JP6262108B2 - Method for producing functional film - Google Patents

Description

  The present invention relates to a method for producing a functional film having a laminated structure of an organic layer and an inorganic layer. In detail, it is related with the manufacturing method of the functional film which can prevent the damage of an inorganic layer.

Gas barrier films such as optical elements, display devices such as liquid crystal displays and organic EL displays, various semiconductor devices, parts and components that require moisture resistance in various devices such as solar cells, and packaging materials for packaging food and electronic components Has been.
The gas barrier film generally has a structure in which a plastic film such as a polyethylene terephthalate (PET) film is used as a support (substrate) and a gas barrier layer (gas barrier film) 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.

In such a gas barrier film, as a configuration for obtaining higher gas barrier performance, an organic layer 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. An inorganic laminated gas barrier film (hereinafter also referred to as a laminated gas barrier film) is known.
In the laminated gas barrier film, it is the inorganic layer that mainly exhibits gas barrier properties. 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. By forming, a uniform inorganic layer free from cracks and cracks is formed, and excellent gas barrier performance is obtained.

  In the laminated gas barrier film, the inorganic layer is very thin. Therefore, if the surface is damaged, the barrier performance is greatly deteriorated.

By the way, in the laminated gas barrier film, it is advantageous that the support is thin in consideration of optical characteristics, weight, cost, and the like.
In recent years, devices that use gas barrier films are also required to be lighter and thinner, and in this respect as well, it is required to reduce the thickness of the support for the gas barrier film.

However, a thin support, for example, a support having a thickness of 50 μm or less, is easily bent. When the support is bent after the inorganic layer is formed, the inorganic layer is damaged such as cracks and cracks, resulting in deterioration of the barrier performance.
Further, if the gas barrier film is thin, handling in a so-called roll-to-roll is deteriorated, it is difficult to carry, and it is easy to be wrinkled at the time of bonding. For a user who manufactures a display or the like using a gas barrier film, a decrease in the handleability of the gas barrier film is a major factor that decreases the productivity.

In order to eliminate such inconveniences, Patent Document 1 and Patent Document 2 describe a surface of the laminated gas barrier film opposite to the surface on which the organic layer or inorganic layer of the support is formed (hereinafter also referred to as the back surface). ), A method for producing a gas barrier film (functional film) in which an organic layer or an inorganic layer is formed by a so-called roll-to-roll using a support formed by adhering a protective film. Is described.
According to this method, by attaching a protective film to the back surface of the support, it is possible to ensure the self-supporting property of the support, and even when a thin support is used, the inorganic layer caused by bending or the like. Damage can be prevented.
Moreover, a gas barrier film with good handleability can be provided to the user by providing the user with the gas barrier film with the protective film attached.

JP 2011-149057 A JP 2011-167967 A

  However, as a result of investigations, the present inventors have found that such a conventional method may not sufficiently prevent damage to the inorganic film.

In the conventional method, first, a protective film is attached to the back surface of the support, and then an organic layer is formed and an inorganic layer is formed thereon.
The organic layer is generally formed by a coating method under atmospheric pressure. On the other hand, the formation of the inorganic layer is generally performed by a vapor deposition method under reduced pressure such as plasma CVD. That is, the sticking body of the protective film and the support is formed with an organic layer under atmospheric pressure, and then an inorganic layer is formed under reduced pressure. After the inorganic layer is formed, the adhesive body is released to atmospheric pressure.

Here, when sticking a protective film on the back surface of a support body, it is inevitable that air mixes between a support body and a protective film.
The air between the support and the protective film expands due to the reduced pressure for forming the inorganic layer and contracts when released to the atmospheric pressure after forming the inorganic film. This expansion and contraction causes the support to bend and damage the inorganic layer.
This problem is more prominent as the support is thinner.

  An object of the present invention is to solve such conventional problems, and has an organic layer and an inorganic layer on the support, and improves the self-supporting property of the support on the back surface of the support. Provided is a functional film manufacturing method capable of suitably preventing damage to an inorganic layer even when the support is thin in a functional film having a protective film for protecting the inorganic layer. .

  In order to solve this problem, the method for producing a functional film of the present invention includes forming an organic layer on a support, forming an inorganic layer on the organic layer, and then laminating on the inorganic layer. Before performing, the manufacturing method of the functional film characterized by sticking the back film which consists of an adhesion layer and a protective film on the surface on the opposite side to the organic layer formation surface of a support body is provided.

In such a method for producing a functional film of the present invention, the thickness of the support is preferably 12 to 50 μm.
Moreover, it is preferable that the total thickness of a support body, an organic layer, and an inorganic layer is 55 micrometers or less.
Moreover, it is preferable that the thickness of an adhesion layer is 5-200 micrometers, and the thickness of a protective film is 12-100 micrometers.
Moreover, it is preferable that the adhesive force of a support body and an adhesion layer is 5-50 N / 25mm, and the adhesive force of an adhesion layer and a protective film is 0.01-0.5 N / 25mm.
Moreover, it is preferable that an adhesion layer is formed with an optical transparent adhesive.
Moreover, after forming an inorganic layer by the vapor-phase deposition method under reduced pressure and forming an inorganic layer, it is preferable to stick a back film on a support body in the state which maintained the pressure reduction.

According to the present invention, the support has an organic layer and an inorganic layer, and a back film for protecting the inorganic layer by improving the self-supporting property of the support is provided on the back of the support. In the stuck functional film, even if the support is thin, damage to the inorganic layer can be suitably prevented.
Furthermore, according to the present invention, the adhesive layer for attaching the back film may be deteriorated or altered by irradiation with ultraviolet rays in the formation of the organic layer or irradiation with vacuum ultraviolet rays in the plasma in the formation of the inorganic layer. Can be prevented.

It is a figure which shows notionally an example of the functional film by the manufacturing method of this invention. It is a conceptual diagram for demonstrating the manufacturing method of the functional film of this invention. It is a conceptual diagram for demonstrating an example of the utilization method of the functional film by the manufacturing method of this invention. It is a figure which shows notionally an example of the laminated body manufactured with the utilization method of a functional film shown in FIG.

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

  In FIG. 1, an example of the gas barrier film manufactured with the manufacturing method of the functional film of this invention is shown notionally.

  In addition, the manufacturing method of the functional film of this invention can be utilized for manufacture of various functional films besides manufacture of a gas barrier film. That is, this invention can be utilized for manufacture of various well-known functional films, such as various optical films, such as a filter which permeate | transmits the light of a specific wavelength, and an antireflection film.

However, according to the present invention, a functional film having an inorganic layer free from damage such as cracks and cracks can be obtained by having a back film described later. Moreover, this invention forms the adhesion layer for sticking a back film with an optical transparent adhesive etc., and utilizes this adhesion layer as an adhesive for sticking a functional film to apparatuses, such as a display. Also when it does, degradation and modification | denaturation of the adhesion layer can be suppressed.
Therefore, the present invention is more suitable for a gas barrier film that often requires high optical properties, has a large performance deterioration due to damage to the inorganic layer, and is often used by being laminated with an optical member. Used for In addition, a gas barrier film having a water vapor transmission rate of 9 × 10 ⁻⁵ g / (m ² · day) or less is peculiar in that the performance is greatly deteriorated with respect to the intended performance even if the inorganic layer is slightly damaged. There's a problem. Therefore, in the present invention, a gas barrier film having a water vapor transmission rate of 9 × 10 ⁻⁵ g / (m ² · day) or less is particularly preferably used.

A gas barrier film 10 shown in FIG. 1 basically includes a support 12, an organic layer 14, an inorganic layer 16, and a back film 20. The back film 20 is composed of an adhesive layer 24 and a protective film 26.
In the gas barrier film 10, the support 12, the organic layer 14, and the inorganic layer 16 constitute the aforementioned organic-inorganic laminated gas barrier film.
Moreover, in order to ensure the self-supporting property of the support body 12, the back surface film 20 is affixed on the surface on the opposite side to the formation surface of the organic layer 14 of the support body 12 (hereinafter, this surface is also called a back surface). .

In the gas barrier film 10, the support 12 is for supporting the organic layer 14 and the inorganic layer 16.
As the support 12, various known sheet-like materials that are used as a support for a gas barrier film can be used.
Specifically, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyethylene (PE), polypropylene (PP), polystyrene, polyamide, polyvinyl chloride, polycarbonate, polyacrylonitrile, polyimide, polyacrylate, polymethacrylate, polycarbonate Preferred examples include films made of various resin materials (polymer materials) such as (PC), cycloolefin polymer (COP), cycloolefin copolymer (COC), triacetyl cellulose (TAC), and transparent polyimide.
The support 12 has various functions such as a protective layer, an adhesive layer, a light reflection layer, an antireflection layer, a light shielding layer, a planarization layer, a buffer layer, and a stress relaxation layer on the surface of such a film. The layer (film | membrane) for this may be formed.

What is necessary is just to set the thickness of the support body 12 suitably according to the use etc. of the gas barrier film 10. FIG.
Here, in recent years, the gas barrier film 10 is required to be thin and light. In addition, devices that use the gas barrier film 10 are also required to be thin, small, and light. Therefore, it is advantageous that the support 12 is thin if it can support the organic layer 14 and the inorganic layer 16.

Considering this point, the thickness of the support 12 is preferably 12 to 50 μm.
By setting the thickness of the support 12 to 12 μm or more, the organic layer 14 and the inorganic layer 16 can be favorably supported, and deformation due to ultraviolet irradiation or the like when forming the organic layer 14 can be prevented. This is preferable in that it can be prevented.
In addition, by setting the thickness of the support 12 to 50 μm or less, it is preferable in terms of reducing the thickness and weight of the gas barrier film 10 from which only the back film 20 or the protective film 26 has been peeled off and improving the light transmittance. . Note that the gas barrier film 10 from which only the back film 20 or the protective film 26 is peeled can be made thin and lightweight, that is, it is possible to reduce the thickness and weight of an apparatus using the gas barrier film.

As described above, in the gas barrier film 10, the organic layer 14 is formed on one surface of the support 12, and the inorganic layer 16 is formed on the organic layer 14.
The organic layer 14 is a layer made of an organic compound and is basically a cross-linked (polymerized) monomer and / or oligomer.

The organic layer 14 of the support 12 functions as a base layer for properly forming the inorganic layer 16 that exhibits gas barrier properties.
By having the organic layer 14 serving as such a base layer, the surface of the inorganic layer 16 can be formed by embedding irregularities on the surface of the support 12 and foreign matters adhering to the surface of the support 12. The inorganic layer 16 can be in a state suitable for film formation. This eliminates areas where the inorganic compound that becomes the inorganic layer 16 is difficult to deposit, such as irregularities on the surface of the support 12 and shadows of foreign matter, and forms an appropriate inorganic layer 16 on the entire surface of the substrate without any gaps. It becomes possible to film.

Various known organic compounds can be used as the material for forming the organic layer 14.
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, acrylic compounds, thermoplastic resins, or polysiloxane, etc. An organic silicon compound film is preferably exemplified. A plurality of these may be used in combination.

Among these, the organic layer 14 composed of a polymer of a radical polymerizable compound and / or a cationic polymerizable compound having an ether group as a functional group is preferable from the viewpoint of excellent glass transition temperature and strength.
In particular, in addition to the glass transition temperature and strength, acrylic resins and methacrylic compounds mainly composed of acrylate and / or methacrylate monomers and oligomers, such as low refractive index, high transparency, and excellent optical properties. The resin is preferably exemplified as the organic layer 14.
Among them, in particular, dipropylene glycol di (meth) acrylate (DPGDA), trimethylolpropane tri (meth) acrylate (TMPTA), dipentaerythritol hexa (meth) acrylate (DPHA), etc. An acrylic resin or a methacrylic resin mainly composed of a polymer of acrylate and / or methacrylate monomers or oligomers is preferably exemplified. It is also preferable to use a plurality of these acrylic resins and methacrylic resins.

What is necessary is just to set the thickness of the organic layer 14 suitably according to the use etc. of the gas barrier film 10. FIG. According to the study by the present inventors, the thickness of the organic layer 14 is preferably 0.5 to 5 μm, and more preferably 1 to 3 μm.
By setting the thickness of the organic layer 14 to 0.5 μm or more, irregularities on the surface of the support 12 and foreign matters attached to the surface of the support 12 are suitably embedded, so that the surface of the organic layer 14, that is, the inorganic layer The film-forming surface of 16 can be planarized.
In addition, by setting the thickness of the organic layer 14 to 5 μm or less, it is possible to suitably suppress the occurrence of problems such as cracks in the organic layer 14 and curling of the gas barrier film 10 caused by the organic layer 14 being too thick. .

An inorganic layer 16 is formed on the organic layer 14.
The inorganic layer 16 is a layer made of an inorganic compound. In the gas barrier film 10, the inorganic layer 16 mainly exhibits the target gas barrier property.

The material for forming the inorganic layer 16 is not limited, and various layers 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 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 16 may be appropriately set according to the forming material, the required gas barrier property, and the like. According to the study of the present inventor, the thickness of the inorganic layer 16 is preferably 5 to 200 nm, more preferably 10 to 100 nm, and particularly preferably 15 to 75 nm.
By setting the thickness of the inorganic layer 16 to 5 nm or more, the inorganic layer 16 that stably exhibits sufficient gas barrier performance can be formed. In addition, the inorganic layer 16 is generally brittle, and if it is too thick, there is a possibility of causing cracks, cracks, peeling, etc. However, if the thickness of the inorganic layer 16 is 200 nm or less, cracks will occur. Can be prevented.

In the present invention, the total thickness of the support 12, the organic layer 14 and the inorganic layer 16 is preferably 55 μm or less, and more preferably 28 μm or less.
By making the total thickness of the support 12, the organic layer 14, and the inorganic layer 16 equal to or less than 55 μm, it is possible to reduce the thickness and weight when only the back film 20 or the protective film 26 is peeled from the gas barrier film 10. It is preferable in terms of reducing the thickness and weight of the apparatus using the film 10 and increasing the protective effect of the inorganic layer 16 by having the back film 20.

A back film 20 is attached to the back surface of the support 12 (the surface opposite to the surface on which the organic layer 14 is formed).
As described above, the back film 20 is adhered to the back surface of the support 12 in order to secure the self-supporting property of the support 12 and prevent damage such as cracking of the inorganic layer 16. The back film 20 is composed of an adhesive layer 24 and a protective film 26. The back film 20 is adhered to the back surface of the support 12 by the adhesive layer 24.
In general, the gas barrier film 10 is finally finally peeled off from the back film 20 or only the protective film 26 is left leaving the adhesive layer 24.

The protective film 26 mainly secures the self-supporting property of the support 12.
For the protective film 26, various known sheet-like materials can be used. Specifically, the film which consists of various resin materials (polymer material) illustrated with the above-mentioned support body 12 is illustrated suitably.
In addition, since the protective film 26 is finally peeled and discarded, it is preferable to use an inexpensive film such as a PET film.

What is necessary is just to set the thickness of the protective film 26 suitably according to the forming material of the protective film 26, the required mechanical strength, or the like.
According to the study of the present inventor, the thickness of the protective film 26 is preferably 12 to 100 μm, and more preferably 25 to 75 μm.
By making the thickness of the protective film 26 12 μm or more, the self-supporting property of the support 12 can be suitably secured, and when the back film 20 is stuck on the support 12, the protective film 26 is more wrinkled. This is preferable in that it can be surely prevented, and when the adhesive layer 24 is formed on the protective film 26, the protective film 26 can be more reliably prevented from wrinkling.
In addition, by setting the thickness of the protective film 26 to 100 μm or less, the gas barrier film 10 can be made thinner and lighter, and can be reduced in diameter when wound on a roll.

The adhesive layer 24 adheres the back film 20 to the back surface of the support 12.
The adhesive layer 24 may be made of various adhesives as long as the back film 20 (protective film 26) can be attached to the back surface of the support 12.
Specific examples include acrylic resin adhesives, epoxy resin adhesives, urethane resin adhesives, vinyl resin adhesives, rubber adhesives, and the like.

Here, in the functional film using the conventional back film shown by patent document 1 etc., the back film was finally peeled and discarded.
On the other hand, in the gas barrier film 10 according to the present invention, the adhesive force between the adhesive layer 24 and the support 12 is made stronger than the adhesive force between the adhesive layer 24 and the protective film 26, and finally only the protective film 26 is provided. It is preferable to peel off and leave the adhesive layer 24.
Specifically, the adhesive layer 24 and the support 12 have an adhesive force of 5 to 50 N / 25 mm, and the adhesive layer 24 and the protective film 26 have an adhesive force of 0.01 to 0.5 N / 25 mm. It is preferable that only the protective film 26 can be peeled while being stuck to the support 12.

By setting the adhesive force between the adhesive layer 24 and the support 12 to 5 N / 25 mm or more, it is preferable in that the adhesive layer 24 can be prevented from being unnecessarily peeled off during transportation or when the protective film 26 is peeled off.
Moreover, by setting the adhesive force between the adhesive layer 24 and the support 12 to 50 N / 25 mm or less, it is possible to prevent the adhesive layer 24 and the support 12 from being integrated, and as a result, the protective film When peeling 26, the deformation of the pressure-sensitive adhesive layer 24 accompanying the peeling and the force of this deformation are directly transmitted to the inorganic layer 16, which is preferable in terms of preventing the inorganic layer 16 from being broken.
On the other hand, by setting the adhesive force between the adhesive layer 24 and the protective film 26 to 0.01 N / 25 mm or more, it is preferable in that the protective film 26 can be prevented from being unnecessarily peeled off during transportation.
Furthermore, by setting the adhesive force between the adhesive layer 24 and the protective film 26 to 0.5 N / 25 mm or less, only the protective film 26 can be reliably peeled off, and the inorganic layer 16 is destroyed when the protective film 26 is peeled off. It is preferable at the point which can prevent that the adhesion layer 24 remains after peeling the protective film 26.

Accordingly, the gas barrier film 10 from which the protective film 26 has been peeled off is effectively used as an adhesive gas barrier film by effectively using the adhesive layer 24 that has been discarded together with the protective film 26 in the past. Costs can be reduced.
In addition, what is necessary is just to measure adhesive force based on the peeling test method of JISZ0237.

In the gas barrier film 10 that leaves the adhesive layer 24 and peels only the protective film 26, the adhesive layer 24 is formed using an adhesive having excellent optical properties such as an optical clear adhesive OCA. It is preferable to do this.
By setting it as such an adhesion layer 24, the gas barrier film 10 which peeled off the protective film 26 can be used as a gas barrier film which has adhesiveness and was excellent in an optical characteristic, and is optical characteristics, such as a display. Can be suitably used as a gas barrier film used for applications requiring the above.

  When the gas barrier film 10 is configured to peel the back film 20 without leaving the adhesive layer 24, the adhesive force between the adhesive layer 24 and the support 12, the adhesive layer 24 and the protective film 26 What is necessary is just to reverse adhesive force with the above.

In the gas barrier film 10, the thickness of the adhesive layer 24 may be appropriately set according to the material for forming the adhesive layer 24.
According to the study of the present inventors, the thickness of the adhesive layer 24 is preferably 5 to 200 μm, more preferably 15 to 100 μm.
By setting the thickness of the adhesive layer 24 to 5 μm or more, it is preferable in that air bubbles can be suitably prevented from interposing between the adhesive layer 24 and the support 12 and good adhesive force can be secured.
In addition, by setting the thickness of the adhesive layer 24 to 200 μm or less, the gas barrier film 10 can be made thinner and lighter, and can be reduced in diameter when wound on a roll.

  Hereafter, with reference to FIG. 2, the manufacturing method of the functional film of this invention is demonstrated in detail by demonstrating the manufacturing method of the gas barrier film 10. FIG.

The manufacturing method of the present invention uses a long support 12 and feeds the processing material from a roll formed by winding the processing material and conveys it in the longitudinal direction while processing the organic layer 14 and the like. And a so-called roll-to-roll (hereinafter also referred to as RtoR), in which a processed material to be processed is wound into a roll shape, may be used. The gas barrier film 10 may be manufactured by a batch type (single-wafer type).
In view of productivity, it is preferable to use RtoR.

In the manufacturing method of the present invention, first, as shown in the first and second stages of FIG. 2, the organic layer 14 is formed on one surface of the support 12.
The organic layer 14 may be formed by a known method according to the forming material. A preferable example is a coating method.
That is, when forming the organic layer 14, first, an organic compound (monomer, dimer, trimer, oligomer, etc.) that becomes the organic layer 14, a polymerization initiator, a silane coupling agent, a surfactant, a thickening agent. Adjust the paint made by dissolving the agent in an organic solvent.
Next, this paint is applied to the formation surface of the organic layer 14 and dried.
After drying, the organic compound 14 is formed by polymerizing the organic compound by ultraviolet irradiation, electron beam irradiation, heating, or the like.

After the organic layer 14 is formed on one surface of the support 12, the inorganic layer 16 is then formed on the organic layer 14 as shown in the third stage of FIG. 2.
The inorganic layer 16 may also be formed by a known method corresponding to the forming material. Preferable examples include plasma CVD such as CCP-CVD and ICP-CVD, sputtering such as magnetron sputtering and reactive sputtering, and vapor deposition methods (vapor deposition) such as vacuum deposition.

On the other hand, the protective film 26 is prepared, and the adhesive layer 24 is formed on one surface of the protective film 26 to form the back film 20 (see the fourth stage in FIG. 2).
The adhesive layer 24 may also be formed by a known method. As an example, a method of forming the adhesive layer 24 by applying an adhesive or further drying and (semi-) curing, an adhesive tape (adhesive tape) is used to protect the adhesive tape. The method of sticking on the film 26 and making it the adhesion layer 24 is illustrated.

When such a back film 20 is prepared, before any layer (film) is laminated on the inorganic layer 16, as shown in the fourth to fifth stages of FIG. The back film 20 is adhered by the adhesive layer 24 to obtain the gas barrier film 10.
The manufacturing method of the present invention can suitably prevent damage such as cracking of the inorganic layer 16 by having such a configuration.

In an organic-inorganic laminated type gas barrier film in which an organic layer 14 is formed on a support 12 and an inorganic layer 16 is formed thereon, a certain layer is usually formed on the inorganic layer 16. For example, on the inorganic layer 16, a protective organic layer for protecting the inorganic layer 16, an adhesive layer for imparting adhesiveness, a quantum dot layer 30 described later, and the like are formed. In addition, a surface protective film for protecting the inorganic layer 16 may be stuck on the inorganic layer 16.
However, if the self-supporting property of the support 12 is insufficient, the support 12 is bent when these layers are formed on the inorganic layer 16. As described above, the inorganic layer 16 is very thin. Therefore, the inorganic layer 16 is damaged by this bending, and the gas barrier property is greatly lowered.
As described above, in recent years, it has been required to reduce the thickness of the organic-inorganic laminated gas barrier film, and accordingly, the support 12 is required to be thinned. This occurs remarkably when 12 is used.

This problem can be solved by sticking a back film to the back surface of the support 12 as shown in Patent Document 1 and Patent Document 2.
As shown in Patent Document 1 and Patent Document 2, the attachment of the back film usually improves the handleability of the thin support 12, the handling property when forming the organic layer 14, and the inorganic layer 16. This is performed first in consideration of handling properties when forming. That is, after sticking the back film 20 on the back surface of the support 12, the organic layer 14 is formed, and the inorganic layer 16 is formed thereon.

However, in such a method for producing the gas barrier film 10, as described above, the air mixed between the support 12 and the back film 20 expands due to the reduced pressure when the inorganic layer 16 is formed. The support 12 is bent and the inorganic layer 16 is damaged due to air contraction or the like due to release of the atmosphere after the formation.
The damage of the inorganic layer 16 due to the expansion and contraction of air is more noticeable as the support 12 is thinner, for example, 50 μm or less.

On the other hand, in the manufacturing method of the present invention, after the inorganic layer 16 is formed, the back film 20 is attached to the back surface of the support 12 before any layer is formed on the inorganic layer 16 .
Therefore, according to the present invention, damage to the inorganic layer 16 due to the expansion and contraction of air mixed between the support 12 and the back film 20 can be prevented. Furthermore, after forming the inorganic layer 16 and before forming the layer on the inorganic layer 16, the back film 20 is adhered to the back surface of the support 12, so that a protective organic layer or the like is formed on the inorganic layer 16. Even so, damage to the inorganic layer 16 due to the support 12 being bent or the like can be suitably prevented.
Therefore, according to the manufacturing method of the present invention, it is possible to manufacture the gas barrier film 10 having an excellent gas barrier property in which the inorganic layer 16 is prevented from being damaged.

Further, in the conventional method of first attaching the back film 20 to the back surface of the support 12, the adhesive layer 24 of the back film 20 is irradiated with ultraviolet rays by the formation of the organic layer 14 or in plasma by the formation of the inorganic layer 16. Of vacuum ultraviolet irradiation. As a result, the pressure-sensitive adhesive layer 24 is deteriorated or deteriorated by the irradiation of ultraviolet rays, and its function is lowered.
For this reason, even if only the protective film 26 is peeled off while leaving the adhesive layer 24 to obtain a gas barrier film having adhesiveness, sufficient adhesiveness is often not obtained. In particular, when OCA or the like is used for the adhesive layer 24, not only the adhesiveness but also the optical characteristics are significantly deteriorated due to deterioration and alteration. The adhesive layer 24 will not be able to express its intended function.

On the other hand, according to the manufacturing method of the present invention in which the back film 20 is adhered after the inorganic layer 16 is formed, the back film 20 adhered to the support 12 is irradiated with ultraviolet rays when the organic layer 14 is formed. However, it is not subjected to irradiation of vacuum ultraviolet in the plasma when forming the inorganic layer 16. Therefore, the adhesive layer 24 does not deteriorate or deteriorate due to ultraviolet irradiation.
Therefore, according to this invention, the gas barrier film 10 which has favorable adhesiveness can be obtained by peeling the protective film 26. FIG. In addition, when the adhesive layer 24 is formed of OCA or the like, the optical properties of the adhesive layer 24 are not deteriorated. Therefore, the protective film 26 is peeled from the gas barrier film 10 to have excellent optical properties and adhesiveness. Thus, a gas barrier film exhibiting the intended function can be obtained.

As described above, in the gas barrier film 10 according to the present invention, when only the protective film 26 is peeled off, the adhesive force between the adhesive layer 24 and the support 12 is more than the adhesive force between the adhesive layer 24 and the protective film 26. Strengthen.
Preferably, the adhesive force between the adhesive layer 24 and the support 12 is 5 to 50 N / 25 mm (hereinafter also referred to as strong adhesive), and the adhesive force between the adhesive layer 24 and the protective film 26 is 0.01 to 0.5 N / 25 mm (hereinafter also referred to as slight adhesion).

In the production method of the present invention, the method in which the adhesive force between the adhesive layer 24 and the support 12 is made strong and the adhesive force between the adhesive layer 24 and the protective film 26 is made slightly adhesive is various adhesives and adhesive tapes. Any known method can be used.
As an example, the surface of the protective film 26 is subjected to a release treatment such as silicon treatment or fluorine treatment using the support 12 and the adhesive layer 24 that becomes strong adhesive, and the adhesive force between the protective film 26 and the adhesive layer 24 is increased. The method of reducing is illustrated. Alternatively, the support 12 is subjected to a treatment for improving adhesiveness such as plasma treatment or corona treatment, the surface of the protective film 26 is subjected to the same release treatment, and the adhesive layer 24 and the support 12 are made strong adhesive, A method in which the adhesive layer 24 and the protective film 26 are slightly adhered can also be used.
According to these methods, the adhesive force of the adhesive layer 24 when the protective film 26 is peeled off becomes the adhesive force of the adhesive layer 24 itself. Therefore, by peeling off the protective film 26 from the gas barrier film 10, good adhesiveness can be obtained. A gas barrier film having properties can be obtained.

In the example shown in FIG. 2, the adhesive layer 24 is formed on the protective film 26 to produce the back film 20, and the back film 20 is adhered to the back surface of the support 12 on which the inorganic layer 16 is formed. 10 is manufactured.
However, the manufacturing method of the present invention can use other procedures.
For example, after the inorganic layer 16 is formed, the pressure-sensitive adhesive layer 24 is formed on the back surface of the support 12 as described above, and the protective film 26 is attached to the pressure-sensitive adhesive layer 24, thereby forming the back surface of the support 12. The back film 20 may be stuck.

You may stick the back surface film 20 to the back surface of the support body 12 in the vacuum chamber in which the inorganic layer 16 was formed.
For example, if the inorganic layer 16 is formed by RtoR, a roll formed by winding the back film 20 inside the vacuum chamber is prepared, and in synchronization with the transport speed of the support 12 on which the inorganic layer 16 is formed, What is necessary is just to send out the back film 20 from this roll, and just to laminate | stack and stick to the back surface of the support body 12 by a well-known method.
The smaller the amount of air mixed between the support 12 and the back film 20, the better, but this prevents the air from mixing between the support 12 and the back film 20.

In addition, a surface protective film for mainly protecting the inorganic layer 16 may be attached to the surface of the inorganic layer 16 after the back film 20 is attached to the back surface of the support 12.
As the surface protective film, various films exemplified for the support 12 can be used. The thickness of the surface protective film is preferably 20 to 100 μm, and more preferably 25 to 70 μm.
The surface protective film may be attached using an adhesive layer similar to the adhesive layer 24. Depending on the material for forming the surface protective film, self-adhesion may be performed without using the adhesive layer, or thermocompression bonding may be performed without using the adhesive layer. The adhesive force between the surface protective film and the inorganic layer 16 is preferably 0.02 to 0.06 N / 25 mm.

  3 and 4 conceptually show an example in which the gas barrier film 10 produced by the production method of the present invention is used for a quantum dot laminate.

As is well known, a quantum dot is a state of electrons whose movement direction is limited in all three dimensions, and when semiconductor nanoparticles are three-dimensionally surrounded by a high potential barrier, These nanoparticles become quantum dots.
Quantum dots exhibit various quantum effects. For example, the “quantum size effect” in which the density of states of electrons (energy level) is discretized appears. According to this quantum size effect, the absorption wavelength and emission wavelength of light can be controlled by changing the size of the quantum dot.

With the power saving of the backlight of LCD (Liquid Crystal Display), it has been proposed to use emitted quantum dots in order to increase light use efficiency and improve color reproducibility.
For example, a quantum dot layer formed by dispersing a large number of quantum dots in a matrix such as a resin is formed, and this quantum dot layer is disposed between the backlight and the liquid crystal panel.
The quantum dot layer has a function of converting and emitting the wavelength of light incident on the quantum dot layer by the action of the quantum dots. That is, when light enters the quantum dot layer from the backlight, the quantum dots are excited and emit fluorescence. Here, by using quantum dots having different light emission characteristics, it is possible to realize white light by emitting light having a narrow half-value width of red light, green light, and blue light. Since the half-value width of the fluorescence due to quantum dots is narrow, it is possible to design white light obtained by appropriately selecting the wavelength to have high luminance or excellent color reproducibility.

  Here, there is a problem that the quantum dots are easily deteriorated by moisture and oxygen, and the light emission intensity is reduced by the photooxidation reaction. For this reason, a gas barrier film is laminated on both sides of the quantum dot layer, and the quantum dot layered body in which the quantum dot layer is protected by the gas barrier film is used.

  The gas barrier film 10 produced by the production method of the present invention can also be suitably used for this quantum dot laminate.

First, two gas barrier films 10 are produced by the production method of the present invention. At this time, the adhesive layer 24 is preferably formed by OCA.
In addition, it is preferable that the two gas barrier films 10 both have a strong adhesion between the adhesive layer 24 and the support 12 and a slight adhesion between the adhesive layer 24 and the protective film 26.

  Next, as shown in the upper part of FIG. 3, a coating material 30 a that becomes the quantum dot layer 30 is applied on the inorganic layer 16 of the single gas barrier film 10. Here, since the back film 20 is stuck to the back surface of the support 12 in the gas barrier film 10, the support 12 is not bent and the inorganic layer 16 is not damaged even when the coating material 30 a is applied.

This paint may be prepared in the same manner as the known method for forming the quantum dot layer 30.
As an example, quantum dots are put into a resin such as a polyester resin (for example, polyethylene terephthalate, polyethylene naphthalate), (meth) acrylic resin, polyvinyl chloride resin, or polyvinylidene chloride resin as a matrix and stirred. And then disperse.
The quantum dots can be referred to, for example, [0060] to [0066] of JP 2012-169271 A, but are not limited to those described here. As the quantum dots, commercially available products can be used without any limitation. The emission wavelength of the quantum dots can usually be adjusted by the composition and size of the particles.

Next, as shown in the middle part of FIG. 3, another gas barrier film 10 is laminated with the inorganic layer 16 facing the coating material 30 a.
Since the back film 20 is adhered to the back surface of the support 12 also in the gas barrier film 10 to be laminated, the support 12 is not bent and the inorganic layer 16 is not damaged even when laminated on the paint 30a.
Further, the resin of the coating material 30 a is cured by ultraviolet irradiation or the like to form the quantum dot layer 30, and the gas barrier film 10 is attached to both surfaces of the quantum dot layer 30. Thereby, the quantum dot laminated body which pinched and protected the quantum dot layer 30 with the two gas barrier films 10 is formed.

As described above, the gas barrier film 10 according to the production method of the present invention has an excellent gas barrier property in which the inorganic layer 16 is not damaged.
Therefore, quantum dots that are vulnerable to moisture and oxygen can be suitably protected.

For example, as shown in the lower part of FIG. 3, the quantum dot laminate is formed by peeling off the protective film 26 of one gas barrier film 10 and, as shown in FIG. 4, an optical film such as a diffusion sheet on the adhesive layer 24. 32 is stuck.
The quantum dot laminate to which the diffusion sheet 32 is attached is, for example, peeled off from the protective film 26 of the other back film 20 and attached to an LCD backlight unit or the like.

  As mentioned above, although the manufacturing method of the functional film of this invention was demonstrated in detail, this invention is not limited to the above-mentioned example, Even if various improvements and changes are performed in the range which does not deviate from the summary of this invention. Of course it is good.

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

[Example 1]
As the protective film 26, a long PET film (Lumirror, manufactured by Toray Industries, Inc.) having a width of 1000 mm and a thickness of 50 μm was prepared.
Using a general processing apparatus using RtoR, one surface of the protective film 26 was subjected to a mold release process using a fluorine coat.
Further, using a general film forming apparatus that forms a film by a coating method using RtoR, an acrylic OCA (manufactured by Panac Co., PDS1) is applied to the surface of the protective film 26 that has been subjected to the release treatment, and then dried. Then, a pressure-sensitive adhesive layer 24 having a thickness of 25 μm was formed to produce a back film 20.

On the other hand, a long PET film (Cosmo Shine A4300 manufactured by Toyobo Co., Ltd.) having a width of 1000 mm and a thickness of 38 μm was prepared as the support 12.
In addition, as a coating material for forming the organic layer 14, MEK (methyl ethyl ketone), TMPTA (manufactured by Daicel Cytec), a photopolymerization initiator (Irg189 manufactured by Ciba Chemicals), a silane coupling agent (KBM5103 manufactured by Shin-Etsu Silicone) ) And a thickener (Acrit 8BR500 manufactured by Taisei Fine Chemical Co., Ltd.) were added to prepare. That is, the organic layer 14 is a layer formed by polymerizing TMPTA.
The addition amount of the photopolymerization initiator is 2% by mass excluding the organic solvent, the addition amount of the silane coupling agent is 10% by mass excluding the organic solvent, and the addition amount of the thickener is the organic solvent. The concentration was 1% by mass (that is, 87% by mass of the organic compound in the solid content). Moreover, the solid content concentration of the paint obtained by diluting the components blended in these ratios with MEK was 15% by mass (that is, MEK was 85% by mass).

  Using this paint, an organic layer 14 having a thickness of 2 μm was formed on one surface of the support 12 by a general film forming apparatus that forms a film by a coating method using RtoR. This film forming apparatus is an apparatus for drying the applied paint and curing the paint by ultraviolet irradiation.

A silicon nitride film having a thickness of 50 nm was formed as the inorganic layer 16 on the organic layer 14 by using a general film forming apparatus that forms a film by capacitively coupled plasma CVD with RtoR. In addition, this film-forming apparatus is an apparatus which forms a film while winding a to-be-processed material around the drum which comprises an electrode pair.
Silane gas (SiH ₄ ), ammonia gas (NH ₃ ), nitrogen gas (N ₂ ), and hydrogen gas (H ₂ ) were used as the film forming gas. The supply amounts were 100 sccm for silane gas, 200 sccm for ammonia gas, 500 sccm for nitrogen gas, and 500 sccm for hydrogen gas. The film forming pressure was 50 Pa.
The power source was a high frequency power source with a frequency of 13.5 MHz, and the plasma excitation power was 3000 W. The drum was supplied with 500 W of bias power from a bias power source. During film formation, the temperature of the drum was adjusted to −20 ° C.

  Using a general apparatus for laminating a long sheet-like material by RtoR, the adhesive layer 24 was prepared on the back surface of the support 12 on which the organic layer 14 and the inorganic layer 16 were formed, with the adhesive layer 24 facing the support 12. The back film 20 was laminated and adhered to produce a gas barrier film 10 as shown in FIG.

When the adhesive strength between the support 12 and the protective film 26 of the gas barrier film 10 and the adhesive layer 24 was measured by a peel test method based on JIS Z 0237, the adhesive strength between the support 12 and the adhesive layer 24 was 15. The adhesive force between the protective film 26 and the adhesive layer 24 was 0.03 N / 25 mm.
Further, when the protective film 26 was peeled off, only the protective film 26 could be peeled off cleanly, leaving the adhesive layer 24 on the support 12. Moreover, when observed visually, the adhesion layer 24 maintained favorable transparency.

[Example 2]
A gas barrier film 10 as shown in FIG. 1 was produced in the same manner as in Example 1, except that the support 12 was changed to a long PET film (Cosmo Shine A4300, manufactured by Toyobo Co., Ltd.) having a thickness of 50 μm.
When the adhesive strength between the support 12 and the protective film 26 of the gas barrier film 10 and the adhesive layer 24 was measured in the same manner as in Example 1, the adhesive strength between the support 12 and the adhesive layer 24 was 15.5 N / 25 mm, The adhesive force between the protective film 26 and the adhesive layer 24 was 0.03 N / 25 mm.
Further, when the protective film 26 was peeled off, only the protective film 26 could be peeled off cleanly, leaving the adhesive layer 24 on the support 12. Moreover, when observed visually, the adhesion layer 24 maintained favorable transparency.

[Example 3]
A gas barrier film 10 as shown in FIG. 1 was produced in the same manner as in Example 1 except that the support 12 was changed to a long PET film (Toyobo Co., Ltd., Cosmo Shine A4300) having a thickness of 23 μm.
When the adhesive strength between the support 12 and the protective film 26 of the gas barrier film 10 and the adhesive layer 24 was measured in the same manner as in Example 1, the adhesive strength between the support 12 and the adhesive layer 24 was 15.5 N / 25 mm, The adhesive force between the protective film 26 and the adhesive layer 24 was 0.03 N / 25 mm.
Further, when the protective film 26 was peeled off, only the protective film 26 could be peeled off cleanly, leaving the adhesive layer 24 on the support 12. Further, when visually observed, the pressure-sensitive adhesive layer 24 maintained good transparency, but some wrinkles were observed in the support 12 and the pressure-sensitive adhesive layer 24.

[Example 4]
A gas barrier film 10 as shown in FIG. 1 was produced in the same manner as in Example 1 except that the support 12 was changed to a long PET film having a thickness of 12 μm (manufactured by Toray Industries, Inc., Lumirror).
When the adhesive strength between the support 12 and the protective film 26 of the gas barrier film 10 and the adhesive layer 24 was measured in the same manner as in Example 1, the adhesive strength between the support 12 and the adhesive layer 24 was 15.5 N / 25 mm, The adhesive force between the protective film 26 and the adhesive layer 24 was 0.03 N / 25 mm.
Further, when the protective film 26 was peeled off, only the protective film 26 could be peeled off cleanly, leaving the adhesive layer 24 on the support 12. Further, when visually observed, the pressure-sensitive adhesive layer 24 maintained good transparency, but some wrinkles were observed in the support 12 and the pressure-sensitive adhesive layer 24.

[Comparative Example 1]
Prior to the formation of the organic layer 14 and the inorganic layer 16, a gas barrier film 10 as shown in FIG. 1 was produced in the same manner as in Example 1 except that the back film 20 was adhered to one surface of the support 12.
When the adhesive strength between the support 12 and the protective film 26 of the gas barrier film 10 and the adhesive layer 24 was measured in the same manner as in Example 1, the adhesive strength between the support 12 and the adhesive layer 24 was 20.5 N / 25 mm, The adhesive force between the protective film 26 and the adhesive layer 24 was 5.2 N / 25 mm. Note that this increase in adhesive strength is considered to be caused by ultraviolet irradiation when forming the organic layer 14 and plasma when forming the inorganic layer 16.
Moreover, when the protective film 26 was peeled off, the adhesive layer 24 was left on the support 12 and only the protective film 26 could be peeled off. However, cracks and wrinkles were observed in the protective film 26 after peeling. . Moreover, when observed visually, some cloudiness was recognized by the adhesion layer 24, and some cracks were recognized by the support body 12. FIG.

[Example 5]
One surface of the protective film 26 is subjected to easy adhesion treatment by plasma treatment instead of mold release treatment, and the adhesive layer 24 is formed with an acrylic resin adhesive (PX adhesive, PX adhesive material), and further, an adhesive layer A back film 20 was produced in the same manner as in Example 1 except that 24 was formed on the surface of the protective film 26 that had been subjected to the easy adhesion treatment. The pressure-sensitive adhesive layer 24 was cured by irradiation with ultraviolet rays so as to be in a semi-cured state (half cure).
A gas barrier film 10 as shown in FIG. 1 was produced in the same manner as in Example 1 except that this back film 20 was used.
When the adhesive strength between the support 12 and the protective film 26 and the adhesive layer 24 of the gas barrier film 10 was measured in the same manner as in Example 1, the adhesive strength between the support 12 and the adhesive layer 24 was 0.025 N / 25 mm, The adhesive force between the protective film 26 and the adhesive layer 24 was 25 N / 25 mm.
Further, when the back film 20 was peeled off, it could be peeled off from the support 12 neatly.

[Comparative Example 2]
Prior to the formation of the organic layer 14 and the inorganic layer 16, a gas barrier film 10 as shown in FIG. 1 was produced in the same manner as in Example 3 except that the back film 20 was adhered to one surface of the support 12.
When the adhesive force between the support 12 and the protective film 26 of the gas barrier film 10 and the adhesive layer 24 was measured in the same manner as in Example 1, the adhesive force between the support 12 and the adhesive layer 24 was 5.3 N / 25 mm, The adhesive force between the protective film 26 and the adhesive layer 24 was 20.4 N / 25 mm. Note that this increase in adhesive strength is considered to be caused by ultraviolet irradiation when forming the organic layer 14 and plasma when forming the inorganic layer 16.
Moreover, when the protective film 26 was peeled off, the adhesive layer 24 was left on the support 12 and only the protective film 26 could be peeled off. However, cracks and wrinkles were observed in the protective film 26 after peeling. . Further, when visually observed, some cracks in the support 12 and some remaining adhesive layer 24 on the support 12 were recognized.

[Gas barrier properties]
About the gas barrier film produced in this way,
The water vapor transmission rate [g / (m ² · day)] 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. The evaluation is as follows.
A; less than 3 × 10 ⁻⁵ g / (m ² · day) B; 3 × 10 ⁻⁵ g / (m ² · day) or more and less than 5 × 10 ⁻⁵ g / (m ² · day) C; 5 × 10 ^-5 g / (m ² · day) or more and less than 9 × 10 ^-5 g / (m ² · day) D; 9 × 10 ^-5 g / (m ² · day) or more 3 × 10 ^-4 g / ( Less than m ² · day) E; 3 × 10 ^-4 g / (m ² · day) or more The results are shown in the following table.

As shown in the above table, after the organic layer 14 and the inorganic layer 16 are formed, the back film 20 is pasted. According to the manufacturing method of the present invention, the thin support 12 having a thickness of 50 μm or less is used. However, it is possible to manufacture the gas barrier film 10 having high gas barrier properties by preventing the inorganic layer 16 from being damaged. Further, according to the production method of the present invention, the cloudiness of the adhesive layer 24 and the damage to the support 12 after peeling off the protective film 26 and the like do not occur as described above.
In Example 3 where the thickness of the support 12 is 23 μm and Example 4 where the thickness of the support is 12 μm, since the support 12 is thin, the support 12 and the adhesive after the protective film 26 is peeled off. Some wrinkles are observed in the tank 24, and the gas barrier properties are inferior to those of the other examples. However, the wrinkles are sufficiently practical and the gas barrier properties are sufficiently high as compared with the comparative example.
On the other hand, the comparative example by the conventional manufacturing method which forms the organic layer 14 and the inorganic layer 16 after sticking the back surface film 20 has low gas barrier property. This is because when the inorganic layer 16 is formed, the air mixed between the back film 20 and the support 12 expands and contracts, resulting in damage to the inorganic layer 14 and a decrease in gas barrier properties. It is thought that. Further, in the comparative example, as described above, the adhesive layer 24 was observed to be clouded, and when the protective film 26 and the like were peeled off, some damage to the support 12 was also observed.
From the above results, the effects of the present invention are clear.

  It can be suitably used as a protective film for an organic EL device or a quantum dot layer.

DESCRIPTION OF SYMBOLS 10 Gas barrier film 12 Support body 14 Organic layer 16 Inorganic layer 20 Back film 24 Adhesive layer 26 Protective film 30 Quantum dot layer 32 Diffusion sheet

Claims (7)

An organic layer is formed on the support, an inorganic layer is formed on the organic layer by a vapor deposition method under reduced pressure , and then the organic layer of the support is formed before being stacked on the inorganic layer. the plane of the layer-forming surface and opposite side, Ri Do and a peelable protective film from the adhesive layer and the adhesive layer, the adhesive strength between the support and the adhesive layer, the adhesive between the protective film and the adhesive layer The manufacturing method of the functional film characterized by sticking a back film stronger than force .   The method for producing a functional film according to claim 1, wherein the support has a thickness of 12 to 50 μm.   The method for producing a functional film according to claim 1, wherein the total thickness of the support, the organic layer, and the inorganic layer is 55 μm or less.   The method for producing a functional film according to claim 1, wherein the pressure-sensitive adhesive layer has a thickness of 5 to 200 μm, and the protective film has a thickness of 12 to 100 μm.   The adhesive force between the support and the adhesive layer is 5 to 50 N / 25 mm, and the adhesive force between the adhesive layer and the protective film is 0.01 to 0.5 N / 25 mm. A method for producing the functional film described in 1.   The method for producing a functional film according to claim 1, wherein the pressure-sensitive adhesive layer is formed of an optical transparent adhesive. After forming the said inorganic layer , the manufacturing method of the functional film of any one of Claims 1-6 which sticks a back film on the said support body in the state which maintained the pressure reduction.