substrate 24) is loaded into the unwind chamber 62.
The substrate 12 is pulled out from the substrate roll R in the unwinding chamber 62 and is transported in the longitudinal direction while being wound around the drum 68, and the inorganic layer 14 is formed in the film forming chamber 64. It is transported to the take-out chamber 62 and wound (rolled).

The drum 68 is a cylindrical member that rotates counterclockwise in the drawing around the center line.
The drum 68 wraps the substrate 12 guided by a guide roller 76a of the unwind chamber 62, which will be described later, on a predetermined area of the peripheral surface and conveys the substrate 12 in the longitudinal direction while holding it at a predetermined position. It is conveyed into the film chamber 64 and sent again to the guide roller 76b in the unwind chamber 62.

Here, the drum 68 also functions as a counter electrode of a shower electrode 80 (film formation electrode) of the film formation chamber 64 described later. That is, in the illustrated film forming apparatus 50, the drum 68 and the shower electrode 80 constitute an electrode pair.
The drum 68 is connected to a bias power supply 94 for applying a bias electric field to the substrate 12 (applying a bias potential). As the bias power source 94, all known power sources such as a high frequency power source and a pulse power source for applying a bias electric field to the deposition target substrate, which are used in various film forming apparatuses, can be used.

The drum 68 may also serve as a temperature adjusting unit for the substrate 12 (that is, the film formation temperature) on which the inorganic layer 14 is formed. Therefore, it is preferable that the drum 68 includes a temperature adjusting means.
The temperature adjusting means of the drum 68 is not particularly limited, and various temperature adjusting means such as a temperature adjusting means for circulating a refrigerant or the like, a cooling means using a Peltier element or the like can be used.

As described above, the vacuum chamber 60 includes the unwinding chamber 62 and the film forming chamber 64. In the illustrated example, the unwinding chamber 62 and the film forming chamber 64 are arranged in the vertical direction with the unwinding chamber 62 facing upward.
The unwinding chamber 62 and the film forming chamber 64 are (substantially) hermetically separated by the drum 68 and the partition walls 70 a and 70 b extending from the inner wall surface 60 a on the side surface side of the vacuum chamber 60 to the vicinity of the peripheral surface of the drum 68. Is done.

  The unwinding chamber 62 includes a rotating shaft 72, a winding shaft 74, guide rollers 76a and 76b, and a vacuum exhaust means 78.

The rotating shaft 72 is a known object that rotates while pivotally supporting the substrate roll R. The take-up shaft 74 is a well-known long take-up shaft for taking up the film-formed substrate 12.
Further, the guide rollers 76a and 76b are ordinary guide rollers that guide the substrate 12 along a predetermined transport path.

The substrate roll R is attached to the rotating shaft 72.
When the substrate roll R is mounted on the rotating shaft 72, the substrate 12 passes through a predetermined path (inserted) through the guide roller 76a, the drum 68, and the guide roller 76b to the winding shaft 74. )
In the film forming apparatus 50, the feeding of the substrate 12 from the substrate roll R and the winding of the film-formed substrate 12, that is, the gas barrier film 10 (20, 30) on the winding shaft 74 are performed in synchronization. The inorganic layer 14 (silicon nitride) is continuously formed on the surface of the substrate 12 in the film forming chamber 64 while the long substrate 12 is transferred in the longitudinal direction along a predetermined transfer path.

The vacuum exhaust means 78 is for depressurizing the inside of the unwinding chamber 62 to a predetermined degree of vacuum.
In the film forming apparatus 50, an evacuation unit 78 is also provided in the unwinding chamber 62, and the inside of the unwinding chamber 62 is maintained at a predetermined degree of vacuum, whereby the pressure in the unwinding chamber 62 is changed to the inorganic layer in the film forming chamber 64. 14 is prevented from being affected.

In the present invention, the vacuum exhaust means 78 is not particularly limited, and vacuum pumps such as turbo pumps, mechanical booster pumps, rotary pumps, and dry pumps, further auxiliary means such as cryocoils, the degree of ultimate vacuum and the amount of exhaust. Various known (vacuum) evacuation means used in a vacuum film forming apparatus using an adjusting means or the like can be used.
In this regard, the same applies to the vacuum exhaust means 92 described later.

As described above, in the film forming apparatus 50, the film forming chamber 64 is provided under the unwinding chamber 62 (below the partition walls 70 a and 70 b).
The film forming chamber 64 includes a shower electrode 80, a source gas supply unit 86, a high frequency power supply 90, and a vacuum exhaust unit 92. In this film forming chamber 64, as an example, the inorganic layer 14 is formed on the surface of the substrate 12 (organic layer 28) by CCP-CVD (Capacitively Coupled Plasma).

The shower electrode 80 is a film forming electrode, and constitutes an electrode pair in CCP-CVD together with the drum 68 (counter electrode) described above.
In the illustrated example, the shower electrode 80 has, for example, a substantially rectangular parallelepiped shape made of aluminum and having a maximum surface facing the peripheral surface of the drum 68. Moreover, the shower electrode 80 is a curved surface shape so that the opposing surface with the drum 68 may become a parallel surface spaced apart from the surrounding surface of the drum 68 as a preferable aspect.

A hollow portion 80 a is formed in the shower electrode 80.
A large number of gas supply holes 80b are formed to communicate from the hollow portion 80a to the surface facing the drum 68 (substrate 12) to supply the source gas. In the shower electrode 80, the gas supply hole 80 b is formed entirely on the surface facing the drum 68.

In the present invention, as the shower electrode 80, a known shower electrode (shower plate) used in an apparatus for performing film formation by plasma CVD or the like can be used.
Further, the surface of the shower electrode 80 facing the drum 68 may be roughened by depositing a sprayed film, blasting or the like in order to prevent the deposited film from being peeled off.

The source gas supply unit 86 is a known gas supply unit used in a plasma CVD apparatus for supplying source gas.
The source gas supply unit 86 supplies source gas to the hollow portion 80 a of the shower electrode 80. Accordingly, the source gas flows into the gas supply hole 80b from the hollow portion 80a, and is supplied from the gas supply hole 80b between the shower electrode 80 and the drum 68 (substrate 12), that is, between the electrode pair in CCP-CVD. .

The high frequency power supply 90 is a known high frequency power supply used in a plasma CVD apparatus.
The high frequency power supply 90 supplies plasma excitation power (film formation power) to the shower electrode 80 that is a film formation electrode.

  In the film forming chamber 64, the source gas is supplied from the source gas supply unit 86 to the hollow portion 80a of the shower electrode 80, and the source gas is discharged from the gas supply hole 80b communicating with the hollow portion 80a. A source gas is supplied between the drum 68 (substrate 12), plasma excitation power is supplied from the high-frequency power source 90 to the shower electrode 80, and a bias electric field is preferably applied to the substrate 12 from the bias power source 94, whereby the CCP. An inorganic layer 14 (silicon nitride film) is formed on the surface of the substrate 12 by -CVD.

  Here, as described above, in the gas barrier film 10 of the present invention, the inorganic layer 14 made of silicon nitride is formed by plasma CVD using silane gas, ammonia gas, and hydrogen gas (or nitrogen gas) as a source gas. Is preferred.

In the manufacture of a semiconductor device, when silicon nitride is formed as a passivation film, silane gas and ammonia gas and hydrogen gas as a dilution gas are used as source gases, and the substrate (that is, a silicon wafer or the like) is heated to a very high temperature. Thus, film formation is performed by plasma CVD. According to this silicon nitride film forming method, it is known that hydrogen adhering to the silicon nitride film during film formation can be extracted by the source gas hydrogen, and the hydrogen gas concentration in the silicon nitride film can be reduced to nearly 0%. Yes.
In manufacturing this semiconductor device, a very dense and hard silicon nitride film is formed by high-temperature film formation and hydrogen extraction.

Here, the extraction of hydrogen in the film formation of silicon nitride occurs in a high temperature film formation such as the manufacture of a semiconductor device, and the film is formed at a temperature of 100 ° C. or less like the film formation of silicon nitride by plasma CVD on PET. It was thought that this would not occur in low temperature film formation.
In addition, when a silicon nitride film is formed by plasma CVD using a plastic film such as a PET film as a substrate, hydrogen generated by etching the substrate (an organic compound serving as a film formation surface) is mixed into the film. Therefore, adding hydrogen gas to the source gas is disadvantageous in terms of the density of the silicon nitride film to be formed.
However, according to the study by the present inventors, in the film formation of silicon nitride by plasma CVD using silane gas and ammonia gas as the source gas, by using hydrogen gas as the diluent gas for the source gas, the effect is higher than at high temperatures. Although it is small, the same hydrogen extraction effect can be obtained even at a low temperature of 100 ° C. or lower. Moreover, by adjusting the supply amount of hydrogen gas, the effect of extracting hydrogen is controlled, the amount of hydrogen in the film is adjusted, the compressive stress of the silicon nitride film is controlled, and the peak intensity ratio in FT-IR Control can also be performed.

In the film formation of the inorganic layer 14 (silicon nitride), the film formation conditions such as the supply amount of source gas, plasma excitation power, film formation pressure, bias electric field strength, substrate temperature (film formation temperature) are not limited.
As described above, the compressive stress of the inorganic layer 14 and the Si—N bond peak, Si—H bond peak, and N—H bond peak in the FT-IR of the inorganic layer 14 are applied to the substrate 12. It can be controlled by adjusting the bias electric field, the amount of hydrogen gas introduced, the amount of silane gas and ammonia gas supplied, the substrate temperature, and the like.
Therefore, in the production of the gas barrier film 10 of the present invention, the film forming conditions of the inorganic layer 14 are the thickness of the inorganic layer 14, the target film forming speed, the film forming apparatus to be used, and the type and thickness of the substrate 12. The conditions under which the compressive stress of the inorganic layer 14 and the peak of each bond in the FT-IR are within the predetermined range may be set as appropriate.

  The substrate 12, ie, the gas barrier film 10 (20, 30) on which the inorganic layer 14 is formed in the film forming chamber 64, is again conveyed to the unwinding chamber 62, guided by the guide roller 76b, and conveyed to the winding shaft 74. Then, it is wound into a roll shape and supplied to the next step as a roll formed by winding the gas barrier film 10.

In the present invention, in the gas barrier films 20 and 30 as shown in FIG. 1 (B) and FIG. 1 (C), the organic layer 28 may be formed by a known method as described above. As with the layer 14, RtoR is preferable.
In this case, as an example, a coating material that becomes the organic layer 28 is applied to the conveyance path of the support 26 from the roll formed by winding the support 26 to the roll of the film-formed support 26. The support 26 is transported in the longitudinal direction using a coating means, a drying means for drying the paint applied by the coating apparatus, and a film forming apparatus in which the light irradiation means for forming the organic layer 28 by crosslinking the dried paint is disposed. Meanwhile, coating, drying and crosslinking are continuously performed.

  As mentioned above, although the functional film of this invention was demonstrated in detail, this invention is not limited to the said Example, In the range which does not deviate from the summary of this invention, it is possible to perform various improvements and changes. Of course.

  Hereinafter, the present invention will be described in more detail with reference to specific examples of the present invention.

<Example 1>
[Invention Example 1]
A gas barrier film having an inorganic layer 14 made of silicon nitride was produced on a substrate 24 having an organic layer 28 on the surface of a support 26.
That is, this gas barrier film has the same configuration as the gas barrier film 20 shown in FIG. 1B except that it does not have the uppermost organic layer 28 that is a protective layer.

  As the support 26, a long PET film having a width of 1000 mm and a thickness of 100 μm (Cosmo Shine A4300 manufactured by Toyobo Co., Ltd.) was used.

An organic compound was charged into an organic solvent and stirred to prepare a coating material for the organic layer 28.
As the organic compound, TMPTA (manufactured by Daicel-Cytec) was used. MEK was used as the organic solvent. A surfactant (BYK378 manufactured by BYK Japan) and a photopolymerization initiator (Irg184 manufactured by Ciba Chemicals) were added to the paint.

Using the organic layer film forming apparatus using RtoR as described above, the surface of the support 26 is coated with a paint, dried, irradiated with light, and crosslinked to form the organic layer 28 on the surface of the support 26. Was formed into a substrate 24.
A die coater was used as the coating means. Hot air was used as the drying means. An ultraviolet irradiation device was used as the light irradiation means.

  Next, the substrate roll around which the substrate 24 is wound is loaded into the film forming apparatus 50 shown in FIG. 2, and the surface of the substrate 24 (organic layer 28) is silicon nitride having a film thickness of 30 nm as the inorganic layer 14 by CCP-CVD. A film was formed to produce a gas barrier film.

The drum 68 is made of stainless steel and has a diameter of 1000 mm. The drum 68 has a built-in temperature adjusting means, and the surface temperature of the drum 68 was controlled at 70 ° C. during film formation.
The high frequency power supply 90 was a high frequency power supply with a frequency of 13.5 MHz, and the plasma excitation power supplied to the shower electrode 80 was 2000 W. The bias power source 94 was a high frequency power source having a frequency of 100 kHz, and 200 W bias power was supplied to the drum 68.

Silane gas (SiH ₄ ), ammonia gas (NH ₃ ), and hydrogen gas (H ₂ ) were used as the film forming gas. The supply amount was 100 sccm for silane gas, 200 sccm for ammonia gas, and 1500 sccm for hydrogen gas. The film forming pressure was 100 Pa.

About the produced gas barrier film, 800 in the ATR (total reflection type infrared absorption method) mode of FT-IR is used using an infrared spectroscopic device (a device in which ATR-PRO410-S is attached to FT-IR6100 manufactured by JASCO Corporation). peak intensity of Si-N bond located ~900cm ^-1, measured peak intensity of Si-H bond located 2100~2200cm ^-1, and the peak intensity of the N-H bond located 3300～3400Cm ^-1 .
From this measurement result, SiH / SiN, which is the intensity ratio between the peak intensity of the Si—N bond and the peak intensity of the Si—H bond, and the intensity of the peak intensity of the Si—N bond and the peak intensity of the N—H bond. The ratio NH / SiN was calculated.
As a result, SiH / SiN was 0.11, and NH / SiN was 0.03.

In addition, a film in which a silicon nitride film having a thickness of about 300 nm was formed on the surface of the same support 26 in the same manner was produced, and the (residual) compressive stress of the inorganic layer 14 was measured.
The compressive stress was calculated from the Stony equation by measuring the film thickness of the silicon nitride film using a step meter (dektak manufactured by ULVAC, Inc.), measuring the warpage of the produced film with a micrometer.
As a result, the compressive stress of the inorganic layer 14 was 590 MPa.

[Invention Example 2]
A gas barrier film was produced in the same manner as in Invention Example 1, except that the bias power supplied to the drum 68 was 400 W.
For the produced gas barrier film, SiH / SiN and NH / SiN were calculated in the same manner as in Invention Example 1. As a result, SiH / SiN was 0.06 and NH / SiN was 0.04.
Further, the compressive stress of the inorganic layer 14 was measured in the same manner as in Invention Example 1. As a result, the compressive stress of the inorganic layer 14 was 1820 MPa.

[Invention Example 3]
A gas barrier film was produced in the same manner as in Invention Example 1, except that the supply amount of hydrogen gas was 5000 sccm and the bias power supplied to the drum 68 was 400 W.
For the produced gas barrier film, SiH / SiN and NH / SiN were calculated in the same manner as in Invention Example 1. As a result, SiH / SiN was 0.04 and NH / SiN was 0.03.
Further, the compressive stress of the inorganic layer 14 was measured in the same manner as in Invention Example 1. As a result, the compressive stress of the inorganic layer 14 was 2650 MPa.

[Invention Example 4]
A gas barrier film was produced in the same manner as in Example 1 except that the supply amount of ammonia gas was 150 sccm and the bias power supplied to the drum 68 was 400 W.
For the produced gas barrier film, SiH / SiN and NH / SiN were calculated in the same manner as in Invention Example 1. As a result, SiH / SiN was 0.06 and NH / SiN was 0.02.
Further, the compressive stress of the inorganic layer 14 was measured in the same manner as in Invention Example 1. As a result, the compressive stress of the inorganic layer 14 was 2520 MPa.

[Comparative Example 1]
A gas barrier film was produced in the same manner as in Invention Example 1 except that no bias power was supplied to the drum 68.
For the produced gas barrier film, SiH / SiN and NH / SiN were calculated in the same manner as in Invention Example 1. As a result, SiH / SiN was 0.15 and NH / SiN was 0.06.
Further, the compressive stress of the inorganic layer 14 was measured in the same manner as in Invention Example 1. As a result, the compressive stress of the inorganic layer 14 was 70 MPa.

[Comparative Example 2]
A gas barrier film was produced in the same manner as in Invention Example 1, except that the plasma excitation power was 1000 W.
For the produced gas barrier film, SiH / SiN and NH / SiN were calculated in the same manner as in Invention Example 1. As a result, SiH / SiN was 0.16 and NH / SiN was 0.05.
Further, the compressive stress of the inorganic layer 14 was measured in the same manner as in Invention Example 1. As a result, the compressive stress of the inorganic layer 14 was 180 MPa.

[Comparative Example 3]
A gas barrier film was produced in the same manner as in Example 1 except that the surface temperature of the drum 68 was 0 ° C. and the bias power supplied to the drum 68 was 400 W.
For the produced gas barrier film, SiH / SiN and NH / SiN were calculated in the same manner as in Invention Example 1. As a result, SiH / SiN was 0.1 and NH / SiN was 0.1.
Further, the compressive stress of the inorganic layer 14 was measured in the same manner as in Invention Example 1. As a result, the compressive stress of the inorganic layer 14 was 110 MPa.

[Measurement of gas barrier properties]
About each produced gas barrier film, water-vapor-permeation rate [g / (m < ² > * day)] was measured by the calcium corrosion method (method described in Unexamined-Japanese-Patent No. 2005-283561).
As a result, the water vapor transmission rate is
Invention Example 1 is 2.4 × 10 ⁻⁵ [g / (m ² · day)],
Invention Example 2 is 1.8 × 10 ⁻⁵ [g / (m ² · day)],
Invention Example 3 is 1.5 × 10 ⁻⁵ [g / (m ² · day)],
Invention Example 4 is 2.3 × 10 ⁻⁵ [g / (m ² · day)],
Comparative Example 1 is 5.3 × 10 ⁻⁴ [g / (m ² · day)],
Comparative Example 2 is 2.1 × 10 ⁻⁴ [g / (m ² · day)],
Comparative Example 3 is 3.2 × 10 ⁻⁴ [g / (m ² · day)],
Met.
The above results are shown in Table 1 below.

As shown in Table 1, the inorganic layer 14 has a compressive stress of 200 to 4000 MPa, SiH / SiN is in the range of 0.02 to 0.14, and NH / SiN is in the range of 0.005 to 0.09. In all examples, a very excellent gas barrier property of less than 1 × 10 ⁻⁴ [g / (m ² · day)] is expressed.
In contrast, a comparative example having a compressive stress of less than 200 MPa and any of SiH / SiN and NH / SiN being higher than the range of the present invention is less than 1 × 10 ⁻³ [g / (m ² · day)]. Although it has a high gas barrier property, the gas barrier property as in the present invention example is not obtained.

<Example 2>
[Invention Example 5]
The same substrate 24 as in Invention Example 1 was produced. When the surface roughness Ra of the organic layer 28 of this substrate 24 (surface roughness Ra of the inorganic layer film-forming surface) was measured with an atomic force microscope (10 × 10 μm), the surface roughness Ra was 1.1 nm. .
Further, the surface of the organic layer 28 of the same substrate 24 is treated by rubbing it on a metal rod to produce three types of substrates 24 having surface roughness Ra of 4.7 nm, 10.2 nm, and 18.3 nm. did.
The inorganic layer 14 made of silicon nitride having a thickness of 30 nm was formed on the surface of the organic layer 28 of the above four types of substrates 24 in the same manner as in Invention Example 1 to prepare four types of gas barrier films.
For each gas barrier film produced, SiH / SiN and NH / SiN were calculated in the same manner as in Invention Example 1. As a result, in all the gas barrier films, SiH / SiN was 0.11, and NH / SiN was 0.03.
Further, the compression stress of the inorganic layer 14 was measured for each produced gas barrier film in the same manner as in Invention Example 1. as a result,
A gas barrier film having a surface roughness Ra of 1.1 nm is 590 MPa,
A gas barrier film having a surface roughness Ra of 4.7 nm is 610 MPa,
A gas barrier film having a surface roughness Ra of 10.2 nm is 600 MPa,
The gas barrier film having a surface roughness Ra of 18.3 nm was 590 MPa.

The water vapor permeability of the produced gas barrier film was measured in the same manner as in Example 1.
As a result, the water vapor transmission rate is
A gas barrier film having a surface roughness Ra of 1.1 nm is 2.4 × 10 ⁻⁵ [g / (m ² · day)],
A gas barrier film having a surface roughness Ra of 4.7 nm is 9.2 × 10 ⁻⁵ [g / (m ² · day)],
A gas barrier film having a surface roughness Ra of 10.2 nm is 3.0 × 10 ⁻⁴ [g / (m ² · day)],
A gas barrier film having a surface roughness Ra of 18.3 nm is 8.8 × 10 ⁻³ [g / (m ² · day)],
Met.

[Invention Example 6]
Four types of gas barrier films were produced in the same manner as in Invention Example 5 except that the inorganic layer 14 made of silicon nitride having a thickness of 30 nm was formed in the same manner as in Invention Example 2.
For each gas barrier film produced, SiH / SiN and NH / SiN were calculated in the same manner as in Invention Example 1. As a result, in all the gas barrier films, SiH / SiN was 0.06 and NH / SiN was 0.04.
Further, the compression stress of the inorganic layer 14 was measured for each produced gas barrier film in the same manner as in Invention Example 1. as a result,
A gas barrier film having a surface roughness Ra of 1.1 nm is 1800 MPa,
A gas barrier film having a surface roughness Ra of 4.7 nm is 1820 MPa,
A gas barrier film having a surface roughness Ra of 10.2 nm is 1820 MPa,
The gas barrier film having a surface roughness Ra of 18.3 nm was 1830 MPa.

The water vapor permeability of the produced gas barrier film was measured in the same manner as in Example 1.
As a result, the water vapor transmission rate is
A gas barrier film having a surface roughness Ra of 1.1 nm is 1.8 × 10 ⁻⁵ [g / (m ² · day)],
The gas barrier film having a surface roughness Ra of 4.7 nm is 5.5 × 10 ⁻⁵ [g / (m ² · day)],
A gas barrier film having a surface roughness Ra of 10.2 nm is 1.9 × 10 ⁻⁴ [g / (m ² · day)],
A gas barrier film having a surface roughness Ra of 18.3 nm is 5.6 × 10 ⁻³ [g / (m ² · day)],
Met.

[Comparative Example 4]
Four types of gas barrier films were produced in the same manner as in Invention Example 5 except that the inorganic layer 14 made of silicon nitride having a thickness of 30 nm was formed in the same manner as in Comparative Example 1.
For each gas barrier film produced, SiH / SiN and NH / SiN were calculated in the same manner as in Invention Example 1. As a result, in all the gas barrier films, SiH / SiN was 0.15 and NH / SiN was 0.06.
Further, the compression stress of the inorganic layer 14 was measured for each produced gas barrier film in the same manner as in Invention Example 1. as a result,
A gas barrier film having a surface roughness Ra of 1.1 nm is 50 MPa,
A gas barrier film having a surface roughness Ra of 4.7 nm is 40 MPa,
A gas barrier film having a surface roughness Ra of 10.2 nm is 70 MPa,
The gas barrier film having a surface roughness Ra of 18.3 nm was 70 MPa.

The water vapor permeability of the produced gas barrier film was measured in the same manner as in Example 1.
as a result,
The gas barrier film having a surface roughness Ra of 1.1 nm is 5.3 × 10 ⁻⁴ [g / (m ² · day)],
A gas barrier film having a surface roughness Ra of 4.7 nm is 4.4 × 10 ⁻³ [g / (m ² · day)],
A gas barrier film having a surface roughness Ra of 10.2 nm is 2.5 × 10 ⁻² [g / (m ² · day)],
A gas barrier film having a surface roughness Ra of 18.3 nm is 9.2 × 10 ⁻² [g / (m ² · day)],
Met.

[Comparative Example 5]
Four types of gas barrier films were produced in the same manner as in Invention Example 5 except that the inorganic layer 14 made of silicon nitride having a thickness of 30 nm was formed in the same manner as in Comparative Example 2.
For each gas barrier film produced, SiH / SiN and NH / SiN were calculated in the same manner as in Invention Example 1. As a result, in all the gas barrier films, SiH / SiN was 0.16 and NH / SiN was 0.05.
Further, the compression stress of the inorganic layer 14 was measured for each produced gas barrier film in the same manner as in Invention Example 1. as a result,
The gas barrier film having a surface roughness Ra of 1.1 nm is 180 MPa,
A gas barrier film having a surface roughness Ra of 4.7 nm is 180 MPa,
The gas barrier film having a surface roughness Ra of 10.2 nm is 180 MPa,
The gas barrier film having a surface roughness Ra of 18.3 nm was 170 MPa.

The water vapor permeability of the produced gas barrier film was measured in the same manner as in Example 1.
as a result,
A gas barrier film having a surface roughness Ra of 1.1 nm is 2.1 × 10 ⁻⁴ [g / (m ² · day)],
A gas barrier film having a surface roughness Ra of 4.7 nm is 1.9 × 10 ⁻³ [g / (m ² · day)],
A gas barrier film having a surface roughness Ra of 10.2 nm is 7.9 × 10 ⁻³ [g / (m ² · day)],
A gas barrier film having a surface roughness Ra of 18.3 nm is 7.4 × 10 ⁻² [g / (m ² · day)],
Met.

The above results are shown in FIG.
As described above, the larger the surface roughness Ra of the substrate 24 is, the more disadvantageous the gas barrier property is. However, in the conventional gas barrier film, when the surface roughness Ra of the substrate 24 is 5 nm, the water vapor transmission rate is 1 × 10. ^-3 [g / (m ² · day)] has been exceeded. On the other hand, the gas barrier film of the present invention has a high gas barrier property that the water vapor permeability is less than 1 × 10 ⁻³ [g / (m ² · day)] even when the surface roughness Ra of the substrate 24 is 10 nm. ing.
Further, according to the gas barrier film of the present invention, even if the surface roughness Ra of the substrate 24 is further increased, the gas barrier property superior to that of the conventional gas barrier film can be maintained.

<Example 3>
[Invention Example 7]
As the support 26, a long polyimide film having a width of 1000 mm and a thickness of 75 μm (Kapton 300H manufactured by Toray DuPont) was used.
An organic layer 28 was formed on the surface of the support 26 in the same manner as in Invention Example 1 to produce a substrate 24.
The surface of the substrate 24 (organic layer 28) is made of silicon nitride having a thickness of 30 nm in the same manner as in Invention Example 1, except that the supply amount of hydrogen gas is 5000 sccm and the bias power supplied to the drum 68 is 400 W. The inorganic layer 14 was formed into a gas barrier film.
That is, this gas barrier film also has the same configuration as the gas barrier film 20 shown in FIG. 1B except that it does not have the uppermost organic layer 28 that is a protective layer.

For the produced gas barrier film, SiH / SiN and NH / SiN were calculated in the same manner as in Invention Example 1. As a result, SiH / SiN was 0.06 and NH / SiN was 0.03.
Further, the compressive stress of the inorganic layer 14 was measured in the same manner as in the inventive examples. As a result, the compressive stress of the inorganic layer 14 was 2230 MPa.

[Comparative Example 6]
A gas barrier film was produced in the same manner as in Invention Example 7, except that the surface temperature of the drum 68 during the formation of the inorganic layer 14 made of silicon nitride was changed to 250 ° C. (Invention Example 7 = 70 ° C. in Invention Example 1). did.

For the produced gas barrier film, SiH / SiN and NH / SiN were calculated in the same manner as in Invention Example 1. As a result, SiH / SiN was 0.003 and NH / SiN was 0.002.
Further, the compressive stress of the inorganic layer 14 was measured in the same manner as in the inventive examples. As a result, the compressive stress of the inorganic layer 14 was 370 MPa.

[Comparative Example 7]
Other than changing the supply amount of hydrogen gas to 1500 sccm, the plasma excitation power to 500 W (Invention Example 7 = 2000 W in Invention Example 1), and the bias power supplied to the drum 68 to 600 W when the inorganic layer 14 made of silicon nitride is formed Produced a gas barrier film in the same manner as in Invention Example 7.

For the produced gas barrier film, SiH / SiN and NH / SiN were calculated in the same manner as in Invention Example 1. As a result, SiH / SiN was 0.15 and NH / SiN was 0.12.
Further, the compressive stress of the inorganic layer 14 was measured in the same manner as in the inventive examples. As a result, the compressive stress of the inorganic layer 14 was 250 MPa.

[Gas barrier properties]
About the produced gas barrier film, the water-vapor-permeation rate was measured similarly to Invention Example 1.
The water vapor transmission rate was measured immediately after the production (initial stage) and after the work of winding and spreading the film on a 6 mm diameter rod was repeated 100 times (after the winding).
As a result, the water vapor transmission rate of the gas barrier film of Invention Example 7 was initially 9.1 × 10 ⁻⁵ [g / (m ² · day)], and after winding was 1.9 × 10 ⁻⁴ [g / ( m ² · day)].
On the other hand, the water vapor transmission rate of the gas barrier film of Comparative Example 6 was 8.4 × 10 ⁻⁵ [g / (m ² · day)] in the initial stage and 3.6 × 10 ⁻² [g / after winding. (m ² · day)]
The water vapor transmission rate of the gas barrier film of Comparative Example 7 is 1.1 × 10 ⁻³ [g / (m ² · day)] in the initial stage, and 4.7 × 10 ⁻² [g / (m ² · day) after winding. day)] ^10-3 .
The results are shown in Table 2 and Table 3 below.

As shown in Tables 2 and 3, Invention Example 7 which is a gas barrier film of the present invention has an initial gas barrier property of 1.9 × 10 ⁻⁴ [g / (m ² · day) even after winding. )], Which maintains a very high gas barrier property.
On the other hand, in Comparative Example 6 in which SiH / SiN and NH / SiN are small, that is, the amount of hydrogen in the inorganic layer 14 is too small, the flexibility of the inorganic layer 14 is low, and the initial high gas barrier property equivalent to that of the present invention is obtained. However, after winding, it was 3.6 × 10 ^-2 [g / (m ² · day)], and the gas field area was greatly reduced.
In Comparative Example 7, where SiH / SiN and NH / SiN are large, that is, the amount of hydrogen in the inorganic layer 14 is too large, the film density is low and sufficient gas barrier properties cannot be obtained even at the initial stage.
From the above results, the effects of the present invention are clear.

  It can be suitably used for gas barrier films and the like used for solar cells and organic EL displays.

10, 20, 30 Gas barrier film 12, 24 Substrate 14 Inorganic layer 26 Support 28 Organic layer 50 Film forming device 60 Vacuum chamber 62 Unwinding chamber 64 Film forming chamber 68 Drum 70a, 70b Partition wall 72 Rotating shaft 74 Winding shaft 76a, 76b Guide roller 78, 92 Vacuum exhaust means 80 Shower electrode 82 Exhaust means 86 Raw material gas supply part 90 High frequency power supply 94 Bias power supply

Claims (3)

A flexible sheet-like substrate having an organic layer formed on the surface of a plastic film and an inorganic layer made of silicon nitride formed on the surface of the organic layer with the organic layer of the substrate as a base And having a layer
And the residual compressive stress of the said inorganic layer is 200-4000 MPa,
In the Fourier transform infrared absorption spectrum of the inorganic layer, the Si—N bond peak located at 800 to 900 cm −1, the Si—H bond peak located at 2100 to 2200 cm −1, and 3300 to 3400 cm − The N—H bond peak located at 1 satisfies “0.02 <SiH / SiN <0.14” and “0.005 <NH / SiN <0.09” .
Furthermore, the said inorganic layer is formed only in the one surface side of the said plastic film, The functional film characterized by the above-mentioned . The functional film of Claim 1 which has an organic layer in the outermost surface. The functional film of Claim 1 or 2 which has multiple combinations of the said inorganic layer and the organic layer used as the foundation | substrate of this inorganic layer.