JP6627521B2 - Functional film and method for producing quantum dot (QD) -containing laminated member containing the same - Google Patents

Description

  The present invention relates to a method for producing a functional film and a quantum dot (QD) -containing laminated member containing the same.

  In recent years, various functional films in which a thin film layer is formed on a substrate have been proposed. For example, gas barrier films are widely used for packaging these products that prevent deterioration of foods, industrial supplies, pharmaceuticals, and the like by blocking water vapor, oxygen, and the like. Gas barrier films are also used in organic electronic devices such as liquid crystal display devices, photoelectric conversion devices, and organic electroluminescence devices (hereinafter, referred to as “organic EL devices”).

  In recent years, semiconductor nanoparticles (also referred to as “quantum dots” (QDs)) have attracted commercial attention because their electronic characteristics can be adjusted by their size. Semiconductor nanoparticles are expected to be used in a wide variety of fields such as, for example, biomarkers, catalysis, biological imaging, liquid crystal display devices, photoelectric conversion devices, and organic electronic devices. Here, since the semiconductor nanoparticles deteriorate when they come in contact with water vapor or oxygen, various methods for shielding the semiconductor nanoparticles from water vapor or oxygen have been proposed, and a method for preventing deterioration by using a gas barrier film has been proposed. Is being considered. For example, in Patent Document 1, a gas barrier film is arranged so as to sandwich a quantum dot layer (light emitting layer) in which phosphor particles functioning as quantum dots (QD) are dispersed in an ultraviolet curable resin or a thermosetting resin. Is disclosed.

  Various studies have been made also on the adhesiveness between different kinds of members regarding the functional film. For example, Patent Document 2 discloses a step of applying a base polymer layer to a substrate, a step of applying an oxide layer on the base polymer layer, and a step of co-depositing silane and acrylate on the oxide layer to form an overcoat polymer layer. And a method for producing a gas barrier film having a step of forming a gas barrier film, and discloses that the gas barrier film produced by such a method has improved adhesiveness.

JP-T-2013-544018 JP-T-2013-530074

  Here, the functional film may have a problem of adhesion between adjacent members to which the functional film is applied, and between each member when the functional film itself has a laminated structure. Are known. The technique of Patent Document 1 also has a problem that adhesion between the quantum dot-containing resin layer and the gas barrier film cannot be maintained due to film shrinkage that occurs when the quantum dot-containing resin layer is cured.

Further, the silane disclosed in Patent Document 2 is only a cyclic aza-silane, and such a cyclic aza-silane is described as a system exhibiting a function only in combination with a sputter-deposited SiO ₂ layer. is there. As described above, the effect of improving the adhesiveness obtained by the technique of Patent Document 2 is limited to the combination of the composition of the specific oxide layer and the type of silane, and the improvement of the functionality of the functional film is obtained. From the viewpoint of productivity and productivity, further versatility has been demanded. Further, the technique of Patent Document 2 confirms the improvement of the adhesive property, but is not sufficient, and further improvement of the adhesive property has been demanded.

  Therefore, an object of the present invention is to provide a method for producing a functional film having improved adhesion to an adjacent member to which the functional film is applied.

  Another object of the present invention is to provide a quantum dot (QD) -containing laminated member having good adhesion between a functional film and a quantum dot (QD) -containing resin layer.

  The above object of the present invention is achieved by the following means.

A step of forming a metal (M) -containing layer A (excluding an organosilicon compound-containing layer having a polymerizable substituent) on a substrate by vapor-phase film formation;
An organosilicon compound-containing layer B having a polymerizable substituent is provided on the surface of the metal (M) -containing layer A opposite to the side on which the substrate is present, so as to be in contact with the metal (M) -containing layer A. Forming a layer by continuous vapor deposition from the formation of the metal (M) -containing layer A;
Before the step of forming the metal (M) -containing layer A by vapor deposition, the metal (M) -containing layer A is disposed between the base material and the metal (M) -containing layer A and is in contact with the metal (M) -containing layer A. as, it is seen including a step of forming a non-transition metal (M2) containing layer C (excluding the organic silicon compound-containing layer having a polymerizable substituent group),
The metal (M) -containing layer A contains a transition metal (M1), and has a composition in a region where the metal (M) -containing layer A and the non-transition metal (M2) -containing layer C are adjacent to each other (M2 _{) (M1) x O y N} z (0.02 <x <50, y> 0, when expressed z ≧ 0), the satisfy the following formula (1), method for producing a functional film.
(2y + 3z) / (a + bx) <1.0 Expression (1)
(In the formula (1), a represents the maximum valence of the non-transition metal (M2), and b represents the maximum valence of the transition metal (M1).)

  According to the present invention, there is provided a means for producing a functional film having improved adhesion to an adjacent member to which the functional film is applied.

In the production method according to one embodiment of the present invention, a schematic view showing a preferred example of an apparatus used for flash vapor deposition, which is a kind of thermal vapor deposition for forming the organosilicon compound-containing layer B having a polymerizable substituent. It is. In the manufacturing method according to one embodiment of the present invention, a metal (M) -containing layer A is formed on a substrate by vapor phase film formation, and then an organosilicon compound-containing layer B having a polymerizable substituent is formed by continuous vapor phase film formation. FIG. 1 is a schematic view showing a preferred example of a vacuum film forming machine for forming by a method. It is a mimetic diagram showing a preferred example of a functional film manufactured by a manufacturing method concerning one form of the present invention. FIG. 4 is a schematic view showing a preferred example of a functional film manufactured by a manufacturing method according to another embodiment of the present invention. It is a mimetic diagram showing a desirable example of a lamination member containing a QD containing resin layer manufactured by a manufacturing method concerning other one form of the present invention.

≫Production method of functional film≫
The invention according to one embodiment of the present invention includes a step of forming a metal (M) -containing layer A (excluding an organosilicon compound-containing layer having a polymerizable substituent) on a substrate by vapor-phase film formation; On the surface of the (M) -containing layer A opposite to the side where the substrate is present, the organosilicon compound-containing layer B having a polymerizable substituent is contacted with the metal (M) -containing layer A, And forming the layer by continuous vapor deposition from the formation of the metal (M) -containing layer A. According to the method for manufacturing a functional film according to one embodiment of the present invention having such a configuration, a functional film with improved adhesion can be manufactured.

  The metal (M) -containing layer and an adjacent member to which the functional film is applied, for example, a resin layer, generally have different physical properties, and thus have low adhesiveness. In order to improve the adhesion between the metal (M) -containing layer and the resin layer, a layer made of a compound having both a substituent interacting with the metal (M) -containing layer and a substituent interacting with the resin layer is formed. It is known that an organic silicon compound is suitable as a material for forming such a layer. Here, as a result of intensive studies, the present inventor has found that in a functional film having a metal (M) -containing layer, the organosilicon compound-containing layer in contact with the metal (M) -containing layer is replaced with an organosilicon compound having a polymerizable substituent. It has been found that the adhesiveness of the functional film is greatly improved by using the containing layer. The reason for this is that a covalent bond is formed by a chemical reaction between the polymerizable substituent and the resin layer, and one end of the organosilicon compound having a polymerizable substituent is incorporated into the polymer, so that these interfaces are formed. It is presumed that this is because a physically and chemically strong structure is formed by the above method.

  In addition, the present inventor has found that, in a functional film having a metal (M) -containing layer, the adhesiveness of the functional film changes depending on the forming method when forming the organosilicon compound-containing layer in contact with the metal (M) -containing layer. I discovered that Specifically, the adhesion is improved by forming the metal (M) -containing layer and the organosilicon compound-containing layer in a continuous vapor-phase film formation, that is, while forming these layers while maintaining a vacuum state. I found that. The reason for this is that when the metal (M) -containing layer is formed at normal pressure or when the metal (M) -containing layer is exposed to the atmosphere during formation of these layers, the surface of the metal (M) -containing layer is formed of water, oxygen, or nitrogen. It is presumed that such a reaction can be suppressed by continuous vapor deposition. More specifically, as a result of suppressing the formation of a film on the surface of the metal (M) -containing layer due to such a reaction by continuous vapor phase film formation, the substituent of the organosilicon compound that interacts with the metal (M) -containing layer becomes a metal. (M) It becomes possible to interact favorably with the constituent material of the containing layer. The interaction forms the organosilicon compound-containing layer with the substituent interacting with the metal (M) -containing layer facing the metal-containing layer and the polymerizable substituent facing the organosilicon compound-containing layer. It will be. That is, the organosilicon compound-containing layer can be formed in a state where the polymerizable substituent is exposed on the surface of the organosilicon compound-containing layer opposite to the side in contact with the metal (M) -containing layer A. It is estimated that the chemical reaction between the polymerizable substituent and the resin layer can be more efficiently generated, and that the adhesiveness between the organosilicon compound-containing layer and the resin layer can be improved. Is done. It is also presumed that such interaction improves the adhesion between the organosilicon compound-containing layer and the metal (M) -containing layer.

  As described above, the effect of improving the adhesiveness can be enhanced by making the substituent of the organosilicon compound-containing layer that interacts with the resin layer a polymerizable substituent, thereby further strengthening the interaction, and the metal (M) -containing layer. The polymerizable substituent by the substituent interacting with the metal (M) -containing layer A of the organosilicon compound-containing layer in such a state that the effect of exposing it to the surface on the side opposite to the side in contact with the metal (M) -containing layer A is sufficiently obtained. Presumed to be achieved. The above mechanism is based on a guess, and its correctness does not affect the technical scope of the present invention.

  Hereinafter, preferred embodiments of the present invention will be described. In this specification, “X to Y” indicating a range means “X or more and Y or less”. Unless otherwise specified, operations, physical properties, and the like are measured under conditions of room temperature (20 to 25 ° C.) / Relative humidity of 40 to 50% RH.

In the present invention, “(meth) acrylate” and “(meth) acryl” are generic terms for acrylate and methacrylate. Similarly, a compound containing (meth) such as (meth) acryl is a generic term for a compound having “meth” in a name and a compound not having “meth” in a name. The acryloyl group is an acrylic acid-derived acyl group represented by “CH ₂ ＣＨCH—C (＝ O) —”, and the methacryloyl group is “CH ₂ ＣC (CH ₃ ) —C ( ＯO)-”and is an acyl group derived from methacrylic acid, and“ (meth) acryloyl group ”is a collective term for these.

<Metal (M) -containing layer A forming step>
The present invention provides a step of forming a metal (M) -containing layer A (excluding an organic silicon compound-containing layer B having a polymerizable substituent described below) on a substrate by vapor phase film formation (metal (M) -containing layer). A forming step).

(Base material)
The substrate is not particularly limited as long as it can hold the metal (M) -containing layer A and the like. As the substrate, a resin substrate (plastic film or sheet) is preferably used, and a film or sheet made of a colorless and transparent resin is more preferable. The resin substrate used is not particularly limited in material, thickness and the like, and can be appropriately selected depending on the purpose of use and the like.

  The resin base material is not particularly limited. For example, poly (meth) acrylate, polyethylene terephthalate (PET), polybutylene terephthalate, polyethylene naphthalate (PEN), polycarbonate (PC), polyarylate, polyvinyl chloride ( PVC), polyethylene (PE), polypropylene (PP), polystyrene (PS), nylon (Ny), aromatic polyamide, polyetheretherketone, polysulfone, polyethersulfone, polyimide, polyetherimide, cycloolefin polymer, cycloolefin Resin films such as copolymers, heat-resistant transparent films (product name Sila-DEC, manufactured by Chisso Corporation) having silsesquioxane having an organic-inorganic hybrid structure as a basic skeleton, and these films Or the like can be used a resin film formed by laminating more layers.

  The thickness of the substrate is not particularly limited, but is preferably in the range of 5 to 300 μm, and more preferably in the range of 10 to 150 μm.

  In one embodiment of the present invention, the substrate is preferably transparent. Since the base material is transparent and the layer formed on the base material is also transparent, it is possible to obtain a transparent functional film. For example, a transparent substrate such as an organic EL device can be used. Become.

  The substrate preferably has a high surface smoothness. As the surface smoothness, those having an average surface roughness (Ra) of 2 nm or less are preferable. The lower limit is not particularly limited, but is practically preferably 0.01 nm or more. If necessary, both surfaces of the substrate, at least the side on which the metal (M) -containing layer A is provided, may be polished to improve smoothness.

  At least the side of the substrate on which the metal (M) -containing layer A is provided may be subjected to various known treatments for improving adhesion, such as a corona discharge treatment, a flame treatment, an oxidation treatment, or a plasma treatment. Alternatively, the above processes may be performed in combination as needed. Further, the resin substrate may be subjected to an easy adhesion treatment.

  As the resin base material, a commercially available product may be used. For example, U34 manufactured by Toray Industries, Inc., which is a commercially available polyethylene terephthalate film, can be used.

(Metal (M) -containing layer A)
The metal contained in the metal (M) -containing layer A is not particularly limited, and either a transition metal (M1) or a non-transition metal (M2) may be used. Among these, it is preferable to contain a transition metal (M1) from the viewpoint of improving the adhesiveness. When the metal (M) -containing layer A is a transition metal (M1) -containing layer containing a transition metal (M1), a non-transition metal (M2 ) It is more preferable to further provide the containing layer C from the viewpoint that a high gas barrier property can be imparted to a film to be produced.

  That is, a preferred embodiment of the present invention is a method for producing a functional film, wherein the metal (M) is a transition metal (M1). Here, the transition metal (M1) refers to an element of Groups 3 to 11 of the long-period periodic table, and for example, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Hf, Ta, W, Re, Os, Ir, Pt, Au and the like can be mentioned.

  From a similar viewpoint, the transition metal (M1) more preferably contains a transition metal selected from the group consisting of elements of Groups 5 to 11. Examples of the transition metals of Groups 5 to 11 include V, Cr, Mn, Fe, Co, Ni, Cu, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Ta, W, Re, Os, Ir, Pt, Au and the like can be mentioned.

  Among them, the transition metal (M1) is more preferably a transition metal selected from the group consisting of Group 5 elements, and particularly preferably Nb. This is because the transition metal (M1) (especially, Nb) is considered to easily bond to Si in the organosilicon compound-containing layer B having a polymerizable substituent described below. When a non-transition metal (M2) -containing layer C described later is further provided, the transition metal (M1) (particularly, Nb) may contain Si or non-transition metal in the organosilicon compound-containing layer B having a polymerizable substituent. This is because it is considered that a bond easily occurs to the non-transition metal (M2) in the (M2) -containing layer C. In addition, as described in detail later, when the non-transition metal (M2) is Si, an effect that the gas barrier property given to the manufactured film is significantly improved can be obtained.

  Further, the transition metal (M1) is particularly preferably Nb from the viewpoint that a compound having good transparency is obtained and the optical characteristics are excellent.

  Here, the transition metal (M1) can be used only with the transition metal (M1) or in combination with the non-transition metal (M2), but is preferably used only with the transition metal (M1). The transition metal (M1) can be used alone or in combination of two or more, but it is preferable to use the transition metal (M1) alone.

  However, even if the metal contained in the metal (M) -containing layer A is a non-transition metal (M2), the effect of improving the adhesion intended by the present invention can be obtained. The non-transition metal (M2) is not particularly limited, and examples thereof include Al, Si, Zn, Ga, Ge, Cd, In, Sn, Hg, Tl, Pb, and Cn.

  The metal (M) -containing layer A preferably contains the metal (M) in the form of an oxide, a nitride, an oxynitride, an oxycarbide or the like. Among these, an oxide is preferable, and an oxide of a transition metal (M1) is preferable.

Further, the oxide of the transition metal (M1) is preferably an oxygen-deficient transition metal oxide, and particularly preferably an oxygen-deficient niobium oxide. Here, the oxygen-deficient niobium oxide is not particularly limited, and for example, a composition of Nb ₁₂ O ₂₉ can be used.

Here, the oxygen-deficient transition metal oxide refers to a metal oxide MO _{x1 in} which x1 <x2 when a stoichiometrically obtained transition metal oxide is _{MOx2 .} For example, taking the oxide of Nb (niobium) as an example, the stoichiometrically obtained oxide of Nb is diniobium pentoxide, which is NbO _2.5 , so that x2 = 2.5 is there. Although Nb can also have a composition of diniobium trioxide, x2 in one embodiment of the present invention means x2 of the stoichiometric compound having the highest degree of oxidation. When the transition metal (M1) is laminated under conditions that cause oxygen deficiency, the adhesion becomes better. The reason for this is that the transition metal (M1) is more difficult to bond with oxygen alone, and the bond is more likely to occur with Si in the later-described organosilicon compound-containing layer B having a polymerizable substituent. It is considered to be. In addition, when a non-transition metal (M2) -containing layer C described later is further provided, a higher gas barrier property can be imparted to a manufactured film. The reason for this is that the transition metal (M1) is more difficult to bond with only oxygen, and the Si in the organosilicon compound-containing layer B having a polymerizable substituent and the non-transition metal (M2) -containing layer C This is considered to be because the bond becomes more likely to occur with the non-transition metal (M2).

  The content of the metal compound such as a metal oxide contained in the metal (M) -containing layer A is not particularly limited as long as the effect of the present invention is not impaired. , 50% by mass or more, more preferably 80% by mass or more, still more preferably 95% by mass or more, particularly preferably 98% by mass or more, and 100% by mass. (That is, the metal (M) -containing layer A is made of a metal compound).

  When the metal contained in the metal (M) -containing layer A is a transition metal (M1), the transition metal (M1) -containing layer that is the metal (M) -containing layer A may be a single layer or a laminate of two or more layers. It may be a structure. When the transition metal (M1) -containing layer has a laminated structure of two or more layers, the metal (or metal compound) contained in each transition metal (M1) -containing layer may be the same or different. Is also good.

  When the metal contained in the metal (M) -containing layer A is a non-transition metal (M2), the non-transition metal (M2) -containing layer, which is the metal (M) -containing layer A, includes It is treated as being a single layer that is present between the organic silicon compound-containing layer B having a polymerizable substituent and the organic silicon compound-containing layer having a polymerizable substituent.

From the viewpoint of adhesiveness, the thickness of the metal (M) -containing layer A (in the case of a laminate structure of two or more layers, the total thickness) is preferably in the range of 1 to 200 nm, and 2 to 100 nm. It is more preferably within the range, more preferably within the range of 3 to 50 nm. In particular, when the thickness of the metal (M) -containing layer A is 50 nm or less, the productivity of forming the metal (M) -containing layer A is further improved. It does not need to be formed in such a manner, and a base layer (smooth layer, primer layer), an anchor coat layer (anchor layer), a protective layer, a moisture absorbing layer or an antistatic layer, and a non-transition metal-containing layer described below Another functional layer such as the layer C may be provided.

  The vapor deposition method is not particularly limited. For example, a physical vapor deposition (PVD) method such as a sputtering method, a vapor deposition method, an ion plating method, or an ion assist vapor deposition method, or a plasma CVD (Chemical Vapor) method. Chemical vapor deposition (CVD) methods such as a Deposition method and an ALD (Atomic Layer Deposition) method. Among them, a film is formed by physical vapor deposition (PVD), more preferably a sputtering method, because a film can be formed without damaging the lower layer and high productivity is obtained.

  That is, a preferred embodiment of the present invention is a method for producing a functional film in which the vapor phase film formation for forming the metal (M) -containing layer A is a sputter film formation. The film formation by the sputtering method may be performed by single-electrode sputtering, magnetron sputtering, dual magnetron sputtering (DMS) using an intermediate frequency region, ion beam sputtering, ECR (Electron Cyclotron Resonance) sputtering, or the like. Two or more kinds can be used in combination. The method of applying the target is appropriately selected depending on the type of the target, and any one of AC sputtering such as DC (direct current) sputtering or RF (high frequency) sputtering may be used.

  Further, for example, a reactive sputtering method using a transition mode intermediate between the metal mode and the oxide mode can also be used. By controlling the sputtering phenomenon so as to be in the transition region, a metal oxide film can be formed at a high film formation speed, which is preferable. When DC sputtering or dual magnetron sputtering is performed, a metal (M) is used as a target and oxygen is introduced into a process gas to form a metal oxide thin film. In the case of forming a film by RF (high-frequency) sputtering, a metal oxide target can be used.

  As the inert gas used for the process gas, He, Ne, Ar, Kr, Xe, or the like can be used, and it is preferable to use Ar. Further, by introducing a reaction gas such as oxygen, nitrogen, carbon dioxide, carbon monoxide, or the like into the process gas, a metal compound thin film such as a metal oxide, nitride, oxynitride, or oxycarbide can be formed. .

  The film forming conditions in the sputtering method include applied power, discharge current, discharge voltage, time and the like, and these can be appropriately selected according to a sputtering apparatus, a material of the film, a film thickness, and the like.

Among them, a sputtering method using a metal oxide as a target is preferable because the film formation rate is higher and the productivity is higher. As described above, the target is preferably an oxide of metal (M1), more preferably an oxygen-deficient transition metal oxide, and an oxygen-deficient niobium oxide (for example, Nb ₁₂ O ₂₉ or the like). It is particularly preferred to use

  Hereinafter, known conditions can be appropriately adopted as conditions for the sputtering method. Preferred conditions in the sputtering method are described below, but the present invention is not limited to these.

The pressure (degree of vacuum) of the chamber is preferably set to 10 Pa or less, more preferably 1 Pa or less. The pressure of the chamber is preferably as small as possible, but is preferably 1 × 10 ⁻⁸ Pa or more from the viewpoint of productivity. In this specification, it is assumed that 10 Pa or less is in a vacuum state.

  It is preferable to use a film-forming drum (also referred to as a film-forming roller) having a cooling function, and the temperature thereof is preferably from −15 ° C. to 25 ° C.

  The transport speed of the substrate is preferably 0.5 m / min or more and 100 m / min or less.

  It is preferable to use an AC power supply as the power supply. When an AC power supply is used, the power is not particularly limited, and conditions for forming a target film can be appropriately selected.

Deposition pressure can not generally be defined differently because depending on the type of device, 1.0 × 10 ^-8 Pa or more, it is preferable to 10Pa or less.

  The ratio of the flow rate of the process gas (sccm) to the flow rate of the reaction gas in the sputtering gas (sccm: cubic centimeter per minute) (process gas flow rate (sccm) / reaction gas flow rate (sccm)) depends on the metal to be formed. (M) Since it differs depending on the type of the containing layer A, it cannot be unconditionally specified, but is preferably 0.01 or more and 100 or less.

  The thickness of the metal (M) -containing layer A formed by the sputtering method is controlled by the transport speed of the film at the time of film formation, the power and voltage applied to the target, the oxygen concentration, the shape of the opening (film formation area), and the like. be able to.

  In addition, about the preferable form of the manufacturing apparatus which can be used for the metal (M) containing layer A formation process, it describes together in the description of the vacuum film-forming machine which can be used for the below-mentioned organosilicon compound containing layer B formation process. I do.

<Organosilicon compound-containing layer B forming step>
The present invention provides an organosilicon compound-containing layer B having a polymerizable substituent on a surface of the metal (M) -containing layer A opposite to the side on which the base material is present so as to be in contact with the metal (M) -containing layer A. (The step of forming the organosilicon compound-containing layer B) by the continuous vapor phase film formation from the formation of the metal (M) -containing layer A.

  The functional film is formed of an organic material such that the metal (M) contained in the metal (M) -containing layer A and an adjacent member to which the functional film is applied, for example, a resin layer, are bonded through a chemical bond. The silicon compound containing layer B is formed. With this configuration, a strong bond is formed between the metal (M) -containing layer A and the resin layer, so that the adhesion between the two layers is improved, and the separation between the two layers is performed. Strength is improved.

  The present invention is characterized in that an organic silicon compound-containing layer B having a polymerizable substituent is used. Hereinafter, as a preferred embodiment of the present invention, the polymerization is performed such that the polymerizable substituent is exposed on the surface of the organic silicon compound-containing layer B having a polymerizable substituent on the side opposite to the side in contact with the metal (M) -containing layer. The form in which the organosilicon compound-containing layer B having a sexual substituent is formed will be described in detail.

  In the functional film having the metal (M) -containing layer A, the organosilicon compound-containing layer B in contact with the metal (M) -containing layer A is referred to as an organosilicon compound-containing layer B having a polymerizable substituent. The reason that the adhesiveness is improved by such a configuration is that a polymerizable substituent and an adjacent member, in particular, a covalent bond is formed by a chemical reaction between the adjacent member that is a resin layer, and an organosilicon compound having a further polymerizable substituent. It is speculated that one end is incorporated into the polymer to form a physically and chemically strong structure at these interfaces.

  On the other hand, in an organosilicon compound-containing layer using an organosilicon compound having no polymerizable substituent, the adhesiveness under high-temperature and high-humidity conditions is not sufficient, assuming that the organosilicon compound-containing layer is used under severe conditions for a longer time than before. There are cases.

  Here, when the adjacent member is a resin layer, the effect of the present invention is further enhanced when the adjacent member is an ultraviolet curable resin layer from the viewpoint of reactivity with the organosilicon compound having a polymerizable substituent. When the resin layer is an ultraviolet-curable resin layer having the same polymerizable substituent as the organosilicon compound having a polymerizable substituent, a particularly remarkable effect can be obtained.

  Examples of the polymerizable substituent of the organosilicon compound having a polymerizable substituent include a (meth) acryloyl group, a vinyl group, and an epoxy group.

  That is, a preferred embodiment of the present invention is a method for producing a functional film in which the polymerizable substituent of the organosilicon compound is a substituent selected from the group consisting of a (meth) acryloyl group, a vinyl group, and an epoxy group. . Such a functional group has high polymerizability, and can further improve the adhesiveness with a resin layer as an adjacent member.

  The organosilicon compound having a polymerizable substituent interacts with the constituent material of the metal (M) -containing layer A as a substituent other than the polymerizable substituent to form a chemical bond (covalent bond). It is preferable to further have a reactive group from the viewpoint of adhesiveness.

  Here, the reason why the adhesiveness is improved is that a reactive group other than the polymerizable substituent (for example, an alkoxysilyl group in a (meth) acryloyl group-containing silane coupling agent) is mixed with a constituent material of the metal (M) -containing layer. Form a chemical bond (covalent bond) between the polymerizable substituent and the side of the organosilicon compound-containing layer B having a polymerizable substituent that is in contact with the metal (M) -containing layer. In order to form the organosilicon compound-containing layer B having a polymerizable substituent as a state exposed on the opposite surface, the adhesion between the organosilicon compound-containing layer B having a polymerizable substituent and the resin layer is improved. Is presumed to be from The reactive group is a substituent that interacts well between the organosilicon compound-containing layer B having a polymerizable substituent and the metal (M) -containing layer A, and has a polymerizable substituent due to the interaction. This is presumed to be because the effect of improving the adhesion between the organosilicon compound-containing layer B and the metal (M) -containing layer A is further improved.

  In addition, "a polymerizable substituent such as a (meth) acryloyl group is exposed on the surface of the organosilicon compound-containing layer B having a polymerizable substituent opposite to the side in contact with the metal (M) -containing layer." Can be confirmed by scraping off the surface layer of the organosilicon compound-containing layer B having a polymerizable substituent, performing measurement by pyrolysis gas chromatography, and checking with a sample.

  Thus, as the organosilicon compound having a polymerizable substituent, an alkoxysilyl group and one or more functional groups selected from the group consisting of a (meth) acryloyl group, a vinyl group and an epoxy group (polymerizable group) And a silane coupling agent containing a silane coupling agent.

  As described above, "the reactive group other than the polymerizable substituent of the organosilicon compound having a polymerizable substituent forms a chemical bond (covalent bond) with the constituent material of the metal (M) -containing layer A. As a result, the polymerizable substituent is exposed on the surface of the organosilicon compound-containing layer B having the polymerizable substituent on the surface opposite to the side in contact with the metal (M) -containing layer, and the organic compound having the polymerizable substituent is exposed. Examples of the compound used for "forming the silicon compound-containing layer B" include a compound containing at least one polymerizable substituent and at least one alkoxysilyl group in one molecule.

  From the viewpoint of adhesiveness, the polymerizable substituent is preferably a (meth) acryloyl group, a vinyl group and an epoxy group, more preferably a (meth) acryloyl group, and more preferably an acryloyl group. Is more preferred.

  Here, as the compound containing a (meth) acryloyl group and an alkoxysilyl group in one molecule, a silane coupling agent containing a (meth) acryloyl group (a silane coupling agent containing a (meth) acryloyl group) is preferably used. . The (silane) coupling agent containing a (meth) acryloyl group is not particularly limited. For example, 3- (meth) acryloyloxypropyltrimethoxysilane, 3- (meth) acryloyloxypropyltriethoxysilane, 3- (meth) acryloyl Examples thereof include oxypropylmethyldimethoxysilane, 3- (meth) acryloyloxypropylmethyldiethoxysilane, and an acrylic oligomer having an acryl group. Among these, a silane coupling agent containing an acryloyl group (an acryloyl group-containing silane coupling agent) is more preferable, and 3-acryloyloxypropyltrimethoxysilane, 3-acryloyloxypropyltriethoxysilane, and 3-acryloyl Oxypropylmethyldimethoxysilane, 3-acryloyloxypropylmethyldiethoxysilane, more preferably an acrylic oligomer having an acryl group, and particularly preferably 3-acryloyloxypropyltrimethoxysilane, 3-acryloyloxypropyltriethoxysilane Most preferably, it is 3-acryloyloxypropyltrimethoxysilane. The commercially available (meth) acryloyl group-containing silane coupling agent is not particularly limited. For example, KBM-5103, KBM-502, KBM-503, KBE-502, KBE-503, KR-513 (Shin-Etsu) Chemical Industry Co., Ltd.). One of these (meth) acryloyl group-containing silane coupling agents may be used alone, or two or more thereof may be used in combination. Examples of the “compound containing a (meth) acryloyl group and an alkoxysilyl group in one molecule” other than the (meth) acryloyl group-containing silane coupling agent include, for example, a polyorganosilsesquioki having a (meth) acryloyl group introduced therein. An organic-inorganic hybrid material such as sun or a polysiloxane-modified acrylic resin containing an unsaturated double bond may be used. These materials may be independently prepared with reference to conventionally known knowledge, or commercially available products may be used.

  Here, as the compound containing at least one vinyl group and one alkoxysilyl group in one molecule, a silane coupling agent containing a vinyl group (vinyl group-containing silane coupling agent) is preferably used. The vinyl group-containing silane coupling agent is not particularly limited, and examples thereof include vinyl trimethoxy silane and vinyl triethoxy silane. The commercially available vinyl group-containing silane coupling agent is not particularly limited, and examples thereof include KBM-1003 and KBE-1003 (manufactured by Shin-Etsu Chemical Co., Ltd.). One of these vinyl group-containing silane coupling agents may be used alone, or two or more thereof may be used in combination.

  Here, as the compound containing at least one epoxy group and one alkoxysilyl group in one molecule, a silane coupling agent containing an epoxy group (an epoxy group-containing silane coupling agent) is preferably used. The epoxy group-containing silane coupling agent is not particularly limited. For example, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane Examples thereof include ethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, and 3-glycidoxypropyltriethoxysilane. The commercially available epoxy group-containing silane coupling agent is not particularly limited, and examples thereof include KBM-303, KBM-402, KBM-403, KBE-402, and KBE-403. One of these (meth) acryloyl group-containing silane coupling agents may be used alone, or two or more thereof may be used in combination.

  The thickness of the organosilicon compound-containing layer B having a polymerizable substituent is preferably 30 nm or less. By setting the thickness of the organosilicon compound-containing layer B having a polymerizable substituent to 30 nm or less, the surface orientation of the organosilicon compound-containing layer B having an exposed polymerizable substituent having a polymerizable substituent is improved. By doing so, the adhesiveness to the resin layer as an adjacent member is further improved, and the possibility of peeling from the adjacent member due to cohesive failure of the organosilicon compound-containing layer B having a polymerizable substituent can be further reduced. In addition, since such a configuration makes it difficult for deterioration factors (such as water vapor and oxygen) to enter from the side surface of the organosilicon compound-containing layer B having a polymerizable substituent, the organic silicon compound-containing layer B is particularly arranged adjacent to the side surface. For example, deterioration of a member such as a quantum dot (semiconductor nanoparticle) included in the QD-containing resin layer can be sufficiently prevented. From the same viewpoint, the thickness of the organosilicon compound-containing layer B having a polymerizable substituent is more preferably 25 nm or less, and further preferably 20 nm or less. The lower limit of the thickness of the organosilicon compound-containing layer B is not particularly limited as long as the effects of the present invention can be obtained, but is preferably 0.1 nm or more, more preferably 1 nm or more. In the present invention, the thickness of the organosilicon compound-containing layer B having a polymerizable substituent can be measured by a transmission electron microscope (TEM).

  As described above, as a method of forming the organosilicon compound-containing layer B having a polymerizable substituent thinly, for example, a method in which the organosilicon compound-containing layer B having a polymerizable substituent has a side in contact with the metal (M) -containing layer is used. Is a method of forming an organosilicon compound-containing layer B having a polymerizable substituent such that a polymerizable substituent such as a (meth) acryloyl group is exposed on the surface on the opposite side.

  In the step of forming the organic silicon compound-containing layer B, a part of the polymerizable functional groups of the organic silicon compound having a polymerizable substituent may be polymerized to form a polymerizable polymer. However, even in such a case, if completely polymerized, unreacted polymerizable functional groups will be lost, and the effect of improving adhesiveness will not be obtained, so polymerization should not be performed completely. . In particular, the polymerization is preferably performed when the organosilicon compound-containing layer B having a polymerizable substituent is formed using an organosilicon compound having a polymerizable substituent that is in a liquid state at room temperature and in a normal humidity environment. .

  Such a polymerization method may be a thermal polymerization method or a photopolymerization method, but is preferably a thermal polymerization method. Here, the thermal polymerization method is a method in which a polymerization reaction is advanced by heat generated when forming the organic silicon compound-containing layer B having a polymerizable substituent (that is, heat generated during vapor phase film formation). Alternatively, a method of heating the formed organosilicon compound-containing layer B having a polymerizable substituent to promote the polymerization reaction may be used. Among these, a method in which the polymerization reaction is advanced by heat generated when forming the organic silicon compound-containing layer B having a polymerizable substituent is more preferable.

  The organic silicon compound-containing layer B having a polymerizable substituent may be formed so as to contain a polymerization initiator according to the curing means so that the polymerization reaction proceeds easily. The polymerization initiator is not particularly limited, but for example, a thermal polymerization initiator or the like can be appropriately used.

  Further, the organic silicon compound-containing layer B having a polymerizable substituent may contain an additive such as the above-mentioned polymerization initiator. The additive is not particularly limited as long as it does not impair the effects of the present invention, and known additives used for forming a layer can be used. The method of incorporating these additives into the organosilicon compound-containing layer B having a polymerizable substituent is not particularly limited. For example, an organosilicon compound having a polymerizable substituent as a raw material for vapor-phase film formation and Examples thereof include a method using a mixture of a polymerization initiator, and a method of co-evaporating an organosilicon compound having a polymerizable substituent and a polymerization initiator.

  The peel strength between the metal (M) -containing layer A and the adjacent member through the organosilicon compound-containing layer B having a polymerizable substituent is 2 N / 20 mm or more. It is preferable to form the organosilicon compound-containing layer B having a substituent, more preferably 3 N / 20 mm or more, still more preferably 4 N / 20 mm or more, and particularly preferably 5 N / 20 mm or more. The upper limit of the peel strength is not particularly limited. Here, as the value of the peel strength, a value measured by using a peel tester FGPX-0.5 manufactured by Nidec Shinpo Co., Ltd. is adopted.

  The vapor deposition method is not particularly limited. For example, a physical vapor deposition (PVD) method such as a sputtering method, a vapor deposition method, an ion plating method, or an ion assist vapor deposition method, or a plasma CVD (Chemical Vapor) method. Chemical vapor deposition (CVD) methods such as a Deposition method and an ALD (Atomic Layer Deposition) method.

  Among these, a physical vapor deposition (PVD) method is preferable, an evaporation method is more preferable, and a thermal evaporation method is more preferable.

  That is, a preferred embodiment of the present invention is a method for producing a functional film, wherein the vapor phase film forming method for forming the organosilicon compound-containing layer B having a polymerizable substituent is a thermal evaporation method.

  In the manufacturing method according to the present invention, the step of forming the organosilicon compound-containing layer B needs to be formed by continuous vapor deposition. Here, the continuous vapor deposition means that a vacuum state is maintained from the end of the step of forming the metal (M) -containing layer A to the start of the step of forming the organosilicon compound-containing layer B, that is, the vacuum state. This means that the step of forming the metal (M) -containing layer A and the step of forming the organosilicon compound-containing layer B were performed while maintaining the state.

  The method and conditions for thermal evaporation are not particularly limited, and known methods and conditions can be appropriately used. In the thermal evaporation, it is preferable that the chamber pressure (degree of vacuum), the type and temperature of a film forming drum (also referred to as a film forming roller), and the substrate transfer speed are the same as those in the sputtering method. However, the present invention is not limited to this.

  It is preferable to use a flash evaporation method as the thermal evaporation method. The flash vapor deposition method is described in, for example, International Publication No. WO 2014/103756, JP-T-2013-530074, US Pat. No. 5,440,446, and US Pat. No. 7,018,713. Some or all of known methods, devices and conditions, such as the method, device and conditions described above, can be used alone or in combination as appropriate. Further, these methods, devices and conditions may be appropriately changed and used.

  Although a specific example of the flash vapor deposition apparatus is not particularly limited, for example, the apparatus shown in FIG. In addition, the flash evaporation apparatus used for the flash evaporation method of the present invention is not limited to the following apparatuses.

  Hereinafter, an apparatus used in one embodiment of the present invention will be described with reference to the accompanying drawings. In the description of the drawings, the same elements will be denoted by the same reference symbols, without redundant description. In addition, the dimensional ratios in the drawings are exaggerated for convenience of description, and may be different from the actual ratios. Note that the present invention is not limited to only one mode described below.

  The flash vapor deposition unit in the flash vapor deposition apparatus of FIG. 1 is provided with a raw material vapor deposition unit 150 provided to face the surface of the film forming drum 126 and arbitrarily provided downstream of the raw material vapor deposition unit 150 in the transport direction D. And a raw material supply unit 154 connected to the raw material deposition unit 150 via a pipe 152.

  The raw material vapor deposition unit 150, the raw material supply unit 154, and the optionally provided curing unit of the flash vapor deposition unit are connected to a control unit (not shown). The control unit controls the raw material deposition unit 150, the raw material supply unit 154, and, if necessary, the curing unit.

  The raw material supply unit 154 evaporates a liquid compound (for example, an organic silicon compound having a polymerizable substituent alone) serving as a raw material of the silicon compound layer B having a polymerizable substituent to be formed, and The steam is supplied to the raw material deposition section 150 through the pipe 152.

  As shown in FIG. 1, the raw material supply unit 154 is provided with a liquid compound, is kept at a predetermined reduced pressure, and is provided with an exhaust unit and a stirring unit for reducing the inside pressure to a predetermined pressure. A tank 170, a syringe pump 172 connected to the tank 170, and a liquid ejecting unit 176 connected to the tank 170 via a pipe 174. In the raw material supply unit 154, a gas supply unit 178 is further connected to the liquid ejection unit 176 via a pipe 174.

  The liquid compound in the tank 170 is stirred by the stirring means under reduced pressure, and is defoamed to remove excess gas. This compound is pumped from the tank 170 to the liquid ejecting unit 176 by the syringe pump 172. The syringe pump pressure and the liquid sending amount are appropriately set depending on the thickness of the layer to be formed.

  The liquid ejecting unit 176 has a hollow configuration, and has a heating plate 180 provided therein. Although not shown, an exhaust unit for evacuating the inside of the liquid ejecting unit 176 and a heating unit for heating the heating plate 180 are provided. Further, the liquid ejecting unit 176 is provided with a droplet ejecting port 176 a at a connection portion with the pipe 174. Although not shown, an ultrasonic wave applying unit (ultrasonic sprayer) and a cooling unit are provided at the liquid droplet ejection port.

  In the liquid ejecting unit 176, while the inside is in a vacuum state, the liquid monomer compound pumped by the syringe pump 172 is turned into fine droplets at the droplet ejection port to which the ultrasonic wave is applied, and the heating plate 180 is heated. Injected toward. When the compound in the form of fine droplets contacts the heating plate 180, it evaporates to obtain an evaporator. The compound that has become the evaporator is supplied to the raw material deposition section 150 through the pipe 152.

  The evaporation efficiency of the compound can be improved by applying ultrasonic waves to make the liquid compound into fine particles. Further, it is preferable to cool the compound by a cooling means in order to prevent a thermosetting of the compound due to a rapid rise in temperature due to the application of ultrasonic waves to the injection port.

The gas supply section 178 of the raw material supply section 154 pushes out the residual compound inside the pipe 174 through which the compound passes to the liquid injection section 176. The gas supply unit 178 includes various gas cylinders storing an inert gas such as an Ar gas, a He gas, and a N ₂ gas, and a valve that adjusts a flow rate of the supplied inert gas.

  The pushing out of the residual compound inside the pipe 174 by the gas supply unit 178 is performed at the time of maintenance. Therefore, the gas supply unit 178 is not used during normal film formation.

  The raw material vapor deposition section 150 is a vapor of a liquid compound (for example, an organic silicon compound having a polymerizable substituent alone) serving as a raw material of the silicon compound layer B having a polymerizable substituent supplied from the raw material supply section 154. Is supplied onto the exposed surface of the metal (M) -containing layer A of the laminate Z including the base material and the metal (M) -containing layer A wound around the drum 126 to cause aggregation.

  The raw material deposition unit 150 includes a heating control unit (not shown), and includes a heating nozzle 150a whose periphery is heated to a temperature equal to or higher than the aggregation temperature and equal to or lower than the evaporation temperature.

  In addition, the curing unit in the curing unit that may be arbitrarily provided is not particularly limited as long as curing is possible. As the curing unit, for example, a heating unit or an active energy ray irradiation unit may be used. The active energy ray irradiation means is not particularly limited, and examples thereof include a UV irradiation means for irradiating ultraviolet rays (UV), an electron beam irradiation means for irradiating an electron beam, and a microwave irradiation means for irradiating a microwave.

  Known conditions can be appropriately adopted as the flash evaporation method. At the time of flash vapor deposition, it is preferable that a heated nitrogen gas flow is intensively added to the organosilicon compound having a polymerizable substituent. In addition, thermal evaporation involves heating a mixture of an organosilicon compound having polymerizable substituents and a gas resulting from the intensive addition of a stream of nitrogen gas in an ultrasonic nebulizer, with additional heated nitrogen gas. It is preferable that the film is deposited by being introduced into a deposited deposition source. As for the conditions of flash evaporation, the heating temperature of the evaporation source is preferably 150 ° C. or more and 300 ° C. or less. The frequency of the ultrasonic nebulizer, the jetting speed through the ultrasonic nebulizer, the flow rate of the nitrogen gas flow supplied into the ultrasonic nebulizer, the temperature of the nitrogen gas flow supplied into the ultrasonic nebulizer, Known conditions can be appropriately adopted as the flow rate. However, the present invention is not limited to these conditions.

  The curing method is not particularly limited, but it is preferable to use a heating method or an active energy ray irradiation method. Here, as the active energy ray irradiation method, it is preferable to perform electron beam irradiation for irradiating an electron beam. It is preferable to use a multifilament electron beam curing gun as the electron beam irradiation condition means. Known conditions can be appropriately adopted as the acceleration voltage and irradiation current when using such a multifilament electron beam curing gun.

  In the manufacturing method according to the present invention, it is preferable that the metal (M) -containing layer A step and the organosilicon compound-containing layer B forming step be performed by a vacuum film forming machine that enables continuous vapor phase film formation. . Such a vacuum film forming machine is not particularly limited. For example, the devices described in U.S. Pat. No. 5,440,446 and U.S. Pat. No. 7,018,713, or a vacuum forming machine similar thereto are used. A film machine or the like can be used.

  FIG. 2 shows that, in the manufacturing method according to one embodiment of the present invention, a metal (M) -containing layer A is formed on a substrate by vapor phase film formation, and then a step of forming an organosilicon compound-containing layer B is continuous vapor phase film formation. FIG. 1 is a schematic view showing a preferred example of a vacuum film forming machine for forming by a method.

  More specifically, FIG. 2 shows a roll-to-roll method in which a metal (M) -containing layer A is first formed on a substrate by a sputtering method, and a vacuum state is maintained. It is a schematic diagram which shows the vacuum film-forming machine for performing B formation process as a continuous vapor-phase film formation by a thermal vapor deposition method.

  In the description of FIG. 2, the simplest configuration of the functional film manufactured by the manufacturing method of the present invention is described from the viewpoint of simplicity. That is, in the following description, the case where the metal (M) -containing layer A is formed on the exposed surface of the base material is described. However, one embodiment of the present invention relates to a laminate in which various functional layers (for example, an underlayer and a non-transition metal (M2) -containing layer C described below) are provided on a substrate instead of the substrate alone. Forming the metal (M) -containing layer A on the exposed surface of the functional layer by further supplying and providing a step of forming an arbitrary functional layer between the base material and the metal (M) -containing layer A. Obviously, it may be in the form.

  Hereinafter, an apparatus used in one embodiment of the present invention will be described with reference to the accompanying drawings. In the description of the drawings, the same elements will be denoted by the same reference symbols, without redundant description. In addition, the dimensional ratios in the drawings are exaggerated for convenience of description, and may be different from the actual ratios. Note that the present invention is not limited to only one mode described below.

  2 includes a vacuum chamber 2, a coolable film forming drum 3, a sputtering device 5, a surface hydrophilic treatment device 6 (for example, a corona treatment device), and a thermal evaporation device 7. .

  Here, the chamber 2 is connected to a vacuum pump (not shown). The sputtering device 5 has a target (for example, an oxygen-deficient niobium oxide target) and a cathode, and is connected to a discharge power supply. The sputter region where the sputtering is performed is a region separated by two partition walls (not shown). The sputtering device 5 is arranged between the partition walls, and a reactive gas supply device and an inert gas supply device are provided in such a region. Is connected. The corona processing device 6 is connected to a power supply. Further, the surface hydrophilization region where the surface hydrophilization treatment is performed is a region partitioned between two partition walls (not shown), and has a configuration in which the corona treatment device 6 is disposed between the partition walls. In addition, the thermal evaporation apparatus 7 has an evaporation source (not shown) (for example, a flash evaporation unit including the material evaporation section 150, the pipe 152, and the material supply section 154 in the above-described flash evaporation apparatus in FIG. 1). . The thermal vapor deposition region where thermal vapor deposition is performed is a region separated by two partition walls (not shown), and has a configuration in which the thermal vapor deposition device 7 is disposed between the partition walls.

  The vacuum film forming machine 1 is supplied to a film forming drum 3 capable of cooling a base material 8 in a chamber 2, and the film forming drum 3 capable of cooling sends out a film in a rotation direction indicated by an arrow 4.

  The fed film is first sent to a sputter region, and in the sputter region, a metal (M) -containing layer A 9 is formed on the base material 8 by performing sputter film formation using the sputtering device 5. Next, the laminate of the base material 8 and the metal (M) -containing layer A 9 is further sent out to the surface hydrophilization treatment region in the rotation direction indicated by the arrow 4, and optionally using the surface hydrophilization treatment device 6. Perform hydrophilic treatment. Thereafter, the laminate of the base material 8 and the metal (M) -containing layer A 9 is further sent out to the thermal evaporation region in the rotation direction indicated by the arrow 4, and thermal evaporation is performed using the thermal evaporation device 7. The functional film 110 can be manufactured by forming the organosilicon compound-containing layer B10 on the exposed surface of the metal (M) -containing layer A9.

  In order to manufacture layers other than those described above by vapor phase film formation, a vapor phase film formation apparatus may be optionally provided in the chamber. For example, when the metal (M) -containing layer A9 has a laminated structure, a plurality of sputter regions may be provided, and sputter deposition may be performed by a plurality of sputter devices 5 arranged in each region. Further, for example, in order to form another layer such as a non-transition metal (M2) -containing layer C described later by vapor deposition, a vapor deposition apparatus such as a further sputtering apparatus 5 or a thermal evaporation apparatus 7 is used. It may be provided. Optionally, a further surface treatment device (for example, a surface hydrophilic treatment device or the like) may be provided.

  Further, the film formation of each layer by the vacuum film forming machine 1 may be repeated as desired or necessary when forming an alternate layer composed of a plurality of layers. Here, the alternating layer may be formed by repeating the film formation of the layer necessary for the alternating structure by the vacuum film forming machine 1 along the direction of the arrow 4, or the cooling film forming drum 3 may be used. The film may be formed by rotating the film in the direction opposite to the direction of arrow 4 to perform film formation again, and then rotating the film in the direction of arrow 4 repeatedly.

  Further, in the vacuum film forming machine 1, a vacuum state between the partition walls and a film forming atmosphere such as a film forming atmosphere gas such as a reaction gas or an inert gas can be independently controlled. May be provided with a vacuum pump, a reaction gas supply device and an inert gas supply device. In addition, the film formation atmosphere may be controlled for the entire chamber 2. In this case, at least one of a vacuum pump, a reactive gas supply device, and an inert gas supply device may be provided at an arbitrary position in the chamber 2. Just fine.

  Here, the various members and devices used in the vacuum film forming machine 1 are not particularly limited as long as they have the respective functions, and known members can be used as appropriate.

<Step of forming non-transition metal (M2) -containing layer C>
In a preferred embodiment of the present invention, the metal (M) -containing layer A is a transition metal (M1) -containing layer, and the metal (M) -containing layer A is formed with a base material before the step of forming the metal (M) -containing layer A by vapor deposition. A non-transition metal (M2) -containing layer C (excluding an organosilicon compound-containing layer having a polymerizable substituent) so as to be disposed between and in contact with the metal (M) -containing layer A Is a production method further comprising a step of forming

  The non-transition metal (M2) -containing layer C can be preferably provided when the above-mentioned metal (M) -containing layer A is a non-transition metal (M2) -containing layer. This is a layer different from the organosilicon compound layer B having a sexual substituent.

  The non-transition metal (M2) -containing layer C does not need to be formed so as to be in contact with the surface of the substrate, and may be provided between the substrate and the underlayer (smooth layer, primer layer), anchor coat layer (anchor layer), Other layers described later such as a protective layer, a moisture absorbing layer and an antistatic layer may be provided.

  The non-transition metal (M2) -containing layer C preferably contains a metal (M2) selected from the group consisting of elements of Groups 12 to 14. Specifically, Al, Si, Zn, Ga, Ge, Cd, In, Sn, Hg, Tl, Pb, Cn and the like can be mentioned, and among them, Si is preferable. The non-transition metal (M2) can be used alone or in combination, but is preferably used alone.

  The non-transition metal (M2) -containing layer preferably contains the non-transition metal (M2) and at least one of carbon (C), oxygen (O) and nitrogen (N). It preferably contains at least one of oxygen (O) and nitrogen (N), and more preferably contains non-transition metal (M2), oxygen (O) and nitrogen (N).

Here, the non-transition metal (M2) -containing layer C preferably contains the non-transition metal (M2) in the form of an oxide, a nitride, an oxynitride, an oxycarbide, or the like. (Composition SiO _x ), oxynitride (composition SiO _x N _y ) or oxycarbide (composition SiO _x C _y ), and more preferably Si oxide (composition SiO _x ) or acid More preferably, it is contained in the form of a nitride (composition SiO _x N _y ).

  The chemical composition of the non-transition metal (M2) -containing layer C can be measured by measuring the atomic composition ratio using an XPS (X-ray Photoelectron Spectroscopy) surface analyzer. Alternatively, the non-transition metal (M2) -containing layer C is cut, and the cut surface can be measured by measuring the atomic composition ratio with an XPS surface analyzer. The chemical composition of the non-transition metal (M2) -containing layer is determined by the type and amount of the raw material used for forming the non-transition metal (M2) -containing layer C, and when forming or modifying the coating layer. Can be controlled according to the conditions described above.

  The content of the metal compound such as the metal oxide contained in the non-transition metal (M2) -containing layer C is not particularly limited, but is 50% by mass or more based on the total mass of the non-transition metal (M2) -containing layer C. Is preferably 80% by mass or more, more preferably 95% by mass or more, particularly preferably 98% by mass or more, and 100% by mass (that is, non-transition metal (M2 )) The containing layer C is most preferably made of a metal compound.

  The thickness of the non-transition metal (M2) -containing layer C is not particularly limited, but is preferably from 10 to 500 nm, and more preferably from 30 to 300 nm, from the viewpoint of gas barrier properties.

  As a method for forming the non-transition metal (M2) -containing layer C, a conventionally known film forming method can be applied, but a vacuum film forming method such as a physical vapor deposition (PVD) method or a chemical vapor deposition (CVD) method is used. Or a method of forming a coating film formed by applying a liquid containing a metal compound, preferably a liquid containing a silicon compound, by modifying the coating film (hereinafter, also simply referred to as a coating method).

  Hereinafter, the vacuum film forming method and the coating method will be described.

(Vacuum deposition method)
The physical vapor deposition (PVD) method is a method in which a target substance, for example, a thin film such as a carbon film is deposited on the surface of a substance in a vapor phase by a physical method. , An RF sputtering method, an AC sputtering method, an ion beam sputtering method, a magnetron sputtering method, etc.), a vacuum evaporation method, an ion plating method, and the like.

  The sputtering method is a method in which a target is placed in a vacuum chamber, and a rare gas element (usually argon) ionized by applying a high voltage is caused to collide with the target, thereby repelling atoms on the surface of the target and attaching the target to a substrate. . At this time, a reactive sputtering method may be used in which an element which is repelled from a target by an argon gas is reacted with nitrogen or oxygen to form an inorganic layer by flowing a nitrogen gas or an oxygen gas into the chamber. .

  The chemical vapor deposition (CVD) method is a method in which a raw material gas containing a component of a target thin film is supplied onto a base material, and the film is deposited by a chemical reaction on the base material surface or in a gas phase. In addition, there is a method of generating plasma or the like for the purpose of activating a chemical reaction, and known CVD methods such as a thermal CVD method, a catalytic chemical vapor deposition method, a photo CVD method, a vacuum plasma CVD method, and an atmospheric pressure plasma CVD method. System and the like. Although not particularly limited, it is preferable to apply a plasma CVD method from the viewpoint of a film formation rate and a processing area.

  The non-transition metal (M2) -containing layer C obtained by a vacuum plasma CVD method or a plasma CVD method at an atmospheric pressure or a pressure near the atmospheric pressure includes a metal compound as a raw material (also referred to as a raw material), a decomposition gas, a decomposition temperature, It is preferable to select conditions such as the input power because the target compound can be produced. For details of the conditions for forming the non-transition metal (M2) -containing layer C by the plasma CVD method, for example, the conditions described in paragraphs [0033] to [0051] of WO2012 / 067186 may be appropriately adopted. it can. The non-transition metal (M2) -containing layer formed by such a method is preferably a layer containing an oxide, a nitride, an oxynitride, or an oxycarbide.

(Coating method)
The non-transition metal (M2) -containing layer C according to the present invention is formed, for example, by further modifying a coating film formed by applying a liquid containing a metal compound, preferably a liquid containing a silicon compound. It may be formed by a method (coating method). Hereinafter, a silicon compound will be described as an example of the metal compound.

(Silicon compound)
The silicon compound is not particularly limited as long as a coating solution containing the silicon compound can be prepared. For example, polysilazane compounds, polysiloxane compounds, silazane compounds, aminosilane compounds, silylacetamide compounds, silylimidazole compounds, and other nitrogen-containing silicon compounds are used.

(Polysilazane compound)
In the present invention, a polysilazane compound (also simply referred to as polysilazane) is a polymer having a silicon-nitrogen bond. Specifically, Si-N in the structure, Si-H, having a bond such as _{N-H, SiO 2, Si} 3 N 4, and both the intermediate solid solution _SiO x _{N y} preceramic inorganic, such as It is a polymer.

  Examples of the polysilazane compound are not particularly limited, and are disclosed, for example, in paragraphs [0043] to [0058] of JP-A-2013-022799 and paragraphs [0038] to [0056] of JP-A-2013-226758. Are adopted as appropriate.

  The polysilazane compound is commercially available in the form of a solution dissolved in an organic solvent. Commercially available polysilazane solutions include NN120-10, NN120-20, NAX120-20, NN110, and NN310 manufactured by AZ Electronic Materials Co., Ltd. , NN320, NL110A, NL120A, NL120-20, NL150A, NP110, NP140, SP140 and the like.

  Other examples of the polysilazane compound include, for example, a silicon alkoxide-added polysilazane obtained by reacting a silicon alkoxide with the above-mentioned polysilazane (JP-A-5-238827), and a glycidol-added polysilazane obtained by reacting glycidol (JP-A-6-208). JP-A-122852), an alcohol-added polysilazane obtained by reacting an alcohol (JP-A-6-240208), and a metal carboxylate-added polysilazane obtained by reacting a metal carboxylate (JP-A-6-299118). ), An acetylacetonate complex-added polysilazane obtained by reacting a metal-containing acetylacetonate complex (JP-A-6-306329), and a metal-particle-added polysilazane obtained by adding metal particles (JP-A-7-196986). Gazette Such include polysilazane compounds ceramic at low temperatures.

  Among them, polysilazanes such as perhydropolysilazane and organopolysilazane are preferable, and perhydropolysilazane is particularly preferable, from the viewpoints of low film forming properties, few defects such as cracks, and low residual organic matter.

  When polysilazane is used, the content of polysilazane in the non-transition metal (M2) -containing layer C before the modification treatment is 100 mass% when the total mass of the non-transition metal (M2) -containing layer C is 100 mass%. %. When the non-transition metal (M2) -containing layer C contains a material other than polysilazane, the content of polysilazane in the layer is preferably in the range of 10 to 99% by mass, and more preferably 40 to 95% by mass. Is more preferably within the range, particularly preferably within the range of 70 to 95% by mass.

  The method of forming the non-transition metal (M2) -containing layer C by a coating method as described above is not particularly limited, and a known method can be applied. However, the non-transition metal containing a silicon compound and, if necessary, a catalyst in a solvent. It is preferable to apply the coating liquid for forming the (M2) -containing layer C by a known wet coating method, evaporate and remove the solvent, and then perform a modification treatment.

  The solvent is not particularly limited as long as it can dissolve the compound containing the non-transition metal (M2). However, when polysilazane is used as the compound containing the non-transition metal (M2), it does not contain water and a reactive group (for example, a hydroxyl group or an amine group) which easily react with polysilazane. An inert organic solvent is preferred, and an aprotic organic solvent is more preferred. Specifically, examples of the solvent include aprotic solvents; for example, hydrocarbons such as aliphatic hydrocarbons, alicyclic hydrocarbons, and aromatic hydrocarbons such as pentane, hexane, cyclohexane, toluene, xylene, solvesso, and terpenes. Hydrogen solvents; halogen hydrocarbon solvents such as methylene chloride and trichloroethane; esters such as ethyl acetate and butyl acetate; ketones such as acetone and methyl ethyl ketone; dibutyl ether, dioxane, tetrahydrofuran, mono- and polyalkylene glycol dialkyl ethers (diglymes ) And ethers such as alicyclic ethers. The solvent is selected depending on the purpose such as the solubility of polysilazane and the evaporation rate of the solvent, and may be used alone or in the form of a mixture of two or more.

  The concentration of the compound containing the non-transition metal (M2) in the coating solution is not particularly limited, and varies depending on the thickness of the non-transition metal (M2) -containing layer C and the pot life of the coating solution. %, More preferably 4 to 50% by mass.

  As the catalyst, a basic catalyst is preferable, and particularly, an amine catalyst, a metal catalyst such as a Pt compound, a Pd compound, and a Rh compound, and an N-heterocyclic compound are exemplified. Among these, it is preferable to use an amine catalyst. The amine catalyst is not particularly limited, but for example, N, N, N ', N'-tetramethyl-1,6-diaminohexane and the like can be used. At this time, the concentration of the catalyst to be added is preferably 0.1 to 10% by mass, more preferably 0.1 to 7% by mass, based on the compound containing the non-transition metal (M2) in the coating solution. Range. By setting the catalyst addition amount in this range, excessive silanol formation due to rapid progress of the reaction, a decrease in film density, an increase in film defects, and the like can be avoided.

(Modification of non-transition metal (M2) -containing layer C formed by coating method)
The modification treatment of the non-transition metal (M2) -containing layer C formed by the coating method refers to a conversion reaction of a silicon compound into silicon oxide or silicon oxynitride.

  For the conversion reaction of the silicon compound into silicon oxide or silicon oxynitride, a known method can be appropriately selected and applied. Specific examples of the modification treatment include a plasma treatment, an ultraviolet irradiation treatment, and a heat treatment. However, in the case of modification by heat treatment, since formation of a silicon oxide film or a silicon oxynitride layer by a substitution reaction of a silicon compound requires a high temperature of 450 ° C. or more, it is difficult to apply the method to a flexible substrate such as plastic. . Therefore, the heat treatment is preferably performed in combination with another reforming treatment.

  Therefore, as the reforming treatment, from the viewpoint of adaptation to a plastic substrate, a conversion reaction by a plasma treatment or an ultraviolet irradiation treatment capable of a conversion reaction at a lower temperature is preferable, a conversion reaction by an ultraviolet irradiation treatment is more preferable, and a vacuum ultraviolet ray is preferable. A conversion reaction by irradiation treatment is more preferred.

(Heat treatment)
By performing the heat treatment on the coating film containing the silicon compound in combination with another modification treatment, preferably an excimer irradiation treatment described below, the modification treatment can be performed efficiently.

  The heating conditions are preferably in the range of 50 to 300 ° C., more preferably 70 to 200 ° C., preferably 0.005 to 60 minutes, more preferably 0.01 to 10 minutes. By performing the drying operation, condensation is performed, and the non-transition metal (M2) -containing layer C can be formed.

  Examples of the heat treatment include a method in which the base material is brought into contact with a heating element such as a heat block to heat the coating film by heat conduction, a method in which the atmosphere is heated by an external heater using a resistance wire or the like, an infrared region such as an IR heater. And the like, but the method is not particularly limited. Further, a method capable of maintaining the smoothness of the coating film containing the silicon compound may be appropriately selected.

(Vacuum ultraviolet irradiation treatment: excimer irradiation treatment)
The most preferred modification treatment method is treatment by irradiation with vacuum ultraviolet rays (excimer irradiation treatment). The treatment by vacuum ultraviolet irradiation uses light energy of 100 to 200 nm, which is larger than the interatomic bonding force in the polysilazane compound, and preferably uses light energy of a wavelength of 100 to 180 nm. In this method, a silicon oxide film is formed at a relatively low temperature (about 200 ° C. or lower) by causing an oxidation reaction with active oxygen or ozone to proceed while cutting directly. When performing the excimer irradiation treatment, it is preferable to use the heat treatment together as described above, and the details of the heat treatment conditions at that time are as described above.

  The radiation source may be any that emits light at a wavelength of 100-180 nm, but is preferably an excimer radiator (eg, a Xe excimer lamp) having a maximum emission at about 172 nm, and a low-pressure mercury vapor having a bright line at about 185 nm. Lamps, medium- and high-pressure mercury vapor lamps with wavelength components below 230 nm, and excimer lamps with a maximum emission at about 222 nm.

  Among them, the Xe excimer lamp emits ultraviolet light having a short wavelength of 172 nm at a single wavelength, and thus has excellent luminous efficiency. Since this light has a large oxygen absorption coefficient, a very small amount of oxygen can generate radical oxygen atom species and ozone at a high concentration.

  It is known that the energy of light having a short wavelength of 172 nm has a high ability to dissociate the bond of an organic substance. The high energy of the active oxygen, ozone and ultraviolet radiation enables the polysilazane coating to be modified in a short time.

  The excimer lamp has a high light generation efficiency, and can be turned on by inputting low power. In addition, since long-wavelength light that causes a temperature rise due to light is not emitted, and energy is irradiated in the ultraviolet region, that is, at a short wavelength, the surface temperature of the object to be fired is prevented from rising. . Therefore, it is suitable for a flexible film material such as polyethylene terephthalate (PET) which is considered to be easily affected by heat. Generally, when the substrate temperature at the time of the vacuum ultraviolet irradiation treatment is 150 ° C. or more, when a resin substrate is used as a substrate, the substrate is deformed or its strength is deteriorated. Will be impaired. However, in the case of a film having high heat resistance such as polyimide, a modification treatment at a higher temperature is possible. Therefore, there is no general upper limit for the temperature of the substrate during the irradiation of the vacuum ultraviolet rays, and the temperature can be appropriately set depending on the type of the substrate.

  Oxygen is necessary for the reaction during irradiation with vacuum ultraviolet rays, but vacuum ultraviolet rays are absorbed by oxygen and the efficiency of the ultraviolet irradiation step is likely to decrease. It is preferable to carry out the reaction in a state where the water vapor concentration is low. That is, the oxygen concentration at the time of vacuum ultraviolet irradiation is preferably in the range of 10 to 20,000 ppm by volume, and more preferably in the range of 50 to 10000 ppm by volume. Also, the steam concentration during the conversion process is preferably in the range of 1000-4000 ppm by volume.

  The gas used for vacuum ultraviolet irradiation that satisfies the irradiation atmosphere is preferably a dry inert gas, and particularly preferably a dry nitrogen gas from the viewpoint of cost. The oxygen concentration can be adjusted by measuring the flow rates of the oxygen gas and the inert gas introduced into the irradiation chamber and changing the flow rate ratio.

In vacuum ultraviolet irradiation step, preferably the illuminance of the vacuum ultraviolet rays in the coated surface of the polysilazane coating film is subjected is in the range of ^{1mW / cm 2 ~10W / cm 2} , in the range of from 30~200mW / cm ² More preferably, it is more preferably in the range of 50 to 160 mW / cm ² . If it is 1 mW / cm ² or more, sufficient reforming efficiency can be obtained, and if it is 10 W / cm ² or less, abrasion does not easily occur in the coating film and the substrate is hardly damaged.

Irradiation energy amount of the VUV in the coated surface (integrated quantity of light) is preferably in the range of 10 to 10000 mJ / cm ^2, more preferably in the range of 100~8000mJ / cm ^2, 200~6000mJ / Cm ² is more preferably within the range. If it is 10 mJ / cm ² or more, the modification can proceed sufficiently. If it is 10,000 mJ / cm ² or less, cracks due to excessive reforming and thermal deformation of the base material are unlikely to occur.

Further, the vacuum ultraviolet light used for the reforming may be generated by a plasma formed of a gas containing at least one of CO, CO ₂ and CH ₄ . Further, as a gas containing at least one of CO, CO ₂ and CH ₄ (hereinafter also referred to as a carbon-containing gas), a carbon-containing gas may be used alone, but a rare gas or H ₂ is used as a main gas. It is preferable to add a small amount of a carbon-containing gas. As a plasma generation method, a capacitively coupled plasma or the like can be given.

  In addition, the vacuum ultraviolet irradiation is applicable to both batch processing and continuous processing, and can be appropriately selected depending on the shape of the base material to be used.

  When the non-transition metal (M2) -containing layer C has a laminated structure of two or more layers, the non-transition metal (M2) -containing layer C may be composed of only a layer formed by a vacuum film formation method, or may be a coating method. Or a combination of a layer formed by a vacuum film forming method and a layer formed by a coating method.

(Oxygen deficiency area)
In a preferred embodiment of the present invention, the metal (M) -containing layer A is a transition metal (M1) -containing layer, and the metal (M) -containing layer A and the non-transition metal (M2) -containing layer C are adjacent to each other. when representing the composition in _{(M2) (M1) x O} y N z (0.02 <x <50, y> 0, z ≧ 0), satisfies the following formula (1), in the manufacturing method of the functional film is there.

(2y + 3z) / (a + bx) <1 Expression (1)
(In the formula (1), a represents the maximum valence of the non-transition metal (M2), and b represents the maximum valence of the transition metal (M1).)
The composition in the region where the transition metal (M1) layer, which is the metal (M) -containing layer A, and the non-transition metal (M2) -containing layer C are adjacent (hereinafter, also referred to as a mixed region) is (M2) (M1) _xO. when expressed in _{y N z (0.02 <x <} 50, y> 0, z ≧ 0), is preferably a method of manufacturing a functional film satisfying the following formula (1).

  This is because, in a region where the transition metal (M1) layer, which is the metal (M) -containing layer A, and the non-transition metal (M2) -containing layer C are adjacent to each other, the composite of the transition metal (M1) and the non-transition metal (M2) It indicates that the oxygen deficiency composition of the oxide is contained over a predetermined thickness or more.

As described above, the composition of the composite oxide of transition metal (M1) and non-transition metals (M2), represented by _{(M2) (M1) x O} y N z. As is apparent from this composition, the composite oxide may partially include a nitride structure. Here, the maximum valence of the non-transition metal (M2) is a, the maximum valence of the transition metal (M1) is b, the valence of O is 2, and the valence of N is 3.

  When the composite oxide (including a partially nitrided oxide) has a stoichiometric composition, (2y + 3z) / (a + bx) = 1. This formula means that the total number of the bonds of the transition metal (M1) and the non-transition metal (M2) and the total number of the bonds of O and N are the same, and in this case, the transition metal (M1) and Both the non-transition metal (M2) is bonded to either O or N. In this specification, when two or more kinds are used in combination as the non-transition metal (M2) or when two or more kinds are used in combination as the transition metal (M1), the maximum valence of each element is set to each element. The composite valence calculated by weighted averaging based on the existence ratio of is used as the values of a and b of the “maximum valence”.

  On the other hand, when (2y + 3z) / (a + bx) <1.0, the total number of O and N bonds is insufficient with respect to the total number of bonds of the transition metal (M1) and the non-transition metal (M2). This state is "oxygen deficiency" of the composite oxide. In the oxygen-deficient state, the remaining bonds of the transition metal (M1) and the non-transition metal (M2) have a possibility of bonding to each other, and the transition metal (M1) and the non-transition metal (M2) It is considered that, when is directly bonded, a denser and denser structure is formed than in the case where O and N are bonded between metals, and as a result, gas barrier properties are improved.

  The mixed region is a region satisfying 0.02 <x <50. In this region, since both the transition metal (M1) and the non-transition metal (M2) participate in the direct bonding between metals, the region satisfying this condition exists with a thickness equal to or more than a predetermined value, so that the gas barrier property can be improved. It is thought to contribute to the improvement of

  Note that it is considered that the closer the abundance ratio of the transition metal (M1) and the non-transition metal (M2) is, the more the gas barrier property can be improved. Therefore, the mixed region is a region satisfying 0.1 <x <10. Is preferably contained in a thickness of 5 nm or more, more preferably a region satisfying 0.2 <x <5 is included in a thickness of 5 nm or more, and a region satisfying 0.3 <x <4 is included in a thickness of 5 nm or more. More preferably, it is included.

  As described above, it was confirmed that if there was a mixed region satisfying (2y + 3z) / (a + bx) <1.0, the effect of improving gas barrier properties was exhibited. The maximum value preferably satisfies (2y + 3z) / (a + bx) ≦ 0.9, more preferably satisfies (2y + 3z) / (a + bx) ≦ 0.85, and (2y + 3z) / (a + bx) ≦ 0.8 It is more preferable to satisfy the following.

  Here, as the value of (2y + 3z) / (a + bx) in the mixed region decreases, the effect of improving gas barrier properties increases, but absorption of visible light also increases. Therefore, in the case of a functional film used for an application where transparency is desired, the minimum value in the mixed region is preferably (2y + 3z) / (a + bx) ≧ 0.2, and (2y + 3z) / ( (a + bx) ≧ 0.3 is more preferable, and (2y + 3z) / (a + bx) ≧ 0.4 is more preferable.

The thickness of the mixed region where good gas barrier properties can be obtained is preferably 5 nm or more, more preferably 8 nm or more, and more preferably 10 nm or more, as the sputtering thickness in terms of SiO _2. It is particularly preferably at least 20 nm.

  The functional film having the above-described configuration exhibits a very high gas barrier property that can be used as a substrate for an electronic device such as an organic EL device.

  Here, as a result of various studies by the present inventors, it was found that a functional film was formed using the oxygen-deficient composition film of the compound (oxide) of the transition metal (M1) alone, or the non-transition metal (M2) When a functional film is formed by using an oxygen-deficient composition film of a compound (oxide) alone, the gas barrier property tends to improve as the degree of oxygen deficiency increases. Did not connect. In response thereto, a transition metal (M1) -containing layer, which is a metal (M) -containing layer A containing a compound (oxide) containing a transition metal (M1) as a main component, and a non-transition metal (M2) as a main component. A non-transition metal (M2) -containing layer C containing a compound (oxide) to form a mixed region in which the transition metal (M1) and the non-transition metal (M2) are simultaneously present, and further, the mixed region It has been found that when the oxygen deficiency composition is used, the gas barrier property is further improved as the degree of oxygen deficiency increases.

  This is because, as described above, the bond between the transition metal (M1) and the non-transition metal (M2) is more likely to occur than the bond between the transition metals (M1) and the bond between the non-transition metals (M2). Then, it is considered that a dense and high-density structure is formed in the mixed region by setting the mixed region to the oxygen deficiency composition.

  Based on the findings described above, the present inventor satisfies 0.02 <x <50, which is a condition for both the transition metal (M1) and the non-transition metal (M2) to participate in direct bonding between metals. By changing the thickness of the oxygen deficiency composition of the composite oxide of the transition metal (M1) and the non-transition metal (M2), a study was made on a critical thickness at which an effect of improving gas barrier properties was observed. As a result, as described above, it was confirmed that when the thickness was 5 nm or more, a very remarkable effect of improving gas barrier properties was observed.

  The method for producing the above-mentioned mixed region is not particularly limited. For example, a transition metal (M1) layer, which is a metal (M) -containing layer A, is formed on the exposed surface of the non-transition metal (M2) -containing layer C by vapor phase. A method of forming a non-transition metal (M2) -containing layer C by implanting a transition metal (M1) having kinetic energy into the non-transition metal (M2) -containing layer C, or a method of forming a transition metal ( M1) A method of forming a layer or a method of forming the non-transition metal (M2) -containing layer C by co-evaporation.

  Among these, a method of forming a transition metal (M1) layer, which is a metal (M) -containing layer A, on the exposed surface of the non-transition metal (M2) -containing layer C by vapor deposition is used. Is more preferable, and such a vapor-phase film formation is more preferably a sputtering method. The film-forming conditions for the metal (M) -containing layer A in this method include the ratio of the transition metal (M1) alone or the transition metal (M1) compound and oxygen in the film-forming raw material, the inert gas during the film formation, and the reactivity. One or two or more conditions selected from the group consisting of the ratio with the gas, the supply amount of the gas at the time of film formation, the degree of vacuum at the time of film formation, the power at the time of film formation, and the film formation time are exemplified. By adjusting the film formation conditions (preferably, the oxygen partial pressure), a thin film made of a composite oxide having a desired oxygen deficiency composition can be formed with a desired film thickness.

The non-transition metal (M2) -containing layer C is preferably formed under a composition and under conditions such that the water vapor permeability (WVTR) of the functional film is less than 5 g / m ² · day, and 1 g / m ² · day. preferably formed by a the compositional and conditions below, 5 × ¹⁰ -1 it is more preferable to form the composition and conditions such that ^{g /} m less than ^{2 · day, 1 × 10 -1} g / m More preferably, it is formed under the composition and condition of less than ² · day, and even more preferably, it is formed under the composition and condition of less than 5 × 10 ⁻² g / m ² · day. It is particularly preferable to form the film under the composition and under the condition of less than ^-2 g / m ² · day. The lower limit of the water vapor permeability is not particularly limited because the lower the water vapor permeability, the more preferable the water vapor permeability is, for example, from 1 × 10 ⁻⁶ g / m ² · day or more from the viewpoint of productivity. . When the functional film is a gas barrier film, the gas barrier property can be evaluated by water vapor permeability (WVTR). The water vapor transmission rate (WVTR) (g / m ² · day) was measured by the MOCON method using a MOCON water vapor transmission rate measuring device Aquatran (manufactured by MOCON) under an environment of a temperature of 38 ° C. and a relative humidity of 100% RH. It can be evaluated by value. The detailed method of measuring the water vapor permeability is described in Examples.

<Step of hydrophilizing the surface of metal (M) -containing layer A>
One preferred embodiment of the present invention is that, after the step of forming the metal (M) -containing layer A by vapor phase film formation, and before the step of forming the organosilicon compound-containing layer B having a polymerizable substituent by vapor phase film formation. The method for producing a functional film further includes a step of hydrophilizing the surface of the metal (M) -containing layer A.

  In the production method according to the present invention, as described above, the step of forming the organosilicon compound-containing layer B needs to be performed by continuous vapor deposition.

  Accordingly, the environment from the end of the step of forming the metal (M) -containing layer A to the start of the step of forming the organosilicon compound-containing layer B is also kept in a vacuum state. Processing needs to be performed. Accordingly, the step of hydrophilizing the surface of the metal (M) -containing layer A is also performed while maintaining the vacuum state.

  In the present invention, from the effect of continuous vapor deposition, good adhesion can be obtained without the need for treatment of the surface of the metal (M) -containing layer A. By further including a step of hydrophilizing, a more excellent adhesive property can be obtained. The reason for this is that the substituent that interacts with the metal (M) -containing layer A of the organosilicon compound between the constituent material of the metal (M) -containing layer A by the hydrophilic treatment of the surface of the metal (M) -containing layer A As a result, the polymerizable substituent is more likely to be exposed from the surface of the organosilicon compound-containing layer B having the polymerizable substituent on the side opposite to the side in contact with the metal (M) -containing layer A. I guess. It is speculated that this is because the effect of improving the adhesion between the organosilicon compound-containing layer and the adjacent member to which the functional film is applied, for example, the resin layer, due to the interaction is further enhanced.

  The surface hydrophilic treatment method is not particularly limited, and a known method can be appropriately used, and examples thereof include an oxygen plasma treatment, a corona treatment, an excimer (vacuum ultraviolet) treatment, and a UV ozone treatment. Among these, corona treatment is preferred. There is no particular limitation on the specific method for performing the surface hydrophilization treatment, and conventionally known knowledge can be appropriately referred to.

  As an apparatus for performing the surface hydrophilization treatment, the surface hydrophilicity is maintained in a vacuum state from the end of the step of forming the metal (M) -containing layer A to the start of the step of forming the organosilicon compound-containing layer B. There is no particular limitation as long as the processing can be performed.

  For example, when the vacuum film forming machine 1 of FIG. 2 which is a preferred example of the vacuum film forming machine in the manufacturing method according to one embodiment of the present invention is used, the laminate of the base material 8 and the metal (M) -containing layer A 9 is Further, it is sent to the surface hydrophilization treatment area in the rotation direction indicated by the arrow 4 and the surface hydrophilization treatment can be performed using the surface hydrophilization treatment device 6.

  Hereinafter, the method and conditions of the surface hydrophilization treatment are not particularly limited, and known methods and conditions can be appropriately used. In the surface hydrophilization treatment, the pressure (vacuum degree) of the chamber, the type and temperature of the film forming drum (also referred to as a film forming roller), and the transfer speed of the substrate are set to the same conditions as in the above-described sputtering method. Is preferred. However, the present invention is not limited to this.

<Process for forming other layers>
In the manufacturing method according to one embodiment of the present invention, other layers are formed in portions other than between the metal (M) -containing layer A and the organosilicon compound-containing layer B, which must have a direct contact configuration. The method may further include a step.

  The position where the other layer is formed is, for example, between the base material and the metal (M) -containing layer A, or between the metal (M) -containing layer A when a plurality of metal (M) -containing layers A are present. When a plurality of non-transition metal (M2) -containing layers C are present, the surface between the non-transition metal (M2) -containing layers C or the side of the base material on which the metal (M) -containing layer A is not formed is formed. No.

(Underlayer (smooth layer, primer layer) formation step)
The manufacturing method according to one embodiment of the present invention may further include, for example, a step of forming an underlayer (smooth layer, primer layer) between the base material and the metal (M) -containing layer A.

  The underlayer is flattened to flatten the rough surface of the substrate on which the projections and the like are present, or to fill the unevenness and pinholes generated in the metal (M) -containing layer A by the projections on the substrate. It is provided for. Such an underlayer may be formed of any material, but preferably contains a carbon-containing polymer, and more preferably is composed of a carbon-containing polymer. That is, the functional film of the present invention preferably further has an underlayer containing a carbon-containing polymer between the substrate and the metal (M) -containing layer A.

  The underlayer contains a carbon-containing polymer, preferably a curable resin. The curable resin is not particularly limited, and the active energy ray-curable resin obtained by irradiating the active energy ray-curable material or the like with active energy rays such as ultraviolet rays and curing the same or a thermosetting material is heated. And a thermosetting resin obtained by curing. The curable resins may be used alone or in combination of two or more.

  As the active energy ray-curable material used for forming the underlayer, specifically, a UV-curable organic / inorganic hybrid hard coat material OPSTAR (registered trademark) series manufactured by JSR Corporation (a polymerizable unsaturated group is added to silica fine particles) A compound obtained by bonding an organic compound having the formula (1), for example, Z7501 or the like. Specific examples of thermosetting materials include Tutprom Series (organic polysilazane) manufactured by Clariant, SP COAT heat-resistant clear paint manufactured by Ceramic Coat, Nano Hybrid Silicone manufactured by Adeka, and DIC Co., Ltd. Unidick (registered trademark) V-8000 series, EPICLON (registered trademark) EXA-4710 (ultra-high heat-resistant epoxy resin), silicon resin X-12-2400 (trade name) manufactured by Shin-Etsu Chemical Co., Ltd., Nitto Boseki stock Inorganic / organic nanocomposite material SSG coated by company, thermosetting urethane resin composed of acrylic polyol and isocyanate prepolymer, phenol resin, urea melamine resin, epoxy resin, unsaturated polyester resin, silicone resin, polyamideamine-epichlorohydrin Butter, and the like can be mentioned.

  The smoothness of the underlayer is a value expressed by the surface roughness specified in JIS B 0601: 2001, and the maximum sectional height Rt (p) is preferably in the range of 10 to 30 nm.

  The surface roughness is calculated from a cross-sectional curve of irregularities continuously measured by an atomic force microscope (AFM) using a detector having a stylus having a very small tip radius, and measured with a stylus having a very small tip radius. This is the roughness related to the amplitude of fine irregularities, which is measured many times in a section having a direction of several tens of μm.

  The thickness of the underlayer is not particularly limited, but is preferably in the range of 0.1 to 10 μm.

  When the underlayer contains a curable resin, curing is preferably performed by irradiation with active energy rays, and more preferably performed by irradiation with ultraviolet rays. The condition of the ultraviolet irradiation treatment is not particularly limited as long as the curing treatment can be performed, and a known method can be appropriately used.

≪Functional film≫
FIG. 3 is a schematic view showing a preferred example of a functional film manufactured by the manufacturing method according to one embodiment of the present invention.

  FIG. 4 is a schematic view showing a preferred example of a functional film manufactured by a manufacturing method according to another embodiment of the present invention.

  Hereinafter, gas barrier films manufactured by the manufacturing methods according to the two embodiments of the present invention will be described with reference to the attached drawings. In the description of the drawings, the same elements will be denoted by the same reference symbols, without redundant description. In addition, the dimensional ratios in the drawings are exaggerated for convenience of description, and may be different from the actual ratios. In addition, the functional film manufactured by the manufacturing method of the present invention is not limited to the embodiment described below.

  FIG. 3 shows a functional film 20 manufactured by the manufacturing method according to one embodiment of the present invention. The functional film 20 has a metal (M) -containing layer A 9 and an organic silicon compound-containing layer B 10 having a polymerizable substituent in contact with the metal (M) -containing layer A 9 on the base material 8.

  FIG. 4 shows a functional film 30 manufactured by the manufacturing method according to one embodiment of the present invention. The functional film 30 has a non-transition metal (M2) -containing layer C11, a metal (M) -containing layer A9, and a polymerizable substituent in contact with the metal (M) -containing layer A9 on the base material 8. An organic silicon compound-containing layer B10. Such a functional film 30 has a configuration having a non-transition metal (M2) -containing layer C11, and this configuration is a preferable configuration as a gas barrier film.

  FIGS. 3 and 4 show an example in which the polymerizable substituent of the organosilicon compound having a polymerizable substituent is an acryloyl group.

  Here, the definitions and preferred examples of each term are the same as those described for the formation of each layer.

  When the film produced by the method for producing a functional film according to one embodiment of the present invention is a gas barrier film, the metal (M) -containing layer A is a transition metal (M1) -containing layer from the viewpoint of improving gas barrier properties. And before the step of forming the metal (M) -containing layer A by vapor phase film formation, it is arranged between the base material and the metal (M1) -containing layer A and is in contact with the metal (M) -containing layer A. Preferably, the functional film further includes a step of forming the non-transition (M2) -containing layer C.

In addition, from the same viewpoint, the composition in the region where the metal (M) -containing layer A is a transition metal (M1) -containing layer and the metal (M) -containing layer A and the non-transition metal (M2) -containing layer C are adjacent to each other. when expressed in the _{(M2) (M1) x O} y N z (0.02 <x <50, y> 0, z ≧ 0), satisfies the following formula (1), produced by the method for producing a functional film It is more preferable that the functional film is a functional film.

(2y + 3z) / (a + bx) <1 Expression (1)
(In the formula (1), a represents the maximum valence of the non-transition metal (M2), and b represents the maximum valence of the transition metal (M1).)
Here, in order to exhibit particularly excellent gas barrier properties, it is more preferable to have a region satisfying the following formula (1) at 5 nm or more. The upper limit of the region satisfying the above formula (1) is not particularly limited, but is preferably 500 nm or less, more preferably 300 nm or less, and furthermore, optical characteristics, from the viewpoint of compatibility with other physical properties. From the viewpoint of (light transmittance), the thickness is particularly preferably 15 nm or less.

隣接 Adjacent member to which functional film is applied 適用
The field to which the functional film manufactured by the manufacturing method according to one embodiment of the present invention is applied is not particularly limited, but includes, for example, food, industrial supplies, packaging of pharmaceuticals, a liquid crystal display element, a photoelectric conversion element, and an organic material. Organic electronic devices, such as an electroluminescence element, can be used.

  Here, the functional film manufactured by the manufacturing method according to an embodiment of the present invention is particularly effective when the adjacent member to which the functional film is applied is a QD-containing resin layer (light emitting layer). Can be obtained. In this case, the functional film is particularly preferably a gas barrier film from the viewpoint of preventing the QD-containing resin layer (light-emitting layer) from being deteriorated by water or oxygen.

(QD-containing resin layer (light-emitting layer))
Hereinafter, a quantum dot (QD), a resin, and the like, which are main components of the QD-containing resin layer, will be described.

(Quantum dot)
In general, semiconductor nanoparticles having a quantum confinement effect in a nanometer-sized semiconductor material are also referred to as “quantum dots”. Such a quantum dot is a small lump of about several tens of nanometers in which several hundred to thousands of semiconductor atoms are collected. When the quantum dot reaches an energy excited state by absorbing light from an excitation source, the energy of the quantum dot becomes large. Emit energy corresponding to the band gap.

  Therefore, it is known that quantum dots have unique optical properties due to the quantum size effect. Specifically, (1) it is possible to emit various wavelengths and colors by controlling the size of the particles, and (2) it is possible to emit fine particles of various sizes with excitation light having a wide absorption band and a single wavelength. It can emit light, (3) it has a good symmetric fluorescence spectrum, and (4) it has excellent durability and fading resistance as compared with organic dyes.

  The quantum dots contained in the QD-containing resin layer may be known, and can be produced using any method known to those skilled in the art. For example, suitable QDs and methods for forming suitable QDs include U.S. Patent No. 6,225,198, U.S. Patent Application Publication No. 2002/0066401, U.S. Patent Nos. 6,207,229, and 6,322,901. No. 6,949,206, No. 7,572,393, No. 7,267,865, No. 7,374,807, U.S. Patent Application No. 11 / 299,299, and U.S. Patent No. 6,861,155. One.

  The quantum dots are made from any suitable material, preferably an inorganic material, and more preferably an inorganic conductor or semiconductor material. Suitable semiconductor materials include any type of semiconductor, including II-VI, III-V, IV-VI and IV semiconductors.

Suitable semiconductor materials include Si, Ge, Sn, Se, Te, B, C (including diamond), P, BN, BP, BAs, AlN, AlP, AlAs, AlSb, GaN, GaP, GaAs, GaSb. , InN, InP, InAs, InSb, AlN, AlP, AlAs, AlSb, GaN, GaP, GaAs, GaSb, ZnO, ZnS, ZnSe, ZnTe, CdS, CdSe, CdSeZn, CdTe, HgS, HgSe, HgTe, BeSe , BeTe, MgS, MgSe, GeS , GeSe, GeTe, SnS, SnSe, SnTe, PbO, PbS, PbSe, PbTe, CuF, CuCl, CuBr, CuI, Si 3 N 4, Ge 3 N 4, Al 2 O 3, _{(Al, Ga, In) 2} (S, Se, Te) 3, Al 2 O, and two or more but include suitable combination of such semiconductor, and the like.

  Further, the following core / shell type quantum dots, for example, CdSe / ZnS, InP / ZnS, PbSe / PbS, CdSe / CdS, CdTe / CdS, CdTe / ZnS and the like can also be preferably used.

(resin)
For the QD-containing resin layer, a binder resin can be used as a binder for holding the quantum dots. For example, polycarbonate, polyarylate, polysulfone (including polyethersulfone), polyester such as polyethylene terephthalate and polyethylene naphthalate, polyethylene, polypropylene, cellophane, cellulose diacetate, cellulose triacetate, cellulose acetate Cellulose ester such as pionate, cellulose acetate butyrate, polyvinylidene chloride, polyvinyl alcohol, ethylene vinyl alcohol, syndiotactic polystyrene, norbornene, polymethylpentene, polyetherketone, polyetherketoneimide Resins, polyamide resins, fluororesins, nylon resins, acrylic resins such as polymethyl (meth) acrylate, epoxy resins, etc. It is possible. Among these, an acrylic resin or an epoxy resin is preferable from the viewpoints of retention of quantum dots, prevention of deterioration, and productivity.

  As the binder resin, a resin precursor such as a monomer or an oligomer may be used and cured later, or the resin itself may be contained, but it is preferable to use a resin precursor.

  As the binder resin, for example, pentaerythritol diacrylate which is an acrylic resin precursor can be used in the case of an acrylic resin, and in the case of an epoxy resin, for example, Epotech (registered trademark) OG-142 (Epotech) And the like can be used.

  In addition, the binder resin, as a combination with the organosilicon compound having a polymerizable substituent, is preferably a resin that can chemically react with the organosilicon compound having a polymerizable substituent, the resin precursor has It is more preferable that the polymerizable substituent of the organosilicon compound having a polymerizable substituent and the polymerizable substituent is capable of undergoing a polymerization reaction, and has a polymerizable substituent and a polymerizable substituent of the resin precursor. More preferably, the polymerizable substituents of the organosilicon compound are the same substituent.

  The QD-containing resin layer preferably has a thickness in the range of 50 to 200 μm.

  The content of the quantum dots in the QD-containing resin layer varies depending on the compound to be used, but is generally preferably in the range of 15 to 60% by volume.

(Production method of QD-containing laminated member)
Another aspect of the present invention is to provide a method for producing a QD-containing laminated member including a functional film and a QD-containing resin layer.

  The method for forming the QD-containing laminated member is not particularly limited, and a coating solution for forming a light-emitting layer containing quantum dots, a binder resin and a solvent is provided on the organic silicon compound-containing layer B having a polymerizable substituent of the functional film. It is preferable that the method includes a step of forming a quantum dot-containing coating film by coating, and it is more preferable that the method further includes a step of curing the quantum dot-containing coating film.

  When the first functional film and the second functional film, which are two functional films manufactured by the manufacturing method according to one embodiment of the present invention, are used, the polymerizable substituent of the functional film is used. On the organosilicon compound-containing layer B having, in addition to the step of applying a coating solution for forming a light emitting layer containing a quantum dot, a binder resin and a solvent to form a quantum dot-containing coating film, the second functional film It is preferable that the method includes a step of arranging the organic silicon compound-containing layer side so as to be in contact with the quantum dot (QD) -containing coating film (that is, sandwiching the quantum dot (QD) -containing coating film between two functional films). It is more preferable that the method further includes a step of subsequently performing a curing treatment on the quantum dot-containing coating film.

  According to these methods, the polymerization reaction of the polymerizable substituent of the resin precursor and the polymerizable substituent of the organosilicon compound having the polymerizable substituent can be performed with higher efficiency. A QD-containing laminated member having extremely good adhesiveness with a QD can be produced.

  Further, the coating solution for forming a light emitting layer may contain a photopolymerization initiator as needed. The photopolymerization initiator is not particularly limited as long as the curing reaction of the binder resin is possible, and a known photopolymerization initiator can be used. The photopolymerization initiator is preferably a radical-based photopolymerization initiator, for example, an alkylphenone-based photopolymerization initiator and the like, and specific examples include, for example, 1-hydroxy-cyclohexyl-phenyl-ketone and the like. Out. The photopolymerization initiator may be a commercially available product, for example, Irgacure (registered trademark) 184 manufactured by BASF Japan can be used. The addition amount of the photopolymerization initiator is not particularly limited, but is preferably 0.1% by mass to 10% by mass based on the mass of the resin or the resin precursor.

  The solvent is not particularly limited as long as it can dissolve the material forming the light emitting layer forming coating solution, and a known solvent can be used. Among these, it is preferable to use toluene from the viewpoint of solubility and drying property. The solvent is preferably contained in an amount of 1% by mass to 20% by mass based on the total mass of the coating solution.

  The curing method is not particularly limited as long as the resin layer can be formed, and can be appropriately selected according to the type of the resin. Examples thereof include a heat treatment and an active energy ray irradiation treatment. Among them, it is preferable to use the active energy ray irradiation treatment, and it is more preferable to use the ultraviolet irradiation treatment from the viewpoints of productivity and less deterioration of other layers.

It The ultraviolet irradiation treatment conditions, but is not particularly limited as long as it can be to a curing treatment, the illuminance is preferably from 10~5000mW / cm ^2, the amount of irradiation energy (integrated light quantity) is 100~5000mJ / cm ² Is preferred.

  FIG. 5 is a schematic view showing a preferred example of a QD-containing laminated member manufactured by a method of manufacturing a QD-containing laminated member according to another embodiment of the present invention.

  Hereinafter, a QD-containing laminated member manufactured by a manufacturing method according to another embodiment of the present invention will be described with reference to the accompanying drawings. In the description of the drawings, the same elements will be denoted by the same reference symbols, without redundant description. In addition, the dimensional ratios in the drawings are exaggerated for convenience of description, and may be different from the actual ratios. In addition, the QD-containing laminated member manufactured by the manufacturing method of the present invention is not limited to the embodiment described below.

  FIG. 5 shows an example of a QD-containing laminated member manufactured by a manufacturing method according to another embodiment of the present invention. The QD-containing laminated member 40 includes, on the base material 8, a non-transition metal (M2) -containing layer C11, a metal (M) -containing layer A9, and a polymerizable substituent that is in contact with the metal (M) -containing layer A9. And a functional film 30 having an organic silicon compound-containing layer B10 on both sides of the QD-containing resin layer 41. Here, the metal (M) -containing layer A9 is a transition metal (M1) -containing layer.

  With such a configuration, the QD-containing laminated member 40 having good adhesion between the functional film 30 and the QD-containing resin layer 41 is obtained. In addition, the functional film 30 is formed by forming the non-transition metal (M2) -containing layer C11 with a composition and conditions having good gas barrier properties, thereby suppressing the deterioration of the quantum dots due to water or oxygen. 40. Further, the transition metal (M1) -containing layer or the non-transition metal (M2) -containing layer C11, which is the metal (M) -containing layer A9, is formed with the above-described composition and conditions for forming the oxygen-deficient region. The QD-containing laminated member 40 in which the deterioration of the quantum dots due to water and oxygen is suppressed.

  Here, the definitions and preferred examples of each term are the same as those described for the formation of each layer and the QD-containing resin layer (light-emitting layer).

The present invention will be specifically described with reference to the following Examples and Comparative Examples. However, the technical scope of the present invention is not limited only to the following examples. Unless otherwise specified, "%"
And "parts" mean "% by mass" and "parts by mass", respectively.

≫Manufacture of functional films≫
<Production of functional film 101>
(Preparation of base material)
A polyethylene terephthalate (PET) film (U34, manufactured by Toray Industries, Inc.) having a 125 μm-thick double-sided adhesive layer was used as the base material.

(Formation of underlayer)
OPSR, a UV-curable organic / inorganic hybrid hard coat material manufactured by JSR Corporation
(Registered trademark) A coating liquid obtained by diluting Z7501 with butyl acetate to a solid content concentration of 35% is applied to one of the above-mentioned base materials with a bar coater so that the dry film thickness becomes 2 μm. Drying was performed at 80 ° C. for 2 minutes. Then, in an air ^atmosphere, and subjected to ultraviolet irradiation treatment with 700mW / cm 2, 250mJ / cm 2 conditions a high pressure mercury lamp, to form a base layer. In the production of the present film, a laminated film of the substrate and the underlayer is referred to as a deposition substrate.

(Metal (M) -containing layer A forming step)
On the exposed surface of the underlying layer of the deposition substrate, using a vacuum film forming machine similar to the apparatus described in US Pat. No. 5,440,446 and US Pat. No. 7,018,713, The metal (M) -containing layer A was formed by sputtering as a vapor phase film forming method. The vacuum film forming machine used is capable of performing a sputtering process and a thermal vapor deposition process in a roll-to-roll manner while maintaining a vacuum state, and further capable of optionally providing other processes such as surface treatment. It is. In such a vacuum film forming apparatus, a plurality of types of targets can be set when performing sputtering, and a plurality of layers of different metal types can be formed continuously while maintaining a predetermined vacuum state. In addition, as a continuous vapor deposition, a thermal evaporation step can be provided before and after the sputtering step while maintaining a predetermined vacuum state. Hereinafter, the same apparatus was used as a vacuum film forming machine.

The pressure in the film forming chamber was reduced to 0.0013 Pa, and while maintaining the contact between the back surface of the base material side of the deposition base material and the film formation drum cooled to −10 ° C., the transfer speed of the deposition base material was reduced to 3 Pa. At 0.7 m / min, an alternating current power supply (AC) was used to control two pairs of cathodes, each containing a commercially available polycrystalline silicon (Si) target. During sputter deposition, a voltage signal from each power supply was used as an input for the proportional-integral-differential control loop to maintain a predetermined oxygen flow to each cathode. The AC power source uses a power of 1000 W, a film pressure of 0.19 Pa, and a gas mixture of 200 sccm of argon (Ar) and 10 sccm of oxygen (O ₂ ) to form a 10 nm thick SiO _x (x < 2) A layer was formed.

  Here, with respect to the layer thickness, data of a change in the layer thickness with respect to the film formation time is obtained, the layer thickness formed per unit time is calculated, and then the film formation time is set so as to be the set layer thickness. The layer thickness was adjusted. Hereinafter, in the film formation by sputtering, similarly, the film thickness formed per unit time is calculated, and the conditions are applied.

(Organic silicon compound-containing layer B forming step)
Immediately after the formation of the metal (M) -containing layer A, while maintaining the pressure of the film forming chamber at 0.0013 Pa while maintaining the film in contact with the film forming drum cooled to −10 ° C. The transport speed of the deposition base material was maintained at 3.7 m / min. Next, prior to the film formation, vinyltrimethoxysilane (KBM-1003 manufactured by Shin-Etsu Kogyo Co., Ltd.), which is a vinyl group-containing silane coupling agent, as an organosilicon compound having a polymerizable substituent was vacuum degassed at a pressure of 2.7 Pa. Was sprayed at a flow rate of 1.0 mL / min through an ultrasonic nebulizer operated at a frequency of 60 kHz. A 10 sccm nitrogen gas stream heated to 100 ° C. was intensively added to KBM-1003 in an ultrasonic nebulizer. The mixture of KBM-1003 and gas was introduced into a heated evaporation source maintained at 260 ° C., along with an additional 25 sccm of heated nitrogen gas. The resulting vapor stream is condensed on the exposed surface of the metal (M) -containing layer to form a 20 nm-thick organosilicon compound-containing layer made of a vinyl group-containing silane coupling agent. Produced.

  Here, with respect to the layer thickness, data of a change in the layer thickness with respect to the film formation time is obtained, the layer thickness formed per unit time is calculated, and then the film formation time is set so as to be the set layer thickness. The layer thickness was adjusted. Hereinafter, in the film formation by thermal evaporation, similarly, the film thickness formed per unit time is calculated, and the conditions are applied.

  The film was always present in a vacuum environment from the start of the step of forming the metal (M) -containing layer to the end of the formation of the organosilicon compound-containing layer.

<Preparation of functional film 102>
In the production of the functional film 101, the functional film 102 was formed in the same manner except that a commercially available metal Ta target was used in place of the commercially available polycrystalline silicon (Si) target in the step of forming the metal (M) -containing layer A. Was prepared.

<Preparation of functional film 103>
Except for using a commercially available oxygen-deficient niobium oxide (composition: Nb ₁₂ O ₂₉ ) instead of commercially available polycrystalline silicon (Si) in the step of forming the metal (M) -containing layer A in the production of the functional film 101 Produced a functional film 103 in the same manner.

<Preparation of functional film 104>
In the production of the functional film 103, in the step of forming the organosilicon compound-containing layer B, 3-glycidoxypropyltrimethoxysilane which is an epoxy group-containing silane coupling agent is used instead of vinyltrimethoxysilane which is a silane coupling agent. A functional film 104 was produced in the same manner except that (Shin-Etsu Industrial Co., Ltd. KBM-403) was used.

<Preparation of functional film 105>
In the production of the functional film 103, in the step of forming the organosilicon compound-containing layer B, 3-methacryloxypropyltriethoxysilane (a methacryloyl group-containing silane coupling agent) is used instead of vinyltrimethoxysilane as a silane coupling agent. A functional film 105 was produced in the same manner except that 3-methacryloyloxypropyltriethoxysilane (KBM-503 manufactured by Shin-Etsu Industrial Co., Ltd.) was used.

(Preparation of functional film 106)
In the production of the functional film 103, in the step of forming the organosilicon compound-containing layer B, 3-acryloxypropyltrimethoxysilane (an acryloyl group-containing silane coupling agent) is used instead of vinyltrimethoxysilane as a silane coupling agent. A functional film 106 was produced in the same manner except that 3-acryloyloxypropyltrimethoxysilane (KBM-5103 manufactured by Shin-Etsu Industrial Co., Ltd.) was used.

(Preparation of functional film 107)
In the production of the functional film 106, a non-transition metal (M2) -containing layer C forming step is provided by the following method before the metal (M) -containing layer A forming step, and the metal (M) -containing layer A is converted to a non-transition metal ( M2) A functional film 107 was produced in the same manner except that the functional film 107 was formed directly on the exposed surface of the containing layer C.

  The film was always in a vacuum environment from the start of the step of forming the non-transition metal (M2) -containing layer C to the completion of the step of forming the organosilicon compound-containing layer B.

(Step of forming non-transition metal (M2) -containing layer C: vapor deposition method)
In the step of forming the metal (M) -containing layer A of the functional film 101, an AlO _1.5 layer having a thickness of 150 nm is formed using a commercially available Al target instead of a commercially available polycrystalline silicon (Si) target. A non-transition metal (M2) -containing layer C was formed in the same manner except that the film forming conditions were changed.

(Preparation of functional film 108)
In the production of the functional film 107, a functional film 108 was produced in the same manner except that the step of forming the non-transition metal (M2) -containing layer C was changed as follows.

(Step of forming non-transition metal (M2) -containing layer C: vapor deposition method)
In the step of forming the metal (M) -containing layer A of the functional film 101, the non-transition metal (M2) was formed in the same manner except that the film forming conditions were changed so as to form an SiO _x (x <2) layer having a thickness of 150 nm. The containing layer C was formed.

(Preparation of functional film 109)
In the production of the functional film 106, the following non-transition metal (M2) -containing layer C forming step is provided before the metal (M) -containing layer A forming step, and the metal (M) -containing layer A is converted to the non-transition metal (M2). ) A functional film 109 was produced in the same manner except that the functional film 109 was formed directly on the exposed surface of the containing layer C.

  The film was always present in a vacuum environment from the start of the step of forming the metal (M) -containing layer A until the step of forming the organosilicon compound-containing layer B was completed. In the production of the present film, a laminated film of the base material, the underlayer, and the non-transition metal (M2) -containing layer C is referred to as a deposition base material.

(Step of forming non-transition metal (M2) -containing layer C: coating method)
A dibutyl ether solution containing 20% by mass of uncatalyzed perhydropolysilazane (PHPS) (manufactured by AZ Electronic Materials Co., Ltd., NN120-20) and an amine catalyst (N, N, N ', N'-tetramethyl-1, 6-diaminohexane (TMDAH)) and a 20% by mass dibutyl ether solution of perhydropolysilazane containing 5% by mass (manufactured by Merck Performance Materials GK, NAX120-20) at a ratio of 4: 1 (mass ratio). Then, the coating solution was further diluted with dibutyl ether to a solid content concentration of 5% by mass for adjusting the dry film thickness.

Thereafter, the coating solution prepared above was applied to the exposed surface of the base material side of the deposition base material with a bar coater, and then dried at 80 ° C. for 1 minute as a drying condition. Next, the dried coating film was subjected to vacuum ultraviolet irradiation using a Xe excimer lamp having a wavelength of 172 nm under the conditions of an oxygen concentration of 0.1% by volume and an irradiation energy of 0.5 J / cm ² , thereby obtaining a non-transition metal. A 150 nm-thick non-transition metal (M2) -containing layer C made of Si oxynitride containing Si as (M2) was formed.

(Preparation of functional film 110)
In the production of the functional film 109, the following surface of the metal (M) -containing layer A is hydrophilized while maintaining a vacuum state between the step of forming the metal (M) -containing layer A and the step of forming the organosilicon compound-containing layer B. A functional film 110 was produced in the same manner except that a processing step was provided.

  The film was always present in a vacuum environment from the start of the step of forming the metal (M) -containing layer A until the step of forming the organosilicon compound-containing layer B was completed.

(Step of hydrophilizing the surface of metal (M) -containing layer A)
Using a corona treatment device (manufactured by Kasuga Electric Co., Ltd.) placed in the chamber, under the conditions of an output of 300 W, an electrode length of 240 mm, a work electrode distance of 3.0 mm, and a transfer speed of 3.7 m / min, a metal (M) -containing layer The exposed surface of A was subjected to a surface hydrophilic treatment (corona treatment).

(Preparation of functional film 111)
In the production of the functional film 106, the metal (M) -containing layer A forming step is not provided, and the organosilicon compound-containing layer B having a polymerizable substituent is formed on the exposed surface of the deposition base material in the organosilicon compound-containing layer B forming step. A functional film 111 was produced in the same manner except that the functional film 111 was formed directly on the functional film 111.

(Preparation of functional film 112)
In the production of the functional film 106, a functional film 112 was produced in the same manner except that the step of forming the organosilicon compound-containing layer B was not provided.

(Preparation of functional film 113)
After forming the metal (M) -containing layer A on the exposed surface of the deposition base material in the same manner as the production of the functional film 106, the metal (M) -containing layer A was formed without forming the organosilicon compound-containing layer B having a polymerizable substituent. The film on which the (M) -containing layer A was vapor-deposited was taken out of the chamber into the atmosphere. Next, the film on which the metal (M) -containing layer A was deposited by sputtering was set in the chamber again. Then, without providing the step of forming the metal (M) -containing layer A, the organosilicon compound-containing layer B is formed in the same manner as the functional film 106, and the organosilicon compound-containing layer B having a polymerizable substituent is formed. The functional film 113 was produced by directly forming the metal (M) -containing layer A on the exposed surface.

(Preparation of functional film 114)
After forming the metal (M) -containing layer A on the exposed surface of the deposition base material in the same manner as the production of the functional film 106, the metal (M) -containing layer A was formed without forming the organosilicon compound-containing layer B having a polymerizable substituent. The film on which the (M) -containing layer A was vapor-deposited was taken out of the chamber into the atmosphere. Next, the functional film 114 was produced by directly forming the organosilicon compound-containing layer B having a polymerizable substituent on the exposed surface of the metal (M) -containing layer A in the atmosphere by the following method.

(Step of forming organosilicon compound-containing layer B: coating method)
Solid content comprising 50% by mass of dipentaerythritol hexaacrylate which is a polyfunctional acrylate compound and 50% by mass of 3-acryloxypropyltrimethoxysilane (KBM-5103 manufactured by Shin-Etsu Chemical Co., Ltd.) which is an acryloyl group-containing silane coupling agent. Was diluted with propylene glycol monomethyl ether (PGME) to a solid concentration of 1% to prepare a coating liquid for forming an organosilicon compound-containing layer B.

  Next, the coating liquid for forming the organosilicon compound-containing layer B is applied to the exposed surface of the metal (M) -containing layer A with a bar coater so that the dry film thickness becomes 20 nm, and then dried at 80 ° C. for 1 minute. Was dried.

Next, under an air atmosphere, an organic silicon compound-containing layer B having a polymerizable substituent was formed by performing an ultraviolet irradiation treatment with a high-pressure mercury lamp under the conditions of 500 mW / cm ² and 200 mJ / cm ² .

(Preparation of functional film 115)
In the production of the functional film 106, in the step of forming the organosilicon compound-containing layer B, a silane coupling agent having no polymerizable substituent is used instead of 3-acryloxypropyltrimethoxysilane, which is a silane coupling agent. A functional film 115 was produced in the same manner except that n-propyltriethoxysilane (KBM-3033 manufactured by Shin-Etsu Kogyo Co., Ltd.) was used.

(Preparation of functional film 116)
In the production of the functional film 106, in the step of forming the organosilicon compound-containing layer B, a silane coupling agent having no polymerizable substituent is used instead of 3-acryloxypropyltrimethoxysilane, which is a silane coupling agent. The functional film 116 was produced in the same manner except that Nn-butyl-aza-2,2-dimethoxysilacyclopentane (Cyclic Azasilane SIB1932.4, manufactured by Gelest) was used.

《Evaluation》
<Evaluation of adhesion>
The following adhesiveness evaluation was performed about the functional films 101-116. First, a resin A was prepared by adding 3 parts by mass of a photopolymerization initiator (IRGACURE (registered trademark) 184, manufactured by BASF Japan) to 100 parts by mass of pentaerythritol diacrylate, which is a polyfunctional acrylate compound. .

  On the other hand, according to the method described in JP-T-2013-505347, semiconductor nanoparticles (CdSe / ZnS) that emit red and green light were synthesized. The semiconductor nanoparticles were dispersed in a toluene solvent such that the red component and the green component were 0.75 mg and 4.12 mg, respectively. The resin A prepared above was added to this dispersion to prepare a coating liquid for forming an acrylic resin-containing light-emitting layer in which the content of semiconductor nanoparticles was 1% (based on solid content).

The coating liquid for forming an acrylic resin-containing light emitting layer was applied onto each of the organosilicon compound-containing layers B of each of the prepared functional films to form a quantum dot (QD) -containing coating film. Next, the same functional film was disposed so that the organosilicon compound-containing layer B side was in contact with the quantum dot (QD) -containing coating film (the quantum dot (QD) -containing coating film was sandwiched between two functional films), and 800 mW. / Cm ² , 300 mJ / cm ² , by curing with a high-pressure mercury lamp to irradiate an ultraviolet ray with a high-pressure mercury lamp to cure the quantum dot-containing coating film, and using the acrylic resin-containing functional films 101 to 103 and 105 to 116 respectively. A QD-containing laminated member having a light-emitting layer (QD-containing resin layer) was produced.

  In the production of the QD-containing laminated member using the functional film 104, in the preparation of the resin A, Epotech (registered trademark) OG-142 (manufactured by Epotech), which is an epoxy resin, is used instead of pentaerythritol diacrylate. A QD-containing laminated member having an epoxy resin-containing light-emitting layer (QD-containing resin layer) was prepared in the same manner except that the light-emitting layer was used.

  Here, in forming each QD-containing laminated member, the thickness of the resin-containing light-emitting layer (QD-containing resin layer), which is a cured layer of the quantum dot-containing coating film, was 100 µm.

  However, when the both surfaces of the quantum dot-containing coating film are sandwiched between two functional films and cured, one of the functional films of the QD-containing laminated member is peeled off as a release film to form a QD sheet for evaluation, and then The following adhesive evaluation was performed.

  Next, the produced QD sheets for evaluation were stored in an environment of 60 ° C. and 90% RH for 500 hours and 1000 hours, and then allowed to stand in an environment of 23 ° C. and 45% RH for 24 hours, followed by JIS K 5600-. 5-6: Adhesion was evaluated according to the test method described in 1999. Specifically, 100 square cuts were made using a cutter guide with a gap of 1 mm. Next, a tape of 18 mm width (Cellotape (registered trademark) CT-18 manufactured by Nichiban Co., Ltd.) was stuck on the cut surface on the square, and a 2.0 kg roller was completely reciprocated 20 times, and then adhered to 180 degrees. By observing the peeled surface after abruptly peeling at the peeling angle, the number of squares that did not peel was counted and evaluated according to the following evaluation criteria. Rank 3 or higher has practically applicable adhesiveness.

  In the following evaluation criteria, for example, a case where 90 out of 100 squares remain without being peeled off is expressed as “90/100”.

  Table 1 shows the evaluation results.

7: 100/100
6: 99 / 100-98 / 100
5: 97/100 to 95/100
4: 94 / 100-80 / 100
3: 79 / 100-50 / 100
2: 49 / 100-1 / 100
1: 0/100.

<Evaluation of water vapor barrier properties>
For the functional films 107 to 110, the following water vapor transmission rate (WVTR) was evaluated. The evaluation of the water vapor permeability (WVTR) was carried out by using AQUATRAN manufactured by MOCON and measuring the water vapor permeability (g / (m ² · day)) after the numerical value was stabilized under the conditions of 38 ° C. and 100% RH. Was evaluated according to the following evaluation criteria. When the value of the water vapor permeability (WVTR) was small, that is, when the water vapor barrier property was high, it was determined that the gas barrier property was good. Rank 3 or higher has gas barrier properties that are preferable as a gas barrier film. Table 1 shows the evaluation results.

5: 1 × 10 ⁻² (g / (m ² · day)) Less than 4: 1 × 10 ⁻² (g / (m ² · day)) or more 5 × 10 ⁻² (g / (m ² · day)) Less than 3: 5 × 10 ⁻² (g / (m ² · day)) or more and less than 1 × 10 ⁻¹ (g / (m ² · day)) 2: 1 × 10 ⁻¹ (g / (m ² · day)) day)) or more and less than 5 × 10 ⁻¹ (g / (m ² · day)) 1: not less than 5 × 10 ⁻¹ (g / (m ² · day)).

<Composition analysis>
The following composition analysis was performed on the functional films 107 to 110. Specifically, the composition distribution profile was measured in the thickness direction from the surface side (organic silicon compound-containing layer side) of each of the functional films 107 to 110 by XPS analysis. The XPS analysis conditions are as follows.

(XPS analysis conditions)
・ Equipment: QUANTERASXM manufactured by ULVAC-PHI
・ X-ray source: monochromatic Al-Kα
-Sputter ion: Ar (2 keV)
Depth profiles: in terms of SiO ₂ sputter thickness, repeat the measurement at a predetermined thickness intervals to obtain the thickness direction depth profile. The thickness interval was 1 nm (data for every 1 nm in the thickness direction is obtained).

  -Quantification: The background was determined by the Shirley method, and quantified using the relative sensitivity coefficient method from the obtained peak areas. For data processing, MultiPak manufactured by ULVAC-PHI was used. The analyzed elements are Si, Al, Nb, O, N, and C.

As a result, the composition in the mixing region (metal (M) a transition metal is a layer containing A (M1) containing layer and the non-transition metals (M2) region and the containing layer _{adjacent) (M2) (M1) x} O y N _{When represented by z} (0.02 <x <50, y> 0, z ≧ 0), the region length in the thickness direction of the region satisfying the following expression (1) was confirmed. Here, the non-transition metal (M2) in the functional film 107 is Al, the non-transition metal (M2) in the functional films 108 to 110 is Si, and the transition metal (M1) in the functional films 107 to 110 is Nb.

(2y + 3z) / (a + bx) <1 Expression (1)
(In the formula (1), a is the maximum valence of the non-transition metal (M2), 4 is for Si, 3 is for Al, b is the maximum valence of the transition metal (M1), In the case of Nb, it represents 5.)
Table 2 shows the evaluation results.

  The term “intermediate process” in Table 1 describes the environment from the end of the step of forming the metal (M) -containing layer A to the start of the step of forming the organosilicon compound-containing layer B, and the processing performed during that time. . Here, the continuous vapor phase refers to continuous vapor deposition, and a vacuum state is maintained from the end of the step of forming the metal (M) -containing layer A to the start of the step of forming the organosilicon compound-containing layer B. This means that the step of forming the metal (M) -containing layer A and the step of forming the organosilicon compound-containing layer B were performed while maintaining the vacuum state.

  From the results in Table 1 above, the functional film No. manufactured by the manufacturing method according to the embodiment of the present invention. Nos. 101 to 110 are functional film Nos. Manufactured by the manufacturing method having no configuration of the present invention. The effect of the present invention was confirmed because of having higher adhesiveness as compared with 111 to 116.

  Functional film no. From the comparison of 101 to 103, when the metal (M) contained in the metal (M) -containing layer A is a transition metal (M1), higher adhesiveness can be obtained. It has been confirmed that higher adhesion can be obtained when the transition metal is selected from the group consisting of the elements described above, and particularly high adhesion can be obtained when the transition metal is Nb.

  Functional film no. From the comparison of 103 to 105, higher adhesiveness can be obtained when the polymerizable substituent of the organosilicon compound having a polymerizable substituent is a (meth) acryloyl group, and higher adhesiveness can be obtained when the polymerizable substituent is an acryloyl group. It was confirmed that it was possible to obtain.

  Functional film no. From the comparison of 106 to 110, when the metal (M) -containing layer A is a non-transition metal (M1) -containing layer and a step of forming a non-transition metal (M2) -containing layer is further provided, the functional film becomes more It was confirmed that high adhesiveness could be obtained, and among these, when the non-transition metal (M2) was Si, higher adhesiveness could be obtained.

  Functional film no. 108-No. From the comparison of No. 110, when the step of forming the non-transition metal (M2) -containing layer is a step of converting and forming a coating film of the polysilazane compound, particularly, the film in the thickness direction of the region satisfying the above formula (1) It was confirmed that higher adhesiveness can be obtained when the thickness (region length) is 5 nm or more.

  Functional film No. 109 and No. From the comparison of 110, it is obtained when a step of hydrophilizing the surface of the metal (M) -containing layer A is provided between the step of forming the metal (M) -containing layer A and the step of forming the organosilicon compound-containing layer B. It was confirmed that the functional film could obtain higher adhesiveness.

  Also, from the results in Table 2 above, the functional film No. manufactured by the manufacturing method according to the preferred embodiment of the present invention. From the comparison of 107 to 110, when the metal (M) -containing layer A is a non-transition metal (M1) -containing layer and the non-transition metal contained in the non-transition metal (M2) -containing layer is Si, the gas barrier property is low. It was confirmed that the film was good, and further, when the functional film formed an oxygen-deficient region, it exhibited extremely excellent gas barrier properties.

DESCRIPTION OF SYMBOLS 1 ... Vacuum film-forming machine 2 ... Chamber 3 ... Coolable film-forming drum 4 ... Rotation direction 5 ... Sputtering apparatus 6 ... Surface hydrophilic treatment apparatus 7 ... Thermal vapor deposition apparatus 8 ... Substrate 9 ... Metal (M) containing layer A
10 ... Organic silicon compound-containing layer B having a polymerizable substituent
11: non-transition metal (M2) -containing layer C
20, 30, 110: Functional film 40: Quantum dot (QD) -containing laminated member 41: Quantum dot (QD) -containing resin layer 126: Film forming drum
136 ... Control unit,
150: raw material deposition section
150a: heating nozzle 152: pipe,
154: raw material supply section,
170 ... tank,
172: syringe pump,
174 ... Piping,
176 ... liquid ejecting unit,
176a: Droplet ejection port,
178 ... gas supply unit,
180 ... heating plate,
ω ... rotation direction,
Z: A laminate including a substrate and a metal (M) -containing layer.

Claims (11)

A step of forming a metal (M) -containing layer A (excluding an organosilicon compound-containing layer having a polymerizable substituent) on a substrate by vapor-phase film formation;
On a surface opposite to the side where the substrate is present in the metal (M) containing layer A, in contact with the metal (M) containing layer A, organic silicon compound-containing layer B having a weight polymerizable substituent A continuous vapor deposition from the formation of the metal (M) -containing layer A;
Before the step of forming the metal (M) -containing layer A by vapor deposition, the metal (M) -containing layer A is disposed between the base material and the metal (M) -containing layer A and is in contact with the metal (M) -containing layer A. as, it is seen including a step of forming a non-transition metal (M2) containing layer C (excluding the organic silicon compound-containing layer having a polymerizable substituent group),
The metal (M) -containing layer A contains a transition metal (M1), and has a composition in a region where the metal (M) -containing layer A and the non-transition metal (M2) -containing layer C are adjacent to each other (M2 _{) (M1) x O y N} z (0.02 <x <50, y> 0, when expressed z ≧ 0), the satisfy the following formula (1), method for producing a functional film.
(2y + 3z) / (a + bx) <1.0 Expression (1)
(In the formula (1), a represents the maximum valence of the non-transition metal (M2), and b represents the maximum valence of the transition metal (M1).)   The method for producing a functional film according to claim 1, wherein the vapor-phase deposition for forming the metal (M) -containing layer A is a sputtering deposition. The gas for forming the organic silicon compound-containing layer B having a polymerizable substituent phase deposition is a thermal evaporation method, method for producing a functional film according to claim 1 or 2.   The method for producing a functional film according to any one of claims 1 to 3, wherein the polymerizable substituent is a substituent selected from the group consisting of a (meth) acryloyl group, a vinyl group, and an epoxy group. The method for producing a functional film according to any one of claims 1 to 4, wherein the transition metal (M1) is a transition metal selected from the group consisting of elements of Groups 5 to 11. The method for producing a functional film according to claim 5 , wherein the transition metal (M1) is a transition metal selected from the group consisting of Group 5 elements. The method for producing a functional film according to any one of claims 1 to 6, wherein the non-transition metal (M2) is a metal selected from the group consisting of elements of Groups 12 to 14. The method for producing a functional film according to claim 7 , wherein the non-transition metal (M2) is Si. The method for producing a functional film according to claim 8 , wherein the step of forming the non-transition metal (M2) -containing layer C is a step of forming a coating film of a polysilazane compound by further modifying the coating film. After the step of forming the metal (M) -containing layer A by vapor phase film formation and before the step of forming the organosilicon compound-containing layer B having a polymerizable substituent by vapor phase film formation, the metal (M) The method for producing a functional film according to any one of claims 1 to 9 , further comprising the step of)) performing a hydrophilic treatment on the surface of the containing layer A. A quantum dot (QD), a binder resin and a solvent are provided on the organosilicon compound-containing layer B having a polymerizable substituent of the functional film produced by the production method according to any one of claims 1 to 10. A method for producing a quantum dot (QD) -containing laminated member, comprising a step of applying a light-emitting layer-forming coating solution containing the same.