JP6317681B2 - Functional film and method for producing functional film - Google Patents

Description

  The present invention relates to a functional film having an inorganic layer and an organic layer serving as a base layer for the inorganic layer, and a method for producing the functional film.

Packaging parts and parts, food, electronic parts, medical parts, etc. that require moisture resistance in various devices such as optical elements, liquid crystal displays, organic EL (Electro Luminescence) displays, various semiconductor devices, solar cells, etc. Gas barrier films such as packaging materials are used.
The gas barrier film generally has a configuration in which a plastic film such as a polyethylene terephthalate (PET) film is used as a support and a gas barrier layer that exhibits gas barrier properties is formed thereon. Moreover, as a gas barrier layer used for a gas barrier film, the layer which consists of various inorganic compounds, such as a silicon nitride, silicon oxide, aluminum oxide, is known, for example.
For the formation of an inorganic layer made of these inorganic compounds, thin film formation by a vacuum film formation method such as sputtering or plasma CVD (chemical vapor deposition) is used for film formation.

In addition, the gas barrier film is required to have various characteristics depending on applications such as not only excellent gas barrier properties but also high permeability (high visible light transmittance) and high oxidation resistance.
In particular, when used in an apparatus that needs to transmit light, such as a liquid crystal display, an organic EL display, or a solar cell, it is required to have high transparency.

In such a gas barrier film, an organic / inorganic structure having a laminated structure in which an organic layer made of an organic compound and an inorganic layer made of an inorganic compound are alternately laminated on a support as a configuration that can obtain higher gas barrier performance. A laminated gas barrier film (hereinafter also referred to as a laminated gas barrier film) is known.
In a laminated gas barrier film, an inorganic layer is formed on an organic layer serving as a base, whereby the formation surface of the inorganic layer is smoothed by the organic layer, and the inorganic layer is formed on the organic layer having good smoothness. Form. Thereby, the uniform inorganic layer without a crack, a crack, etc. is formed, and the outstanding gas barrier performance is acquired. Moreover, more excellent gas barrier performance can be obtained by repeatedly including a plurality of laminated structures of the organic layer and the inorganic layer.

For example, Patent Document 1 describes a functional film having a support, an organic layer formed on the support, and an inorganic layer formed on the organic layer.
Patent Document 2 describes a functional film in which a laminated film of an organic film and an inorganic film is formed on a support.

  Moreover, in such a functional film, in order to improve the adhesion between the support and the organic layer formed on the support, an easy-adhesion layer is formed between the support and the organic layer. To be done.

JP 2013-31794 A JP 2011-184770 A

  Here, when an inorganic layer is formed on the underlying organic layer by a vapor deposition method such as plasma CVD, a photopolymerization initiator (crosslinking agent) is used to reduce damage to the organic layer due to plasma. Therefore, it is necessary to increase the surface hardness of the organic layer by increasing the amount of the additive. In particular, in order to improve the film formation rate of the inorganic layer by the CVD method for the purpose of cost reduction, since higher plasma resistance is required when the power is increased, an organic material having higher heat resistance and / or higher hardness. A layer is required.

  However, when the amount of the crosslinking agent added is increased and crosslinked strongly at the time of curing, and the hardness of the organic layer is increased, due to the difference in thermal expansion coefficient between the organic layer and the support, or at the time of bending or processing, Stress concentration occurs at the interface between the support or the easy-adhesion layer and the organic layer, and a crack occurs in the organic layer based on the interface between the organic layer and the support or the easy-adhesion layer. New knowledge was obtained that the inorganic layer was damaged.

  The object of the present invention is to solve such problems of the prior art, suppress damage to the organic film due to plasma during the formation of the inorganic layer, and prevent cracks from occurring in the organic layer. Then, it is providing the functional film which can express high gas-barrier property by suppressing the damage of an inorganic layer, and has high transparency, and the manufacturing method of a functional film.

As a result of earnest research to achieve the above-mentioned problems, the present inventor has found that the support, the inorganic layer, the organic layer serving as the base of the inorganic layer, and a plurality of easy adhesion formed between the organic layer and the support are formed. Layer, the surface hardness of the organic layer is H or more in pencil hardness, the thickness of the bottommost easy adhesion layer in contact with the support is 0.3 μm or more, and the top layer easy adhesion in contact with the organic layer When the thickness of the layer is 0.1 μm or less, the damage to the organic film due to the plasma during the formation of the inorganic layer is suppressed, and cracks are prevented from occurring in the organic layer. The present invention was completed by finding out that damage can be suppressed, high gas barrier properties can be expressed, and high transparency can be expressed.
That is, this invention provides the functional film of the following structures, and the manufacturing method of a functional film.

(1) a support;
An inorganic layer;
An organic layer as a base for the inorganic layer;
A plurality of easy adhesion layers formed between the organic layer and the support,
The surface hardness of the organic layer is H or more in pencil hardness,
A functional film in which the thickness of the lowermost easily adhesive layer in contact with the support is 0.3 μm or more and the thickness of the uppermost easily adhesive layer in contact with the organic layer is 0.1 μm or less.
(2) The functional film according to (1), wherein a difference in refractive index between the lowermost easily adhesive layer and the uppermost easily adhesive layer is 0.01 to 0.1.
(3) The refractive index of the lowermost easily adhesive layer is closer to the refractive index of the support than the refractive index of the uppermost easily adhesive layer, and the refractive index of the uppermost easily adhesive layer is lower than that of the lowermost easily adhesive layer. The functional film according to (1) or (2), which is closer to the refractive index of the organic layer than the refractive index of.
(4) The functional film according to any one of (1) to (3), wherein the inorganic layer is made of silicon nitride.
(5) The functional film according to any one of (1) to (4), wherein the inorganic layer has a residual compressive stress of 200 to 4000 MPa.
(6) Furthermore, the functional film in any one of (1)-(5) which has 1 or more the structure which laminated | stacked the organic layer and the inorganic layer formed on an inorganic layer.
(7) An easy adhesion layer forming step of forming a plurality of easy adhesion layers on the support;
An organic layer forming step of forming an organic layer on the easy adhesion layer;
An inorganic layer forming step of forming an inorganic layer on the organic layer;
In the easy-adhesion layer forming step, at least a lowermost easy-adhesion layer having a thickness of 0.3 μm or more in contact with the support and an uppermost easy-adhesion layer having a thickness of 0.1 μm or less in contact with the organic layer are formed. And
In the organic layer forming step, an organic layer is formed using a coating containing an organic compound to be an organic layer and a polymerization initiator having a solid content concentration of 5% by mass or more,
In the inorganic layer forming step, a functional film manufacturing method in which an inorganic layer is formed by a vapor deposition method.

  According to the present invention as described above, it is possible to suppress damage to the organic film due to plasma during the formation of the inorganic layer, and to prevent the occurrence of cracks in the organic layer, thereby suppressing damage to the inorganic layer. In addition, it is possible to provide a functional film having high gas barrier properties and high transparency and a method for producing the functional film.

FIG. 1 is a diagram conceptually illustrating an example of the functional film of the present invention. FIG. 2 (A) to FIG. 2 (B) are diagrams conceptually showing another example of the functional film of the present invention. It is a figure which shows notionally another example of the functional film of this invention. It is a figure which shows notionally an example of the manufacturing apparatus which enforces the manufacturing method of the functional film of this invention, Comprising: It is a figure which shows the formation apparatus of an easily bonding layer. It is a figure which shows notionally an example of the manufacturing apparatus which enforces the manufacturing method of the functional film of this invention, Comprising: It is a figure which shows the formation apparatus of an organic layer. It is a figure which shows notionally an example of the manufacturing apparatus which enforces the manufacturing method of the functional film of this invention, Comprising: It is a figure which shows the film-forming apparatus of an inorganic layer.

Hereinafter, the functional film of the present invention and the method for producing the functional film will be described in detail based on preferred embodiments shown in the accompanying drawings.
The description of the constituent elements described below may be made based on typical embodiments of the present invention, but the present invention is not limited to such embodiments.
In the present specification, a numerical range expressed using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.

  FIG. 1 conceptually shows an example of the functional film of the present invention.

In addition, the manufacturing method of the functional film of this invention is not limited to the manufacturing method of a gas barrier film. That is, the present invention can be used in various ways for producing known functional films such as filters that transmit light of a specific wavelength and various optical films such as an antireflection film.
In the functional film having an inorganic layer like the functional film of the present invention, it is the inorganic layer that mainly exhibits the intended function. Therefore, the manufacturing method of this invention can be used as a manufacturing method of the functional film which has an inorganic layer which expresses the target functions, such as the light transmittance of a specific wavelength.

Of the functional films, the gas barrier film greatly affects the barrier performance when the inorganic layer is broken. As described above, when the organic layer serving as the base of the inorganic layer is damaged by plasma, or when a crack occurs from the interface with the support or the easy adhesion layer, the inorganic layer is easily damaged. .
Therefore, the present invention is more suitably used for a gas barrier film that is formed at a high density and has a high gas barrier property.

The gas barrier film 10a which is a functional film of the present invention shown in FIG. 1 includes a support 12, a first easy-adhesion layer 20, a second easy-adhesion layer 22, an organic layer 16, and an inorganic layer 14. Are stacked in this order. In FIG. 1, hatching of the support 12 is omitted.
That is, the gas barrier film 10 a has an organic layer 16 that is a base of the inorganic layer 14 between the inorganic layer 14 and the support 12, and a plurality of easy adhesions between the organic layer 16 and the support 12. That is, the first easy-adhesion layer 20 and the second easy-adhesion layer 22 are provided.
The first easy-adhesion layer 20 is the lowermost easy-adhesion layer in contact with the support 12, and the second easy-adhesion layer 22 is the uppermost easy-adhesion layer in contact with the organic layer 16.

  Here, in the present invention, the surface hardness of the organic layer is H or more in pencil hardness, the thickness of the first easy-adhesion layer 20 which is the lowermost easy-adhesion layer is 0.3 μm or more, The thickness of the second easy-adhesion layer 22 that is an easy-adhesion layer is 0.1 μm or less.

  As described above, when an inorganic layer is formed by a vapor deposition method such as plasma CVD, a material having a high Tg (glass transition temperature) that can withstand high temperatures as an organic layer in order to reduce damage to the organic layer due to plasma. In addition, it was necessary to increase the hardness of the surface in contact with plasma. However, when the surface hardness of the organic layer is increased, the interface between the support or the easy-adhesion layer and the organic layer may be caused by a difference in thermal expansion coefficient between the organic layer and the support, or at the time of bending or processing. It has been found that there is a problem in that stress concentration occurs, cracks occur in the organic layer starting from the interface between the organic layer and the support or the easy adhesion layer, and the inorganic layer is damaged due to the crack.

  On the other hand, in the present invention, the surface hardness of the organic layer is set to H or higher in pencil hardness, thereby reducing damage to the organic layer 16 due to plasma and being the first easy-adhesion layer as the lowest layer. By making the thickness of the easy-adhesion layer 20 0.3 μm or more, the difference in thermal expansion coefficient between the organic layer 16 and the support 12 is absorbed, and as a cushion for the organic layer 16 during bending or processing It is possible to prevent the concentration of stress on the interface between the organic layer 16 and the second easy-adhesion layer 22 from occurring, and to prevent the organic layer 16 from cracking. Therefore, damage to the inorganic layer 14 due to damage to the organic layer 16 can be prevented, and high gas barrier properties can be exhibited.

Here, when a thick easily bonding layer having a thickness of 0.3 μm or more is formed between the support 12 and the organic layer 16, the interface between the layers increases. Therefore, the support and the easily bonding layer or the easily bonding layer is used. When the difference in refractive index between the organic layer and the organic layer is large, the reflectivity at these interfaces increases, the visible light transmission (transparency) decreases, and the appearance of interference fringes due to optical interference is poor. May occur.
On the other hand, in the present invention, the easy-adhesion layer has two or more layers, and the thickness of the second easy-adhesion layer 22 that is the uppermost easy-adhesion layer is 0.1 μm or less. It is possible to prevent the light reflectance at the interface between the organic layer and the organic layer from increasing, and to prevent deterioration of the optical characteristics due to the easily adhesive layer.

  In the gas barrier film 10a shown in FIG. 1, the inorganic layer 14 is formed as the outermost layer, but is not limited to this, for example, as in the gas barrier film 10b shown in FIG. An organic layer 16 b for protecting the inorganic layer 14 may be further formed on the inorganic layer 14.

Further, one or more combinations of an organic layer and an inorganic layer may be further provided on the inorganic layer 14. For example, a gas barrier film 10c shown in FIG. 2B has a plurality of easy-adhesion layers on the support 12, and has an organic layer 16 on the easy-adhesion layer. It has the inorganic layer 14 on it, Furthermore, it has the organic layer 16c on this inorganic layer 14, and you may have the inorganic layer 14c on this organic layer 16c. This one set of organic layer 16c and inorganic layer 14c has a configuration in which an organic layer and an inorganic layer are laminated. That is, the structure which forms an inorganic layer and an organic layer alternately, and has a total of two combinations of an inorganic layer and an organic layer may be sufficient.
Or the structure which has a total of 3 or more sets of organic layers and inorganic layers which laminated | stacked the inorganic layer and the organic layer alternately further may be sufficient.
The gas barrier property can be further improved by having a plurality of combinations of the inorganic layer and the organic layer.

Moreover, although the gas barrier film 10a shown in FIG. 1 was set as the structure which has two easy-adhesion layers of the 1st easy-adhesion layer 20 and the 2nd easy-adhesion layer 22 as a some easy-adhesion layer, this invention Is not limited to this, and may have three or more easy-adhesion layers.
For example, the gas barrier film 10 d shown in FIG. 3 includes a first easy-adhesion layer 20 that contacts the support 12 and a second easy-adhesion layer that contacts the organic layer 16 between the support 12 and the organic layer 16. 22, and a third easy-adhesion layer 21 formed between the first easy-adhesion layer 20 and the second easy-adhesion layer 22. That is, the gas barrier film 10d has a configuration having three easy-adhesion layers.
Thus, it is good also as a structure which has an easily bonding layer of 3 layers or more. By adopting a configuration in which three or more easy-adhesion layers are laminated, the change in refractive index between layers can be moderated, the increase in reflectance can be suppressed, and the light transmittance can be further improved.

  Next, materials, dimensions, etc. will be described for the components of the functional film of the present invention.

There is no limitation in particular as the support body 12, The support body used with a conventionally well-known functional film can utilize variously.
For example, a gas barrier film, an optical film, a protective film, etc., as long as the organic layer 16 and the inorganic layer 14 described later can be formed, such as various resin films such as a PET film and various metal sheets such as an aluminum sheet. Various supports (base films) used for various functional films are usable.
The support has a surface on which various films such as a protective film, an adhesive film, a light reflection layer, an antireflection layer, a light shielding layer, a planarization layer, a buffer layer, and a stress relaxation layer are formed. Also good.

Specific examples of the resin film used as the support 12 include polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyethylene, polypropylene, polystyrene, polyamide, polyvinyl chloride, polycarbonate, polyacrylonitrile, polyimide, and polyacrylate. And a plastic film made of a polymer material such as polymethacrylate.
In the present invention, the support 12 is a film-like material such as a long film or a cut sheet-like film.

In the present invention, the thickness of the support 12 is preferably 10 to 200 μm.
By setting the thickness of the support 12 to 10 μm or more, it is possible to impart sufficient mechanical strength to the gas barrier film, and to prevent the occurrence of curling or the like when a high-density inorganic layer is formed. (Two roll) process suitability can be imparted, that is, it is preferable in that bending during conveyance and winding failure can be suppressed.
Further, by setting the thickness of the support 12 to 200 μm or less, a gas barrier film having good optical properties can be obtained, a thin gas barrier film can be obtained, and a gas barrier film having good flexibility can be obtained. A gas barrier film can be obtained, and a product using the gas barrier film is preferable in that it can be reduced in weight and thickness.
Considering the above points, the thickness of the support 12 is more preferably 20 to 100 μm.

The organic layer 16 is a layer formed using a polymerizable compound and a polymerization initiator. Basically, in order to form the organic layer 16 as a film, a mixture of the polymerizable compound and the polymerization initiator is heated or lighted. Polymerized and cured by external energy such as
The organic layer 16 functions as a base layer for properly forming the inorganic layer 14 that mainly exhibits gas barrier properties. By having such an organic layer 16 as a base, the surface on which the inorganic layer 14 is formed can be flattened and made uniform, and a state suitable for the formation of the inorganic layer 14 can be achieved.
In the laminated gas barrier film in which the underlying organic layer 16 and the inorganic layer 14 are laminated, it becomes possible to form a dense inorganic layer 14 having no defects (fine holes) on the entire surface of the film. A gas barrier film having excellent gas barrier properties can be obtained. Further, it is possible to obtain a gas barrier film having not only gas barrier properties but also transparency, durability, and flexibility. Moreover, the gas barrier film which has the outstanding gas barrier property is obtained, so that there are many lamination | stacking number of the combination of the organic layer 16 and the inorganic layer 14 of a foundation | substrate.

Here, in the present invention, the surface hardness of the organic layer 16 is H or more in pencil hardness. Thereby, when forming the inorganic layer 14 on the organic layer 16, the damage to the organic layer 16 by a plasma can be reduced and it can prevent that the organic layer 16 is damaged. That is, it is possible to suppress the surface of the organic layer 16 from being roughened by plasma. Therefore, the inorganic layer 14 can be formed on a flat surface, and high gas barrier properties can be expressed.
In addition, when the surface hardness of the organic layer 16 is too high, the organic layer 16 may be easily cracked, and the flexibility may be reduced.
From the above viewpoint, the surface hardness of the organic layer 16 is preferably H to 6H and more preferably H to 2H in terms of pencil hardness.

  The pencil hardness of the surface of the organic layer 16 can be measured by JIS K5600-5-4 scratch hardness (pencil method).

In the gas barrier film of the present invention, the material for forming the organic layer 16 is not limited as long as the surface hardness can be H or more in pencil hardness, and various known organic compounds can be used.
Specifically, polyester, acrylic resin, methacrylic resin, methacrylic acid-maleic acid copolymer, polystyrene, transparent fluororesin, polyimide, fluorinated polyimide, polyamide, polyamideimide, polyetherimide, cellulose acylate, polyurethane, poly Ether ether ketone, polycarbonate, alicyclic polyolefin, polyarylate, polyethersulfone, polysulfone, fluorene ring modified polycarbonate, alicyclic modified polycarbonate, fluorene ring modified polyester, acryloyl compound, thermoplastic resin, or polysiloxane, etc. An organic silicon compound film is preferably exemplified. A plurality of these may be used in combination.

The thickness of the organic layer 16 is preferably 0.1 to 50 μm.
By setting the thickness of the organic layer 16 to 0.1 μm or more, the surface of the organic layer 16, that is, the formation surface of the inorganic layer 14 can be planarized.
In addition, by setting the thickness of the organic layer 16 to 50 μm or less, it is possible to suitably suppress the occurrence of problems such as cracks in the organic layer 16 and curling of the gas barrier film 10a due to the organic layer 16 being too thick. be able to.
Considering the above points, the thickness of the organic layer 16 is more preferably 0.15 to 5 μm.

In addition, when it has the some organic layer 16, the thickness of each organic layer 16 may be the same, or may mutually differ.
Similarly, when a plurality of organic layers 16 are provided, the material for forming each organic layer 16 may be the same or different. However, in consideration of production suitability, it is preferable to form all the organic layers 16 with the same material.

In the present invention, the organic layer 16 is basically formed by a coating method.
That is, when the organic layer 16 is formed, first, as an organic compound that becomes the organic layer 16, monomers, dimers, trimers, oligomers, and the like, and further, a polymerization initiator, a silane coupling agent, a surfactant, and an increasing viscosity agent A paint prepared by dissolving the above in an organic solvent is prepared. Next, this paint is applied to the surface of the film forming material and dried. After drying, an organic compound is polymerized by ultraviolet irradiation, electron beam irradiation, heating, or the like to form the organic layer 16.
Here, in the present invention, by forming the organic layer 16 using a coating containing a polymerization initiator having a solid content concentration of 5% by mass or more, the crosslinking performance at the time of curing is increased, and the surface hardness of the organic layer 16 is increased. Can be H or more in pencil hardness.
This will be described in detail later.

  The inorganic layer 14 is a layer made of an inorganic compound. In the gas barrier film 10a, the inorganic layer 14 mainly exhibits the target gas barrier property.

The material for forming the inorganic layer 14 is not limited, and various layers made of an inorganic compound that exhibits gas barrier properties can be used.
Specifically, metal oxides such as aluminum oxide, magnesium oxide, tantalum oxide, zirconium oxide, titanium oxide, and indium tin oxide (ITO); metal nitrides such as aluminum nitride; metal carbides such as aluminum carbide; silicon oxide, Silicon oxides such as silicon oxynitride, silicon oxycarbide, silicon oxynitride carbide; silicon nitrides such as silicon nitride and silicon nitride carbide; silicon carbides such as silicon carbide; hydrides thereof; mixtures of two or more of these; and Inorganic compounds such as these hydrogen-containing materials are preferably exemplified.
In particular, silicon nitride, silicon oxide, silicon oxynitride, and aluminum oxide are suitably used for the gas barrier film because they are highly transparent and can exhibit excellent gas barrier properties. Of these, silicon nitride is particularly suitable for its excellent gas barrier properties and high transparency.

In the present invention, 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 that stably expresses sufficient gas barrier performance can be formed. Further, the inorganic layer 14 is generally brittle, and if it is too thick, there is a possibility that cracks, cracks, peeling, etc. may occur. However, if the thickness of the inorganic layer 14 is 200 nm or less, cracks will occur. Can be prevented.
In consideration of such points, the thickness of the inorganic layer 14 is preferably 15 to 100 nm, and particularly preferably 20 to 75 nm.

In addition, when it has the some inorganic layer 14 like the gas barrier film 10c shown to FIG. 2 (B), the thickness of each inorganic layer 14 may be the same, or may mutually differ.
Similarly, in the case of having a plurality of inorganic layers 14 as in the gas barrier film 10c, the forming material of each inorganic layer 14 may be the same or different. However, in consideration of productivity, production cost, etc., it is preferable to form all the inorganic layers 14 with the same material.

In addition, the present invention can be suitably used when the inorganic layer 14 having a residual compressive stress in a predetermined range is formed in order to develop a high gas barrier property.
Specifically, the residual compressive stress of the inorganic layer 14 is preferably 200 to 4000 MPa, and more preferably 500 to 3000 MPa.
By setting the residual compressive stress of the inorganic layer 14 within the above range, it is possible to prevent the generation of fine cracks and cracks in the inorganic layer 14 due to the irregularities on the surface on which the inorganic layer 14 is formed, and to generate fine cracks and cracks. However, they can be prevented from spreading, and thereby high gas barrier properties can be expressed.

In the gas barrier film 10 of the present invention, the inorganic layer 14 may be formed (film formation) by a known inorganic layer forming method according to the forming material.
Specifically, CCP (Capacitively Coupled Plasma) -CVD and ICP (Inductively Coupled Plasma) -CVD and other plasma CVD, magnetron sputtering and reactive sputtering, etc., vacuum deposition, atomic layer deposition A vapor phase film formation method (vapor phase deposition method) such as (ALD (Atomic Layer Deposition)) is preferably exemplified.
In the atomic layer deposition method, a raw material gas containing the thin film material A and a raw material gas containing the thin film material B are alternately supplied and reacted on the substrate surface to form a uniform thin film AB on the substrate. Is the method.
Among these, plasma CVD can form an inorganic layer exhibiting high gas barrier properties, but the present invention can be more suitably applied because the organic layer is easily damaged by plasma.

The plurality of easy-adhesion layers are layers for improving the adhesion between the support 12 and the organic layer 16. That is, it is only necessary that the function of improving the adhesion between the support 12 and the organic layer 16 can be expressed by a plurality of layers.
For example, in the gas barrier film 10 a shown in FIG. 1, the first easy-adhesion layer 20 is made of a material having high adhesion to the support 12, and the second easy-adhesion layer 22 has high adhesion to the organic layer 16. The adhesion between the support 12 and the organic layer 16 can be improved by being made of a material and having high adhesion between the first easy-adhesion layer 20 and the second easy-adhesion layer 22.
Moreover, when it has three or more easy-adhesion layers like the gas barrier film 10d shown in FIG. 3, each easy-adhesion layer should just be formed with the material with high adhesiveness with the layer which contact | connects up and down.
In the following description, when it is not necessary to distinguish the first easy-adhesion layer 20, the second easy-adhesion layer 22, and the third easy-adhesion layer 21, these are collectively referred to as an easy-adhesion layer.

The material for forming the easy adhesion layer is not particularly limited, and various materials for the easy adhesion layer used in conventionally known functional films can be used.
For example, organic compounds such as acrylic resins, urethane resins, polyester resins, olefin resins, fluorine resins, vinyl resins, chlorine resins, styrene resins, various graft resins, epoxy resins, silicone resins, etc. Is preferably exemplified.

In the present invention, the method for applying the easy-adhesion layer is not particularly limited, and for example, known methods such as bar coater application and slide coater application are used. As the coating solvent, water, toluene, methyl alcohol, isopropyl alcohol, methyl ethyl ketone, and the like, and aqueous and organic solvent based coating solvents such as a mixed system thereof can be used. Among these, the method using water as a coating solvent is preferable in view of cost and ease of production.
The easy-adhesion layer may be formed by a coating method after the support 12 is stretched, or a paint for the easy-adhesion layer is applied before the support is stretched and then stretched together with the easy-adhesion layer. May be. It is preferable to form it after extending | stretching the support body 12 at the point which can control the thickness of an easily bonding layer more suitably.

  Here, as described above, in the present invention, the thickness of the first easy-adhesion layer 20 is 0.3 μm or more. As a result, even if the surface hardness of the organic layer 16 is H or more in pencil hardness, the difference in thermal expansion coefficient between the organic layer 16 and the support 12 is absorbed, and as a cushion for the organic layer 16 during bending or processing. It is possible to prevent the concentration of stress on the interface between the organic layer 16 and the second easy-adhesion layer 22 from occurring, and to prevent the organic layer 16 from cracking. Therefore, damage to the inorganic layer 14 due to damage to the organic layer 16 can be prevented, and high gas barrier properties can be exhibited.

If the thickness of the first easy-adhesion layer 20 is too thick, cracks in the first easy-adhesion layer 20, curling due to an increase in internal stress of the gas barrier film, cost increase due to an increase in drying time, etc. may occur. is there.
From the above viewpoint, the thickness of the first easy-adhesion layer 20 is preferably 0.3 to 0.5 μm.

  As described above, in the present invention, the thickness of the second easy-adhesion layer 22 is 0.1 μm or less. Thereby, even if it is a case where the thick 1st easily bonding layer 20 of 0.3 micrometer or more is formed, preventing the reflectance of the light in the interface of an easily bonding layer and an organic layer increasing, It is possible to prevent the deterioration of the optical characteristics due to the easy adhesion layer.

In addition, from a viewpoint of forming the 2nd easily bonding layer 22 appropriately, the 2nd easily bonding layer 22 has preferable 0.01 micrometer or more.
From the above viewpoint, the thickness of the second easy-adhesion layer 22 is preferably 0.01 to 0.1 μm, and more preferably 0.03 to 0.1 μm.

  Moreover, when it has three or more easy-adhesion layers, if the thickness of the 1st easy-adhesion layer and the 2nd easy-adhesion layer satisfy | fills the said range, the 1st easy-adhesion layer and the 2nd easy-adhesion layer The thickness of each easy-adhesion layer other than the layer is not particularly limited, but is preferably 0.01 to 0.3 μm from the viewpoint of optical properties, flexibility, productivity, suitability for coating, appearance suitability, etc. 0.05 to 0.3 μm is more preferable.

The refractive index of the first easy-adhesion layer 20 is preferably closer to the refractive index of the support 12 than the refractive index of the second easy-adhesion layer 22, and the refractive index of the first easy-adhesion layer 20. More preferably, the refractive index of the second easy-adhesion layer is closer to the refractive index of the organic layer 16. Thereby, the increase in the reflectance at the interface between the first easy-adhesion layer 20 and the support 12 and the interface between the second easy-adhesion layer 22 and the organic layer 16 is suppressed, and the transmittance decreases. Can be prevented.
It is also preferable that the refractive index of each layer between the support 12 and the organic layer 16 be gradually changed. Thereby, it can suppress that the reflectance in the interface of each layer increases, and can prevent the transmittance | permeability fall.

In addition, it is preferable that the refractive index difference of the 1st easily bonding layer 20 and the 2nd easily bonding layer 22 is 0.01-0.1.
Thereby, the difference of the refractive index of the support body 12 and the organic layer 16 is absorbed, and the fall of the transmittance | permeability can be prevented more suitably.

Next, the manufacturing method of the functional film of this invention is demonstrated.
The method for producing the functional film of the present invention comprises:
A preparation step of preparing a support;
An easy-adhesion layer forming step of forming a plurality of easy-adhesion layers on the support;
An organic layer forming step of forming an organic layer on the easy adhesion layer;
An inorganic layer forming step of forming an inorganic layer on the organic layer;
In the easy-adhesion layer forming step, at least a lowermost easy-adhesion layer having a thickness of 0.3 μm or more in contact with the support and an uppermost easy-adhesion layer having a thickness of 0.1 μm or less in contact with the organic layer are formed. And
In the organic layer forming step, an organic layer is formed using a coating containing an organic compound to be an organic layer and a polymerization initiator having a solid content concentration of 5% by mass or more,
In the inorganic layer forming step, a functional film is produced by forming an inorganic layer by a vapor deposition method.

The method for producing a functional film of the present invention (hereinafter also referred to as the production method of the present invention) is a method for forming an inorganic layer by plasma in an inorganic layer forming step by vapor phase deposition such as plasma CVD. In order to reduce the damage of the organic layer, in the organic layer forming step, the surface hardness of the organic layer is increased by forming the organic layer using a coating containing a polymerization initiator having a solid content concentration of 5% by mass or more.
However, when the surface hardness of the organic layer is increased, the interface between the support or the easy-adhesion layer and the organic layer may be caused by a difference in thermal expansion coefficient between the organic layer and the support, or at the time of bending or processing. The stress concentration occurs, and the organic layer cracks from the interface between the organic layer and the support or the easy-adhesion layer, and the inorganic layer is damaged due to the crack.
Therefore, in the present invention, in the easy-adhesion layer forming step, at least the bottommost easy-adhesion layer having a thickness of 0.3 μm or more in contact with the support and the thinnest layer having a thickness of 0.1 μm or less in contact with the organic layer. An upper easy adhesion layer is formed. By forming the lowermost easily adhesive layer of 0.3 μm or more, the organic layer 16 is prevented from being cracked.
Here, when a thick easy-adhesion layer having a thickness of 0.3 μm or more is formed, there is a possibility that the light transmittance may be lowered. Therefore, by forming an uppermost easily adhesive layer having a thickness of 0.1 μm or less, it is possible to prevent an increase in light reflectivity at the interface between the easily adhesive layer and the organic layer. To prevent deterioration of optical characteristics.
Hereinafter, the manufacturing method of the present invention will be described with reference to FIGS.

4-6 conceptually shows an example of a production apparatus for producing each layer of the functional film of the present invention.
The manufacturing apparatus shown in FIG. 4 is an easy-adhesion layer forming apparatus 30 that forms an easy-adhesion layer, and the manufacturing apparatus shown in FIG. 5 is an organic forming apparatus 31 that forms the organic layer 16, and the manufacturing apparatus shown in FIG. Is an inorganic film forming apparatus 32 for forming the inorganic layer 14.

The easy adhesion layer forming device 30 shown in FIG. 4, the organic layer forming device 31 shown in FIG. 5, and the inorganic film forming device 32 shown in FIG. 6 are both formed from a roll formed by winding a long material to be formed. The above-mentioned Roll to Roll (hereinafter, referred to as “roll to roll”) is formed by feeding the material, forming each layer (film formation) while conveying the material to be formed in the longitudinal direction, (RtoR)).
Such RtoR can produce an efficient gas barrier film with high productivity.

Here, in FIG. 4, an easy-adhesion layer forming apparatus for forming the first easy-adhesion layer 20 will be described. However, an easy-adhesion layer such as the second easy-adhesion layer 22 is also formed by the same easy-adhesion layer forming apparatus. be able to.
Moreover, the manufacturing apparatus shown in FIGS. 4-6 has the 1st easily bonding layer 20, the 2nd easily bonding layer 22, organic on the surface of the elongate support body 12 as shown to FIG. 2 (A). The layer 16 and the inorganic layer 14 are sequentially formed to manufacture the gas barrier film 10a and the like.
Therefore, in the easy-adhesion layer forming apparatus 30 shown in FIG. 4, when the first easy-adhesion layer 20 is formed, the film forming material Za is the support 12, and the second easy-adhesion layer 22 is formed. The material to be deposited Za when formed is a material in which the first easy-adhesion layer 20 (or a third easy-adhesion layer) is formed on the surface of the support 12 and is shown in FIG. In the organic layer forming apparatus 31, when the organic layer 16 is formed, the film forming material Zb is the first easy-adhesive layer 20 and the second easy-adhesive layer 22 formed on the surface of the support 12. Material.
On the other hand, in the inorganic film forming apparatus 32 shown in FIG. 6, the film forming material Zc is a material in which a plurality of easy adhesion layers and the organic layer 16 are formed on the surface of the long support 12.

The production method of the present invention is not limited to the production of a functional film such as a gas barrier film by RtoR using a long substrate, but a so-called single wafer type composition using a cut sheet substrate. A functional film may be produced using a membrane method.
In the production method of the present invention, when a plurality of organic layers 16 and / or inorganic layers 14 are formed, the formation method may be the same or different in each layer.

The easy-adhesion layer forming apparatus 30 shown in FIG. 4 applies the coating material that becomes the first easy-adhesion layer 20 while transporting a long film-forming material Za in the longitudinal direction, and dries the first material. This is an apparatus for forming the easy adhesion layer 20.
In the illustrated example, the easy-adhesion layer forming apparatus 30 includes, as an example, a coating unit 36, a drying unit 38, a rotating shaft 42, a winding shaft 46, and conveying roller pairs 48 and 50.
In addition to the illustrated members, the easy-adhesion layer forming apparatus 30 forms a film by coating while conveying a long film-forming material such as a pair of transport rollers, a guide member for the film-forming material Za, and various sensors. You may have the various members provided in the well-known apparatus to perform.

In the easy-adhesion layer forming apparatus 30, a material roll 61 formed by winding a long film-forming material Za that is the support 12 is loaded on the rotating shaft 42.
When the material roll 61 is loaded on the rotating shaft 42, the film forming material Za is pulled out from the material roll 61, passes through the conveying roller pair 48, passes through the coating unit 36 and the drying unit 38, and is conveyed to the conveying roller pair 50. Then, it passes through a predetermined conveyance path that reaches the winding shaft 46.

  In the easy-adhesion layer forming apparatus 30 using RtoR, the film-forming material Za is fed from the material roll 61, and the film-forming material Za on which the first easy-adhesion layer 20 is formed on the take-up shaft 46 is wound. Are performed synchronously. As a result, while the long film-forming material Za is transported in the longitudinal direction along a predetermined transport path, the coating material serving as the first easy-adhesion layer 20 is applied by the coating unit 36, and the coating material is dried by the drying unit 38. Thus, the first easy-adhesion layer 20 is formed.

The applying means 36 applies a paint for forming the first easy-adhesion layer 20 prepared in advance on the surface of the film forming material Za.
This paint is obtained by dissolving an organic compound such as a monomer, which becomes the first easy-adhesion layer 20, in a coating solvent. In addition, necessary components such as a silane coupling agent, a surfactant, a polymerization initiator, and an increasing viscosity agent may be appropriately added to the coating material.
Here, the coating material of the first easy-adhesion layer 20 is applied onto the film formation material Za so that the thickness after curing is 0.3 μm or more.

In the coating unit 36, there is no particular limitation on the coating method for the film forming material Za.
Therefore, the application of the paint is all known coating methods such as die coating, dip coating, air knife coating, curtain coating, roller coating, wire bar coating, gravure coating, slide coating, etc. Is available.

As described above, the film forming material Za is then transported to the drying unit 38, and the coating applied by the coating unit 36 is dried.
The drying method of the paint by the drying means 38 is not limited, and any known drying means can be used as long as the paint can be dried to remove and cure the coating solvent. Various known methods can be used. As an example, heat drying with a heater, heat drying with warm air, and the like are exemplified.

The film forming material Za on which the first easy-adhesion layer 20 is formed in this manner is nipped and conveyed by the conveying roller pair 50 to reach the take-up shaft 46, and is again wound into a roll shape by the take-up shaft 46. The material roll 62 is formed by winding the film forming material Za on which the first easy-adhesion layer 20 is formed.
This material roll 62 is a material roll 61 formed by winding the film-forming material Za having the first easy-adhesion layer 20 formed on the support 12, and forms an easy-adhesion layer 22 that forms the second easy-adhesion layer 22. Supplied to the device 30.

The second easy-adhesion layer 22 is formed by the easy-adhesion layer forming apparatus 30 in the same manner as described above according to the forming material. Here, as described above, the second easy-adhesion layer 22 is formed to have a thickness of 0.1 μm or less.
The material roll 62 formed by winding the film formation material Za on which the second easy adhesion layer 22 is formed is formed by winding the film formation material Zb formed by forming a plurality of easy adhesion layers on the support 12. The material roll 61 is supplied to the organic layer forming apparatus 31 that forms the organic layer 16.

The organic layer forming apparatus 31 shown in FIG. 5 applies a coating material to be the organic layer 16 while transporting a long film-forming material Zb in the longitudinal direction, and is dried by light irradiation or after drying. The organic compound contained in the coating film is crosslinked and cured to form the organic layer 16.
The organic layer forming apparatus 31 shown in FIG. 5 has the same configuration as the easy-adhesive layer forming apparatus 30 in FIG. 4 except that the light irradiation means 40 is provided on the downstream side of the drying means 38. Therefore, in the following description, different points from the easy-adhesion layer forming apparatus 30 are mainly performed.
The organic layer forming apparatus 31 performs film formation by coating while conveying a long material to be formed such as a pair of conveying rollers, a guide member for the material Zb to be formed, and various sensors in addition to the illustrated members. You may have the various members provided in a well-known apparatus.

  In the organic layer forming apparatus 31, when a material roll 61 formed by winding a long film forming material Zb as the support 12 is loaded on the rotating shaft 42, the film forming material Zb is removed from the material roll 61. Pulled out, passes through a pair of conveying rollers 48, passes through a lower part of the coating unit 36, the drying unit 38, and the light irradiation unit 40, passes through a pair of conveying rollers 50, and reaches a winding shaft 46, and then passes through a predetermined conveying path. The

  The organic layer forming apparatus 31 applies the coating material to be the organic layer 16 by the coating unit 36 while drying the coating material by the drying unit 38 while transporting the long film-forming material Zb in the longitudinal direction along the predetermined transport path. The organic layer 16 is formed by curing by the light irradiation means 40.

  In addition, when the layer formed by the organic layer forming apparatus 31 is a thermally crosslinkable material, the organic layer forming apparatus 31 may be heated and dried by the drying unit 38 to form a layer, and light irradiation The means 40 may not be provided.

The coating means 36 applies a paint for forming the organic layer 16 prepared in advance on the surface of the film forming material Zb.
This paint is obtained by dissolving an organic compound such as a monomer and a polymerization initiator, which are formed into an organic layer 16 by crosslinking and polymerization in an organic solvent, in the organic solvent. In addition, necessary components such as a silane coupling agent, a surfactant, and an increasing viscosity agent may be appropriately added to the coating material.
Here, in the present invention, the organic layer 16 is formed using a paint containing a polymerization initiator having a solid content concentration of 5% by mass or more as a paint for forming the organic layer 16. As a result, the organic layer 16 having a surface hardness of H or higher in pencil hardness is formed.

There is no particular limitation on the method of applying the coating material to the film forming material Zb in the applying means 36.
Therefore, the application of the paint is all known coating methods such as die coating, dip coating, air knife coating, curtain coating, roller coating, wire bar coating, gravure coating, slide coating, etc. Is available.
Above all, because the coating can be applied in a non-contact manner, the surface of the film-forming material Zb is not damaged, and the bead formation is excellent in the embedding of the surface of the film-forming material Zb, etc. Are preferably used.

Next, the film forming material Zb is conveyed to the drying means 38, and the coating material applied by the applying means 36 is dried.
The drying method of the paint by the drying means 38 is not limited, and before the film-forming material Zb reaches the light irradiation means 40, the paint is dried and the organic solvent is removed so that crosslinking is possible. Any known drying means can be used as long as it can be used, or a material that can be crosslinked by heating, as long as it can be heated sufficiently for crosslinking. Various known methods can be used. As an example, heat drying with a heater, heat drying with warm air, and the like are exemplified.

  Next, the film forming material Zb is transported to the light irradiation means 40. The light irradiation means 40 irradiates the coating material applied by the coating means 36 and dried by the drying means 38 with ultraviolet rays or visible light, and crosslinks and cures an organic compound such as a monomer contained in the coating material. It is what.

  When the coating film is cured by the light irradiation means 40, the light irradiation area by the light irradiation means 40 in the film forming material Zb may be made an inert atmosphere by nitrogen substitution or the like, if necessary. Further, if necessary, a temperature of the film forming material Zb, that is, the coating film, may be adjusted at the time of curing by using a backup roller or the like that contacts the back surface.

The temperature of the film forming material Zb when the coating film is cured by the light irradiation means 40 is preferably 30 ° C. or higher, more preferably 50 ° C. or higher, and more preferably 60 ° C. or higher.
By setting the temperature of the film-forming material Zb in the curing step within the above range, it is preferable in that the crosslinking density can be increased and the hardness and scratch resistance can be improved.

  In the present invention, the crosslinking of the organic compound that becomes the organic layer is not limited to photopolymerization. That is, for the crosslinking of the organic compound, various methods such as heat polymerization, electron beam polymerization, and plasma polymerization can be used according to the organic compound that becomes the easy adhesion layer or the organic layer.

  A material roll 62 obtained by winding the film forming material Zb on which the organic layer 16 is formed is supplied to the inorganic film forming apparatus 32. The film forming material Zb on which the organic layer 16 is formed is the film forming material Zc for forming the inorganic layer 14 in the inorganic film forming apparatus 32.

  The easy-adhesion layer forming device 30 shown in FIG. 4 and the organic layer forming device 31 shown in FIG. 5 are each configured to form one easy-adhesion layer or one organic layer. However, the present invention is not limited to this. It is good also as a structure formed continuously. That is, for example, the easy-adhesion layer forming apparatus includes a coating unit and a drying unit for forming the first easy-adhesion layer 20 in the transport path from the rotating shaft 42 to the winding shaft 46, and a second easy-adhesion. It is good also as a structure which has the application means and drying means for forming the layer 22, and forms the 1st easily bonding layer 20 and the 2nd easily bonding layer in order. Alternatively, the manufacturing apparatus forms the organic layer 16 by applying means and drying means for forming the first easy-adhesion layer 20, applying means and drying means for forming the second easy-adhesion layer 22. The first easy-adhesion layer 20, the second easy-adhesion layer 22, and the organic layer 16 may be formed in this order.

An inorganic film forming apparatus 32 shown in FIG. 6 is an apparatus for forming the inorganic layer 14 by plasma CVD as an example of a manufacturing apparatus that performs the manufacturing method of the present invention.
The inorganic film forming apparatus 32 is an apparatus for forming the inorganic layer 14 on the surface of the film forming material Zc by vapor deposition, and includes a vacuum chamber 52 and an unwinding chamber 54 formed in the vacuum chamber 52. The film forming chamber 56 and the drum 80 are included.
In addition to the illustrated members, the inorganic film forming apparatus 32 conveys a long material to be formed such as a conveying roller pair, a guide member for regulating the position of the film forming material Zc in the width direction, and various sensors. However, various members provided in a known apparatus that performs film formation by a vapor deposition method may be included.

  The inorganic film forming apparatus 32 using RtoR synchronizes the feeding of the film forming material Zc from the material roll 62 and the winding of the film forming material Zc with the inorganic layer formed on the winding shaft 92. Then, the inorganic film 14 is formed in the film forming chamber 56 while the long film forming material Zc is conveyed in the longitudinal direction while being wound around the drum 80, and the film is wound in the unwinding chamber 54. It is wound around a take-up shaft 92 and wound into a roll.

The drum 80 is a cylindrical member that rotates in the clockwise direction in the drawing around a rotation axis that passes through the center of the drum 80 and is parallel to a direction perpendicular to the paper surface.
The drum 80 wraps the film forming material Zc guided by a guide roller 84a of the unwind chamber 54, which will be described later, on a predetermined area of the peripheral surface, and conveys it in the longitudinal direction while holding it at a predetermined position. Then, the film is transferred into the film forming chamber 56 and sent to the guide roller 84 b in the unwinding chamber 54.

  Here, the drum 80 also functions as a counter electrode of a film formation electrode 82 in the film formation chamber 56 described later, and is grounded. That is, the drum 80 and the film forming electrode 82 constitute an electrode pair.

If necessary, the drum 80 may be connected to a bias power source for applying a bias voltage to the drum 80. Alternatively, the ground and the bias power supply may be connected to be switchable.
As the bias power source, all known power sources such as a high frequency power source and a pulse power source for applying a bias voltage, which are used in various film forming apparatuses, can be used.
Further, the drum 80 may include a temperature adjusting means, and the film forming material Zc may be cooled, for example, during the formation of the inorganic layer 14.

The unwinding chamber 54 is a region in the vacuum chamber 52 other than the film forming chamber 56 described later. That is, the unwind chamber 54 is formed by the inner wall surface of the vacuum chamber 52, the peripheral surface of the drum 80, and the partition walls 60a and 60b extending from the inner wall surface of the vacuum chamber 52 to the vicinity of the peripheral surface of the drum 80. Space.
Here, the leading ends of the partition walls 60a and 60b on the drum 80 side are close to the peripheral surface of the drum 80 to a position where they do not come into contact with the film forming material Zc to be conveyed, and the unwind chamber 54 and the film forming chamber 56 And are separated in a substantially airtight manner.

  Such an unwinding chamber 54 includes the above-described winding shaft 92, guide rollers 68, 84 a, 84 b and 90, a rotating shaft 64, and a vacuum exhaust means 70.

  The rotating shaft 64 is loaded with a material roll 62 around which a long film-forming material Zc is wound. The guide rollers 68 and 84a are normal guide rollers that guide the film forming material Zc on the upstream side of the drum 80 in the transport path of the film forming material Zc. The guide rollers 84b and 90 are ordinary guide rollers that guide the film forming material Zc on the downstream side of the drum 80. The take-up shaft 92 is a known elongate take-up shaft for taking up the film-forming material Zc having the inorganic layer formed thereon.

In the illustrated example, a material roll 62 formed by winding a long film-forming material Zc in a roll shape is mounted on a rotating shaft 64. When the material roll 62 is mounted on the rotating shaft 64, the film forming material Zc passes through the guide rollers 68 and 84a, the drum 80, and the guide rollers 84b and 90, and reaches the take-up shaft 92. Is routed through.
In the inorganic film forming apparatus 32, the film forming material Zc is fed out from the material roll 62 and the film forming material Zc is wound on the take-up shaft 92 in synchronization with each other. Film formation in the film forming chamber 56 is continuously performed while the film forming material Zc is transferred in the longitudinal direction along a predetermined transfer path.

The vacuum exhaust means 70 is a vacuum pump for reducing the pressure in the unwind chamber 54 to a predetermined degree of vacuum. The vacuum evacuation means 70 makes the inside of the unwinding chamber 54 a pressure that does not affect the pressure in the film forming chamber 56.
The vacuum evacuation means 70 is not particularly limited, and various known vacuum evacuation means used in a vacuum film formation apparatus such as a vacuum pump such as a turbo pump, a mechanical booster pump, a dry pump, and a rotary pump, Is available. In this regard, the same applies to other vacuum exhaust means 74 described later.

A film forming chamber 56 is disposed downstream of the unwind chamber 54 in the transport direction of the film forming material Zc.
In the film forming chamber 56, an inorganic layer is formed on the surface of the organic layer 16 of the laminated body, which is the film forming material Zc, by a vapor deposition method.
The film forming chamber 56 is a space formed by an inner wall surface of the vacuum chamber 52, a peripheral surface of the drum 80, and partition walls 60 a and 60 b extending from the inner wall surface of the vacuum chamber 52 to the vicinity of the peripheral surface of the drum 80. It is.

In the inorganic film forming apparatus 32, the film forming chamber 56, for example, forms a film on the surface of the film forming material Zc by CCP-CVD, and includes a film forming electrode 82, a high frequency power supply 83, and vacuum exhaust. Means 74.
The film forming material Zc wound around a predetermined position of the drum 80 and transported to the film forming chamber 56 is transported in the longitudinal direction while being positioned at the predetermined position by the drum 80 to continuously form the inorganic layer 14. The

The film forming electrode 82 constitutes an electrode pair together with the drum 80 when the inorganic film forming apparatus 32 forms a film by CCP-CVD. The film forming electrode 82 is a known film forming electrode used in a vacuum film forming apparatus such as plasma CVD. For example, a so-called shower electrode is used as the film forming electrode 82. The shower electrode has a hollow, substantially rectangular parallelepiped shape, and is disposed with the discharge surface, which is one maximum surface, facing the peripheral surface of the drum 80, and the discharge surface, which is the surface facing the drum 80, has many through holes. Is formed entirely.
The film formation electrode 82 generates plasma for film formation between the discharge surface and the peripheral surface of the drum 80 forming the electrode pair, thereby forming a film formation region.

A source gas is supplied to a film forming region between the film forming electrode 82 and the drum 80 by a source gas supply unit (not shown).
For example, when the film-forming electrode 82 is a shower electrode, the source gas supply means supplies the source gas into the shower electrode. A large number of through holes are formed on the surface of the shower electrode facing the drum 80. Therefore, the source gas supplied to the shower electrode is introduced between the film forming electrode 82 and the drum 80 from this through hole.

As the source gas, a known reaction gas corresponding to the inorganic layer 14 to be formed may be used. For example, when a silicon nitride film used as a gas barrier film or the like is formed as the inorganic layer 14, silane gas and ammonia gas and / or nitrogen gas may be used. Similarly, a silicon oxide film is formed. If present, silane gas and oxygen gas may be used as the source gas.
If necessary, various gases such as an inert gas such as helium gas, neon gas, argon gas, krypton gas, xenon gas, and radon gas, hydrogen gas, and the like may be used in combination with the source gas.

  The vacuum evacuation means 74 is for evacuating the inside of the film forming chamber 56 to obtain a degree of vacuum corresponding to the formation of the inorganic layer 14.

  In the illustrated example, the film formation chamber 56 is configured to form an inorganic layer by CCP-CVD. However, the present invention is not limited to this, and plasma CVD such as ICP-CVD, CVD, magnetron sputtering, and reactivity are not limited thereto. Various known gas layer deposition methods such as sputtering such as sputtering, vacuum deposition, ion plating, and atomic layer deposition (ALD) can be used.

Therefore, the inside of the film forming chamber 56 is composed of various members according to the vapor deposition method to be performed.
For example, if the film forming chamber 56 forms the inorganic layer 14 by the ICP-CVD method, an induction coil for forming an induction magnetic field and a gas supply means for supplying a reaction gas to the film forming region And so on.
If the film formation chamber 56 is for depositing the inorganic layer 14 by vacuum vapor deposition, it has a crucible for filling the film formation material, a shutter for shielding the crucible, a heating means for heating the film formation material in the crucible, and the like. Configured.
Further, if the film formation chamber 56 is for depositing the inorganic layer 14 by sputtering, the film formation chamber 56 includes a target holding unit, a high-frequency electrode, a gas supply unit, and the like.

Note that the formation conditions of the inorganic layer 14, such as temperature and pressure, may be appropriately set according to the film formation method, the target film thickness, film formation rate, and the like.
For example, when the inorganic layer 14 is formed by the CCP-CVD method, the pressure in the film formation chamber 56 is preferably 20 Pa to 200 Pa, and the temperature is preferably 0 ° C. to 80 ° C. When the inorganic layer 14 is formed by the ICP-CVD method, the pressure in the film formation chamber 56 is preferably 0.1 Pa to 10 Pa, and the temperature is preferably 0 ° C. to 80 ° C.

  In addition, when the inorganic layer 14 contacts and cracks another member, there exists a possibility that barrier performance may fall large. Therefore, it is good also as a structure which sticks a protective film immediately after film-forming and protects the inorganic layer 14 formed into a film.

  After the inorganic layer 14, the material roll 63 wound in a roll shape in the unwinding chamber 54 is supplied to the next process as a material roll 63 formed by winding the gas barrier film 10a or the like which is a functional film of the present invention. The

  It should be noted that the number of inorganic layers 14 to be formed and the organic layers are also different when producing gas barrier films having other layer structures such as the gas barrier film 10b shown in FIG. 2A and the gas barrier film 10c shown in FIG. Similar formation of the inorganic layer 14 and the organic layer 16 may be repeated depending on the number of layers 16 and the layer configuration.

  As mentioned above, although the functional film of this invention and the manufacturing method of a functional film were demonstrated in detail, this invention is not limited to the said embodiment, In the range which does not deviate from the summary of this invention, various improvement and change Of course, you may do.

Hereinafter, the present invention will be described in more detail with reference to specific examples of the present invention.
[Example 1]
(Multiple easy adhesion layers)
A long PET film (manufactured by Fuji Film Co., Ltd.) having a thickness of 100 μm was prepared as the support 12.
In addition, the refractive index of PET used as the support body 12 is 1.65.
A material roll formed by winding the support 12 serving as the film forming material Za is loaded on the rotation shaft of the easy-adhesion layer forming apparatus, and the film forming material Za is inserted through a predetermined transfer path and transferred. The first easy-adhesion layer 20 having a thickness of 0.4 μm is formed on the support 12 by the applying means and the drying means, and continuously, the second applying means and the second drying means A second easy adhesion layer 22 having a thickness of 0.05 μm was formed on one easy adhesion layer 20 and wound up.

  The paint for forming the first easy-adhesion layer 20 and the paint for forming the second easy-adhesion layer 22 were prepared with the following composition.

<First easy-adhesion layer coating composition A>
45.1 parts by mass of polyester resin binder (manufactured by Kyoyo Chemical Co., Ltd., plus coat Z-687, solid content 25%)
Compound having a plurality of carbodiimide structures 15.8 parts by mass (Nisshinbo Co., Ltd., Carbodilite V-02-L2, solid content 40%)
7.0 parts by mass of oxazoline compound (Nippon Shokubai Co., Ltd., Epocross K2020E, solid content 40%)
Surfactant A 18.2 parts by mass (manufactured by NOF Corporation, 1% aqueous solution of Lapisol B-90, anionic)
Add distilled water to 1000 parts by mass

<Second easy adhesion layer coating composition A>
95% distilled water
Acrylic resin binder 25.4 parts by mass (manufactured by Daicel Chemical Industries, EM48D, solid content 27.5%)
Compound having a plurality of carbodiimide structures 4.7 parts by mass (Nisshinbo Co., Ltd., Carbodilite V-02-L2, solid content 40%)
Surfactant A 12.7 parts by mass (manufactured by NOF Corporation, 1% aqueous solution of Lapisol B-90, anionic)
Surfactant B 15.5 parts by mass (manufactured by Sanyo Chemical Industries, 1% aqueous solution of NAROACTY CL-95, nonionic)
Silica fine particle dispersion 1.6 parts by mass (manufactured by Nippon Aerosil Co., Ltd., Aerosil OX-50 aqueous dispersion, solid content 10%)
Colloidal silica 3.5 parts by mass

Moreover, the drying conditions of the 1st easily bonding layer 20 were 180 degreeC.
In addition, the refractive index of the polyester resin used as the 1st easily bonding layer 20 is 1.58.

The drying condition of the second easy-adhesion layer 22 was 180 ° C.
In addition, the refractive index of the acrylic resin used as the 2nd easily bonding layer 22 is 1.49.

(Organic layer)
A material roll formed by winding a film-forming material Zb having a plurality of easy-adhesion layers formed on a support is loaded on the rotating shaft of an organic layer forming apparatus as shown in FIG. The organic layer 16 having a thickness of 5 μm was formed on the second easy-adhesion layer 22 by applying means, drying means, and light irradiation means while being inserted and transported through a predetermined transport path.

The coating material for forming the organic layer 16 was prepared by mixing the following components.
DPHA20 (Nippon Kayaku Co., Ltd.) 47.5 parts by mass Methyl ethyl ketone 50.0 parts by mass Photopolymerization initiator (BASF Co., Ltd. Irgacure 184) 2.5 parts by mass

In addition, the solid content concentration of the polymerization initiator of the paint is 5% by mass.
A die coater was used as the coating means. The drying means used a device that blows drying air from a nozzle, and drying was performed at 80 ° C. Further, the polymerization was carried out by irradiating ultraviolet rays from the light irradiation means. The curing with ultraviolet rays was performed so that the ultraviolet ray irradiation amount was about 2000 mJ / cm ² in terms of the cumulative irradiation amount.
In addition, the refractive index of DPHA20 used as the organic layer 16 is 1.48.
Further, the surface hardness of the formed organic layer 16 was measured by a pencil hardness measurement method. As a result, the surface hardness was H in pencil hardness.

(Inorganic layer)
FIG. 6 shows a material roll 62 formed by winding a laminated body to be a film forming material Zc, in which the first easy-adhesion layer 20, the second easy-adhesion layer 22 and the organic layer 16 are formed in this order on the support 12. The inorganic layer 14 was formed while being loaded on the rotating shaft of the inorganic film forming apparatus 32 as shown in FIG.
The pressure in the unwinding chamber was 5 Pa. Moreover, the conveyance speed of the film-forming material Zc was set to 7.5 m / min.

Silane gas (SiH ₄ ), ammonia gas (NH ₃ ), and hydrogen gas (H ₂ ) were used as source gases. The supply amounts were 50 sccm for silane gas, 100 sccm for ammonia gas, and 150 sccm for hydrogen gas. The film forming pressure was 100 Pa.

The shower film-forming electrode was supplied with a plasma excitation power of 5000 W at a frequency of 13.5 MHz from a high-frequency power source. Furthermore, 500 W of bias power was supplied to the drum from a bias power source.
Under such conditions, the inorganic layer 14 having a thickness of 40 nm was formed on the surface of the film formation target material Zc having a thickness of 200 m, thereby producing a functional film.

[Example 2]
A functional film was produced in the same manner as in Example 1 except that the amount of the photopolymerization initiator was 3.5 parts by mass, that is, the solid content concentration of the polymerization initiator was 7% by mass.
The surface hardness of the organic layer was 2H in pencil hardness.

[Example 3]
A functional film was produced in the same manner as in Example 1 except that the amount of the photopolymerization initiator was 5.0 parts by mass, that is, the solid content concentration of the polymerization initiator was 10% by mass.
The surface hardness of the organic layer was 3H in pencil hardness.

[Example 4]
A functional film was produced in the same manner as in Example 1 except that the thickness of the first easy-adhesion layer was 1.0 μm.

[Example 5]
A functional film was produced in the same manner as in Example 1 except that the thickness of the second easy-adhesion layer was 0.09 μm.

[Example 6]
A functional film was produced in the same manner as in Example 1 except that the coating material for forming the second easy-adhesion layer was changed to the following materials.

<Second easy adhesion layer coating composition B>
25.4 parts by mass of polyurethane resin binder (Mitsui Chemicals, Olester UD-350, solid content 38%)
Compound having a plurality of carbodiimide structures 4.7 parts by mass (Nisshinbo Co., Ltd., Carbodilite V-02-L2, solid content 40%)
Surfactant A 12.7 parts by mass (manufactured by NOF Corporation, 1% aqueous solution of Lapisol B-90, anionic)
Surfactant B 15.5 parts by mass (manufactured by Sanyo Chemical Industries, 1% aqueous solution of NAROACTY CL-95, nonionic)
Silica fine particle dispersion 1.6 parts by mass (manufactured by Nippon Aerosil Co., Ltd., Aerosil OX-50 aqueous dispersion, solid content 10%)
Colloidal silica 3.5 parts by mass (manufactured by Nissan Chemical Industries, Snowtex XL, solid content 40.5%)
Sliding agent 1.6 parts by mass (manufactured by Chukyo Yushi Co., Ltd., carnauba wax dispersion cellosol 524 solid content 30%)
Add distilled water to 1000 parts by mass

  In addition, the refractive index of the polyurethane resin used as a 2nd easily bonding layer is 1.51.

[Comparative Example 1]
A functional film was produced in the same manner as in Example 1 except that the amount of the photopolymerization initiator was 2.0 parts by mass, that is, the solid content concentration of the polymerization initiator was 4% by mass.
The surface hardness of the organic layer was 2B in pencil hardness.

[Comparative Example 2]
A functional film was produced in the same manner as in Example 1 except that the second easy-adhesion layer was not formed and the thickness of the first easy-adhesion layer was 0.45 μm.

[Comparative Example 3]
A functional film was produced in the same manner as in Example 1 except that the thickness of the first easy-adhesion layer was 0.15 μm.

[Comparative Example 4]
A functional film was produced in the same manner as in Example 1 except that the thickness of the second easy-adhesion layer was 0.15 μm.
[Evaluation]
About the produced functional film of Examples 1-6 and Comparative Examples 1-4, the light transmittance, gas barrier performance, and elongation resistance were evaluated.

<Transmissivity>
About the produced functional film, the average transmittance | permeability (including PET of a support body) in wavelength 400-700 nm was measured using (Hitachi High-Technologies Corporation U-4100). Further, the transmittance of the support PET film was also measured.
The visible light transmittance [%] of each functional film was evaluated with the transmittance of the PET film of the support as 100%.

<Gas barrier performance>
The water vapor permeability [g / (m ² · day)] of the produced functional film was measured by a calcium corrosion method (a method described in JP-A-2005-283561). The conditions for the constant temperature and humidity treatment were a temperature of 40 ° C. and a humidity of 90% RH.

<Elongation resistance>
A sample was cut out from the produced functional film and subjected to a tensile test using a tensile tester (manufactured by Shimadzu Corporation AG-10NX) to measure the amount of strain at which cracks began to enter the inorganic layer.

<Comprehensive evaluation>
Comprehensive evaluation evaluated as follows based on the transmittance | permeability, gas barrier performance, and elongation resistance.
“A” having a water vapor transmission rate of 1 × 10 ⁻⁴ [g / (m ² / day)] or less, a transmittance of 85% or more, and an elongation resistance of 3% or more.
“B” having a water vapor transmission rate of 1 × 10 ⁻⁴ [g / (m ² / day)] or less, a transmission rate of 85% or more, and an elongation resistance of less than 3%.
A water vapor transmission rate of 1 × 10 ⁻⁴ [g / (m ² / day)] or less and a transmission rate of less than 85% is “C”
“D” for water vapor transmission rate ^exceeding 1 × 10 ⁻⁴ [g / (m ² / day)]
The evaluation results of each example and comparative example are shown in Table 1 below.

  As shown in Table 1 above, the gas barrier films of Examples 1 to 6 which are functional films of the present invention have high transmittance and high gas barrier performance.

On the other hand, Comparative Example 1 having a low surface hardness is damaged during the formation of the inorganic layer, so that a uniform inorganic layer cannot be formed.
Moreover, it turns out that the transmittance | permeability falls in the comparative example 2 with one easy-bonding layer. In addition, interference fringes were generated.
Moreover, it turns out that the comparative example 3 with a thin thickness of a 1st easily bonding layer cannot fully relieve | moderate the stress of an organic layer with high surface hardness, but elongation resistance becomes low.
Moreover, it turns out that the transmittance | permeability falls in the comparative example 4 with a thick 2nd easily bonding layer. In addition, interference fringes were generated.
From the above results, the effects of the present invention are clear.

  It can be suitably used as a protective film for organic EL devices and the like.

10a to 10d Gas barrier film 12 Support 14 Inorganic layer 16 Organic layer 20 First easy-adhesion layer (lowermost easy-adhesion layer)
21 3rd easy adhesion layer 22 2nd easy adhesion layer (topmost easy adhesion layer)
DESCRIPTION OF SYMBOLS 30 Easy-adhesion layer forming apparatus 31 Organic layer forming apparatus 32 Inorganic film-forming apparatus 36 Application | coating means 38 Drying means 40 Light irradiation means 42, 64 Rotating shaft 46, 92 Rolling shaft 48, 50 Pair of conveyance rollers 52 Vacuum chamber 54 Unwinding chamber 56 Film forming chambers 60a, 60b Partition walls 61, 62, 63 Material rolls 68, 84a, 84b, 90 Guide rollers 70, 74 Vacuum exhaust means 80 Drum 82 Film forming electrodes 83 High frequency power supply

Claims (5)

A support;
An inorganic layer;
An organic layer as a base of the inorganic layer;
A plurality of easy-adhesion layers formed between the organic layer and the support,
The surface hardness of the organic layer is H or more in pencil hardness,
The thickness of the lowermost adhesive layer in contact with the support in the 0.3μm or more state, and are the 0.1μm or less the thickness of the adhesive layer of the uppermost layer in contact with the organic layer,
The difference in refractive index between the lowermost easily adhesive layer and the uppermost easily adhesive layer is 0.01 to 0.1,
The refractive index of the lowermost easy-adhesion layer is closer to the refractive index of the support than the refractive index of the uppermost easy-adhesion layer, and the refractive index of the uppermost easy-adhesion layer is less than that of the lowermost easy-adhesion layer. A functional film characterized by being closer to the refractive index of the organic layer than the refractive index of the adhesive layer . Functional film of claim 1 wherein the inorganic layer is composed of silicon nitride. Residual compressive stress of the inorganic layer, functional film according to claim 1 or 2 is 200～4000MPa. Furthermore, the functional film of any one of Claims 1-3 which has 1 or more the structure which laminated | stacked the organic layer and the inorganic layer formed on the said inorganic layer. An easy-adhesion layer forming step of forming a plurality of easy-adhesion layers on the support;
An organic layer forming step of forming an organic layer on the easy adhesion layer;
An inorganic layer forming step of forming an inorganic layer on the organic layer;
In the easy-adhesion layer forming step, at least the lowermost easy-adhesion layer having a thickness of 0.3 μm or more in contact with the support and the easy-adhesion of the uppermost layer having a thickness of 0.1 μm or less in contact with the organic layer Forming a layer,
In the organic layer forming step, the organic layer is formed by using an organic compound to be the organic layer, and a paint containing a polymerization initiator at a solid content concentration of 5% by mass or more,
In the inorganic layer forming step, the inorganic layer is formed by a vapor deposition method ,
The difference in refractive index between the lowermost easy-adhesive layer formed in the easy-adhesive layer forming step and the uppermost easy-adhesive layer is 0.01 to 0.1, and The refractive index is closer to the refractive index of the support than the refractive index of the uppermost easily adhesive layer, and the refractive index of the uppermost easily adhesive layer is higher than the refractive index of the lowermost easily adhesive layer. A method for producing a functional film, characterized by being close to the refractive index of an organic layer .