JP6061820B2 - Functional film and method for producing functional film - Google Patents

Description

  The present invention relates to a functional film formed by alternately forming an organic layer and an inorganic layer on a support, and a method for producing the functional film.

Gas barrier films such as optical elements, display devices such as liquid crystal displays and organic EL displays, various semiconductor devices, parts and components that require moisture resistance in various devices such as solar cells, and packaging materials for packaging food and electronic components Has been.
A gas barrier film is generally formed by forming a film (hereinafter also referred to as a gas barrier film) that exhibits gas barrier properties on a plastic film such as a polyethylene terephthalate (PET) film as a support (substrate). It has a configuration. Moreover, as a gas barrier film used for a gas barrier film, for example, films made of various inorganic compounds such as silicon nitride, silicon oxide, and aluminum oxide are known.

  In such a gas barrier film, an organic layer made of an organic compound (organic compound layer) and an inorganic layer made of an inorganic compound (inorganic compound layer) are alternately arranged on a support as a structure that can provide higher gas barrier performance. An organic / inorganic laminated type gas barrier film having a laminated structure laminated on is known.

In the organic / inorganic laminated gas barrier film, it is the inorganic layer that mainly exhibits gas barrier properties. In an organic / inorganic laminated type gas barrier film, an inorganic layer is formed on an organic layer as a base, thereby smoothing the surface on which the inorganic layer is formed by the organic layer, and on an organic layer having good smoothness. By forming the inorganic layer, a uniform inorganic layer free from cracks and cracks is formed, and excellent gas barrier performance is obtained.
It is also known that an organic / inorganic laminated type gas barrier film can obtain more excellent gas barrier performance by having a plurality of combinations of an organic layer and an inorganic layer as a base.

Here, in the organic / inorganic laminated type gas barrier film, it is difficult to ensure adhesion between layers, in particular, adhesion of an organic layer formed on the inorganic layer.
That is, the inorganic layer that exhibits gas barrier properties has a dense crystal structure. Therefore, the organic layer formed on the inorganic layer penetrates into the layer like the easy-adhesion layer, cannot obtain the anchoring effect, and cannot secure sufficient adhesion.

Therefore, in organic / inorganic laminated gas barrier films, it is known that when an organic layer is formed on an inorganic layer, the organic layer contains a silane coupling agent to ensure the adhesion of the organic layer. ing.
As is well known, a silane coupling agent is a compound having a functional group that binds to an organic material and an inorganic material in the molecule. In the organic / inorganic laminated type gas barrier film, the silane coupling agent is, for example, an organic layer that forms an Si—O—Si bond by silanolation and an organic layer such as an acrylic group. By having a functional group that is easily bonded to a material (resin material), the adhesion of the organic layer on the inorganic layer is ensured.

Specifically, in Patent Document 1, in an organic / inorganic laminated gas barrier film, the organic layer on the inorganic layer has an organic solvent, an organic compound that becomes the organic layer, and a silane coupling agent, and The gas barrier film is formed from a paint that does not have a pH adjuster, and further heats at a higher temperature than the by-product caused by the organic solvent or the silane coupling agent in the step of forming the organic layer. A manufacturing method is described.
Patent Document 2 describes a gas barrier film in which an organic layer has a silane coupling agent represented by the following general formula in an organic / inorganic laminate type gas barrier film.
_{(R 1, R 2, R} 3) Si-NH-Si (R 4, R 5, R 6)
(In the above formula, R _{1 to} R ₆ are each a substituted or unsubstituted alkyl group or an aryl group, provided that at least one of R _{1 to} R ₆ is a radically polymerizable carbon-carbon double bond. including.)

JP 2013-31794 A JP2013-43382A

According to the gas barrier film shown in Patent Documents 1 and 2, it is possible to obtain a gas barrier film that is excellent in the adhesion of the organic layer and has high gas barrier properties.
However, in recent years, the demand for organic / inorganic laminated type gas barrier films has become increasingly severe, and depending on the application and required performance, gas barrier films using a silane coupling agent in these organic layers can be used. However, there are cases where either or both of the adhesion and gas barrier properties of the organic layer are insufficient.

  An object of the present invention is to solve such problems of the prior art, and in an organic / inorganic laminated functional film such as a gas barrier film, excellent adhesion of an organic layer on an inorganic layer, An object of the present invention is to provide a functional film that can be obtained with excellent performance such as high gas barrier properties and a method for producing the functional film.

In order to solve the above problems, the functional film of the present invention is a functional film having a support and organic layers and inorganic layers alternately formed on the support,
It has at least one organic layer formed on the inorganic layer, and the organic layer formed on the inorganic layer contains a silane coupling agent represented by the following general formula [I] A functional film is provided.
_{^{(R 1) 3 -Si-R}} 2 -Si- (R 1) 3 ··· general formula [I]
(In the general formula [I], R ¹ is an alkoxy group which may have a substituent, and R ² is a linear group which may have a linear substituent having 2 to 10 carbon atoms. An alkylene group, and each R ¹ may be the same as or different from each other.)

In such a functional film of the present invention, in general formula [I], R ¹ is preferably at least one selected from —OCH ₃ and —OCH ₂ CH ₃ .
In the general formula [I], R ¹ preferably has no substituent.
In the general formula [I], R ² preferably has no substituent.
Further, the organic layer on the inorganic layer is mainly composed of a resin composed of bifunctional or higher (meth) acrylate, and the content of the silane coupling agent is 1 to 25% by mass. preferable.
Moreover, it is preferable that the glass transition temperature of the organic compound used as an organic layer is higher than the boiling point of the by-product resulting from a silane coupling agent, or the boiling point of the organic solvent used for formation of an organic layer.
Moreover, it is preferable that the thickness of the organic layer on an inorganic layer is 5 micrometers or less.
Further, it is preferable that the inorganic layer is made of silicon nitride, and at least one of —OH group and —O group is introduced into the surface thereof.
Furthermore, the density of the inorganic layer is preferably 2 to 2.4 g / cm ³ .

In addition, the method for producing a functional film of the present invention, when producing a functional film formed by alternately forming an organic layer and an inorganic layer on a support,
Forming an organic layer on the inorganic layer at least once, and
When forming the organic layer on the inorganic layer, an application step of applying at least an organic solvent, an organic compound to be the organic layer, and a paint containing a silane coupling agent represented by the following general formula [I] ,
_{^{(R 1) 3 -Si-R}} 2 -Si- (R 1) 3 ··· general formula [I]
(In the general formula [I], R ¹ is an alkoxy group which may have a substituent, and R ² is a linear group which may have a linear substituent having 2 to 10 carbon atoms. An alkylene group, and each R ¹ may be the same as or different from each other.)
A drying step in which the paint is dried at a temperature higher than the azeotropic point of the by-product and the organic solvent due to the silane coupling agent, or higher than the boiling point of the by-product and the higher boiling point of the organic solvent,
And the manufacturing method of the functional film characterized by performing the hardening process which hardens the dried coating material by light irradiation is provided.

  In such a method for producing a functional film of the present invention, it is preferable to use a long support and form the organic layer and the inorganic layer while transporting the support in the longitudinal direction.

  According to the present invention having the above-described configuration, in an organic / inorganic laminated functional film formed by alternately laminating an organic layer and an inorganic layer, high adhesion of the organic layer on the inorganic layer and excellent High performance such as gas barrier properties can be obtained at the same time.

(A)-(D) are figures which show notionally an example of the functional film of this invention. It is a figure which shows notionally an example of the manufacturing apparatus which enforces the manufacturing method of the functional film of this invention, (A) is a formation apparatus of an organic layer, (B) is a formation apparatus of an inorganic layer.

  Hereinafter, the functional film of the present invention and the method for producing the functional film will be described in detail based on preferred embodiments shown in the accompanying drawings.

The functional film of the present invention is basically an organic / inorganic laminated functional film in which organic layers and inorganic layers are alternately formed on a support.
Further, at least one layer has an organic layer formed on the inorganic layer, and the organic layer formed on the inorganic layer contains a silane coupling agent represented by the general formula [I] To do.

  FIG. 1A conceptually shows an example of a gas barrier film using the functional film of the present invention.

  In addition, the manufacturing method of the functional film and functional film of this invention is not limited to the manufacturing method of a gas barrier film and a gas barrier film. That is, the present invention can be used for various known functional films that express the intended function, such as various optical films such as an optical filter and a light reflection preventing film. However, as will be described later, according to the present invention, the adverse effect due to the substance caused by the self-condensate of the silane coupling agent produced in the organic layer is greatly reduced, and high adhesion on the inorganic layer is achieved. Since an organic layer can be formed and a dense inorganic layer can be formed thereon, it is suitably used for a gas barrier film in which the denseness of the inorganic film greatly contributes to performance.

The gas barrier film 10a shown in FIG. 1 (A) has an organic layer 12a on the support Z (surface / main surface), an inorganic layer 14 on the organic layer 12a, The second organic layer 12b is provided on the second organic layer 12b. The second inorganic layer 14 is provided on the second organic layer 12b. It has the organic layer 12b of the layer.
That is, the second and third organic layers 12b are organic layers formed on the inorganic layer 14, and as described above, the predetermined silane coupling agent represented by the general formula [I] is applied. It contains.
In FIG. 1A (also FIGS. 1B to 1D), only the inorganic layer 14 is hatched to clearly show the configuration.

In addition, the gas barrier film (functional film) of the present invention has an organic layer and an inorganic layer alternately of one organic layer 12a, two organic layers 12b, and two inorganic layers 14, as shown in the illustrated example. In addition, there is no limitation to the configuration in which a total of five layers are stacked.
That is, the gas barrier film of the present invention has various layer configurations as long as it has organic layers and inorganic layers alternately and has one or more organic layers formed on the inorganic layer. Is available.

For example, as shown in FIG. 1B, a third inorganic layer 14 is further provided on the surface of the gas barrier film 10a shown in FIG. 1A, and a fourth organic layer 12b is formed thereon. A gas barrier film 10b having a total of seven organic layers and inorganic layers, which are alternately formed, is also preferably exemplified.
In the gas barrier film of the present invention, basically, the more the combination of the organic layer serving as the base and the inorganic layer formed on the organic layer, the better the gas barrier property. The same applies to the gas barrier film 10a and the like shown in FIG. 1A. However, since the organic layer 12b functions as a protective layer by having the organic layer 12b as the uppermost layer, the inorganic layer 14 is damaged. A decrease in gas barrier properties can be suitably prevented.

Alternatively, as shown in FIG. 1 (C), an inorganic layer 14 is provided on a support Z, an organic layer 12b is provided thereon, a second inorganic layer 14 is provided thereon, and a second inorganic layer 14 is provided thereon. As in the gas barrier film 10c having the uppermost organic layer 12b, the inorganic layer 14 may be provided on the support Z, and the organic layer and the inorganic layer may be alternately provided thereon. That is, in the case of this configuration, all the organic layers become the organic layer 12b formed on the inorganic layer 14.
The organic layers 12a and 12b are generally formed by a coating method using a paint in which an organic compound such as a monomer to be an organic layer is dissolved in an organic solvent. As shown in FIG. 1 (C), by having the inorganic layer 14 on the support Z and alternately forming the organic layer 12b and the inorganic layer 14 thereon, the optical properties such as cycloolefin copolymer can be improved. Although excellent, when the support Z made of a material that is easily dissolved or altered by an organic solvent is used, it is possible to prevent deterioration of the optical properties of the support Z due to the organic solvent.

Furthermore, as shown in FIG. 1 (D), an organic layer 12a is provided on a support Z, an inorganic layer 14 is provided thereon, a second organic layer 12b is provided thereon, and Alternatively, the uppermost layer may be the inorganic layer 14 as in the gas barrier film 10 d having the second inorganic layer 14.
Thus, by using the inorganic layer 14 as the uppermost layer, when the gas barrier film of the present invention is used for an organic EL device (OLED device) or the like, the adverse effect due to the outgas from the organic layer 12b is more preferably prevented. Thus, deterioration of the organic EL device such as generation of dark spots can be prevented more reliably.

In the present invention, the support (substrate / base material) Z is not particularly limited, and various known sheet-like materials used as a support for a gas barrier film can be used.
Preferably, a long sheet-like support Z (web-like support Z) is used so that an organic layer and an inorganic layer can be formed by roll-to-roll described later.

As the support Z, specifically, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyethylene, polypropylene, polystyrene, polyamide, polyvinyl chloride, polycarbonate, polyacrylonitrile, polyimide, polyacrylate, polymethacrylate, polycarbonate Preferred examples include plastic films made of various plastics (polymer materials) such as (PC), cycloolefin polymer (COP), cycloolefin copolymer (COC), triacetylcellulose (TAC), and transparent polyimide.
The support Z has 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 on the surface of such a plastic film. The layer (film | membrane) for obtaining may be formed.

In the gas barrier film 10a, the organic layers 12a and 12b are layers made of an organic compound (a layer (film) containing an organic compound as a main component), and the organic compounds (monomer, dimer, trimer, and oligomer) that become the organic layer 1 or more) is polymerized (crosslinked) and cured.
In the gas barrier film 10a of the present invention, the organic layers 12a and 12b formed as the lower layer of the inorganic layer 14, such as the surface of the support Z, basically have a gas barrier property (target function). Acts as an underlayer. By forming the inorganic layer 14 using the organic layers 12a and 12b as the underlayer, the surface on which the inorganic layer 14 is formed is smoothed, and there are no voids such as cracks, cracks, or non-formed portions (the voids are greatly reduced). The gas barrier film which forms the uniform inorganic layer 14 and expresses high gas barrier performance can be manufactured stably.

Further, as described above, the uppermost organic layer 12b functions as a protective layer, and by having the uppermost organic layer 12b, deterioration of gas barrier properties due to damage of the inorganic layer 14 and the like can be achieved. Can be prevented.
In the gas barrier film of the present invention, not the organic layer 12a but the inorganic layer 14 may be formed on the surface of the support Z, and the top layer may be the inorganic layer 14 as described above. It is.

In the production method of the present invention, the material for forming the organic layers 12a and 12b formed on the surface of the support Z is not particularly limited, and various known organic compounds (resin / polymer materials) can be used. It is.
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, polyethersulfone, polysulfone, fluorene ring modified polycarbonate, alicyclic modified polycarbonate, fluorene ring modified polyester, acryloyl compound, thermoplastic resin, or polysiloxane, etc. An organic silicon compound film is preferably exemplified.

  In particular, polymerization of a radically polymerizable compound and / or a cationically polymerizable compound having an ether group as a functional group from the viewpoints of flattening the formation surface of the inorganic layer 14 and sufficiently exhibiting its function and excellent heat resistance. Organic layers 12a and 12b made of a material are suitable.

Among these, acrylic resins and methacrylic resins mainly composed of a polymer of acrylate and / or methacrylate monomers are suitably used as the organic layers 12a and 12b in that they are excellent in strength and optical characteristics.
Among them, in particular, dipropylene glycol di (meth) acrylate (DPGDA), 1,9-nonanediol di (meth) acrylate (A-NOD-N), 1,6 hexanediol diacrylate (A-HD-N), Bifunctional or higher acrylate and / or methacrylate monomers such as trimethylolpropane tri (meth) acrylate (TMPTA), (modified) bisphenol A di (meth) acrylate, dipentaerythritol hexa (meth) acrylate (DPHA), etc. An acrylic resin and a methacrylic resin mainly composed of a polymer are preferably exemplified. It is also preferable to use a plurality of these acrylic resins and methacrylic resins.

  By forming the organic layers 12a and 12b with an acrylic resin or a methacrylic resin, in particular an acrylic resin or a methacrylic resin having two or more functions, the inorganic film 14 can be formed on a base having a solid skeleton, so that the gas barrier property is more precise. Can be formed.

The thickness of the organic layers 12a and 12b is preferably 5 μm or less. By setting the thickness of the organic layers 12a and 12b to 5 μm or less, occurrence of problems such as cracks in the organic films 12a and 12b and curling of the gas barrier film 10a due to the organic films 12a and 12b being too thick, It can prevent suitably. In particular, the thickness of the organic layer 12b is preferably 5 μm or less.
Moreover, the thickness of the organic layers 12a and 12b is preferably 0.5 μm or more. By setting the thickness of the organic film 16 to 0.5 μm or more, the formation surface of the inorganic layer 14 is made more appropriate, and the appropriate inorganic layer 14 without cracks or cracks is formed over the entire formation surface. Can be formed.
Considering the above points, the thickness of the organic films 12a and 12b is more preferably 1 to 3 μm.

In addition, when it has a some organic layer like the gas barrier film 10a shown to FIG. 1 (A), each organic layer may be formed with the same material, or may be formed with a different material. However, if productivity etc. are considered, it is preferable to form all the organic layers with the same material.
Similarly, when having a plurality of organic layers, the thickness of each organic layer may be the same or different.

What is necessary is just to form such an organic layer 12a and the organic layer 12b by a well-known method. Preferably, it is formed by a coating method in which a paint containing a monomer that becomes the organic layer 12a or the organic layer 12b is prepared, and this paint is applied, and then dried and cured.
Here, the organic layer 12b formed on the inorganic layer 14 contains a predetermined silane coupling agent. That is, a silane coupling agent is added to the coating material for forming the organic layer 12b. This will be described in detail later.

  In the gas barrier film 10a of the present invention, the inorganic layer 14 is a layer made of an inorganic compound (a layer (film) containing an inorganic compound as a main component), and the gas barrier film 10a mainly exhibits gas barrier properties.

As the inorganic layer 14, various types of films made of an inorganic compound that exhibits gas barrier properties can be used.
Specifically, metal oxides such as aluminum oxide, magnesium oxide, tantalum oxide, zirconium oxide, titanium oxide, and indium tin oxide (ITO); metal nitrides such as aluminum nitride; metal carbides such as aluminum carbide; silicon oxide, Silicon oxides such as silicon oxynitride, silicon oxycarbide and silicon oxynitride carbide; silicon nitrides such as silicon nitride and silicon nitride carbide; silicon carbides such as silicon carbide; hydrides thereof; mixtures of two or more of these; and These hydrogen-containing materials are preferably exemplified.
In particular, a film made of a silicon compound is preferably exemplified in that it has high transparency and can exhibit excellent gas barrier properties. Among these, in particular, a film made of silicon nitride is preferable because it has high transparency in addition to more excellent gas barrier properties.

  In addition, like the gas barrier film 10a shown to FIG. 1 (A), when it has the some inorganic layer 14, each inorganic layer 14 may be formed with the same material or a different material. However, if productivity etc. are considered, it is preferable to form all the inorganic layers 14 with the same material.

In the gas barrier film 10a of the present invention, when the inorganic layer 14 on which the organic layer 12b is formed is a silicon compound, —O groups and / or —OH groups are introduced on the surface of the inorganic layer 14. (Ie, the surface layer is preferably siliconized and / or siliconized). In particular, when the inorganic layer 14 on which the organic layer 12b is formed is silicon nitride, it is preferable that —O groups and / or —OH groups are introduced on the surface thereof.
As will be described in detail later, in the gas barrier film 10a of the present invention, the organic layer 12b on the inorganic layer 14 contains a predetermined silane coupling agent. Therefore, adhesion between the inorganic layer 14 and the organic layer 12b can be further increased by introducing —O groups or —OH groups on the surface of the inorganic layer 14 on which the organic layer 12b is formed. This will be described in detail later.

What is necessary is just to determine the thickness of the inorganic layer 14 suitably according to the forming material, the thickness which can express the target gas barrier property. In addition, according to examination of this inventor, it is preferable that the thickness of the inorganic layer 14 shall be 10-200 nm.
By setting the thickness of the inorganic layer 14 to 10 nm or more, the inorganic layer 14 that stably expresses sufficient gas barrier performance can be formed. Further, the inorganic layer 14 is generally brittle, and if it is too thick, there is a possibility that cracks, cracks, peeling, etc. may occur. However, if the thickness of the inorganic layer 14 is 200 nm or less, cracks will occur. Can be prevented.
In consideration of such points, the thickness of the inorganic layer 14 is preferably 10 to 100 nm, and particularly preferably 20 to 75 nm.

  In addition, like the gas barrier film 10a shown to FIG. 1 (A), when it has the some inorganic layer 14, the thickness of each inorganic layer 14 may be the same or different.

In the gas barrier film 10a of the present invention, the inorganic layer 14 preferably has a density of 2 to 2.4 g / cm ³ .
By setting the density of the inorganic layer 14 to 2 g / cm ³ or more, a high gas barrier property can be obtained with a dense film, and sufficient bonding with respect to the bonding of the silane coupling agent contained in the organic layer 12b formed in the upper layer It is preferable in that the number can be obtained.
Moreover, it is preferable at the point that the density of the inorganic layer 14 shall be 2.4 g / cm < ³ > or less, the crack of the inorganic layer 14 resulting from high rigidity can be prevented suitably, transparency can be ensured, etc.

  The inorganic layer 14 may be formed by a known method. Specifically, vapor phase deposition methods (vapor phase film formation methods) such as plasma CVD such as CCP-CVD and ICP-CVD, sputtering such as magnetron sputtering and reactive sputtering, and vacuum deposition are preferable.

Here, in a film made of a silicon compound formed by a vapor deposition method, not all silicon is a target compound such as silicon nitride, and silicon having unbonded bonds also exists. . In particular, a large amount of silicon having unbonded bonds is present on the surface of the film.
Therefore, if the surface of the film is exposed to air (atmosphere) after forming the inorganic layer 14, the —O group or —OH group is bonded to this unbonded bond, and the surface of the inorganic layer 14 is Thus, an -O group or -OH group can be introduced. This will be described in detail later.

As described above, in the gas barrier film 10a shown in FIG. 1A, the second organic layer 12b is formed on the first inorganic layer 14, and the second inorganic layer 14 is formed. A third organic layer 12b is formed.
Here, the gas barrier film 10a (functional film) of the present invention has one or more organic layers 12b formed on the inorganic layer 14, and an organic layer formed on the inorganic layer 14. The layer 12b has the following general formula [I]
_{^{(R 1) 3 -Si-R}} 2 -Si- (R 1) 3 ··· general formula [I]
(In the general formula [I], R ¹ is an alkoxy group which may have a substituent, and R ² is a linear group which may have a linear substituent having 2 to 10 carbon atoms. An alkylene group, and each R ¹ may be the same as or different from each other.)
The silane coupling agent shown by these is contained.
Since the gas barrier film 10a of the present invention has such a configuration, an organic / inorganic laminated type gas barrier film (functional film) in which an organic layer and an inorganic layer are alternately laminated. The high adhesiveness of the upper organic layer 12b and the excellent gas barrier property due to the uniform inorganic layer 14 without defects and damages are both achieved.

  As described above, an organic / inorganic laminated gas barrier film obtained by alternately laminating an organic layer and an inorganic layer can form a uniform inorganic layer without defects by having an organic layer as a base. Thus, a high gas barrier property can be obtained. Furthermore, by having a plurality of combinations of the underlying organic layer and inorganic layer, higher gas barrier properties can be obtained. In order to protect the inorganic layer, it is effective to have an organic layer as the uppermost layer.

Here, in order to obtain a high gas barrier property, for example, it is effective to form a dense inorganic layer having a density of 2 g / cm ³ or more. However, since the inorganic layer is dense, when forming an organic layer on the inorganic layer, it is difficult to obtain an anchoring effect like an easily adhesive layer, and sufficient adhesion can be obtained. Absent.
Therefore, as shown in Patent Document 1 and Patent Document 2, in an organic / inorganic laminated gas barrier film, when an organic layer is formed on an inorganic layer, a silane coupling agent is added to the organic layer. ing.

As is well known, a silane coupling agent is a compound having a functional group that binds to an organic material and an inorganic material in the molecule.
In the organic / inorganic laminated type gas barrier film, the silane coupling agent includes, for example, a group that forms an Si—O—Si bond by silanolation and easily binds to the material forming the organic layer. By having it, the adhesiveness of the organic layer on an inorganic layer is ensured.

In view of the above points, in an organic / inorganic laminated gas barrier film, as a silane coupling agent, for example, a resin material that has radical polymerizability (radical reactivity) such as an acrylic group and forms an organic layer It is considered preferable to use a compound having a functional group (substituent) having high reactivity with.
However, according to the study of the present inventors, in an organic / inorganic laminated type gas barrier film, when a silane coupling agent having such a radical polymerizable functional group is used, the silane coupling agent is an organic layer. It has been found that inconveniences such as insufficient gas barrier properties and insufficient adhesion of the organic layer may occur due to the formation inhibition factor.

As described above, the organic layer is usually formed by a coating method using a paint containing an organic compound that becomes the organic layer. A silane coupling agent is added to the paint.
In the formation of the organic layer using a paint, the paint is applied on the inorganic layer, which is the surface on which the organic layer is formed, and then dried, and then curing according to the organic layer such as ultraviolet irradiation is performed to form the organic layer. The
In addition, as shown in Patent Document 1, in consideration of removal of by-products caused by the silane coupling agent, hydrolysis of the silane coupling agent, progress of silanolation, and the like, the drying of the paint is performed according to silane coupling. It is more advantageous to carry out the reaction at a higher temperature than the by-product resulting from the agent or the boiling point of the solvent used in the paint.

However, in the formation of a conventional organic layer using a silane coupling agent having a radical polymerizable functional group, the silane coupling agent is hydrolyzed by protons due to —OH groups or the like on the surface of the inorganic layer. The reaction proceeds by drying at a high temperature corresponding to the boiling point of the by-product or solvent.
Of course, there are also silane coupling agents that are appropriately bonded to —OH groups and the like on the surface of the inorganic layer by this reaction. However, the hydrolysis causes a self-condensation between the silane coupling agents, resulting in a certain molecular weight. There are many things that end up with structures. In the silane coupling agent thus self-condensed, the functional group portion that causes radical polymerization is retained unreacted. As a result, the self-condensed silane coupling agent has a large molecular weight, so that it becomes a material that is hard to be cured by ultraviolet rays or the like as compared with the organic compound as the main component.

Such a silane coupling agent that is self-condensed by hydrolysis in drying has a too high molecular weight, so it has poor fluidity and is difficult to bond with an organic compound that becomes an inorganic layer and an organic layer. Does not work well.
Therefore, in many cases, sufficient adhesion cannot be obtained in the organic layer formed on the inorganic layer in spite of using the silane coupling agent.

In addition, when a silane coupling agent that cannot be bonded to the self-condensed inorganic layer is combined with an organic compound that becomes the organic layer, the bond of the organic compound is reduced. However, it inhibits the polymerization of the monomer that becomes the organic layer.
Moreover, since the self-condensed silane coupling agent has a certain molecular weight, it also inhibits the polymerization of the organic compound that becomes the organic layer, so that a region that cannot be sufficiently polymerized is generated in the organic layer. In addition, since the self-condensed silane coupling agent has a certain degree of molecular weight and three-dimensional structure, its own polymerizability is also low.

As a result, the organic layer has a low content such as a self-condensed silane coupling agent that cannot be bonded to the inorganic layer, a combination of the self-condensed silane coupling agent and an organic compound, and a polymer of a low molecular weight organic compound. The molecular compound remains.
Such a low molecular weight compound has a small molecular weight as compared with a properly polymerized organic layer, and has low resistance to heat, plasma, and the like. Therefore, when an inorganic layer is formed on the organic layer, gasification or decomposition of these low molecular compounds occurs due to plasma or the like by plasma CVD, which inhibits formation of the inorganic layer. As a result, an appropriate inorganic layer cannot be formed, and a target gas barrier film having gas barrier properties cannot be obtained.
In addition, when the gas barrier film is used for an organic EL device (OLED device) or the like, the low molecular weight compound evaporates due to heat generated during the formation of the organic EL layer and the outgas is generated from the organic layer. It will adversely affect the layers and dark spots will occur. In particular, the organic layer sandwiched between the inorganic layers is sandwiched between the inorganic layers having high gas barrier properties, so that the low molecular compound expands and bursts by heating. Due to this rupture, the inorganic layer is damaged, the gas barrier property is lowered, and the generated gas adversely affects the organic EL layer and the like.

On the other hand, in the gas barrier film of the present invention, the organic layer 12b formed on the inorganic layer 14 has the following general formula [I as a silane coupling agent for ensuring adhesion with the lower inorganic layer 14. ]
_{^{(R 1) 3 -Si-R}} 2 -Si- (R 1) 3 ··· general formula [I]
(In the general formula [I], R ¹ is an alkoxy group which may have a substituent, and R ² is a linear group which may have a linear substituent having 2 to 10 carbon atoms. An alkylene group, and each R ¹ may be the same as or different from each other.)
The silane coupling agent shown by is used.

As shown in the general formula [I], this silane coupling agent does not have a functional group having radical polymerizability.
Accordingly, even if the coating is applied and dried and then cured by ultraviolet irradiation or the like, self-condensation does not occur, so that it appropriately functions as a silane coupling agent.
Further, since this silane coupling agent has a structure in which silicon atoms having an alkoxy group bonded to the inorganic layer 14 are bonded by a linear alkylene group, the silane coupling agent is often entangled with a polymer of a three-dimensionally crosslinked organic compound, and has a high anchor. Adhesiveness due to the ring effect can be obtained. In particular, by making this linear alkylene to a certain length, a silane coupling agent having a bridge shape in which both ends are bonded to the inorganic layer 14 is generated, and a polymer of an organic compound that is more preferably three-dimensionally crosslinked. Tangled.
Therefore, even if the silane coupling agent contained in the organic layer 12b does not have a radical polymerizable functional group, the gas barrier film 10 of the present invention has the adhesion of the organic layer 12b formed on the inorganic layer 14. Can be very expensive.

Furthermore, since this silane coupling agent does not have a radical polymerizable functional group, it does not inhibit the polymerization of the organic compound that becomes the organic layer 12b by the silane coupling agent, and generates a low molecular compound or the like. There is nothing to do. That is, in the gas barrier film 10a of the present invention, the low molecular compound as described above does not exist in the organic layer 12b on the inorganic layer 14.
Therefore, there is no film formation inhibition of the inorganic layer 14 due to gasification of a low molecular compound or damage to the inorganic layer 14, and a very high gas barrier property can be obtained by the uniform inorganic layer 14. Further, when the gas barrier film 10a of the present invention is used for an organic EL device or the like, the generation of dark spots due to the low molecular compound gas does not occur.

In the silane coupling agent represented by the general formula [I], R ¹ bonded to Si is an alkoxy group which may have a substituent. However, in the silane coupling agent represented by the general formula [I], R ¹ preferably has no substituent.
That is, when R ¹ is bonded to the inorganic layer 14, this R ¹ becomes a by-product, but if R ¹ has a substituent, this by-product becomes complicated and has a high boiling point, and the organic layer When the coating material forming 12b is dried, it is difficult to remove by-products.
For the same reason, R ¹ is preferably an alkoxy group having 2 or less carbon atoms, particularly 1 carbon atom.

As such R ¹ , specifically, one or more selected from —OCH ₃ and —OCH ₂ CH ₃ are preferably exemplified. That is, R ¹ is preferably —OCH ₃ , or —OCH ₂ CH ₃ , or —OCH ₃ and —OCH ₂ CH ₃ .
Incidentally, including this example, even R ¹ is any alkoxy group, the silane coupling agent represented by the formula [I], each R ¹ may be the same or different.

On the other hand, in the silane coupling agent represented by the general formula [I], R ² is a linear alkylene group which may have a linear substituent having 2 to 10 carbon atoms.
If the straight-chain carbon number of R ² is less than 2, problems such as an insufficient effect of entanglement with the aforementioned three-dimensionally crosslinked polymer cannot be obtained, and the adhesion of the organic layer 12b cannot be ensured.
On the other hand, if the number of straight carbon atoms of R ² exceeds 10, the number of bonds with the lower inorganic layer 14 is reduced, resulting in inconveniences such as the need to increase the absolute amount of the silane coupling agent.

Here, as described above, by increasing R ² to some extent, the silane coupling agent bonded to the inorganic layer 14 can be bridged, and high adhesion of the organic layer 12b can be obtained. That is, a longer R ² is advantageous in terms of adhesion of the organic layer 12b.
Considering this point, the straight chain length of R ² is preferably 4 or more.

R ² may have a substituent.
However, when R ² has a substituent, the structure of the silane coupling agent becomes complicated, and due to steric hindrance, a reaction rate difference is caused for the reaction of Si at both ends, and the bond with the inorganic layer 14 is on one side Due to the fact that only Si is present, inconveniences such as a decrease in adhesion force occur.
Therefore, when R ² has a substituent, it is preferable that only the middle methylene group having a linear carbon number of 5 or more has a substituent, and no substituent. Is particularly preferred.

In the gas barrier film 10a of the present invention, the amount of the silane coupling agent contained in the organic layer 12b is preferably 25% by mass or less.
Since the silane coupling agent remaining in the organic layer 12b works to lower the glass transition temperature (Tg) of the organic layer 12b, for example, even when the organic layer 12b with a high Tg is formed, the inorganic layer 14 is formed as an upper layer. Therefore, the resistance to etching or heat by plasma CVD is reduced. On the other hand, by setting the content of the silane coupling agent in the organic layer 12b to 25% by mass or less, it is preferable in that an unnecessary silane coupling agent can be prevented from remaining in the organic layer 12b.

Moreover, it is preferable that the quantity of the silane coupling agent which the organic layer 12b contains is 1 mass% or more.
By setting the content of the silane coupling agent to 1% by mass or more, a coating area containing the silane coupling agent can be sufficiently ensured, and the effect is suitably obtained and high adhesion of the organic layer 12 is obtained. It is preferable in terms of

  That is, in the gas barrier film 10a of the present invention, the amount of the silane coupling agent contained in the organic layer 12b is preferably 1 to 25% by mass. Considering the above points, the amount of the silane coupling agent contained in the organic layer 12b in the gas barrier film 10a of the present invention is more preferably 5 to 20% by mass.

In FIG. 2, an example of the manufacturing apparatus which implements the manufacturing method of this invention is shown notionally.
The manufacturing apparatus shown in FIG. 2 includes an organic film forming apparatus 20 that forms (deposits) the organic layers 12a and 12b, and an inorganic film formation apparatus 24 that forms (deposits) the inorganic layer. In FIG. 2, (A) is the organic film forming apparatus 20, and (B) is the inorganic film forming apparatus 24.

Both the organic film forming apparatus 20 and the inorganic film forming apparatus 24 send out the film forming material from a material roll formed by winding a long film forming material (web-shaped film forming material) into a roll shape. The film-forming material is formed while being conveyed in the longitudinal direction, and the film-formed material to be formed is wound again in a roll shape, so-called roll-to-roll (hereinafter referred to as RtoR). This is also an apparatus for forming a film.
In such a production method of the present invention, as a preferred embodiment, an efficient functional film can be produced by using such RtoR.

The production method of the present invention is not limited to the production of a functional film such as a gas barrier film using RtoR using a long support Z, and a so-called sheet using a cut sheet-like support Z. A functional film may be manufactured using a leaf type (batch type) film forming method.
Even when the cut sheet-shaped support Z is used, the method for forming the organic layer 12a, the organic layer 12b, and the inorganic layer 14 is the same as the manufacturing method using RtoR described below.
In the production method of the present invention, when a plurality of organic layers 12 and / or inorganic layers 14 are formed, the formation method (film formation method) may be the same or different for each layer.

Here, in the manufacturing apparatus shown in FIG. 2, the organic layer and the inorganic layer 14 are alternately formed on the support Z as shown in FIG. 1, and the organic layer 12b on the inorganic layer 14 is formed. One or more gas barrier films 10a and the like are produced.
Therefore, in the organic film forming apparatus 20 shown in FIG. 2A, the film forming material Za is a long support Z or a surface on which one or more layers are formed on the surface of the support Z. Is the material of the inorganic layer 14. On the other hand, in the inorganic film forming apparatus 24 shown in FIG. 2B, the film forming material Zb is a long support Z or a surface on which one or more layers are formed on the surface of the support Z. It is a material of the organic layer 12a or the organic layer 12b.

The organic film forming apparatus 20 shown in FIG. 2A applies the organic material 12a or 12b to the organic film 12a or 12b while transporting the film forming material Z in the longitudinal direction, and after drying, the organic material contained in the paint is irradiated with light. This is a device for crosslinking and curing a compound to form the organic layers 12a and 12b.
The organic film forming apparatus 20 in the illustrated example includes, as an example, an application unit 26, a drying unit 28, a light irradiation unit 30, a rotating shaft 32, a winding shaft 34, and conveyance roller pairs 36 and 38.
In addition to the illustrated members, the organic film forming apparatus 20 forms a film by coating while conveying a long film-forming material such as a pair of conveying rollers, a guide member for the film-forming material Zb, and various sensors. You may have the various members provided in the well-known apparatus to perform.

In the organic film forming apparatus 20, a material roll 42 formed by winding the film forming material Za is loaded on the rotating shaft 32.
When the material roll 42 is loaded on the rotating shaft 32, the film forming material Za is pulled out from the material roll 42, passes through the coating unit 26, the drying unit 28, and the light irradiation unit 30, and reaches the winding shaft 34. A predetermined conveyance path is passed (paper is passed).
In the organic film forming apparatus 20, the film forming material Za is fed out from the material roll 42 and the film forming material Za is wound around the winding shaft 34 in synchronization with each other, so that the long film forming material Za is formed. The organic layers 12a and 12b and the like are continuously formed on the film forming material Za while being transported in the longitudinal direction along a predetermined transport path.

  The film formation material Za sent out from the material roll 42 is nipped and conveyed by the conveyance roller pair 36 and is first conveyed to the coating unit 26.

The application part 26 applies the coating material used as the organic layers 12a and 12b to the surface of the film-forming material Za.
Here, in the production method of the present invention, the coating material that becomes the organic layer 12a formed on the surface of the support Z is made of an organic compound (one or more of monomers, dimers, trimers, oligomers, etc.) that becomes the organic layer 12a. It may be a paint used for forming a layer made of a known organic compound dissolved in an organic solvent.
On the other hand, in the manufacturing method of the present invention, the coating material to be the organic layer 12b formed on the inorganic layer 14 is represented by the above general formula [I] in addition to such an organic compound or organic solvent. It is a paint containing a silane coupling agent. In addition, the content of the silane coupling agent is preferably 25% by mass or less in terms of solid concentration (concentration in the solid content of the paint to be the organic layer 12b excluding the organic solvent). Moreover, this coating material does not need to contain the pH adjuster normally added when using a silane coupling agent.

  In addition, even if it is a case where any of organic layer 12a and 12b is formed, organic compounds, such as surfactant, a viscosity modifier, a polymerization initiator, a crosslinking agent, a refractive index modifier, are included in a coating material as needed. The component added when forming the layer which consists of by the apply | coating method may be added.

There is no particular limitation on the method of applying the coating material to the film forming material Za in the application unit 26.
Therefore, the application of the paint is all known coating methods such as die coating, dip coating, air knife coating, curtain coating, roller coating, wire bar coating, gravure coating, slide coating, etc. Is available.
Here, since it is necessary for the application part 26 to apply | coat a coating material on the inorganic layer 14, it is preferable to apply a coating material by the die-coat method (die coater). The inorganic layer 14 is fragile and easily cracked. However, according to the die coating method, since the material other than the paint does not come into contact with the inorganic layer 14, damage to the inorganic layer 14 can be suitably prevented.

The film formation material Za is then conveyed to the drying unit 28. The drying unit 28 dries the paint (coating film) applied by the application unit 26.
Here, in the organic film forming apparatus 20 of the illustrated example, as a preferred embodiment, the drying unit 28 includes a drying unit 28a that performs drying by heating from the front surface side (paint side), and a back surface side (support Z side). It has a drying section 28b for drying by heating, and the paint is dried from both the front side and the back side. For example, the drying unit 28a on the front surface side is a hot air drying unit, and the drying unit 28b on the back surface side is a heat roller (pass roller having a heating mechanism).
That is, the drying unit 28 is for drying the paint by heating the entire support Z. When the organic layer 12b is formed, the paint is sufficiently heated from the inorganic layer 14 side to be dried. Done.

The drying means in the drying unit 28 is not particularly limited, and the coating material is dried (the organic solvent is removed) before the film forming material Za reaches the light irradiation unit 30 according to the conveyance speed of the support Z and the like. Any known heating means can be used as long as the organic compound can be polymerized.
Specifically, a drying unit using a heat roller, a drying unit using warm air, a drying unit using a heat transfer plate, and the like are exemplified. The drying unit 28 may use only one of them, or may use a plurality of them together.

Next, the film forming material Za is transported to the light irradiation unit 30. The light irradiation unit 30 irradiates the coating material applied by the coating unit 26 and dried by the drying unit 28 with ultraviolet rays (UV light), visible light, or the like, and crosslinks (polymerizes) the organic compound contained in the coating material to be cured. Thus, the organic layers 12a and 12b are formed.
In the present invention, the crosslinking of the organic compound is not limited to photopolymerization, and various methods such as electron beam polymerization and plasma polymerization can be used depending on the organic compound to be the organic layers 12a and 12b. Here, in the manufacturing method of the present invention, as described above, acrylic resin such as acrylic resin or methacrylic resin is suitably used as the organic layer 12 and the organic layer 12b, so that photopolymerization and electron beam polymerization are performed. It is preferably used.

In addition, in the light irradiation part 30, you may cure an organic compound, heating the film-forming material Za as needed.
In addition, the heating method can utilize various well-known means like the drying part 28. FIG.

The film forming material Za on which the organic layers 12a and 12b are formed in this way is sandwiched and conveyed by the conveying roller pair 38 to reach the take-up shaft 34, and is taken up again in a roll shape by the take-up shaft 34. .
The film forming material Za on which the organic layers 12a and 12b are formed is shown in FIG. 2B as a material roll 46 that is formed by the inorganic film forming apparatus 24 that forms the inorganic layer 14 as necessary. It is supplied to the inorganic film forming apparatus 24 (its supply chamber 50).
The film forming material Za on which the uppermost organic layer 12b is formed is subjected to the next step or the like as a material roll 46 formed by winding the gas barrier film 10a or the like.

The inorganic film forming apparatus 24 forms (forms) the inorganic layer 14 on the surface of the film forming material Zb, that is, the surface of the organic layer 12 by vapor deposition (vacuum film forming method). The film forming chamber 52 and the winding chamber 54 are provided.
In addition to the members shown in the drawing, the inorganic film-forming apparatus 24 is not limited to a long film-forming material such as a transport roller pair, a guide member that regulates the position of the film-forming material Zb in the width direction, and various sensors. You may have the various members provided in the well-known apparatus which performs the film-forming by a vapor deposition method, conveying.

The supply chamber 50 includes a rotation shaft 56, a guide roller 60, and a vacuum exhaust unit 61.
In the inorganic film forming apparatus 24, the material roll 46 around which the film forming material Zb is wound is loaded on the rotation shaft 56 of the supply chamber 50.
When the material roll 46 is loaded on the rotating shaft 56, the film forming material Zb is passed through a predetermined transport path from the supply chamber 50 through the film forming chamber 52 to the winding shaft 58 of the winding chamber 54. The Also in the inorganic film forming apparatus 24, the film forming material Zb is fed out from the material roll 46 and the film forming material Zb is wound around the winding shaft 58 in synchronism with each other. While the film material Zb is conveyed in the longitudinal direction, the inorganic layer 14 is continuously formed on the film formation material Zb in the film formation chamber 52.

  In the supply chamber 50, the rotating shaft 56 is rotated clockwise in the drawing by a driving source (not shown), the film forming material Zb is fed from the material roll 46, and a predetermined path is guided by the guide roller 60, so that the partition wall 76. From the slit 76 a formed in the step S, the film is sent to the film forming chamber 52.

In the illustrated example of the inorganic film forming apparatus 24, as a preferred embodiment, a vacuum exhaust unit 61 is provided in the supply chamber 50, and a vacuum exhaust unit 82 is provided in the winding chamber 54. In the inorganic film forming apparatus 24, during film formation, the pressure in the supply chamber 50 and the take-up chamber 54 is determined according to the pressure (film formation pressure) in the film formation chamber 52 described later by the respective vacuum exhaust means. Keep the pressure on. This prevents the pressure in the adjacent chamber from affecting the pressure in the film forming chamber 52 (film formation in the film forming chamber 52).
The vacuum evacuation means 61 is not particularly limited, and known (vacuum) evacuation means used in a vacuum film formation apparatus, such as a vacuum pump such as a turbo pump, a mechanical booster pump, a dry pump, and a rotary pump, Various types are available. In this regard, the same applies to the other vacuum exhaust means 74 and 82 described later.

  In the film forming chamber 52, the inorganic layer 14 is formed on the surface of the film forming material Zb, that is, the organic layer 12a or the organic layer 12b by a vacuum film forming method. In the illustrated example, the film forming chamber 52 includes a drum 62, a film forming unit 64, a guide roller 68, a guide roller 72, and a vacuum exhaust unit 74.

  The film formation material Zb conveyed to the film formation chamber 52 is guided to a predetermined path by the guide roller 68 and is wound around a predetermined position of the drum 62. The film forming material Zb is conveyed in the longitudinal direction while being positioned at a predetermined position by the drum 62, and the inorganic layer 14 is formed by the vapor deposition method by the film forming unit 64.

  The vacuum evacuation means 74 evacuates the inside of the film forming chamber 52 to a degree of vacuum corresponding to the formation of the inorganic layer 14 by the vapor deposition method.

The drum 62 is a cylindrical member that rotates counterclockwise in the drawing around the center line.
The film-forming material Zb supplied from the supply chamber 50 and guided along a predetermined path by the guide roller 68 and wound around a predetermined position of the drum 62 is wound around a predetermined region on the peripheral surface of the drum 62 and The inorganic layer 14 is formed on the surface by the film forming means 64 while being supported / guided by 62 and conveyed along a predetermined conveyance path.

The film forming unit 64 forms the inorganic layer 14 on the surface of the film forming material Zb (organic layers 12a and 12b) by a vacuum film forming method.
In the manufacturing method of the present invention, the inorganic layer 14 may be formed by a known vapor deposition method (vacuum film forming method) such as a forming method described in the above-mentioned patent document. Therefore, the film forming method in the film forming means 64 is not particularly limited, and any known film forming method such as CVD, plasma CVD, sputtering, vacuum deposition, ion plating, etc. can be used.

Therefore, the film forming means 64 is composed of various members according to the vacuum film forming method to be performed.
For example, if the film formation chamber 52 is for depositing the inorganic layer 14 by ICP-CVD (inductively coupled plasma CVD), the film formation means 64 may include an induction coil for forming an induction magnetic field, It has gas supply means for supplying the reaction gas to the membrane region.
If the film forming chamber 52 is for depositing the inorganic layer 14 by the CCP-CVD method (capacitive coupling type plasma CVD), the film forming means 64 is hollow and has many small surfaces on the surface facing the drum 62. A high-frequency electrode having a hole and connected to a reaction gas supply source, a shower electrode acting as a reaction gas supply means, and the like are configured.
If the film formation chamber 52 is for depositing the inorganic layer 14 by vacuum deposition, the film forming means 64 includes a crucible (evaporation source) filled with a film forming material, a shutter for shielding the crucible, and film formation in the crucible. It has a heating means for heating the material.
Further, if the film forming chamber 52 is for depositing the inorganic layer 14 by sputtering, the film forming means 64 includes a target holding means, a high frequency electrode, a gas supply means, and the like.

  The film forming material Zb on which the inorganic layer 14 is formed by the film forming unit 64 while being supported / conveyed by the drum 62 is guided to a predetermined path by the guide roller 72, and from the slit 78 a formed in the partition wall 78. It is conveyed to the winding chamber 54.

In the illustrated example, the winding chamber 54 includes a guide roller 80, a winding shaft 58, and a vacuum exhaust unit 82.
The film-formed deposition material Zb transported to the winding chamber 54 is wound into a roll shape by the winding shaft 58 to form a material roll 42. A material roll 42 formed by winding the film forming material Zb on which the inorganic layer 14 is formed is supplied to the organic film forming apparatus 20 (loaded on the rotary shaft 32).

Hereinafter, with the manufacturing apparatus shown in FIG. 2, the organic layer 12 a, the inorganic layer 14, the second organic layer 12 b, the second inorganic layer 14, and the support Z shown in FIG. The production method of the present invention will be described in more detail by explaining the action when producing the gas barrier film 10a having the third organic layer 12b.
Note that the number of organic layers 12a and 12b to be formed and the inorganic barrier layers 10b to 10d shown in FIG. 1B to FIG. The formation of the same organic layer and inorganic layer may be repeated depending on the number of 14 and the layer configuration.

When manufacturing the gas barrier film 10a, first, a support roll formed by winding a long support Z to be a film forming material Za is loaded on the rotary shaft 32 as a material roll 42, and the support Z The organic layer 12 is formed on the surface.
When the material roll 42 is loaded on the rotating shaft 32, the support Z is pulled out from the material roll 42, passes through the conveying roller pair 36, passes through the coating unit 26, the drying unit 28, and the light irradiation unit 30, and is transported. It passes through a predetermined conveyance path that reaches the winding shaft 34 through the roller pair 38.

The film-forming material Za (support Z) pulled out from the material roll 42 is transported to the application unit 26 by the transport roller pair 36, and the coating material to be the organic layer 12a is applied to the surface. As described above, the coating material to be the organic layer 12a may be a normal coating material in which an organic compound such as a monomer corresponding to the organic layer 12a to be formed is dissolved in an organic solvent. In the illustrated example, it is assumed that a paint containing TMPTA as a main component is applied as an example.
The film forming material Za to which the coating material to be the organic layer 12a is applied is then heated by the drying unit 28, the organic solvent is removed, and the coating material is dried.
Next, the film formation material Za from which the paint has been dried is irradiated with ultraviolet rays or the like by the light irradiation unit, and the organic compound is polymerized (crosslinked) and cured to form the organic layer 12a. In addition, you may make it harden | cure the organic compound used as the organic layer 12a or the organic layer 12b in inert atmospheres, such as nitrogen atmosphere, as needed.

The film formation material Za on which the organic layer 12 is formed is transported by the transport roller pair 38 and wound in a roll shape by the winding shaft 34.
When the formation of the organic layer 12a having a predetermined length is completed, the inorganic material shown in FIG. 2 (B) is formed as a material roll 46 formed by winding the film forming material Za on which the organic layer 12a is formed after cutting as necessary. The film is supplied to the film forming apparatus 24 and used for forming the inorganic layer 14.

In the inorganic film forming apparatus 24, the material roll 46 is loaded on the rotation shaft 56 of the supply chamber 50.
When the material roll 46 is loaded on the rotating shaft 56, the film forming material Zb (the support Z on which the organic layer 12 a is formed) is drawn out, and is supplied from the supply chamber 50 through the film forming chamber 52 to the winding chamber 54. A predetermined path to the winding shaft 58 is passed.

The film forming material Zb sent out from the material roll 46 is guided by the guide roller 60 and conveyed to the film forming chamber 52.
The film formation material Zb conveyed to the film formation chamber 52 is guided by the guide roller 68 and wound around the drum 62, supported by the drum 62 and conveyed along a predetermined path, while being formed by the film formation unit 64. For example, the inorganic layer 14 is formed by CCP-CVD. In the illustrated example, it is assumed that silicon nitride is formed as the inorganic layer 14 as an example.
The inorganic layer 14 may be formed by a film forming method using a known vapor deposition method in accordance with the inorganic layer 14 to be formed. Therefore, the process gas to be used, the film formation conditions, and the like may be set / selected as appropriate according to the inorganic layer 14 to be formed, the film thickness, and the like.

The film forming material Zb on which the inorganic layer 14 is formed is guided by the guide roller 72 and conveyed to the winding chamber 54.
The film forming material Zb conveyed to the winding chamber 54 is guided to the winding shaft 58 by the guide roller 58 and wound in a roll shape by the winding shaft 58.

When the formation of the inorganic layer 14 is completed, purified dry air is introduced into all the chambers of the inorganic film forming apparatus 24 and is released into the atmosphere.
Thereafter, the material roll 42 formed by winding the film forming material Zb on which the inorganic layer 14 is formed is taken out from the winding chamber 54 of the inorganic film forming apparatus 20 as necessary.

  In order to form the second organic layer 12b, the material roll 42 formed by winding the film-forming material Zb (the support Z on which the organic layer 12a and the inorganic layer 14 are formed) on which the inorganic layer 14 is formed, Again, the organic film forming apparatus 20 is supplied.

The material roll 42 formed by winding the film forming material Zb is loaded on the rotating shaft 32 in the same manner as the formation of the organic layer 12a, and passes through a predetermined conveyance path where the film forming material Zb reaches the winding shaft 34. Is done.
Here, the organic film forming apparatus 20 is basically an apparatus for forming the organic layers 12a and 12b in the atmosphere. Accordingly, the inorganic layer 14 (nitriding) is performed during a period from when the winding chamber 54 of the inorganic film forming apparatus 24 is opened to the atmosphere to when the coating material 26 is applied by the coating unit 26 onto the inorganic layer 14. The silicon film is exposed to air.
By exposing the inorganic layer 14 to air, —O groups and / or —OH groups are introduced to the surface of the inorganic film 14 (that is, the surface layer of the inorganic film 14 is siliconized and / or silicon hydroxideized). .

In a silicon compound layer formed by a vapor deposition method, not all silicon is a target compound such as silicon nitride, and silicon having unbonded bonds is also present. In particular, a large amount of silicon having an unbonded bond is present on the surface of the inorganic layer 14. Therefore, after the inorganic layer 14 is formed, if the surface of the inorganic layer 14 is exposed to air (atmosphere), -O groups or -OH groups are bonded to the unbonded bonds, and the surface of the inorganic layer 14 is An —O group and / or an —OH group can be introduced.
In the present invention, by having —OH group or the like on the surface of the inorganic layer 14, the reaction of the silane coupling agent suitably proceeds even if the coating material forming the organic layer 12 b does not contain a pH adjuster. be able to.

In the present invention, the timing of exposing the surface of the inorganic layer 14 to air is not limited to the above example. That is, the surface of the inorganic layer 14 on which the organic layer 12b is formed as an upper layer may be exposed to air at any timing or method as long as it is until the upper organic layer is formed.
For example, after the inorganic layer 14 is formed, when the inorganic film forming apparatus 24 is opened to the atmosphere with an inert gas such as nitrogen, the material layer 42 is taken out from the winding chamber 54 and then becomes the organic layer 12b. What is necessary is just to expose the surface of the inorganic layer 14 to air until it applies a coating material.

As described above, in the organic film forming apparatus 20, the film forming material Zb (support Z on which the organic layer 12 a and the inorganic layer 14 are formed) is conveyed in the longitudinal direction, and the coating unit 26 applies the inorganic layer 14. A coating material to be the organic layer 12b is applied thereon. There is no particular limitation on the coating method applied by the coating unit 26, but the die coating method is suitable as described above.
Here, in the manufacturing method of the present invention, the coating material for forming the organic layer 12b on the inorganic layer 14 is represented by the organic solvent, the organic compound that becomes the organic layer 12b, and the general formula [I] described above. Contains a predetermined silane coupling agent. The content of the silane coupling agent is preferably 1 to 25% by mass with respect to the solid content concentration (content (% by mass) when the component (solid content) as solid content) is 100% by mass). It is more preferable that it is 5-20 mass%. Moreover, in the manufacturing method of this invention, when using a silane coupling agent, the coating material used as the organic layer 12b does not need to contain the pH adjuster normally added as an essential component.
In the illustrated example, it is assumed that a paint containing TMPTA as a main component is applied as an example.

Here, the organic compound that becomes the organic layer 12b is a by-product (mainly a by-product (usually alcohol) by-produced by hydrolysis) resulting from the silane coupling agent contained in the paint, and the paint. It is preferable to use one having a Tg (glass transition temperature) higher than the azeotropic point with the organic solvent used. In the following description, for convenience, the azeotropic point of this by-product and the organic solvent is simply referred to as “by-product azeotropic point”.
Alternatively, when the by-product resulting from the silane coupling agent and the organic solvent to be used do not azeotrope, the Tg is higher than the higher one of the boiling point of the by-product and the boiling point of the organic solvent. Is preferably an organic compound that becomes the organic layer 12b. Similarly, in the following description. For convenience, the higher boiling point of the by-product and the organic solvent is defined as the “paint boiling point”.

In the production method of the present invention, after the coating material for forming the organic layer 12b is applied, the coating material is dried at a temperature higher than the byproduct azeotropic point or higher than the coating material boiling point. Preferably, after applying the paint for forming the organic layer 12b, when the azeotrope described above occurs, the temperature is higher than the byproduct azeotropic point, and when the azeotrope does not occur, higher than the paint boiling point. Dry the paint.
Here, if the heat resistance of the organic compound to be the organic layer 12b is too low, the organic compound is softened by heat at the time of drying, so that proper drying cannot be performed, and the organic compound is altered. May occur.
Therefore, by using an organic compound having a Tg higher than the byproduct azeotropic point or paint boiling point as the organic compound to be the organic layer 12b, it is possible to prevent the organic compound from being softened during drying. The proper organic layer 12b can be stably formed by a properly dried paint.

The paint applied by the application unit 26 is dried by the drying unit 28.
Here, in the organic film forming apparatus 20 of the illustrated example, when the drying unit 28 forms the organic layer 12b, the drying unit 28 performs drying of the coating material forming the organic layer 12b at a temperature higher than the byproduct azeotropic point. Alternatively, when the drying unit 28 forms the organic layer 12b, the drying unit 28 dries the coating material forming the organic layer 12b at a temperature higher than the boiling point of the coating material.
If necessary, a heating step of heating the paint at a temperature higher than the byproduct azeotropic point or the paint boiling point may be provided before the paint is dried.

  The production method of the present invention uses a coating material containing the silane coupling agent represented by the general formula [I], and performs drying at a temperature higher than the byproduct azeotropic point or the boiling point of the coating material to form an organic layer 12b (inorganic layer). By forming the upper organic layer), the adhesion between the lower inorganic layer 14 and the organic layer 12b is excellent, and the gas barrier performance is high. Further, when used in an organic EL device, etc. This makes it possible to produce a gas barrier film that also prevents adverse effects due to outgassing.

As shown in Patent Document 1, when the organic layer 12 b is formed on the inorganic layer 14, when the inorganic layer 14 is a silicon compound, the surface of the inorganic layer 14 has —O groups and / or — OH groups have been introduced, and a coating containing an appropriate amount of a silane coupling agent is applied to the surface, and the pH is not adjusted by drying at a temperature higher than the byproduct azeotropic point or the boiling point of the coating. In this case, hydrolysis reaction and dehydration condensation of the silane coupling agent occur.
That is, in a state where —OH groups and the like are introduced on the surface of the inorganic layer, by heating the paint to a temperature higher than the byproduct azeotropic point, etc., —OH groups and the like are released from the surface of the inorganic layer and silane coupling. Hydrolysis reaction of the agent occurs, and the surface of the inorganic layer and the silane coupling agent are bonded by a covalent bond by dehydration condensation. In addition, by heating the paint to a byproduct azeotropic point or higher than the paint boiling point, the by-product and the like are evaporated and removed together with the organic solvent of the paint, so that the reaction cycle becomes faster and the surface of the inorganic layer 14 and the silane Binding with the coupling agent is further promoted.

That is, according to the present invention, the bond between the surface of the inorganic layer 14 and the silane coupling agent and the above-described general formula [ Adhesion between the inorganic layer 14 and the organic layer 12b can be ensured by entanglement between the silane coupling agent represented by I] and an organic compound such as a polymerized monomer.
Moreover, since the coating material used as the organic layer 12b can be apply | coated by the normal method performed in air | atmosphere, productivity can also be improved.

In addition, since the heating is performed at a temperature higher than the temperature at which the by-product due to the silane coupling agent evaporates, by-products such as alcohol generated by hydrolysis of the silane coupling agent during the heating are removed, The amount of remaining by-products can be greatly reduced.
Therefore, it is possible to form an organic layer 12b that does not have a by-product of a silane coupling agent that is an impurity and that expresses high quality and performance appropriately. Moreover, when the inorganic layer 14 is further formed on the organic layer 12b formed on the inorganic layer 14 as will be described later, the adverse effect of evaporation of these by-products etc. on the formation of the inorganic layer 14 is eliminated. Thus, a dense inorganic layer 14 can be formed to produce a gas barrier film with high gas barrier performance.

In addition, since the paint does not require a pH adjuster, an increase in the viscosity of the paint over time due to the addition of the pH adjuster can be prevented.
Further, for the coating material forming the organic layer 12b, the pH adjuster is an impurity when viewed as a material for forming the organic layer. For this reason, the addition of a pH adjusting agent to the paint may cause a variation in viscosity, a decrease in Tg of the organic compound or the organic layer 12b to be formed, etc., but such inconvenience can also be prevented (suppressed).

In addition, as is well known, there is convection of the paint from the bottom to the top in the film by heating the paint. Therefore, by this convection, the reaction between the silane coupling agent and the inorganic layer 14 can be advanced on the surface of the inorganic layer 14 and in the vicinity of the surface as the paint is dried. In addition, as described above, the silane coupling agent represented by the general formula [I] does not self-condensate, and thus this convection is very suitably performed.
As a result, the silane coupling agent is oriented in the vicinity of the surface of the inorganic layer 14 so that the surface side of the organic layer 12b can be made of a high-purity organic compound with little silane coupling agent. Thereby, the surface of the organic layer 12b has characteristics such as an appropriate Tg according to the forming material and the like, and the organic layer 12b can appropriately express the intended function. In addition, since the silane coupling agent can be oriented in the vicinity of the surface of the inorganic layer 14, the effect of addition can be sufficiently obtained even if the amount of the silane coupling agent is small.
Also, as shown in the example, when the drying unit 28 dries the paint from both the front surface side (the paint side) and the back surface side (the support Z side, that is, the inorganic layer 14 side), this effect is It can obtain more suitably and is more preferable.

In the production method of the present invention, the drying temperature of the coating material forming the organic layer 12b may be a by-product azeotropic point or a temperature higher than the boiling point of the coating material. Preferably, as described above, the by-product by the silane coupling agent is used. When the solvent and the organic solvent are azeotroped, the temperature is higher than the azeotropic point of the double product, and when not, the temperature is higher than the boiling point of the paint.
When the drying temperature of the paint is lower than the byproduct azeotropic point or the paint boiling point, the hydrolysis or dehydration condensation reaction of the silane coupling agent does not proceed sufficiently.
There is no particular limitation on the upper limit of the drying temperature of the paint. Here, according to the study of the present inventors, the higher the drying temperature, the better the adhesion between the organic layer and the inorganic layer. On the other hand, if drying is performed at a temperature exceeding the softening point of the support Z, the support Z is damaged by heat and an appropriate product cannot be produced. Therefore, it is preferable that the drying temperature of the paint is equal to or lower than the softening point according to the support Z to be used.

The film-formed member Za that has been dried by the drying unit 28 is then transported to the light irradiation unit 30 and irradiated with ultraviolet rays, visible light, or the like.
By this light irradiation, the organic compound of the coating is polymerized (crosslinked), the coating is cured, and the organic layer 12 b is formed on the inorganic layer 14.

The film formation material Za on which the organic layer 12 b is formed, that is, the gas barrier film 10 a is wound up in a roll shape by the winding roller 34.
When the formation of the organic layer 12b having a predetermined length is completed, the material roll 46 is formed by winding the film-forming material Za on which the organic layer 12b is formed after cutting as necessary. ) And the second inorganic layer 14 is formed.

Similar to the formation of the first inorganic layer 14, the material roll 46 is loaded on the rotation shaft 56 of the supply chamber 50.
When the material roll 46 is loaded on the rotating shaft 56, the film forming material Zb (the support Z on which the organic layer 12 a, the inorganic layer 14, and the organic layer 12 b are formed) is drawn out from the supply chamber 50. A predetermined path extending through 52 to the winding shaft 58 of the winding chamber 54 is passed.
Next, similarly to the formation of the first inorganic layer 14, the film formation material Zb is fed from the material roll 46 and conveyed from the supply quality 50 to the film formation quality 52, where the second inorganic layer 14 ( Similarly to the above, silicon nitride) is formed, conveyed to the winding chamber 54, and wound in a roll shape by the winding shaft 58.

When the formation of the inorganic layer 14 is completed, purified dry air is introduced into all the chambers of the inorganic film forming apparatus 24 and is released into the atmosphere.
Thereafter, the material is cut as necessary, and is taken out from the winding chamber 54 of the inorganic film forming apparatus 20 as a material roll 42 formed by winding the film-formed material Zb on which the second inorganic layer 14 has been formed. .

  The material roll 42 formed by winding the film forming material Zb on which the second inorganic layer 14 is formed is supplied again to the organic film forming apparatus 20 in order to form the third organic layer 12b. .

Similarly to the formation of the second organic layer 12b, the material roll 42 formed by winding the film forming material Zb is loaded on the rotating shaft 32, and the film forming material Zb (the organic layer 12a, the inorganic layer 14, The substrate Z) on which the second organic layer 12b and the second inorganic layer 14 are formed is passed through a predetermined transport path to the winding shaft 34.
Next, as in the formation of the second organic layer 12b described above, the film forming material Zb is conveyed in the longitudinal direction and is applied with a coating material containing a silane coupling agent represented by the general formula [I] in the application unit 26 ( As before, TMPTE is the main component), and in the drying unit 28, the paint is dried at a temperature higher than the byproduct azeotropic point or the boiling point of the paint, and then conveyed to the light irradiation unit 30 to be the third layer. An organic layer 12b is formed.

The film forming material Za on which the uppermost organic layer 12b is formed, that is, the gas barrier film 10a, is wound up in a roll shape by a winding roller.
When the formation of the uppermost organic layer 12b is completed, the gas barrier film 10a is cut as necessary, and then supplied as a material roll 46 formed by winding the gas barrier film 10a to the next step or the like.

  As mentioned above, although the functional film of this invention and the manufacturing method of a functional film were 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, various improvement and change Of course, you may do.

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

[Example 1]
A gas barrier film 10d shown in FIG. 1 (D) having an organic layer 12a, an inorganic layer 14, a second organic layer 12b, and a second inorganic layer 14 was produced using the manufacturing apparatus shown in FIG. .

  As the support Z, a long PEN film having a width of 1000 mm and a thickness of 100 μm (Teonex Q65FA manufactured by Teijin DuPont Films Ltd.) was used.

An organic compound and a photopolymerization initiator were dissolved in an organic solvent (methyl ethyl ketone (MEK)) to prepare a paint for forming the organic layer 12.
As the organic compound, TMPTA (manufactured by Daicel Cytec) was used, and as the photopolymerization initiator, Irg189 (manufactured by Ciba Chemicals) was used. The coating material had a solid content concentration of 15% by mass (MEK 85% by mass). The solid content in the paint was 98% by mass for the organic compound and 2% by mass for the photopolymerization initiator.

A material roll 42 formed by winding the support Z (film formation material Za) was loaded on the rotating shaft 32 of the organic film forming apparatus 20 shown in FIG. 2A and prepared on the surface of the support Z. The material roll 46 formed by winding the film forming material Za on which the organic layer 12a was formed by applying / drying the paint and cross-linking by ultraviolet irradiation was obtained.
The coating amount of the coating in the coating part 26 was adjusted so that the film thickness of the organic layer 12a was 3 μm. The application unit 26 used a die coater. Drying by the drying unit 28 was performed by heating the paint to 80 ° C. with warm air. Further, the light irradiation unit 30 uses an ultraviolet irradiation device and adjusts the light amount so that the ultraviolet irradiation amount is about 500 mJ / cm ² in terms of the integrated irradiation amount.

Next, the material roll 46 is loaded into the inorganic film forming apparatus 24 shown in FIG. 2B, and the inorganic layer is formed on the surface of the support Z (film forming material Zb) on which the organic layer 12a is formed by CCP-CVD. A silicon nitride film having a thickness of 50 nm was formed as No. 14.
The film forming means 64 includes a shower electrode disposed facing the drum 62, a high frequency power source for supplying plasma excitation power to the shower electrode, a bias power source for supplying bias power to the drum 62, and a source gas for the shower electrode. It comprised with the supply means to supply. Further, the drum 62 was made of stainless steel and acted as a counter electrode of the shower electrode.

Silane gas (SiH ₄ ), ammonia gas (NH ₃ ), nitrogen gas (N ₂ ), and hydrogen gas (H ₂ ) were used as the film forming gas. The supply amounts were 100 sccm for silane gas, 200 sccm for ammonia gas, 500 sccm for nitrogen gas, and 500 sccm for hydrogen gas. The film forming pressure was 50 Pa.
The shower film-forming electrode was supplied with 3000 W of plasma excitation power at a frequency of 13.5 MHz from a high frequency power source. Further, a bias power of 500 W was supplied to the drum 62 from a bias power source. During film formation, the temperature of the drum 62 was adjusted to -20 ° C.

When the formation of the inorganic layer 14 was completed, purified air was introduced into the supply chamber 50, the film formation chamber 52, and the winding chamber 54 to release the atmosphere.
Next, the material roll 42 formed by winding the film forming material Zb on which the inorganic layer 14 was formed was taken out from the winding chamber 54.

On the other hand, an organic compound, a silane coupling agent and a photopolymerization initiator were dissolved in an organic solvent (MEK) to prepare a coating material for forming the organic layer 12b.
The same organic compound and photopolymerization initiator as those used in the organic layer 12a were used.
The silane coupling agent has the general formula [I]
(R ¹ ) ₃ —Si—R ² —Si— (R ¹ ) ₃
In which R ¹ is all —OCH ₃ and R ² is — (CH ₂ ) ₂ —.
The coating material had a solid content concentration of 15% by mass (MEK 85% by mass). The solid content in the paint was 88% by mass for the organic compound, 2% by mass for the photopolymerization initiator, and 10% by mass for the silane coupling agent.
The azeotropic point of the by-product (methanol) by the silane coupling agent and MEK, which is an organic solvent, varies depending on the residual amount of MEK and the amount of methanol produced, but is generally about 65 ° C. .

A material roll 42 formed by winding a film forming material Za (support Z on which the organic layer 12a and the inorganic layer 14 are formed) is loaded on the rotating shaft 32 of the organic film forming apparatus 20, and is applied to the surface of the support Z. Then, the prepared coating material was applied / dried, crosslinked by ultraviolet irradiation to form the organic layer 12b, and a material roll 46 formed by winding the film forming material Zb formed with the organic layer 12b was obtained.
The coating amount of the coating unit 26 was adjusted so that the thickness of the organic layer 12 was 3 μm. Drying by the drying unit 28 was performed by heating the paint to 80 ° C. with warm air. Furthermore, the light irradiation part 30 was made so that the irradiation amount of an ultraviolet-ray might be about 500 mJ / cm < ² > in an integrated irradiation amount.

Next, a material roll 46 formed by winding the film forming material Zb (support Z on which the organic layer 12a, the inorganic layer 14, and the organic layer 12b are formed) is loaded into the inorganic film forming apparatus 24 shown in FIG. did.
Further, in the same manner as the first inorganic layer 14, the second inorganic layer 14 has a film thickness of 50 nm on the surface of the support Z (film formation material Zb) on which the second organic layer 12 b is formed. A silicon nitride film was formed to produce a gas barrier film 10d shown in FIG. 1D, and a material roll 46 formed by winding the gas barrier film 10d was obtained.

[Examples 2 and 3]
The silane coupling agent used for forming the organic layer 12b is represented by the general formula [I].
(R ¹ ) ₃ —Si—R ² —Si— (R ¹ ) ₃
Except that R ¹ is all —OCH ₃ and R ² is — (CH ₂ ) ₆ — (Example 2);
The silane coupling agent used for forming the organic layer 12b is represented by the general formula [I].
(R ¹ ) ₃ —Si—R ² —Si— (R ¹ ) ₃
In the same manner as in Example 1, except that R ¹ is all —OCH ₃ and R ² is — (CH ₂ ) ₈ — (Example 3); A gas barrier film 10d shown in FIG. 1 (D) formed by forming the organic layer 12a, the inorganic layer 14, the organic layer 12b, and the inorganic layer 14 was produced, and a material roll 46 formed by winding this was obtained.

[Example 4]
The silane coupling agent used for forming the organic layer 12b is represented by the general formula [I].
(R ¹ ) ₃ —Si—R ² —Si— (R ¹ ) ₃
, R ¹ is all —OCH ₂ CH ₃ and R ² is — (CH ₂ ) ₆ —, and the temperature of the hot air in the drying section 18 in the formation of the organic layer 12b is changed to 100 ° C. Except for the above, a gas barrier film 10d shown in FIG. 1 (D) is formed by forming the organic layer 12a, the inorganic layer 14, the organic layer 12b, and the inorganic layer 14 on the support Z in the same manner as in Example 1. The material roll 46 produced and wound was obtained.
In addition, 100 degreeC of drying temperature is the temperature set according to the boiling point of the by-product (ethanol) by this silane coupling agent.

[Comparative Example 1]
The silane coupling agent used for forming the organic layer 12b is represented by the general formula [I].
(R ¹ ) ₃ —Si—R ² —Si— (R ¹ ) ₃
In the above, two of R ¹ bonded to each Si are —OCH ₃ , one is —C ₃ H ₆ —COCH═CH ₂ having an acrylic group, and R ² is — (CH ₂ ) ₆ —. Except for the change, the gas barrier film 10d shown in FIG. 1D is formed by forming the organic layer 12a, the inorganic layer 14, the organic layer 12b, and the inorganic layer 14 on the support Z in the same manner as in Example 1. And a material roll 46 formed by winding this was obtained.

[Comparative Example 2]
The silane coupling agent used for forming the organic layer 12b is represented by the following formula (CH ₃ O) ₃ —Si— (CH ₂ ) ₅ —CH _3.
1 (D), wherein the organic layer 12a, the inorganic layer 14, the organic layer 12b, and the inorganic layer 14 are formed on the support Z in the same manner as in Example 1 except that the material is changed to the one shown in FIG. A gas barrier film 10d shown in FIG. 6 was produced, and a material roll 46 formed by winding this was obtained.

Thus, about each gas barrier film 10d produced, gas barrier property and adhesiveness were evaluated.
<Gas barrier properties>
The gas barrier property (water vapor permeability [g / (m ² · day)]) of each gas barrier film was measured by a calcium corrosion method (a method described in JP-A-2005-283561).
The water vapor transmission rate is best when it is less than 1 × 10 ⁻⁵ [g / (m ² · day)] (that is, less than 1 × 10 ⁻⁵ E [g / (m ² · day)]);
Excellent when 1 x 10 ^-5 [g / (m ² · day)] or more and less than 4 x 10 ^-5 [g / (m ² · day)];
Good when 4 × 10 ⁻⁵ [g / (m ² · day)] or more and less than 1 × 10 ⁻⁴ [g / (m ² · day)];
The case of 1 × 10 ⁻⁴ [g / (m ² · day)] or more was evaluated as “impossible”.

<Adhesion>
Evaluation was made by a cross-cut peel test in accordance with JIS K5400.
Using a cutter knife, 90 ° cuts were made at 1 mm intervals on the organic layer and inorganic layer forming surfaces of each gas barrier film to make 100 grids with 1 mm intervals. On top of this, the tape affixed with a 2 cm wide Mylar tape (manufactured by Nitto Denko, polyester tape, No. 31B) was peeled off. Evaluation was performed by the number of cells in which the organic layer 12b remained.
The one with 100 remaining masses is the best;
Excellent remaining mass number of 91-99;
Good with a residual mass of 81-90;
A product having a residual mass number of 80 or less was evaluated as “impossible”.
The results are shown in the table below.

As shown in the above table, each of the gas barrier films of the present invention has good gas barrier properties and adhesion of the organic layer 12b. In particular, straight-chain carbon number of R ² is 8, Example 3 R ¹ is -OCH ₃ has a very good gas barrier properties and adhesion.
In addition, Example 1 in which the number of linear carbon atoms of R ² is 2 is considered to be less entangled between the silane coupling agent and the polymerized organic compound, and is slightly inferior to the other examples.

On the other hand, in Comparative Example 1 in which the silane coupling agent contains an acrylic group, the above-described self-condensate of the silane coupling agent is generated, resulting in a decrease in function of the silane coupling agent and inhibition of polymerization. , Low molecular weight substances such as self-condensates remain, resulting in a decrease in polymerizability, a decrease in adhesion, a decrease in gas barrier properties, and the like. It is considered that the adhesiveness is low.
Further, Comparative Example 2 in which the silane coupling agent has only one Si atom exhibits excellent gas barrier properties because it does not exacerbate the factors that inhibit the formation of the inorganic layer 14, but the silane cup The effect of improving the adhesion of the ring agent is low, and it is considered that the adhesion is lower than that of the product of the present invention.
From the above results, the effects of the present invention are clear.

10a, 10b, 10c, 10d Gas barrier films 12a, 12b Organic layer 14 Inorganic layer 20 Organic film forming device 24 Inorganic film forming device 26 Coating unit 28 Drying unit 30 Light irradiation unit 32, 56 Rotating shaft 34, 58 Winding shaft 36, 38 Conveying roller pair 42, 46 Material roll 50 Supply chamber 52 Film forming chamber 54 Winding chamber 60, 68, 72, 80 Guide rollers 61, 74, 82 Vacuum exhaust means 62 Drum 64 Film forming means 76, 78 Partition

Claims (12)

A functional film having a support and organic and inorganic layers alternately formed on the support,
The inorganic layer has a thickness of 200 nm or less;
The organic layer formed on the inorganic layer has at least one organic layer formed on the inorganic layer, and the organic layer formed on the inorganic layer is mainly composed of a resin made of bifunctional or higher (meth) acrylate. ones, and the and functional film is characterized by containing a silane coupling agent represented by the following general formula [I] 1 to 25 wt%.
_{^{(R 1) 3 -Si-R}} 2 -Si- (R 1) 3 ··· general formula [I]
(In the general formula [I], R ¹ is an alkoxy group which may have a substituent, and R ² is a linear group which may have a linear substituent having 2 to 10 carbon atoms. An alkylene group, and each R ¹ may be the same as or different from each other.) The functional film according to claim 1, wherein, in the general formula [I], R ¹ is one or more selected from —OCH ₃ and —OCH ₂ CH ₃ . The functional film according to claim 1 or 2, wherein in the general formula [I], R ¹ has no substituent. Functional film described in the above general formula [I], in any one of claims 1 to 3, R ² is no substituent. The functional film according to claim 1, wherein the inorganic layer is made of silicon nitride .   The glass transition temperature of the organic compound to be the organic layer is higher than the boiling point of the by-product resulting from the silane coupling agent or the boiling point of the organic solvent used for forming the organic layer. 2. The functional film according to item 1.   The functional film according to claim 1, wherein the organic layer on the inorganic layer has a thickness of 5 μm or less.   The functional film according to any one of claims 1 to 7, wherein the inorganic layer is made of silicon nitride, and at least one of -OH group and -O group is introduced on the surface thereof. The density of the said inorganic layer is 2-2.4g / cm < ³ >, The functional film of any one of Claims 1-8. When manufacturing a functional film formed by alternately forming an organic layer and an inorganic layer on a support,
Forming an inorganic layer having a thickness of 200 nm or less, and
Forming an organic layer on the inorganic layer at least once, and
When an organic layer is formed on the inorganic layer, at least an organic solvent, a bifunctional or higher (meth) acrylate serving as the organic layer, and a silane coupling agent represented by the following general formula [I] are paired. An application step of applying a paint containing 1 to 25% by mass in solid content concentration ,
_{^{(R 1) 3 -Si-R}} 2 -Si- (R 1) 3 ··· general formula [I]
(In the general formula [I], R ¹ is an alkoxy group which may have a substituent, and R ² is a linear group which may have a linear substituent having 2 to 10 carbon atoms. And each R ¹ may be the same as or different from each other.
A drying step of drying the paint at a temperature higher than the azeotropic point of the by-product and the organic solvent due to the silane coupling agent or higher than the boiling point of the by-product and the organic solvent;
And the manufacturing method of the functional film characterized by performing the hardening process which hardens the said dried coating material by light irradiation.   The method for producing a functional film according to claim 10, wherein a long support is used and the organic layer and the inorganic layer are formed while the support is conveyed in the longitudinal direction. The method for producing a functional film according to claim 10, wherein a layer made of silicon nitride is formed as the inorganic layer.

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