KR20160035026A - Functional film and method for manufacturing functional film - Google Patents

Abstract

A functional film formed by alternately forming an organic layer and an inorganic layer, wherein the organic layer formed on the inorganic layer is represented by the following general formula [I]
(R ¹ ) ₃ -Si-R ² -Si- (R ¹ ) ₃ In the general formula [I]
(In the formula [I], R ¹ is an alkoxy group which may have a substituent, R ² is an alkylene group of a straight-chain carbon atoms in the straight-chain which may have a 2 to 10, which is the substituent. In addition, each of R ¹ May be the same or different, and have a silane coupling agent. Thus, there is provided a functional film having a high gas barrier property, having a high-quality organic layer with a small amount of outgass and high adhesiveness on the inorganic layer, and a method for producing the functional film.

Description

TECHNICAL FIELD [0001] The present invention relates to a method for producing a functional film and a functional film,

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.

A gas barrier film such as an optical element, a display device such as a liquid crystal display or an organic EL display, various semiconductor devices, a solar cell, and other various devices such as a packaging material for moisture-proofing parts and parts, have.

The gas barrier film is generally formed by using a plastic film such as a polyethylene terephthalate (PET) film as a support (substrate) and forming a film (hereinafter also referred to as a gas barrier film) . As the gas barrier film used for the gas barrier film, a film made of various inorganic compounds such as silicon nitride, silicon oxide, and aluminum oxide is known.

In such a gas barrier film, a laminated structure in which an organic layer (organic compound layer) made of an organic compound and an inorganic layer (inorganic compound layer) made of an inorganic compound are alternately laminated is formed on a support An organic / inorganic laminated gas barrier film is known.

In the organic / inorganic laminate type gas barrier film, it is an inorganic layer that mainly exhibits gas barrier properties. In the organic / inorganic laminated gas barrier film, the inorganic layer is formed on the organic layer which becomes the base (bottom), and the formation surface of the inorganic layer is smoothed by the organic layer. By forming an inorganic layer on the organic layer having good smoothness, a uniform inorganic layer free from gold, cracks, or the like is formed and excellent gas barrier performance is obtained.

In the organic / inorganic laminated gas barrier film, it is also known that more gas barrier performance can be obtained by having a plurality of combinations of the underlying organic layer and the inorganic layer.

Here, in the organic / inorganic laminated gas barrier film, it is difficult to ensure the adhesion between the layers, in particular, the adhesion of the organic layer formed on the inorganic layer.

The inorganic layer exhibiting gas barrier properties has a dense crystal structure. As a result, the organic layer formed on the inorganic layer permeates through the layer like the adhesive layer, and an anchoring effect can not be obtained, and sufficient adhesion can not be ensured.

Correspondingly, in the organic / inorganic laminated gas barrier film, it is known that when forming an organic layer on an inorganic layer, a silane coupling agent is contained in the organic layer to ensure adhesion of the organic layer.

As is well known, a silane coupling agent is a compound having a functional group binding to an organic material and an inorganic material in a molecule. In the organic / inorganic laminate type gas barrier film, the silane coupling agent is a silane coupling agent which forms a bond of Si-O-Si by silanolization with the inorganic layer and forms an organic layer such as an acrylic group By having a functional group that is easy to bond to a material (resin material), the adhesion of the organic layer on the inorganic layer is ensured.

Various proposals have been made for an organic / inorganic laminated gas barrier film using a silane coupling agent.

For example, Patent Document 1 discloses an organic / inorganic laminated gas barrier film in which the organic layer on the inorganic layer has an organic solvent, an organic compound to be an organic layer, and a silane coupling agent, And a method for producing a gas barrier film which is heated at a higher temperature, such as by-products resulting from organic solvents and silane coupling agents, in a process of forming an organic layer.

Patent Document 2 describes a gas barrier film having a silane coupling agent in which the organic layer is represented by the following general formula in the organic / inorganic laminated gas barrier film.

(R ₁ , R ₂ , R ₃ ) Si-NH-Si (R ₄ , R ₅ , R ₆ )

(Wherein R ₁ to R ₆ are each a substituted or unsubstituted alkyl group or aryl group, provided that at least one of R ₁ to R ₆ contains a radically polymerizable carbon-carbon double bond. )

Patent Document 1: JP-A-2013-31794 Patent Document 2: JP-A-2013-43382

According to the gas barrier film shown in Patent Document 1 or 2, a gas barrier film having excellent adhesion to an organic layer and having high gas barrier properties can be obtained.

However, in recent years, the demand for an organic / inorganic laminated gas barrier film has become stricter. As a result, depending on the application and required performance, the gas barrier film using a silane coupling agent for these organic layers may be insufficient in either or both of the adhesion of the organic layer and gas barrier property.

It is an object of the present invention to solve such a problem of the prior art, and it is an object of the present invention to provide a functional film of an organic / inorganic laminate type such as a gas barrier film which is excellent in adhesion between an organic layer on an inorganic layer and a gas barrier property And to provide 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 an organic layer and an inorganic layer alternately formed on the support,

There is provided a functional film characterized in that it has at least one organic layer formed on an inorganic layer and the organic layer formed on the inorganic layer contains a silane coupling agent represented by the following general formula [I].

(R ¹ ) ₃ -Si-R ² -Si- (R ¹ ) ₃ In the general formula [I]

(In the formula [I], R ¹ is an alkoxy group which may have a substituent, R ² is an alkylene group of a straight-chain carbon atoms in the straight-chain which may have a 2 to 10, which is the substituent. In addition, each of R ¹ May be the same or different from each other.)

In the functional film of the present invention, it is preferable that R ¹ in the general formula [I] is at least one selected from -OCH ₃ and -OCH ₂ CH ₃ .

In the general formula [I], it is preferable that R ¹ does not have a substituent.

In the general formula [I], it is preferable that R ² does not have a substituent.

Further, the organic layer on the inorganic layer mainly contains a resin comprising two or more functional (meth) acrylates, and the content of the silane coupling agent is preferably 1 to 25 mass%.

It is also preferable that the glass transition temperature of the organic compound to be an 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.

The thickness of the organic layer on the inorganic layer is preferably 5 占 퐉 or less.

It is preferable that 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 inorganic layer is preferably 2 to 2.4 g / cm ³ .

In the method for producing a functional film of the present invention, when a functional film is formed by alternately forming an organic layer and an inorganic layer on a support,

An organic layer is formed on the inorganic layer at least once,

When the organic layer is formed on the inorganic layer, a coating step of applying at least a coating material containing an organic solvent, an organic compound to be an organic layer, and a silane coupling agent represented by the following general formula [I]

(R ¹ ) ₃ -Si-R ² -Si- (R ¹ ) ₃ In the general formula [I]

(In the formula [I], R ¹ is an alkoxy group which may have a substituent, R ² is an alkylene group of a straight-chain carbon atoms in the straight-chain which may have a 2 to 10, which is the substituent. In addition, each of R ¹ May be the same or different from each other.)

A drying step of drying the coating material at a temperature higher than the azeotropic point of the by-product resulting from the silane coupling agent and the organic solvent or higher than the boiling point of the by-product and the boiling point of the organic solvent,

And a curing step of curing the dried paint by light irradiation is provided.

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

According to the present invention having the above-described constitution, in the organic / inorganic laminate type functional film in which the organic layer and the inorganic layer are alternately laminated, the high adhesion of the organic layer on the inorganic layer, Can be obtained at the same time.

1 (A) to 1 (D) in Fig. 1 conceptually show an example of the functional film of the present invention.
Fig. 2 (A) is a conceptual view of an example of an apparatus for forming an organic layer to which the method for producing a functional film of the present invention is applied, and Fig. 2 (B) Fig. 8 is a diagram conceptually showing an example of an apparatus for forming an inorganic layer to be carried out.

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

The functional film of the present invention is basically an organic / inorganic laminate type functional film formed by alternately forming an organic layer and an inorganic layer on a support.

The functional film of the present invention has at least one organic layer formed on the inorganic layer and the organic layer formed on the inorganic layer contains the silane coupling agent represented by the general formula [I].

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

In addition, the method for producing a functional film and a functional film of the present invention is not limited to a method for producing a gas barrier film and a gas barrier film. That is, the present invention can be applied to various known functional films such as various optical films such as optical filters and antireflection films, which exhibit desired functions. However, as will be described later, according to the present invention, the adverse effects caused by the substances originating in the self-condensation product of the silane coupling agent produced in the organic layer and the like are significantly reduced, the organic layer is formed with high adhesiveness on the inorganic layer, A dense inorganic layer can be formed. Therefore, the present invention is preferably used for a gas barrier film in which the denseness of the inorganic film contributes greatly to the performance.

The gas barrier film 10a shown in Fig. 1 (A) has an organic layer 12a on a support Z (surface / main surface), an inorganic layer 14 on the organic layer 12a, The second organic layer 12b is formed on the first inorganic layer 14 on the first inorganic layer 14 and the second inorganic layer 14 is formed on the second organic layer 12b, (12b).

That is, the second and third layer organic layers 12b are organic layers formed on the inorganic layer 14 and contain a predetermined silane coupling agent represented by the general formula [I] as described above.

1 (A) (FIG. 1 (B) to FIG. 1 (D)), only the inorganic layer 14 is hatched in order to clearly show the structure.

The gas barrier film (functional film) of the present invention has an organic layer and an inorganic layer of one layer of the organic layer 12a, two layers of the organic layer 12b and two layers of the inorganic layer 14 Alternatively, a total of five layers are not limited to the laminated structure.

The gas barrier film of the present invention may have various layer constructions so long as it has an organic layer and an inorganic layer alternately and has one or more organic layers formed on the inorganic layer.

For example, as shown in Fig. 1 (B), the gas barrier film 10a shown in Fig. 1 (A) further has the third inorganic layer 14 on the surface thereof, And a gas barrier film 10b having a total of seven layers including alternately formed organic layers and inorganic layers, each of which has a light-shielding film 12b.

In the gas barrier film of the present invention, basically, the greater the number of combinations of the underlying organic layer and the inorganic layer formed on the organic layer, the more excellent gas barrier properties are exhibited. The gas barrier film 10a and the like shown in Fig. 1 (A) are also the same, but since the organic layer 12b is provided at the uppermost layer, the organic layer 12b functions as a protective layer, It is possible to appropriately prevent the degradation of the gas barrier property caused by the gas barrier property.

The gas barrier film of the present invention may have an inorganic layer 14 on a support Z and alternately have an organic layer and an inorganic layer thereon. For example, it is possible to form a multilayer structure in which an inorganic layer 14 is formed on a support Z, an organic layer 12b is formed on the inorganic layer 14, a second layer 14 is provided thereon, The gas barrier film 10c having the organic layer 12b of the uppermost layer may have the same structure as the gas barrier film 10c. In this configuration, all of the organic layers become the organic layers 12b formed on the inorganic layer 14. [

The organic layer 12a and the organic layer 12b are generally formed by a coating method using a paint obtained by dissolving an organic compound such as a monomer serving as an organic layer in an organic solvent. As shown in Fig. 1 (C), an inorganic layer 14 is formed on a support Z, and an organic layer 12b and an inorganic layer 14 are alternately formed on the inorganic layer 14, It is possible to prevent the deterioration of the optical properties of the support Z caused by the organic solvent when the support Z made of a material which is easily dissolved or altered by the organic solvent is used.

In the gas barrier film of the present invention, the uppermost layer may be the inorganic layer (14). For example, the organic layer 12a is formed on the support Z shown in Fig. 1 (D), the inorganic layer 14 is formed thereon, the second organic layer 12b is formed thereon, Layer may be the same as the gas barrier film 10d having the inorganic layer 14 of the first layer.

When the gas barrier film of the present invention is used as the organic EL device (OLED device) or the like, the outermost layer from the organic layer 12b is more suitably prevented from being adversely affected by the use of the inorganic layer 14 as the uppermost layer, It is possible to more reliably prevent deterioration of the organic EL device, such as generation of an organic EL device.

In the present invention, the support (substrate / substrate) Z is not particularly limited, and various known sheet materials used as a support of the gas barrier film can be used.

Preferably, an elongated sheet-shaped support Z (web-shaped support Z) is used so that an organic layer and an inorganic layer can be formed by roll-to-roll as described later.

Specific examples of the support Z include polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyethylene, polypropylene, polystyrene, polyamide, polyvinyl chloride, polycarbonate, polyacrylonitrile, polyimide, (Polymer material) such as polyacrylate, polymethacrylate, polycarbonate (PC), cycloolefin polymer (COP), cycloolefin copolymer (COC), triacetyl cellulose (TAC) and transparent polyimide A plastic film is suitably exemplified.

The support Z is a layer (film) for obtaining 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, May be formed.

In the gas barrier film 10a, the organic layer 12a and the organic layer 12b are formed by polymerizing (crosslinking) an organic compound to be an organic layer, as a layer made of an organic compound (a layer (film) And then cured. The organic compound to be the organic layer 12a and the organic layer 12b may be any one of monomers, dimers, trimers, and oligomers, or two or more of them may be used in combination.

In the gas barrier film 10a of the present invention, the organic layer 12a and the organic layer 12b, which are formed as a lower layer of the inorganic layer 14, such as the surface of the support Z, basically have gas barrier properties And functions as a base layer of the inorganic layer 14. The formation surface of the inorganic layer 14 is smoothed by forming the inorganic layer 14 with the organic layer 12a and the organic layer 12b as a base layer to form a layer having no voids such as gold, It is possible to stably produce a gas barrier film which exhibits a high gas barrier performance by forming a uniform inorganic layer 14 that is greatly reduced in thickness.

The uppermost organic layer 12b functions as a protective layer. By having this uppermost organic layer 12b, the gas barrier film 10a can prevent deterioration of gas barrier property due to damage of the inorganic layer 14 or the like.

In the gas barrier film of the present invention, the inorganic layer 14 other than the organic layer 12a may be formed on the surface of the support Z, and the uppermost layer may be the inorganic layer 14 as described above.

In the production method of the present invention, the material for forming the organic layer 12a formed on the surface of the support Z and the organic layer 12b formed on the surface of the inorganic layer 14 is not particularly limited, Various compounds (resin / polymer material) can be used.

Specific examples of the resin include polyolefins such as polyester, acrylic resin, methacrylic resin, methacrylic acid-maleic acid copolymer, polystyrene, transparent fluororesin, polyimide, fluorinated polyimide, polyamide, polyamideimide, polyetherimide, cellulose acyl But are not limited to, polyolefins, polyurethanes, polyurethanes, polyurethanes, polyetherketones, polycarbonates, alicyclic polyolefins, polyarylates, polyethersulfones, polysulfones, fluorene ring-modified polycarbonates, alicyclic modified polycarbonates, Ester or acryloyl compound, or a film of polysiloxane or other organic silicon compound is suitably exemplified.

Among them, a cationic polymerizable compound having a radically polymerizable compound and / or an ether group in a functional group, in view of the flatness of the surface on which the inorganic layer 14 is formed and the ability to sufficiently exhibit its function, The organic layer 12a and the organic layer 12b constituted by the polymeric material of the polymeric material are suitable.

Among them, an acrylic resin or a methacrylic resin containing a polymer of a monomer of acrylate and / or methacrylate as a main component is preferably used as the organic layer 12a and the organic layer 12b .

Particularly preferred among them are dipropylene glycol di (meth) acrylate (DPGDA), 1,9-nonene diol di (meth) acrylate (A-NODN), 1,6 hexanediol diacrylate A-HD-N), trimethylol propyl acrylate (TMPTA), (modified) bisphenol A di (meth) acrylate, and dipentaerythritol hexa (meth) acrylate (DPHA) Acrylic resins or methacrylic resins containing a polymer such as monomers of acrylate and / or methacrylate having two or more functional groups as a main component are suitably exemplified. It is also preferable to use a plurality of these acrylic resins or methacrylic resins.

The inorganic film 14 can be formed on the base having a strong skeleton by forming the organic layer 12a and the organic layer 12b from an acrylic resin or a methacrylic resin, particularly an acrylic resin or a methacrylic resin having two or more functionalities. As a result, the inorganic film 14 having higher gas barrier properties can be formed more densely.

The thickness of the organic layer 12a and the organic layer 12b is preferably 5 占 퐉 or less. When the thicknesses of the organic layer 12a and the organic layer 12b are set to 5 占 퐉 or less, cracks of the organic layer 12a and the organic layer 12b, which are caused by the too large thickness of the organic layer 12a and the organic layer 12b, Occurrence of problems such as curling of the film 10a can be suitably prevented. In particular, it is preferable that the thickness of the organic layer 12b is 5 占 퐉 or less.

The thickness of the organic layer 12a and the organic layer 12b is preferably 0.5 占 퐉 or more. The thickness of the organic layer 12a and the thickness of the organic layer 12b is more preferably 0.5 占 퐉 or more so as to more suitably form the inorganic layer 14 so that the proper inorganic layer 14 free from cracks, As shown in Fig.

Considering the above points, the thickness of the organic film 12a and the organic layer 12b is more preferably 1 to 3 占 퐉.

In the case of having a plurality of organic layers like the gas barrier film 10a shown in Fig. 1 (A), the respective organic layers may be formed of the same material or different materials. However, considering productivity and the like, it is preferable to form all the organic layers from the same material.

In the case of having a plurality of organic layers, the thicknesses of the respective organic layers may be the same or different.

The organic layer 12a and the organic layer 12b may be formed by a known method. Preferably, a coating material containing a monomer which becomes the organic layer 12a or the organic layer 12b is prepared, and the coating material is applied, dried and cured, by a coating method.

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 point will be described later in detail.

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) mainly composed of an inorganic compound) . ≪ / RTI > That is, in the functional film of the present invention, the inorganic layer is a layer that expresses a desired function in a species.

As the inorganic layer 14, various membranes made of an inorganic compound exhibiting 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 oxides such as silicon oxide, silicon oxynitride, silicon oxycarbide, and silicon oxynitride; Silicon nitrides such as silicon nitride and silicon carbide; Silicon carbide such as silicon carbide; Their hydrides; Mixtures of two or more thereof; And hydrogen-containing materials thereof, and the like are suitably exemplified.

Particularly, a film made of a silicon compound is preferably exemplified because it has high transparency and can exhibit excellent gas barrier properties. Particularly, the film made of silicon nitride has a higher transparency in addition to better gas barrier properties and is suitably exemplified.

When each of the inorganic layers 14 has a plurality of inorganic layers 14 like the gas barrier film 10a shown in Fig. 1A, the inorganic layers 14 may be formed of the same material or different materials. However, considering productivity and the like, it is preferable to form all the inorganic layers 14 from 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, the -O group and / or the -OH group Group is preferably introduced. That is, it is preferable that the surface layer of the inorganic layer 14 is oxidized and / or hydrolyzed. Particularly, when the inorganic layer 14 on which the organic layer 12b is formed is silicon nitride, it is preferable that -O group and / or -OH group is introduced on the surface.

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. Owing to introduction of -O group or -OH group onto the surface of the inorganic layer 14 on which the organic layer 12b is formed, the adhesion between the inorganic layer 14 and the organic layer 12b can be made higher . This point will be described later in detail.

The thickness of the inorganic layer 14 may be appropriately determined depending on the forming material so that the desired gas barrier properties can be exhibited. According to the study by the present inventors, the thickness of the inorganic layer 14 is preferably 10 to 200 nm.

By setting the thickness of the inorganic layer 14 to 10 nm or more, the inorganic layer 14 can be formed which stably exhibits sufficient gas barrier performance. If the thickness of the inorganic layer 14 is generally 200 nm or less, it is possible to prevent cracks from occurring. have.

In consideration of this, the thickness of the inorganic layer 14 is preferably 10 to 100 nm, and more preferably 20 to 75 nm.

In the case of having the plurality of inorganic layers 14 like the gas barrier film 10a shown in Fig. 1A, 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, it is preferable that a density of 2 ~ 2.4g / cm ^3.

When the density of the inorganic layer 14 is 2 g / cm ³ or more, high gas barrier properties can be obtained with a dense film, and a sufficient number of bonds can be obtained for bonding of the silane coupling agent contained in the organic layer 12b formed in the upper layer And the like.

By setting the density of the inorganic layer 14 to 2.4 g / cm ³ or less, cracking of the inorganic layer 14 due to high rigidity can be suitably prevented, and transparency can be secured.

The inorganic layer 14 may be formed by a known method. Specifically, a vapor deposition method (gas phase film formation method) such as plasma CVD such as CCP-CVD or ICP-CVD, sputtering such as magnetron sputtering or reactive sputtering, or vacuum deposition is suitably exemplified.

Here, in a film made of a silicon compound formed by a vapor deposition method, not all silicon is made of a desired compound such as silicon nitride, and silicon having unbonded bonding hands is also present. Particularly, on the surface of the film, a large amount of silicon having unbonded bonding hands exists.

Therefore, when the surface of the film is exposed to air (atmosphere) after the formation of the inorganic layer 14, -O group or -OH group is bonded to the bonding end of the non-bonding, A -O group or -OH group can be introduced. This point will be described later in detail.

In the gas barrier film 10a shown in Fig. 1 (A), the second organic layer 12b is formed on the first inorganic layer 14, the second inorganic layer 14 is formed on the second inorganic layer 14, The organic layer 12b is formed.

The gas barrier film 10a of the present invention (the functional film of the present invention) has at least one organic layer 12b formed on the inorganic layer 14 and has an organic layer 12b ) Is represented by the following general formula [I]

(R ¹ ) ₃ -Si-R ² -Si- (R ¹ ) ₃ In the general formula [I]

(In the formula [I], R ¹ is an alkoxy group which may have a substituent, R ² is an alkylene group of a straight-chain carbon atoms in the straight-chain which may have a 2 to 10, which is the substituent. In addition, each of R ¹ May be the same or different from each other.)

Lt; / RTI >

The gas barrier film 10a of the present invention has such a constitution that the organic layer 12b on the inorganic layer 14 in the organic / inorganic laminate type gas barrier film, which is obtained by alternately laminating the organic layer and the inorganic layer ) And the excellent gas barrier property by the uniform inorganic layer 14 free from defects or damage are both attained.

As described above, the organic / inorganic laminate type gas barrier film formed by alternately laminating the organic layer and the inorganic layer can form a uniform inorganic layer free from defects by having an organic layer as a base, Can be obtained. Further, by having a plurality of combinations of the organic layer and the inorganic layer in the lower layer, higher gas barrier properties can be obtained. In order to protect the inorganic layer, it is also effective to have an organic layer in the uppermost layer.

Here, in order to obtain a high gas barrier property, it is effective to form a dense inorganic layer having a density of 2 g / cm ³ or more, for example. However, when the organic layer is formed on the inorganic layer, since the inorganic layer is dense, it is difficult to obtain the effect of anchoring like the easy adhesive layer, and sufficient adhesion can not be obtained.

As a result, as shown in Patent Document 1 and Patent Document 2, in the case of forming the organic layer on the inorganic layer, the silane coupling agent is added to the organic layer in the organic / inorganic laminated gas barrier film.

As is well known, a silane coupling agent is a compound having a functional group binding to an organic material and an inorganic material in a molecule.

In the organic / inorganic laminate type gas barrier film, the silane coupling agent has a group which forms a bond of Si-O-Si by silanolization with, for example, an inorganic layer and is easy to bond with the material forming the organic layer Thereby securing the adhesion of the organic layer on the inorganic layer.

In view of the above points, in the organic / inorganic laminate type gas barrier film, as the silane coupling agent, for example, a compound having a radical polymerizing property such as an acrylic group (radical reactivity) and a high reactivity with a resin material forming an organic layer It is considered preferable to use a compound having a functional group (substituent).

However, according to the study by the present inventors, in the organic / inorganic laminated gas barrier film, when such a silane coupling agent having a functional group having radical polymerizability is used, the silane coupling agent is an inhibitor of the formation of the organic layer It is found that sufficient gas barrier property can not be obtained and sufficient adhesion of the organic layer can not be obtained.

The formation of the organic layer is usually carried out by a coating method using a paint containing an organic compound to be an organic layer. The silane coupling agent is added to the coating material.

In the formation of the organic layer using the coating material, the coating material is coated on the inorganic layer, which is the formation surface of the organic layer, followed by drying, and then curing according to the organic layer such as ultraviolet irradiation is performed to form an organic layer.

Also, as shown in Patent Document 1, in consideration of the removal of by-products attributable to the silane coupling agent, the hydrolysis of the silane coupling agent, and the progress of the silanization, drying of the paint is caused by the silane coupling agent And the boiling point of the solvent used for the paint.

However, in the formation of the conventional organic layer using a silane coupling agent having a radically polymerizable functional group, the silane coupling agent is hydrolyzed with a proton by -OH group or the like on the surface of the inorganic layer. Further, by the drying at a high temperature depending on the boiling points of the above-mentioned by-products and the solvent, a reaction such as hydrolysis proceeds.

There is, of course, a silane coupling scheme which, depending on the reaction, properly bonds with the -OH group on the surface of the inorganic layer. However, there are many cases where the silane coupling agents are self-condensed by the hydrolysis in this drying, resulting in a structure having a certain molecular weight. The self-condensed silane coupling system and the functional group causing the radical polymerization remain unreacted. As a result, the self-condensed silane coupling agent has a higher molecular weight, and thus becomes a material which is harder to cure by ultraviolet rays or the like as compared with an organic compound as a main component.

Such a silane coupling agent that is self-condensed by hydrolysis in drying has a too large molecular weight and thus has poor fluidity and is difficult to bond with an organic compound to be an inorganic layer and an organic layer, It does not function.

Thus, in spite of the use of a silane coupling agent, the organic layer formed on the inorganic layer often fails to have sufficient adhesion.

Further, when a silane coupling agent that can not bind to the self-condensed inorganic layer is bonded to an organic compound to be an organic layer, the binding loss of the organic compound is reduced. Therefore, when a polyfunctional organic compound having high crosslinkability is used , The polymerization of the monomer which becomes the organic layer is inhibited.

In addition, since the self-condensed silane coupling agent has a certain molecular weight, the polymerization of the organic compound to be an organic layer is also inhibited, so that a region not sufficiently polymerized in the organic layer is generated.

In addition, the self-condensed silane coupling agent has a certain degree of molecular weight or steric structure, and therefore has low self-polymerization.

As a result, a low molecular weight compound such as a self-condensed silane coupling agent that can not bind to the inorganic layer, a conjugate of a self-condensed silane coupling agent and an organic compound, or a polymer of a low molecular weight organic compound remains in the organic layer.

Such a low-molecular compound has a smaller molecular weight than that of an appropriately polymerized organic layer, and is low in resistance to heat, plasma, and the like. Therefore, when the inorganic layer is formed on the organic layer, gasification or decomposition of these low molecular compounds occurs due to plasma or the like caused by plasma CVD, which hinders the formation of the inorganic layer. As a result, an appropriate inorganic layer can not be formed, and a gas barrier film having a desired gas barrier property can not be obtained.

Further, when the gas barrier film is used in an organic EL device (OLED device) or the like, an out gas is generated from the organic layer due to evaporation of the low-molecular compound due to heat such as the formation of the organic EL layer, And a dark spot is generated. Particularly, in the organic layer sandwiched by the inorganic layer, since the inorganic compound layer is sandwiched by the inorganic layer having a high gas barrier property, the low molecular compound expands and ruptures by heating. This rupture damages the inorganic layer to degrade gas barrier properties, 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 is a silane coupling agent for ensuring adhesion with the underlying inorganic layer 14, I]

(R ¹ ) ₃ -Si-R ² -Si- (R ¹ ) ₃ In the general formula [I]

(In the formula [I], R ¹ is an alkoxy group which may have a substituent, R ² is an alkylene group of a straight-chain carbon atoms in the straight-chain which may have a 2 to 10, which is the substituent. In addition, each of R ¹ May be the same or different from each other.)

Is used as the silane coupling agent.

As shown in the general formula [I], this silane coupling agent does not have a functional group having a radical polymerizable property.

Therefore, even if curing by ultraviolet irradiation or the like is performed after application and drying of the coating material, it does not undergo self-condensation and accordingly functions as a silane coupling agent properly.

The silane coupling agent has a structure in which a silicon atom having an alkoxy group bonded to the inorganic layer 14 is bonded with a straight chain alkylene group, so that the silane coupling agent is intertwined with the polymer of the three-dimensionally crosslinked organic compound and has a high anchoring effect Can be obtained. Particularly, when the straight chain alkylene is made to have a certain length, a silane coupling agent whose both ends are bonded to the inorganic layer 14 in the form of a bridge is generated, and a silane coupling agent having a more suitable three- All.

Thus, even if the silane coupling agent contained in the organic layer 12b does not have a radically polymerizable functional group, the gas barrier film 10 of the present invention can improve the adhesion of the organic layer 12b formed on the inorganic layer 14, Can be made very high.

Further, since the silane coupling agent does not have a radically polymerizable functional group, the silane coupling agent neither inhibits the polymerization of the organic compound to be the organic layer 12b nor produces a low molecular compound or the like. That is, in the gas barrier film 10a of the present invention, the above-mentioned low-molecular compound is not present in the interior of the organic layer 12b on the inorganic layer 14 as well.

This makes it possible to obtain a very high gas barrier property by the uniform inorganic layer 14 without inhibiting film formation of the inorganic layer 14 or damaging the inorganic layer 14 due to gasification of the low molecular compound or the like. In addition, even when the gas barrier film 10a of the present invention is used in an organic EL device or the like, occurrence of dark spots by gas of a low molecular compound 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], it is preferable that R ¹ has no substituent.

This R ¹ becomes a by-product when bound to the inorganic layer 14, but if R ¹ has a substituent, the by-product becomes complicated and has a high boiling point, and the paint forming the organic layer 12b is dried , It becomes difficult to remove by-products.

For the same reason, R ¹ is preferably an alkoxy group having 2 or less carbon atoms, especially 1 carbon atom.

As such R ¹ , specifically, at least one selected from -OCH ₃ and -OCH ₂ CH ₃ is preferably exemplified. That is, R ¹ is preferably -OCH ₃ or -OCH ₂ CH ₃ , or -OCH ₃ and -OCH ₂ CH ₃ .

Incidentally, in this silane coupling agent represented by the general formula [I], R ¹ may be the same or different from each other, even when R ¹ is any alkoxy group, including this example.

On the other hand, in the silane coupling agent represented by the general formula [I], R ² is a straight chain alkylene group which may have a substituent having 2 to 10 carbon atoms in the straight chain.

When the number of carbon atoms in the straight chain of R ² is less than 2, the effect of entanglement with the above-mentioned three-dimensionally crosslinked polymer can not be sufficiently obtained, and the adhesion of the organic layer 12b can not be ensured.

When the number of carbon atoms in the straight chain of R ² exceeds 10, the number of bonds with the inorganic layer 14 in the lower layer is decreased, which necessitates an increase in the absolute amount of the silane coupling agent.

By making R ² longer, the silane coupling agent binding to the inorganic layer 14 can be shaped like a bridge, and the adhesion of the high organic layer 12b can be obtained. That is, the long R ² is advantageous in terms of the adhesion of the organic layer 12b.

Taking this point into consideration, the length of the straight chain 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 a steric hindrance causes a reaction rate difference with respect to the reaction of Si at both ends, Or the like, and the adhesion is reduced due to, for example, Si alone.

Therefore, when R ² has a substituent, it is preferable that only the central methylene group in the case where the number of carbon atoms in the straight chain is 5 or more has a substituent. It is particularly preferable that R ² has no substituent.

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 mass% or less.

The silane coupling agent remaining in the organic layer 12b acts in a direction to lower the glass transition temperature (Tg) of the organic layer 12b. Thus, when an unnecessary silane coupling agent is present, for example, even when the organic layer 12b of high Tg is formed, the resistance to etching and heat by plasma CVD for forming the inorganic layer 14 in the upper layer is lowered Throw away. On the other hand, by setting the content of the silane coupling agent in the organic layer 12b to 25 mass% or less, an unnecessary silane coupling agent can be prevented from remaining in the organic layer 12b.

The amount of the silane coupling agent contained in the organic layer 12b is preferably 1% by mass or more.

By setting the content of the silane coupling agent to 1% by mass or more, it is preferable that a coating area containing the silane coupling agent can be sufficiently secured, the effect is suitably obtained, and high adhesion of the organic layer 12 is obtained .

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

Fig. 2 conceptually shows an example of a manufacturing apparatus that implements the manufacturing method of the present invention.

The manufacturing apparatus shown in Fig. 2 has an organic film forming apparatus 20 for forming (forming) the organic layer 12a and the organic layer 12b and an inorganic film forming apparatus 24 for forming (forming) the inorganic layer 14 . 2 (A) is an organic film forming apparatus 20, and Fig. 2 (B) is an inorganic film forming apparatus 24. Fig.

The organic film forming apparatus 20 and the inorganic film forming apparatus 24 are all formed from a roll of material obtained by winding a long film-forming material (web-form film-forming material) in a roll form, (Roll to Roll (hereinafter, also referred to as RtoR)) in which film formation is performed while the film forming material is transported in the longitudinal direction, and the film forming material on which film formation has been completed is again wound in a roll form Thereby forming a film.

In such a manufacturing method of the present invention, as a preferred embodiment, by using such RtoR, it is possible to produce an efficient functional film.

Further, the production method of the present invention is not limited to producing a functional film such as a gas barrier film by RtoR using a long support (Z). For example, in the production method of the present invention, a functional film may be produced by using a so-called sheet-fed (batch type) film-forming method using a support sheet Z in the form of a cut sheet.

The method of forming the organic layer 12a, the organic layer 12b and the inorganic layer 14 is the same as the method of manufacturing by RtoR described below even when the support Z in the form of a cut sheet is used.

In the case where a plurality of the organic layers 12 and / or the inorganic layers 14 are formed in the manufacturing method of the present invention, the forming method (film forming method) may be the same or different in each layer.

Here, the manufacturing apparatus shown in Figs. 2A and 2B is a manufacturing apparatus as shown in Figs. 1 (A) to 1 (D) in which an organic layer and an inorganic layer 14 are formed on a support Z And the gas barrier film 10a or the like having one or more organic layers 12b formed on the inorganic layer 14 alternately.

Therefore, in the organic film forming apparatus 20 shown in Fig. 2 (A), the film forming material Za is formed by a long supporting body Z and a surface on which at least one layer is formed on the surface of the supporting body Z Is a material which is the inorganic layer (14). On the other hand, in the inorganic film forming apparatus 24 of Fig. 2 (B), the film forming material Zb is formed by a long supporting body Z and a surface having at least one layer formed on the surface of the supporting body Z Or an organic layer 12a or an organic layer 12b.

The organic film forming apparatus 20 shown in Fig. 2 (A) is constituted such that a coating material which becomes the organic layer 12a or 12b is applied and dried while conveying the film forming material Z in the longitudinal direction, Is crosslinked and cured to form the organic layer 12a or 12b.

The organic film forming apparatus 20 shown in the drawing is provided with a coating section 26, a drying section 28, a light irradiation section 30, a rotary shaft 32, a take-up shaft 34, (36 and 38).

The organic film forming apparatus 20 is a known apparatus that performs film formation by coating while conveying a long film forming material such as a conveying roller pair, a guide member of a film forming material (Zb), various sensors, As shown in Fig.

In the organic film forming apparatus 20, the 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 rotary shaft 32, the material Za to be coated is taken out from the material roll 42 and passes through the application portion 26, the drying portion 28 and the light irradiation portion 30 (Notified (passed) through the predetermined conveying path to the take-up shaft 34).

The organic film forming apparatus 20 synchronizes the delivery of the film forming material Za from the material roll 42 and the winding of the film forming material Za on the take-up shaft 34, The organic layer 12a and the organic layer 12b are continuously formed on the film forming material Za while the material Za is conveyed in the longitudinal direction in the predetermined conveying path.

The film-forming material Za fed out from the material roll 42 is sandwiched and conveyed by the pair of conveying rollers 36, and is conveyed to the applying section 26 first.

The application section 26 applies a paint serving as the organic layer 12a or 12b to the surface of the film formation material Za.

In the production method of the present invention, the paint serving as the organic layer 12a formed on the surface of the support Z is a layer composed of a known organic compound obtained by dissolving the organic compound, which becomes the organic layer 12a, And the like.

On the other hand, in the production method of the present invention, the coating material to be the organic layer 12b formed on the inorganic layer 14 is not limited to the organic compound or the organic solvent and may be a silane coupling agent represented by the above-mentioned general formula [I] And further contains a ligneous agent. The content of the silane coupling agent is preferably 25 mass% or less in terms of a large solid concentration. The concentration of the solid content is the concentration in the solid content of the paint serving as the organic layer 12b, excluding the organic solvent. That is, the concentration of the solid content is the content (% by mass) when the solid content component (total solid component content) is 100 mass%.

Further, when using a silane coupling agent, the coating material may not contain a pH adjusting agent, which is usually added.

In the case of forming either the organic layer 12a or the organic layer 12b, a layer composed of an organic compound such as a surfactant, a viscosity adjusting agent, a polymerization initiator, a crosslinking agent, a refractive index adjusting agent, etc., A component added in the case of forming may be added.

In the application section 26, a method of applying the coating material to the film forming material Za is not particularly limited.

Therefore, the application of the coating material can be carried out by a known coating method such as die coating, dip coating, air knife coating, curtain coating, roller coating, wire bar coating, gravure coating, All are available.

Here, since the application portion 26 needs to apply the paint over the inorganic layer 14, it is preferable to apply the paint in accordance with the die coat method (die coater). The inorganic layer 14 is easily broken and gold or the like is likely to be formed. However, according to the die coating method, since the portion other than the coating material does not come into contact with the inorganic layer 14, have.

The film formation material Za is then conveyed to the drying section 28. [ The drying unit 28 dries the coating material (coated 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 section 28 includes a drying section 28a for heating from the front side (painting side) ) Side of the drying unit 28b and drying the coating material from both the front side and the back side. For example, the drying unit 28a on the front side is a warm air drying unit and the drying unit 28b on the back side is a heat roller (a path roller having a heating mechanism).

That is, the drying unit 28 performs drying of the coating material by heating for each support member Z. When the organic layer 12b is formed, the coating material is sufficiently heated even from the inorganic layer 14 side, All.

The drying means in the drying section 28 is not particularly limited and the coating material Za may be dried (organic solvent) before the coating material Za reaches the light irradiation section 30, depending on the conveyance speed of the support Z, And then the organic compound can be polymerized, any known heating means can be used.

Specifically, drying means using a heat roller, drying means using hot air, drying means using a heat transfer plate, and the like are exemplified. The drying unit 28 may use only one of them, or a plurality of them may be used in combination.

The film formation material Za is then conveyed to the light irradiation unit 30. [ The light irradiation unit 30 irradiates ultraviolet rays (UV light), visible light, or the like to the coating material applied by the application unit 26 and dried by the drying unit 28 to crosslink (polymerize) the organic compound contained in the coating material, And the organic layer 12a or the organic layer 12b.

In the present invention, the crosslinking of the organic compound is not limited to the photopolymerization, and various methods depending on the organic compound to be the organic layer 12a or the organic layer 12b, such as electron beam polymerization or plasma polymerization, can be used. Here, in the manufacturing method of the present invention, since acrylic resin such as acrylic resin or methacrylic resin is suitably used as the organic layer 12a and the organic layer 12b, photopolymerization and electron beam polymerization are suitably used do.

In the light irradiation unit 30, the organic compound may be cured while heating the material to be film-formed Za, if necessary.

As in the case of the drying unit 28, various known means can be used for the heating method.

The film forming material Za on which the organic layer 12a and the organic layer 12b are formed is sandwiched and conveyed by the pair of conveying rollers 38 to reach the take-up shaft 34, And wound in a roll shape.

The material film Za on which the organic layer 12a and the organic layer 12b are formed is a material roll 46 on which film formation is performed in the inorganic film forming apparatus 24 forming the inorganic layer 14 2 (B) (the supply chamber 50 thereof).

The film forming material Za on which the organic layer 12b to be the uppermost layer is formed is a material roll 46 formed by winding the gas barrier film 10a or the like and is used in the following steps or the like.

The inorganic film forming apparatus 24 is formed by depositing (forming) the inorganic layer 14 on the surface of the film forming material Zb, that is, the surface of the organic layer 12a or the organic layer 12b according to a vapor deposition method (vacuum film forming method) And has a supply chamber 50, a film formation chamber 52, and a winding chamber 54.

In addition to the illustrated members, the inorganic film forming apparatus 24 may also include a pair of conveying rollers, a guide member for regulating the position in the width direction of the material to be film-formed Zb, various sensors, The film forming apparatus may have various members provided in a known apparatus for performing film formation by means of a film forming apparatus.

The supply chamber 50 has a rotary shaft 56, a guide roller 60, and a vacuum evacuation means 61.

In the inorganic film forming apparatus 24, the material roll 46 wound with the material to be film-formed Zb is loaded on the rotary shaft 56 of the supply chamber 50.

When the material roll 46 is loaded on the rotary shaft 56, the material Zb to be film-formed is transferred from the supply chamber 50 through the film formation chamber 52 to the winding shaft 58 of the winding chamber 54 As shown in FIG. In the inorganic film forming apparatus 24, the feeding of the film forming material Zb from the material roll 46 and the winding of the film-forming material Zb on which the film formation on the winding shaft 58 has been completed are synchronized, The inorganic layer 14 is formed continuously on the film forming material Zb in the film forming chamber 52 while the film forming material Zb is conveyed in the longitudinal direction.

In the supply chamber 50, the rotation shaft 56 is rotated in the clockwise direction by a driving source (not shown) to deliver the film forming material Zb from the material roll 46, And sends the film to the deposition chamber 52 from the slit 76a formed in the partition wall 76. [

In the inorganic film forming apparatus 24 of the illustrated example, a vacuum exhausting means 61 is provided for the supply chamber 50 and a vacuum exhausting means 82 is provided for the winding chamber 54, respectively, as preferred embodiments. In the inorganic film forming apparatus 24, during the film formation, the pressures of the supply chamber 50 and the winding chamber 54 are adjusted by the respective vacuum evacuation means in accordance with the pressure (deposition pressure) of the deposition chamber 52, And maintained at a predetermined pressure. This prevents the pressure of the adjacent chambers from affecting the pressure of the deposition chamber 52 (deposition in the deposition chamber 52).

The vacuum evacuation means 61 is not particularly limited and various known vacuum evacuation means such as a vacuum pump such as a turbo pump, a mechanical booster pump, a dry pump, a rotary pump, etc., It is possible. As for this point, the other vacuum evacuation means 74 and 82 to be described later are also the same.

The film deposition chamber 52 forms the inorganic layer 14 on the surface of the film forming material Zb, that is, the organic layer 12a and the organic layer 12b by a vacuum deposition method. The film forming chamber 52 has a drum 62, a film forming means 64, a guide roller 68, a guide roller 72, and a vacuum evacuation means 74.

The film forming material Zb conveyed to the film forming chamber 52 is guided by a guide roller 68 in a predetermined path and wound around a predetermined position of the drum 62. The film forming material Zb is transported 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 means 64. [

The vacuum evacuation means 74 evacuates the inside of the film formation 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 and rotates in the counterclockwise direction in the drawing about the center line of the cylinder.

The material to be coated Zb which is supplied from the supply chamber 50 and guided in a predetermined path by the guide roller 68 and wound around the drum 62 at a predetermined position is transferred to a predetermined region of the peripheral surface of the drum 62 And is conveyed through a predetermined conveying path while being supported / guided by the drum 62, so that the inorganic layer 14 is formed on the surface by the film forming means 64.

The film forming means 64 forms the inorganic layer 14 on the surface of the film forming material Zb 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 formation method) such as the formation method described in the above-mentioned patent document. Therefore, the film forming method using the film forming means 64 is not particularly limited, and a known film forming method such as CVD, plasma CVD, sputtering, vacuum deposition, ion plating, or the like can be used.

Therefore, the film forming means 64 is composed of various members in accordance with the vacuum film forming method to be performed.

For example, if the film formation chamber 52 is to form the inorganic layer 14 by ICP-CVD (inductively coupled plasma CVD), the film formation means 64 may be an induction coil for forming an induction magnetic field , Gas supply means for supplying the reaction gas to the film forming region, and the like.

If the film forming chamber 52 is to form the inorganic layer 14 by the CCP-CVD method (capacitively coupled plasma CVD), the film forming means 64 is formed in a hollow shape on the surface facing the drum 62 A high-frequency electrode connected to a supply source of the reaction gas with a plurality of small holes, and a shower electrode acting as a reaction gas supply means.

If the film formation chamber 52 is to deposit the inorganic layer 14 by vacuum evaporation, the film formation means 64 may be constituted by a crucible (evaporation source) for filling the film formation material, a shutter for shielding the crucible, And a heating means for heating.

If the film formation chamber 52 is to form the inorganic layer 14 by sputtering, the film formation means 64 is configured with 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 means 64 while being supported by the drum 62 is guided by a guide roller 72 in a predetermined path, To the winding room 54 from the slit 78a formed in the lower portion

In the illustrated example, the winding chamber 54 has a guide roller 80, a winding shaft 58, and a vacuum evacuation means 82.

The film formation material Zb that has been film-completed and conveyed to the winding chamber 54 is wound in a roll shape by a take-up shaft 58 to be a material roll 42. [ The 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 rotating shaft 32) as required.

The organic layer 12a, the inorganic layer 14, and the second organic layer (not shown) are formed on the support Z shown in Fig. 1A by the manufacturing apparatus shown in Figs. 2A and 2B 12b, the second-layer inorganic layer 14, and the third-layer organic layer 12b, the manufacturing method of the present invention is described in more detail do.

When the gas barrier films 10b to 10d shown in Figs. 1 (B) to 1 (D) or other gas barrier films having the layer structure are formed, the organic layer 12a and the organic layer 12b to be formed, The formation of the same organic layer and the inorganic layer may be repeated depending on the number of the inorganic layers 14 and the number of the inorganic layers 14 or the layer structure.

A support roll formed by winding a long support Z to be the material to be film-formed Za is wound around the rotating shaft of the organic film forming apparatus 20 as the material roll 42 32, so that the organic layer 12 is formed on the surface of the support Z.

When the material roll 42 is loaded on the rotary shaft 32, the material Za to be coated is taken out from the material roll 42 and is transported to the application portion 26, the drying portion 28 And the light irradiating unit 30 and passes through a predetermined conveying path leading to the winding shaft 34 via the conveying roller pair 38. [ The material Za to be film-formed is the support Z.

The film formation material Za drawn out from the material roll 42 is conveyed to the application section 26 by the conveying roller pair 36 and the surface of the film material Za is coated with a paint serving as the organic layer 12a. As described above, the paint serving as the organic layer 12a may be any ordinary paint obtained by dissolving an organic compound such as a monomer according to the organic layer 12a to be formed in an organic solvent. In the illustrated example, a paint containing TMPTA as a main component is applied as an example.

The film forming material Za coated with the paint serving as the organic layer 12a is then heated by the drying section 28 to remove the organic solvent and dry the paint.

Subsequently, ultraviolet light or the like is irradiated from the light irradiation part to the film-forming material Za from which the paint has been dried, and the organic compound is polymerized (crosslinked) and cured to form the organic layer 12a. If necessary, the curing of the organic compound to be the organic layer 12a or the organic layer 12b may be performed in an inert atmosphere such as a nitrogen atmosphere.

The film forming material Za on which the organic layer 12 is formed is conveyed by the conveying roller pair 38 and wound in the form of a roll by the take-up shaft 34. [

When the formation of the predetermined length of the organic layer 12a is completed, the material roll 46 formed by winding the film forming material Za on which the organic layer 12a is formed after cutting as required is used as the material roll 46 shown in Fig. 2 (B) Is supplied to the inorganic 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 rotary shaft 56 of the supply chamber 50.

When the material roll 46 is loaded on the rotary shaft 56, the material to be coated Zb is drawn out and reaches the winding shaft 58 of the winding chamber 54 from the supply chamber 50 through the film formation chamber 52 And passes through a predetermined path. This film formation material Zb is a film formation material Za on which the organic layer 12a is formed, that is, the organic layer 12a is formed on the support Z.

The film-forming material Zb fed out from the material roll 46 is guided by the guide roller 60 and conveyed to the film formation chamber 52.

The film forming material Zb conveyed to the film forming chamber 52 is guided by the guide roller 68 and wound around the drum 62 and supported by the drum 62 to be conveyed through a predetermined path, The inorganic layer 14 is formed by the means 64, for example by CCP-CVD. In the illustrated example, it is assumed that silicon nitride is deposited as the inorganic layer 14 as an example.

The inorganic layer 14 may be formed by a known vapor deposition method according to the inorganic layer 14 to be formed. Therefore, the process gas and the film forming conditions to be used may be appropriately set / selected depending on 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 is conveyed to the winding chamber 54. [

The film forming material Zb conveyed to the winding chamber 54 is guided to the take-up shaft 58 by the guide roller 80 and wound in the form of a roll by the take-up shaft 58.

When the formation of the inorganic layer 14 is completed, the cleaned dry air is introduced into the entire chamber of the inorganic film forming apparatus 24 and is released to the atmosphere.

Thereafter, it is taken out from the winding chamber 54 of the inorganic film forming apparatus 24 as a material roll 42 formed by winding a film forming material Zb formed by cutting the inorganic layer 14 as necessary.

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

The material roll 42 supplied to the organic film forming apparatus 20 is loaded on the rotary shaft 32 in the same manner as the formation of the organic layer 12a described above, As shown in FIG. The film forming material Za is a film forming material Zb on which the inorganic layer 14 is formed. Namely, the organic layer 12a and the inorganic layer 14 are formed on the supporting body Z.

Here, the organic film forming apparatus 20 is basically an apparatus for forming the organic layer 12a and the organic layer 12b in the atmosphere. The period from the time when the winding chamber 54 of the inorganic film forming apparatus 24 is opened to the atmosphere until the coating of the organic layer 12b is applied to the inorganic layer 14 by the application portion 26, The inorganic layer 14 (silicon nitride film) is exposed to air.

The -O group and / or the -OH group is introduced into the surface of the inorganic film 14 (that is, the surface layer of the inorganic film 14 is oxidized and / or hydrolyzed do).

In the silicon compound layer formed by the vapor deposition method, not all silicon is formed of a desired compound such as silicon nitride, and silicon having unbonded bonding hands is present. Particularly, on the surface of the inorganic layer 14, a large amount of silicon having unbonded bonding hands exists. When the surface of the inorganic layer 14 is exposed to the air (atmosphere) after the formation of the inorganic layer 14, -O group or -OH group binds to the bond of the inorganic bond 14, -O group and / or -OH group can be introduced to the surface of the substrate.

In the present invention, by having the -OH group or the like on the surface of the inorganic layer 14, the reaction of the silane coupling agent can be appropriately advanced even when the paint forming the organic layer 12b does not contain a pH adjusting agent .

Further, 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 on the upper layer may be exposed to air by any timing or method as long as it is in the upper layer until the organic layer is formed.

For example, after the inorganic layer 14 is formed and the atmosphere of the inorganic film forming apparatus 24 is opened with an inert gas such as nitrogen, the material roll 42 is taken out from the winding chamber 54, The surface of the inorganic layer 14 may be exposed to the air for a period of time until the paint serving as the organic layer 12b is applied.

As described above, in the organic film forming apparatus 20, by the application section 26, while the substrate to be coated Za (the support Z on which the organic layer 12a and the inorganic layer 14 are formed) , And a paint serving as the organic layer (12b) is applied on the inorganic layer (14). The application method of the coating material by the application portion 26 is not particularly limited, but the die coat method is suitable as described above.

Here, in the production method of the present invention, the coating material for forming the organic layer 12b on the inorganic layer 14 is formed of an organic solvent, an organic compound to be the organic layer 12b, Lt; RTI ID = 0.0 > silane coupling agent. ≪ / RTI > The content of the silane coupling agent is preferably from 1 to 25% by mass, more preferably from 5 to 20% by mass, based on the solids concentration. Further, in the production method of the present invention, the paint serving as the organic layer 12b may not contain a pH adjuster added as an essential component when a silane coupling agent is used.

In the illustrated example, a paint containing TMPTA as a main component is applied as an example.

Here, the organic compound to be used as the organic layer 12b is one which has a higher Tg (glass transition temperature) than the azeotropic point of the by-product resulting from the silane coupling agent contained in the coating material and the organic solvent used in the coating material . In the following description, the azeotropic point of the by-product and the organic solvent is simply referred to as "by-product azeotropic point ".

When the by-product due to the silane coupling agent and the organic solvent to be used do not coexist, the organic layer 12b has higher Tg than the higher boiling point of the by-product and the boiling point of the organic solvent, Is preferably used. In the following description, for convenience, the higher boiling point of the by-product and the organic solvent is referred to as "paint boiling point ".

The by-product resulting from the silane coupling agent contained in the coating material is a by-product mainly produced by hydrolysis. The by-product is usually an alcohol.

In the production method of the present invention, the paint for forming the organic layer 12b is applied, and then the paint is dried at a temperature higher than the by-product azeotropic point or at a higher temperature than the paint boiling point. Preferably, after the coating forming the organic layer 12b is applied, if the above-mentioned azeotropy occurs, the temperature is higher than the by-product azeotrope, and if the azeotrope does not occur, Followed by drying.

If the heat resistance of the organic compound to be the organic layer 12b is too low, there is a possibility that the organic compound is softened by heat during the drying, the drying can not be properly carried out, and the organic compound is deteriorated have.

Therefore, it is preferable to use an organic compound having Tg higher than the by-product azeotropic point or the coating boiling point as the organic compound to be the organic layer 12b. This makes it possible to stably form an appropriate organic layer 12b by appropriately drying the coating while preventing the softening of the organic compound from occurring during drying.

The paint applied by the application portion 26 is dried by the drying portion 28. [

In the organic film forming apparatus 20 of the illustrated example, the drying unit 28 performs drying of the paint forming the organic layer 12b at a temperature higher than the by-product azeotropic point when the organic layer 12b is formed. Alternatively, when the organic layer 12b is formed, the drying unit 28 performs drying of the paint forming the organic layer 12b at a temperature higher than the paint boiling point.

If necessary, a heating step of heating the paint at a temperature higher than the by-product azeotropic point or the paint boiling point may be provided before drying the paint.

In the production method of the present invention, drying is carried out at a higher temperature than the by-product azeotropic point or the coating boiling point by using a coating material containing a silane coupling agent represented by the general formula [I] to form an organic layer 12b ). The manufacturing method of the present invention has such a constitution that the adhesion between the lower inorganic layer 14 and the organic layer 12b is excellent and the gas barrier performance is also high and when used in an organic EL device or the like, It is possible to manufacture a gas barrier film which prevents an adverse effect caused by outgas such as generation of a gas barrier film.

When the inorganic layer 14 is a silicon compound, the organic layer 12b is formed on the surface of the inorganic layer 14 with the -O group and / or - An OH group is introduced into the surface of the substrate and a coating containing an appropriate amount of a silane coupling agent is applied to the surface of the substrate and drying is carried out at a temperature higher than the azeotropic boiling point or the coating boiling point to adjust the pH of the silane coupling agent Hydrolysis reaction, and dehydration condensation occur.

The -OH group or the like is released from the surface of the inorganic layer by heating the paint to a temperature higher than the by-product azeotropic point in a state in which the -OH group or the like is introduced into the surface of the inorganic layer to cause the hydrolysis reaction of the silane coupling agent , And the surface of the inorganic layer and the silane coupling agent are bonded by the covalent bond by dehydration condensation. By heating the paint at a by-product azeotropic point or a paint boiling point or more, by-products and the like with the organic solvent of the paint are also evaporated and removed, so that the cycle of the reaction is accelerated and the bonding of the surface of the inorganic layer 14 with the silane coupling agent , Further promoted.

That is, according to the present invention, even when a pH adjuster, which is essential when using a silane coupling agent, is not used, the bonding between the surface of the inorganic layer 14 and the silane coupling agent and the silane coupling represented by the general formula [I] Adhesion between the inorganic layer 14 and the organic layer 12b can be secured by entanglement of an organic compound such as a monomer polymerized with the ring agent.

In addition, since the paint serving as the organic layer 12b can be applied by an ordinary method performed in the atmosphere, the productivity can be improved.

Further, since the heating is carried out at a temperature higher than the temperature at which the by-product by the silane coupling agent evaporates, by-products such as alcohol generated by hydrolysis of the silane coupling agent during heating are removed to remove the by- The amount can be greatly reduced.

Thus, it is possible to form an organic layer 12b which does not have a by-product of a silane coupling agent, which is an impurity, and which exhibits a high-quality and suitable performance. When the inorganic layer 14 is further formed on the organic layer 12b formed on the inorganic layer 14 as described later, the evaporation of these by-products or the like adversely affects the formation of the inorganic layer 14 A dense inorganic layer 14 is formed, and a gas barrier film having a high gas barrier performance can be produced.

Further, since the paint does not require a pH adjuster, it is possible to prevent the viscosity of the paint from increasing with the passage of time due to the addition of the pH adjuster.

In the case of the paint forming the organic layer 12b, as the material for forming the organic layer, in this case, the pH adjusting agent is an impurity. Thereby, there is a possibility that the viscosity change and the organic compound and the organic layer 12b to be formed are lowered in Tg by the addition of the pH adjuster to the paint, but such problems can also be prevented (suppressed).

Also, as is well known, by heating the paint, convection of the paint upward from the lower side occurs in the film. By this convection, the reaction between the silane coupling agent and the inorganic layer 14 can be advanced on the surface and the surface of the inorganic layer 14 together with the drying of the paint. Further, as described above, since the silane coupling agent represented by the general formula [I] does not undergo self-condensation, this convection is suitably carried out.

As a result, the silane coupling agent can be oriented in the vicinity of the surface of the inorganic layer 14, and the surface side of the organic layer 12b can be made of a high-purity organic compound with less silane coupling agent. Thus, the surface of the organic layer 12b has characteristics such as appropriate Tg according to the forming material and the like, so that the organic layer 12b can appropriately express the desired function. In addition, since the silane coupling agent can be oriented in the vicinity of the surface of the inorganic layer 14, the addition amount of the silane coupling agent can be at least sufficiently increased.

Particularly, when the drying unit 28 dries the paint from both the front side (painting side) and the back side (the side of the support Z, that is, the side of the inorganic layer 14) It is more preferable to obtain this effect more appropriately.

In the production method of the present invention, the drying temperature of the paint forming the organic layer 12b may be higher than the by-product azeotropic point or the paint boiling point. The drying temperature of the paint forming the organic layer 12b is preferably higher than the boiling point azeotropic point when the by-product of the silane coupling agent and the organic solvent are coeval. It is preferable that the drying temperature of the paint forming the organic layer 12b is higher than the paint boiling point when the by-product of the silane coupling agent and the organic solvent do not coexist.

When the drying temperature of the paint is less than the by-product azeotropic point or the coating boiling point, the above-mentioned hydrolysis or dehydration condensation reaction of the silane coupling agent does not proceed sufficiently.

The upper limit of the drying temperature of the coating material is not particularly limited. According to the study by the present inventors, the higher the drying temperature is, the better the adhesion between the organic layer and the inorganic layer is obtained. On the other hand, if drying is carried out at a temperature exceeding the softening point of the support (Z), the support Z is damaged by heat and an appropriate product can not be produced. Therefore, the drying temperature of the coating material is preferably set to be equal to or lower than the softening point of the support Z according to the support Z to be used.

The film formation member Za on which the paint serving as the organic layer 12b has been dried by the drying unit 28 is then conveyed to the light irradiation unit 30 and irradiated with ultraviolet rays or visible light.

By this light irradiation, the organic compound of the paint is polymerized (crosslinked), and the paint is cured, and the organic layer 12b is formed on the inorganic layer 14. [

The film-forming material Za on which the organic layer 12b is formed is wound into a roll shape by a take-up roller 34. [

After the formation of the organic layer 12b having a predetermined length is completed, the material roll 46 is cut by a roll as required and then the film-forming material Za on which the organic layer 12b is formed is wound, Is supplied to the inorganic film forming apparatus 24 shown in Fig. 2B to be used for forming the second inorganic layer 14.

The material roll 46 is loaded on the rotary shaft 56 of the supply chamber 50, similarly to the formation of the first-layer inorganic layer 14.

When the material roll 46 is loaded on the rotary shaft 56, the material to be coated Zb is drawn out and reaches the winding shaft 58 of the winding chamber 54 from the supply chamber 50 through the film formation chamber 52 And passes through a predetermined path. This film formation material Zb is a film formation material Za on which the organic layer 12b is formed, that is, the organic layer 12a, the inorganic layer 14 and the organic layer 12b are formed on the support Z .

Next, similarly to the formation of the first-layer inorganic layer 14, the material Zb to be film-formed is delivered from the material roll 46, conveyed from the supply material 50 to the film-forming material 52, The second layer of inorganic layer 14 (silicon nitride in the same manner as before) is formed and transported to the winding chamber 54 and wound in a roll by the take-up shaft 58.

When the formation of the inorganic layer 14 is completed, the cleaned dry air is introduced into the entire chamber of the inorganic film forming apparatus 24 and is released to the atmosphere.

The winding chamber 54 of the inorganic film forming apparatus 24 is wound as the material roll 42 formed by winding the film forming material Zb that has been cut into the second inorganic filler layer 14 as required, .

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 to form the third organic layer 12b.

The material roll 42 is mounted on the rotating shaft 32 in the same manner as the formation of the second organic layer 12b in the previous step and the film forming material Za is drawn out to a predetermined conveying path . This film forming material Za is a film forming material Zb on which the inorganic layer 14 is formed, that is, the organic layer 12a, the inorganic layer 14, the second organic layer 12b, And the second-layer inorganic layer 14 are formed.

Subsequently, the film forming material Za is transferred in the longitudinal direction as in the formation of the above-described second organic layer 12b, and the silane coupling agent represented by the general formula [I] is contained in the coating section 26 And the paint is dried at a temperature higher than the by-product azeotropic point or the paint boiling point in the drying section 28. Next, the paint is conveyed to the light irradiation section 30, The third organic layer 12b is formed.

The film forming material Za on which the organic layer 12b on the uppermost layer is formed, that is, the gas barrier film 10a, is wound in a roll shape by the winding roller 34. [

After the formation of the organic layer 12b on the uppermost layer 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 process or the like.

Although the present invention has been described in detail in the foregoing for the method of producing the functional film and the functional film of the present invention, the present invention is not limited to the above-described embodiments, and various modifications and changes may be made without departing from the gist of the present invention. Of course it can be done.

Example

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

[Example 1]

1 (D) having the organic layer 12a, the inorganic layer 14, the second-layer organic layer 12b, and the second-layer inorganic layer 14 using the manufacturing apparatus shown in Fig. A film 10d was produced.

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

The organic compound and the photopolymerization initiator were dissolved in an organic solvent (methyl ethyl ketone (MEK)) to prepare a coating film for forming the organic layer 12.

The organic compound used was TMPTA (manufactured by Daicel-Cytec), and the photopolymerization initiator used was Irg189 (manufactured by Chiba Chemicals). The coating material had a solid concentration of 15 mass% (MEK 85 mass%). The concentration of the organic compound in the solid content in the coating material was 98% by mass and the photopolymerization initiator in 2% by mass.

The material roll 42 formed by winding the support Z as the film forming material Za is mounted on the rotary shaft 32 of the organic film forming apparatus 20 shown in Fig. , The prepared coating material was applied and dried and crosslinked by ultraviolet irradiation to obtain a material roll 46 obtained by winding the film forming material Za on which the organic layer 12a was formed.

The application amount of the coating material in the application portion 26 was adjusted so that the film thickness of the organic layer 12a became 3 m. In addition, the application section 26 uses a die coater. The drying by the drying unit 28 was conducted by heating the paint to 80 DEG C by hot air. The light irradiating unit 30 was adjusted by using an ultraviolet irradiator so that the dose of ultraviolet light was about 500 mJ / cm ² as the cumulative dose.

Next, the material roll 46 is loaded on the inorganic film forming apparatus 24 shown in Fig. 2 (B), and the surface of the film forming material Zb (the support Z on which the organic layer 12a is formed) A silicon nitride film with a film thickness of 50 nm was formed as the inorganic layer 14 by -CVD.

The film forming means 64 includes a shower electrode disposed to face 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 supply means for supplying the source gas. Further, the drum 62 was made of stainless steel and served as an opposing 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 deposition gas. The supply amount was 100 sccm for the silane gas, 200 sccm for the ammonia gas, 500 sccm for the nitrogen gas, and 500 sccm for the hydrogen gas. The deposition pressure was set at 50 Pa.

Plasma-excited electric power of 3000 W was supplied from the high-frequency power source to the shower film electrode at a frequency of 13.5 MHz. The drum 62 was supplied with a bias power of 500 W from a bias power source. During the film formation, the temperature of the drum 62 was adjusted to -20 占 폚.

When the formation of the inorganic layer 14 is completed, purified dry air is introduced into the supply chamber 50, the film formation chamber 52, and the winding chamber 54, and the air is released to 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 wind-up chamber 54.

On the other hand, a coating material for forming the organic layer 12b was prepared by dissolving the organic compound, silane coupling agent and photopolymerization initiator in an organic solvent (MEK).

The organic compound and the photopolymerization initiator used were the same as the organic layer 12a.

The silane coupling agent is represented by the general formula [I]

(R ¹ ) ₃ -Si-R ² -Si- (R ¹ ) ₃

, R ¹ is all -OCH ₃ and R ² is - (CH ₂ ) ₂ -.

The coating material had a solid concentration of 15 mass% (MEK 85 mass%). The concentration of the organic compound in the solid content in the coating material was 88% by mass, the photopolymerization initiator in 2% by mass, and the silane coupling agent in 10% by mass.

The azeotrope of the by-product (methanol) by the silane coupling agent and MEK as the organic solvent varies depending on the amount of residual MEK and the amount of methanol produced, but is generally about 65 ° C.

The material roll 42 formed by winding the film forming material Za (the supporting body Z on which the organic layer 12a and the inorganic layer 14 are formed) is wound on the rotating shaft 32 of the organic film forming apparatus 20 , The coating film material Za formed by coating the prepared coating material on the surface of the film formation material Za and crosslinking the coating film by ultraviolet irradiation to form the organic layer 12b and the organic layer 12b, To obtain a material roll (46).

The application amount of the coating material by the application portion 26 was adjusted so that the thickness of the organic layer 12 became 3 m. The drying by the drying unit 28 was conducted by heating the paint to 80 DEG C by hot air. In addition, the light irradiating unit 30 was set such that the irradiation amount of ultraviolet light was about 500 mJ / cm ² as the cumulative irradiation amount.

Next, the material roll 46 formed by winding the film forming material Zb (the supporting body Z on which the organic layer 12a, the inorganic layer 14 and the organic layer 12b are formed) is wound is shown in Fig. Film deposition apparatus 24 shown in Fig.

In the same manner as in the case of the first inorganic layer 14, on the surface of the film-forming material Zb having the second organic layer 12b formed thereon, a 50 nm thick silicon nitride And a gas barrier film 10d shown in Fig. 1 (D) was produced, and a material roll 46 was obtained by winding the gas barrier film 10d.

[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

(Example 3) except that R ¹ was all -OCH ₃ and R ² was - (CH ₂ ) ₈ -, the same procedure as in Example 1 was carried out except that the organic layer A gas barrier film 10d shown in Fig. 1 (D), which is formed by forming the inorganic layer 14a, the inorganic layer 14a, the organic layer 12b and the inorganic layer 14, ).

[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

To 100 ℃ the temperature of the hot air in the change, the drying unit in the formation of the organic layer (12b) 18 to - in a, R ¹ a are both -OCH ^₂ CH _3, R ₂ is - (CH _{2) 6} 1 (D), in which an organic layer 12a, an inorganic layer 14, an organic layer 12b and an inorganic layer 14 are formed on a support Z in the same manner as in Example 1, And a material roll 46 made by winding the material barrier film 10d was obtained.

The drying temperature of 100 占 폚 is a temperature set according to the boiling point of the by-product (ethanol) by the 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 which 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 - 1 (D), in which the organic layer 12a, the inorganic layer 14, the organic layer 12b and the inorganic layer 14 were formed on the support Z in the same manner as in Example 1 except for the above- A film 10d was produced, and a material roll 46 was obtained by winding the film 10d.

[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 (a), in which an organic layer 12a, an inorganic layer 14, an organic layer 12b and an inorganic layer 14 are formed on a support Z in the same manner as in Example 1 except that the organic layer 12a, A gas barrier film 10d shown in Fig. 5D was produced, and a material roll 46 was obtained by winding the gas barrier film 10d.

Each gas barrier film 10d thus prepared was evaluated for gas barrier properties and adhesion.

≪ Gas barrier property &

The gas barrier properties (water vapor permeability [g / (m ² · day)]) of each gas barrier film was measured according to the calcium corrosion method (the method described in JP-A-2005-283561).

The case where the water vapor transmission rate is less than 1 × 10 ^-5 [g / (m ² · day)] (ie, less than 1 × 10 ^-5 E [g / (m ² · day)] is the best;

^{1 × 10 -5 [g / (} m 2 · day)] or more, excellent in the ^{4 × 10 -5 [g / (} m 2 · day)] is less than;

4 x 10 ^-5 [g / (m ² · day)] or more and less than 1 × 10 ^-4 [g / (m ² · day)];

1 × 10 ^-4 [g / (m ² · day)] or more; "He said.

≪ Adhesion >

And evaluated by a cross cut peel test conforming to JIS K5400.

On each surface of the organic barrier layer and the inorganic layer of each gas barrier film, a cutter knife was used to insert an angle of 90 DEG with respect to the film surface at intervals of 1 mm to prepare 100 checkerboard scales at intervals of 1 mm. A tape attached with a 2 mm wide Mylar tape (polyester tape, No. 31B, manufactured by Nitto Denko Co., Ltd.) was peeled off thereon. The organic layer 12b was evaluated by the number of the remaining masses.

The number of remaining masses is 100;

Excellent that the number of remaining masses is 91 to 99;

It is preferable that the number of remaining masses is 81 to 90;

It is impossible that the number of remaining masses is 80 or less; "He said.

The results are shown in the following table.

[Table 1]

As shown in the above table, all of the gas barrier films of the present invention have good gas barrier properties and adhesion of the organic layer 12b. In particular, R ² is a straight-chain carbon number is 8, R ¹ is -OCH _3, Example 3, and has a very excellent gas barrier properties and adhesion.

Further, in Example 1 in which R ² has 2 straight-chain carbon atoms, entanglement of the silane coupling agent with the organic compound polymerized is considered to be small, and the adhesion is somewhat poor as compared with the other examples.

On the other hand, in Comparative Example 1 in which the silane coupling agent contains an acrylic group, the above-mentioned silane coupling agent is produced as a self-condensation product, and as a result, the function of the silane coupling agent is deteriorated, A low molecular weight water such as a co-polymer is left, resulting in lowering the polymerizability, lowering the adhesiveness, lowering the gas barrier property, and the like, resulting in lower gas barrier property and lower adhesion .

Further, Comparative Example 2 in which the silane coupling agent has only one Si atom has no factor inhibiting the formation of the inorganic layer 14, so that excellent gas barrier properties are exhibited. However, the silane coupling agent It is considered that the adhesion improving effect is low and the adhesiveness is lower than that of the present invention.

From the above results, the effect of the present invention is apparent.

10a, 10b, 10c, 10d Gas barrier film
12a and 12b,
14 inorganic layer
20 Organic film forming device
24 Inorganic Film-forming Device
26 dispensing part
28 Drying section
30 light irradiation unit
32, 56,
34, 58 Winding axis
36, 38 Conveying roller pair
42, 46 Material roll
50 supply rooms
52 The Tent of Meeting
54 Winding room
60, 68, 72, 80 Guide rollers
61, 74, 82 The vacuum exhaust means
62 Drums
64 Deposition means
76, 78,

Claims (11)

1. A functional film having a support and an organic layer and an inorganic layer alternately formed on the support,
Characterized in that the functional layer 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].
(R ¹ ) ₃ -Si-R ² -Si- (R ¹ ) ₃ In the general formula [I]
(In the formula [I], R ¹ is an alkoxy group which may have a substituent, R ² is an alkylene group of a straight-chain carbon atoms in the straight-chain which may have a 2 to 10, which is the substituent. In addition, each of R ¹ May be the same or different from each other.) The method according to claim 1,
Wherein R ¹ in the general formula [I] is at least one selected from -OCH ₃ and -OCH ₂ CH ₃ . The method according to claim 1 or 2,
In the above general formula [I], R ¹ is a functional film having no substituent. The method according to any one of claims 1 to 3,
In the above general formula [I], R ² has no substituent. The method according to any one of claims 1 to 4,
Wherein the organic layer on the inorganic layer is composed mainly of a resin comprising a bifunctional or higher (meth) acrylate and the content of the silane coupling agent is 1 to 25 mass%. The method according to any one of claims 1 to 5,
Wherein the glass transition temperature of the organic compound to be the organic layer is higher than the boiling point of the by-product due to the silane coupling agent or the boiling point of the organic solvent used for forming the organic layer. The method according to any one of claims 1 to 6,
Wherein the organic layer on the inorganic layer has a thickness of 5 占 퐉 or less. The method 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 into the surface thereof. The method according to any one of claims 1 to 8,
Wherein the inorganic layer has a density of 2 to 2.4 g / cm < ³ >. When a functional film is produced by alternately forming an organic layer and an inorganic layer on a support,
An organic layer is formed on the inorganic layer at least once,
The organic layer is formed on the inorganic layer by a coating step of applying at least a coating material containing an organic solvent, an organic compound to be an organic layer, and a silane coupling agent represented by the following general formula [I]
(R ¹ ) ₃ -Si-R ² -Si- (R ¹ ) ₃ In the general formula [I]
(In the formula [I], R ¹ is an alkoxy group which may have a substituent, R ² is an alkylene group of a straight-chain carbon atoms in the straight-chain which may have a 2 to 10, which is the substituent. In addition, each of R ¹ May be the same or different from each other.)
A drying step of drying the coating material at a higher temperature than the azeotropic point of the by-product resulting from the silane coupling agent and the organic solvent, or higher than the boiling point of the by-product and the boiling point of the organic solvent,
And a curing step of curing the dried paint by light irradiation. The method of claim 10,
A method for producing a functional film, wherein the organic layer and the inorganic layer are formed by using a long support and transporting the support in the longitudinal direction.

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