JP2018140494A - Functional film and electronic device provided with the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a functional film that adheres firmly to a quantum-dot-containing resin layer, does not show any performance degradation after a long time use, and is excellent in stability, and to provide an electronic device provided with the same.SOLUTION: In a functional film 1, a transition metal (M1)-containing layer 4 and an organosilicon-compound-containing layer 6 are layered in the stated order on a base material 2. In the functional film 1, the transition metal (M1) is the one selected from the Group 5 to 11 elements, especially selected from the Group 5 elements. In the functional film 1, the organosilicon compound has a polymerizable substituent selected from an acryloyl group, a methacryloyl group, a vinyl group, or an epoxy group.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a functional film and an electronic device including the functional film. More specifically, the present invention relates to a functional film having high adhesiveness with a quantum dot-containing resin layer, and an electronic device including the functional film.

  As one of techniques for expanding the color reproducibility of a liquid crystal television (LCD (Liquid Crystal Display) TV), a technique using red or green quantum dots (Quantum Dot: QD) has attracted attention.

  Quantum dots are vulnerable to water and oxygen, so they are used by dispersing them in a curable resin such as epoxy resin or acrylic resin. The quantum dot (QD) -containing resin layer should be laminated with two gas barrier films. Thus, a method for producing a QD sheet that is more resistant to water and oxygen is generally known (for example, see Patent Document 1).

  However, the QD-containing resin layer has a problem that the adhesiveness with the gas barrier film cannot be maintained due to film shrinkage that occurs when it is cured.

Special table 2013-544018 gazette

  This invention is made | formed in view of the said problem and the condition, The solution subject is providing a functional film with high adhesiveness with a QD containing resin layer, and an electronic device provided with the same.

  Furthermore, it aims at providing the functional film excellent in stability without performance degradation after long-term use, and an electronic device provided with the same.

  In order to solve the above-mentioned problems, the present inventor has sequentially laminated a transition metal (M1) -containing layer and an organosilicon compound-containing layer on the substrate in the process of examining the cause of the above-mentioned problem. Thus, it was found that a functional film having high adhesiveness with the QD-containing resin layer and an electronic device including the functional film can be provided, and the present invention has been achieved.

  That is, the said subject which concerns on this invention is solved by the following means.

  1. A functional film in which a transition metal (M1) -containing layer and an organosilicon compound-containing layer are sequentially laminated on a substrate.

  2. 2. The functional film according to item 1, wherein the transition metal (M1) is a transition metal selected from the group consisting of elements of Group 5-11.

  3. 3. The functional film according to item 2, wherein the transition metal (M1) is a transition metal selected from the group consisting of Group 5 elements.

  4). The functional film according to any one of Items 1 to 3, wherein the organosilicon compound has a polymerizable substituent.

  5. The functional film according to item 4, wherein the polymerizable substituent is a substituent selected from the group consisting of an acryloyl group, a methacryloyl group, a vinyl group, and an epoxy group.

6). Between the base material and the transition metal (M1) -containing layer, it has a metal (M2) -containing layer,
The functional film according to any one of Items 1 to 5, wherein the metal (M2) is a metal selected from the group consisting of elements of Groups 12 to 14.

  7). The functional film according to item 6, wherein the metal (M2) is Si.

  8). The functional film according to item 7, wherein the metal (M2) -containing layer is a film formed by converting a coating film of a polysilazane compound.

9. The composition in the region where the transition metal (M1) -containing layer and the metal (M2) -containing layer are adjacent to each other is expressed as (M2) (M1) _x O _y N _z (0.02 <x <50, y> 0, z ≧ The functional film according to any one of Items 6 to 8, wherein the functional film satisfies the following formula (1) when represented by 0).

(2y + 3z) / (a + bx) <1 Formula (1)
(In the formula (1), a represents the maximum valence of the metal (M2), and b represents the maximum valence of the transition metal (M1).)

  10. The functional film according to any one of Items 1 to 9, wherein the organic silicon compound-containing layer is formed of a film formed by applying a liquid containing a silane coupling agent.

  11. The functional film according to any one of items 1 to 10, wherein the organosilicon compound-containing layer further contains a polymerizable polymer.

  12 An electronic device comprising the functional film according to any one of items 1 to 11.

  By the said means of this invention, a functional film with high adhesiveness with a QD containing resin layer and an electronic device provided with the same can be provided.

  Furthermore, it is possible to provide a functional film that does not deteriorate in performance after long-term use and has excellent stability, and an electronic device including the functional film.

  The expression mechanism / action mechanism of the effect of the present invention is not clear, but is presumed as follows.

The functional film of the present invention is characterized in that a transition metal (M1) -containing layer and an organosilicon compound-containing layer are sequentially laminated on a substrate.
By having an organosilicon compound-containing layer (for example, a silane coupling agent as an organosilicon compound), the adhesion between the transition metal (M1) -containing layer (inorganic film) and the QD-containing resin layer (organic film) is further increased. It becomes possible to do.

  Moreover, by having a transition metal (M1) containing layer, adhesiveness with a QD containing resin layer can fully be ensured, even if it does not perform the dry surface treatment for raising surface energy.

Furthermore, the functional film of the present invention can obtain higher adhesion and gas barrier property improving effects between the transition metal (M1) -containing layer and the organosilicon compound-containing layer.
This is presumably because a stronger bond is likely to be formed between the transition metal (M1) (preferably a transition metal of Group 5-11, particularly preferably Nb of Group 5) and Si.

Sectional drawing which shows an example of schematic structure of the functional film of this invention Sectional drawing which shows an example of schematic structure of the functional film of this invention Sectional drawing which shows an example of schematic structure of QD sheet Sectional drawing which shows an example of schematic structure of QD sheet

  The functional film of the present invention is characterized in that a transition metal (M1) -containing layer and an organosilicon compound-containing layer are sequentially laminated on a substrate. This feature is a technical feature common to the inventions according to claims 1 to 12.

  As an embodiment of the present invention, from the viewpoint of improving adhesiveness and gas barrier properties, the transition metal (M1) is preferably a transition metal selected from the group consisting of Group 5 to 11 elements. More preferably, the transition metal is selected from the group consisting of these elements.

  The organosilicon compound has a polymerizable substituent, and the polymerizable substituent is preferably a substituent selected from the group consisting of an acryloyl group, a methacryloyl group, a vinyl group, and an epoxy group. Thereby, when resin (layer) is laminated | stacked on an organosilicon compound content layer, a bond can be formed between the said resin and adhesiveness can be improved.

  Moreover, it is a metal which has a metal (M2) content layer between a base material and a transition metal (M1) content layer, and the said metal (M2) is selected from the group which consists of a 12-14 group element, Furthermore, it is preferable that the metal (M2) is Si. This is because, as described above, a stronger bond is easily formed between the transition metal (M1) (preferably a transition metal of Group 5-11, particularly preferably Nb of Group 5) and Si, As a result, higher adhesiveness and gas barrier properties can be obtained.

  From the viewpoint of improving gas barrier properties, the metal (M2) -containing layer is preferably formed of a film formed by converting a polysilazane compound coating film.

Further, from the viewpoint of improving the gas barrier property, the composition in the region where the transition metal (M1) -containing layer and the metal (M2) -containing layer are adjacent to each other is expressed as (M2) (M1) _x O _y N _z (0.02 <x < 50, y> 0, z ≧ 0), the above formula (1) is preferably satisfied.

  Moreover, it is preferable that an organosilicon compound content layer consists of a film | membrane formed by apply | coating the liquid containing a silane coupling agent from a viewpoint of adhesive improvement.

  Moreover, it is preferable that the organosilicon compound-containing layer further contains a polymerizable polymer. Thereby, when resin (layer) is laminated | stacked on an organosilicon compound content layer, a bond can be formed between polymeric polymer and resin, and adhesiveness can be improved.

  The functional film of the present invention can be suitably applied to various electronic devices.

  Hereinafter, the present invention, its components, and modes and modes for carrying out the present invention will be described in detail. In addition, in this application, "-" showing a numerical range is used by the meaning containing the numerical value described before and behind that as a lower limit and an upper limit.

《Functional film》
As shown in FIG. 1, the functional film 1 of the present invention is configured by sequentially laminating a transition metal (M1) -containing layer 4 and an organosilicon compound-containing layer 6 on a substrate 2.
The organosilicon compound-containing layer 6 is formed such that a functional group such as a (meth) acryloyl group is exposed on the exposed surface of the transition metal (M1) -containing layer 4.
In the present invention, a region where a functional group such as a (meth) acryloyl group above the surface of the transition metal (M1) -containing layer 4 in FIG. 1 is referred to as an “organosilicon compound-containing layer”.

  As shown in FIG. 2, the functional film 10 may have a metal (M2) -containing layer 8 between the base material 2 and the transition metal (M1) -containing layer 4.

FIG. 3 shows a QD sheet 20 to which the functional film 1 is applied as an example.
The QD sheet 20 is configured by laminating a QD-containing resin layer 14 (also referred to as a light emitting layer) in which quantum dots 12 are contained in a resin on the functional film 1 (organosilicon compound-containing layer 6). Yes.

  Further, as another aspect, the QD sheet 30 shown in FIG. 4 contains the quantum dots 12 and the organosilicon compound in advance in the resin to form the organosilicon compound-containing layer 26, and the organosilicon compound-containing layer 26 is a transition metal. (M1) It is configured by being laminated on the containing layer 4. That is, the organosilicon compound-containing layer 26 is configured to also serve as the QD-containing resin layer.

  As described above, the functional film of the present invention can be used as a gas barrier film in a QD sheet, but is not particularly limited thereto, for example, an organic layer other than a QD-containing resin layer and a transition metal (M1) It can also be applied as a film for bonding (bonding) the containing layer, an inorganic film with a protective layer, an optical adjustment film, and the like.

<Base material (2)>
As a base material which concerns on this invention, if a transition metal (M1) content layer etc. can be hold | maintained, it will not specifically limit. As the substrate, a resin substrate (plastic film or sheet) is usually used, and a film or sheet made of a colorless and transparent resin is preferably used as the substrate. The resin substrate used is not particularly limited in material, thickness, and the like, and can be appropriately selected according to the purpose of use.

  Examples of the resin base material include poly (meth) acrylic acid ester, polyethylene terephthalate (PET), polybutylene terephthalate, polyethylene naphthalate (PEN), polycarbonate (PC), polyarylate, polyvinyl chloride (PVC), polyethylene ( PE), polypropylene (PP), polystyrene (PS), nylon (Ny), aromatic polyamide, polyether ether ketone, polysulfone, polyethersulfone, polyimide, polyetherimide, cycloolefin polymer, cycloolefin copolymer, and other resins A film, a heat-resistant transparent film (product name Sila-DEC, manufactured by Chisso Corporation) with a silsesquioxane having an organic-inorganic hybrid structure as a basic skeleton, and a tree formed by laminating two or more layers of the above resin Mention may be made of the film, and the like.

  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 100 μm.

  The base material may have functional layers such as a transparent conductive layer, a primer layer, and a clear hard coat layer. As the functional layer, those described in paragraphs [0036] to [0038] of JP-A-2006-289627 can be preferably employed.

  Moreover, it is preferable that the base material which concerns on this invention is transparent. Since the base material is transparent and the layer formed on the base material is also transparent, a transparent functional film can be obtained. For example, a transparent substrate such as an organic EL element 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. Although there is no particular lower limit, it is practically 0.01 nm or more. If necessary, the smoothness may be improved by polishing both surfaces of the substrate, at least the side on which the transition metal (M1) -containing layer is provided.

  At least the transition metal (M1) -containing layer side of the substrate is provided with various known treatments for improving adhesion, such as corona discharge treatment, flame treatment, oxidation treatment, plasma treatment, and a smooth layer described later. Lamination etc. may be performed and it is preferable to perform combining the said process as needed.

<Transition metal (M1) -containing layer (4)>
The functional film of the present invention has a transition metal (M1) -containing layer between the substrate and the organosilicon compound-containing layer.
Here, the transition metal (M1) refers to an element belonging to Group 3 to 11 of the long-period periodic table, 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, Examples thereof include Re, Os, Ir, Pt, and Au.

In a preferred embodiment, the transition metal (M1) -containing layer according to the present invention contains a transition metal (M1) selected from the group consisting of Group 5 to 11 elements.
The transition metal (M1) is not particularly limited as long as it is a transition metal selected from the group consisting of Group 5 to 11 elements, and can be used alone or in combination. Specific examples include V, Cr, Mn, Fe, Co, Ni, Cu, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Ta, W, Re, Os, Ir, Pt, and Au. .

Among them, the transition metal (M1) that can provide good gas barrier properties is preferably a transition metal selected from the group consisting of Group 5 elements. This is because the transition metal (M1) (especially Nb) is considered to be easily bonded to Si in the organosilicon compound-containing layer and the metal (M2) in the metal (M2) -containing layer described later. is there. Furthermore, if the metal (M2) is Si, a significant gas barrier property improvement effect can be obtained.
Further, from the viewpoint of optical characteristics, the transition metal (M1) is particularly preferably Nb from which a compound with good transparency can be obtained.

  The transition metal (M1) -containing layer preferably contains the transition metal (M1) in the form of an oxide, nitride, oxynitride, oxycarbide, or the like.

  The content of the transition metal compound such as a transition metal oxide is not particularly limited as long as the effects of the present invention are not impaired, but may be 50% by mass or more based on the total mass of the transition metal (M1) -containing layer. Preferably, it is 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, a transition metal (M1) -containing layer) Is most preferably a transition metal compound.

As a method for forming the transition metal (M1) -containing layer, a conventionally known film formation method can be applied. For example, from the viewpoint of easy adjustment of the composition ratio between the transition metal and oxygen, a vapor phase film formation method is used. Preferably it is formed.
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). Examples thereof include chemical vapor deposition (CVD) methods such as a deposition method and an ALD (Atomic Layer Deposition) method. Among these, it is possible to form a film without damaging the lower layer, and since it has high productivity, the physical vapor deposition (PVD) method is more preferable, and the sputtering method is particularly preferable.

  Film formation by the sputtering method includes bipolar sputtering, magnetron sputtering, dual magnetron sputtering (DMS) using an intermediate frequency region, ion beam sputtering, ECR (Electron Cyclotron Resonance) sputtering alone, or the like. Two or more types can be used in combination. The target application method is appropriately selected depending on the target type, and either DC (direct current) sputtering or RF (high frequency) sputtering may be used.

Further, for example, a reactive sputtering method using a transition mode that is intermediate between a metal mode and an oxide mode can 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 transition metal oxide thin film can be formed by using transition metal (M1) as a target and introducing oxygen into the process gas. In the case of forming a film by RF (high frequency) sputtering, a transition 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 Ar is preferably used. Furthermore, by introducing oxygen, nitrogen, carbon dioxide, and carbon monoxide into the process gas, transition metal compound thin films such as transition metal oxides, nitrides, oxynitrides, and oxycarbides can be formed.

  Examples of film formation conditions in the sputtering method include applied power, discharge current, discharge voltage, time, and the like, which can be appropriately selected according to the sputtering apparatus, film material, film thickness, and the like.

  Among these, a sputtering method using a transition metal oxide as a target is preferable because it has a higher film formation rate and higher productivity.

  The transition metal (M1) -containing layer may be a single layer or a laminated structure of two or more layers. When the transition metal (M1) -containing layer has a laminated structure of two or more layers, the transition metal (or transition metal compound) contained in the transition metal (M1) -containing layer may be the same or different. May be.

  The thickness of the transition metal (M1) -containing layer (in the case of a laminated structure of two or more layers, the total thickness) may be in the range of 1 to 200 nm from the viewpoint of in-plane uniformity of gas barrier properties. Preferably, it is in the range of 2 to 100 nm, more preferably in the range of 3 to 50 nm. In particular, when the thickness of the transition metal (M1) -containing layer is 50 nm or less, the productivity of film formation of the transition metal (M1) -containing layer is further improved.

<Metal (M2) containing layer (8)>
It is preferable that the functional film of this invention has a metal (M2) content layer between a base material and a transition metal (M1) content layer.
The metal (M2) -containing layer does not need to be formed on the surface of the base material, but a base layer (smooth layer, primer layer), anchor coat layer (anchor layer), protective layer, hygroscopic layer or electrification between the base material and the base material. A functional layer or the like of the prevention layer may be provided.

The metal (M2) -containing layer according to the present invention contains a metal (M2) selected from the group consisting of Group 12-14 elements.
The metal (M2) according to the present invention is not particularly limited as long as it is a metal selected from the group consisting of Group 12-14 elements, and can be used alone or in combination.
Specific examples of the metal (M2) include Al, Si, Zn, Ga, Ge, Cd, In, Sn, Hg, Tl, Pb, and Cn. Among these, Si is preferable.
The metal (M2) -containing layer preferably contains the metal (M2) in the form of an oxide, nitride, oxynitride, oxycarbide, etc., and an oxide of Si (composition SiO _x ), acid Most preferred are nitrides (composition SiO _x N _y ) or oxycarbides (composition SiO _x C _y ).

  The chemical composition in the metal (M2) -containing layer can be measured by measuring the atomic composition ratio using an XPS (X-ray Photoelectron Spectroscopy) surface analyzer. It can also be measured by cutting the metal (M2) containing layer and measuring the atomic composition ratio of the cut surface with an XPS surface analyzer. The chemical composition of the metal (M2) -containing layer depends on the type and amount of raw materials used when forming the metal (M2) -containing layer, the conditions when forming or modifying the coating layer, and the like. Can be controlled.

  Although content of metal compounds, such as a metal oxide contained in a metal (M2) content layer, is not specifically limited, It is preferable that it is 50 mass% or more with respect to the total mass of a metal (M2) content layer, and 80 masses. % Or more, more preferably 95% by weight or more, particularly preferably 98% by weight or more, and 100% by weight (that is, the metal (M2) -containing layer is made of a metal compound. Most preferred).

The metal (M2) -containing layer contains a metal compound and thus has high density and further has gas barrier properties. Here, when the gas barrier property of the metal (M2) -containing layer was calculated as a laminate in which the metal (M2) -containing layer was formed on the substrate, water vapor was measured by a method based on JIS K 7129-1992. The transmittance (WVTR) (38 ° C., 100% RH) is preferably 0.1 g / (m ² · day) or less, and more preferably 0.01 g / (m ² · day) or less.

  As a formation method of the metal (M2) -containing layer, a conventionally known film formation method can be applied, but a vacuum film formation method such as a physical vapor deposition (PVD) method or a chemical vapor deposition (CVD) method, or Examples thereof include a method of modifying a coating film formed by applying a liquid containing a metal compound, preferably a liquid containing a silicon compound (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 of depositing a target material, for example, a thin film such as a carbon film, on the surface of the material in a gas phase by a physical method. For example, a sputtering method (DC sputtering method). RF sputtering method, ion beam sputtering method, magnetron sputtering method, etc.), vacuum deposition method, ion plating method and the like.

  Sputtering is a method in which a target is placed in a vacuum chamber, a rare gas element (usually argon) ionized by applying a high voltage is collided with the target, and atoms on the target surface are ejected and adhered to the substrate. . At this time, a reactive sputtering method may be used in which an inorganic layer is formed by causing nitrogen and oxygen gas to flow into the chamber to react nitrogen and oxygen with an element ejected from the target by argon gas. .

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

  A metal (M2) -containing layer obtained by a vacuum plasma CVD method or a plasma CVD method under atmospheric pressure or a pressure near atmospheric pressure is a raw material (also referred to as a raw material) metal compound, decomposition gas, decomposition temperature, input power, etc. By selecting the conditions, it is preferable because the target compound can be produced. For details of the conditions for forming the metal (M2) -containing layer by the plasma CVD method, for example, the conditions described in paragraphs [0033] to [0051] of International Publication No. 2012/067186 can be appropriately employed. The metal (M2) -containing layer formed by such a method is preferably a layer containing an oxide, nitride, oxynitride or oxycarbide.

(Coating method)
The metal (M2) -containing layer according to the present invention is formed by, for example, modifying a coating film formed by applying a liquid containing a metal compound, preferably a liquid containing a silicon compound (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, silazane compounds, aminosilane compounds, silylacetamide compounds, silylimidazole compounds, and other silicon compounds containing nitrogen are used.

(Polysilazane compound)
In the present invention, the polysilazane compound (also simply referred to as polysilazane) is a polymer having a silicon-nitrogen bond. Specifically, ceramic precursor inorganic such as SiO ₂ , Si ₃ N ₄ , and both intermediate solid solutions SiO _x N _y have bonds such as Si—N, Si—H, N—H in the structure. It is a polymer.

  Examples of the polysilazane compound are not particularly limited, and are disclosed in, for example, paragraphs [0043] to [0058] of JP2013-022799A, paragraphs [0038] to [0056] of JP2013-226758A, and the like. What is done is adopted suitably.

  Moreover, the polysilazane compound is marketed in the solution state melt | dissolved in the organic solvent, As a commercial item of a polysilazane solution, NN120-10, NN120-20, NAX120-20, NN110, NN310 by AZ Electronic Materials KK NN320, NL110A, NL120A, NL120-20, NL150A, NP110, NP140, SP140, and the like.

  As another example of the polysilazane compound that can be used in the present invention, for example, a silicon alkoxide-added polysilazane obtained by reacting the above-mentioned polysilazane with a silicon alkoxide (JP-A-5-238827), a glycidol addition obtained by reacting glycidol Polysilazane (JP-A-6-122852), alcohol-added polysilazane obtained by reacting an alcohol (JP-A-6-240208), metal carboxylate-added polysilazane obtained by reacting a metal carboxylate 6-299118), acetylacetonate complex-added polysilazane obtained by reacting a metal-containing acetylacetonate complex (JP-A-6-306329), metal fine particle-added polysilazane obtained by adding metal fine particles (specialty) Kaihei 7- Such as JP) No. 96986, include polysilazane compounds ceramic at low temperatures.

(Silazane compound)
Examples of silazane compounds include dimethyldisilazane, trimethyldisilazane, tetramethyldisilazane, pentamethyldisilazane, hexamethyldisilazane, 1,3-divinyl-1,1,3,3-tetramethyldisilazane, and the like. However, it is not limited to these.

(Aminosilane compound)
Examples of aminosilane compounds include 3-aminopropyltrimethoxysilane, 3-aminopropyldimethylethoxysilane, 3-arylaminopropyltrimethoxysilane, propylethylenediaminesilane, N- [3- (trimethoxysilyl) propyl] ethylenediamine, 3 Examples include, but are not limited to, -butylaminopropyltrimethylsilane, 3-dimethylaminopropyldiethoxymethylsilane, 2- (2-aminoethylthioethyl) triethoxysilane, bis (butylamino) dimethylsilane, and the like.

(Silylacetamide compound)
Examples of silylacetamide compounds include N-methyl-N-trimethylsilylacetamide, N, O-bis (tert-butyldimethylsilyl) acetamide, N, O-bis (diethylhydrogensilyl) trifluoroacetamide, N, O-bis (Trimethylsilyl) acetamide, N-trimethylsilylacetamide and the like can be mentioned, but not limited thereto.

(Silylimidazole compound)
Examples of silylimidazole compounds include, but are not limited to, 1- (tert-butyldimethylsilyl) imidazole, 1- (dimethylethylsilyl) imidazole, 1- (dimethylisopropylsilyl) imidazole, N-trimethylsilylimidazole, and the like. .

(Other silicon compounds containing nitrogen)
In the present invention, in addition to the above-mentioned silicon compound containing nitrogen, for example, bis (trimethylsilyl) carbodiimide, trimethylsilyl azide, N, O-bis (trimethylsilyl) hydroxylamine, N, N′-bis (trimethylsilyl) urea, 3 -Bromo-1- (triisopropylsilyl) indole, 3-bromo-1- (triisopropylsilyl) pyrrole, N-methyl-N, O-bis (trimethylsilyl) hydroxylamine, 3-isocyanatopropyltriethoxysilane, silicon tetra Although isothiocyanate etc. are used, it is not limited to these.

  Of these, polysilazane such as perhydropolysilazane and organopolysilazane, and polysiloxane such as silsesquioxane are preferable because of their low film-forming properties, few defects such as cracks, and low residual organic matter, and high gas barrier performance. Polysilazane is more preferable, and perhydropolysilazane is particularly preferable because gas barrier performance is maintained even when bent and under high temperature and high humidity conditions.

  When polysilazane is used, the content of polysilazane in the metal (M2) -containing layer before the modification treatment may be 100% by mass when the total mass of the metal (M2) -containing layer is 100% by mass. Moreover, when a metal (M2) content layer contains things other than polysilazane, it is preferable that the content rate of the polysilazane in a layer is in the range of 10-99 mass%, and is in the range of 40-95 mass%. More preferably, it is in the range of 70 to 95% by mass.

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

(Modification of metal (M2) -containing layer formed by coating method)
The modification treatment of the metal (M2) -containing layer formed by the coating method refers to a conversion reaction of a silicon compound to silicon oxide or silicon oxynitride. Specifically, the functional film as a whole has gas barrier properties. This refers to a process for forming an inorganic thin film at a level that can contribute to the development of (water vapor permeability of 0.1 g / (m ² · day) or less).
Here, the water vapor permeability of the functional film is a value measured by a method based on JIS K 7129-1992 under the conditions of 38 ° C. and 100% RH.

  The conversion reaction of the silicon compound to silicon oxide or silicon oxynitride can be applied by appropriately selecting a known method. Specific examples of the modification treatment include plasma treatment, ultraviolet irradiation treatment, and heat treatment. However, in the case of modification by heat treatment, 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 higher, so it is difficult to adapt to a flexible substrate such as plastic. . For this reason, the heat treatment is preferably performed in combination with other reforming treatments.

  Therefore, as the modification treatment, from the viewpoint of adapting to a plastic substrate, a plasma treatment capable of a conversion reaction at a lower temperature or a conversion reaction by ultraviolet irradiation treatment is preferable.

(Plasma treatment)
In the present invention, a known method can be used as the plasma treatment that can be used as the modification treatment, and an atmospheric pressure plasma treatment or the like can be preferably used. The atmospheric pressure plasma CVD method, which performs plasma CVD processing in the vicinity of atmospheric pressure, does not need to be reduced in pressure compared to the plasma CVD method under vacuum, and is not only high in productivity but also because the plasma density is high. The film formation rate is high, and further, under a high pressure condition of atmospheric pressure as compared with the conditions of a normal CVD method, the gas mean free path is very short, so that a very homogeneous film can be obtained.

  In the case of atmospheric pressure plasma treatment, nitrogen gas or a gas containing a group 18 element (specifically, helium, neon, argon, krypton, xenon, or radon) is used as the discharge gas. Among these, nitrogen, helium or argon is preferably used, and nitrogen is particularly preferable because of low cost.

(Heat treatment)
The modification treatment can be efficiently performed by heat-treating the coating film containing the silicon compound in combination with another modification treatment, preferably an excimer irradiation treatment described later.

Moreover, when forming a layer using a sol-gel method, it is preferable to use heat processing.
The heating conditions are preferably in the range of 50 to 300 ° C., more preferably in the range of 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 a metal (M2) -containing layer can be formed.

  As the heat treatment, for example, a method of heating a coating film by contacting a substrate with a heating element such as a heat block, a method of heating an atmosphere with an external heater such as a resistance wire, an infrared region such as an IR heater Although the method using the light etc. is mentioned, it is not specifically limited. Moreover, you may select suitably the method which can maintain the smoothness of the coating film containing a silicon compound.

  As a temperature of the coating film at the time of heat processing, it is preferable to adjust suitably in the range of 50-250 degreeC, and it is more preferable that it is in the range of 50-120 degreeC.

  The heating time is preferably in the range of 1 second to 10 hours, and more preferably in the range of 10 seconds to 1 hour.

(UV irradiation treatment)
As one of the modification treatment methods, treatment by ultraviolet irradiation is preferable. Ozone and active oxygen atoms generated by ultraviolet light (synonymous with ultraviolet light) have high oxidation ability, and can form a silicon oxide film or silicon oxynitride film having high density and insulation at low temperature. Is possible.

By this ultraviolet irradiation, the base material is heated, and O ₂ and H ₂ O contributing to ceramicization (silica conversion), an ultraviolet absorber, and polysilazane itself are excited and activated. The ceramic conversion is promoted, and the obtained metal (M2) -containing layer becomes denser. Irradiation with ultraviolet rays is effective at any time after the formation of the coating film.

  In the ultraviolet irradiation treatment, any commonly used ultraviolet ray generator can be used.

  The ultraviolet ray referred to in the present invention generally refers to an electromagnetic wave having a wavelength of 10 to 400 nm, but in the case of an ultraviolet irradiation treatment other than the vacuum ultraviolet ray (10 to 200 nm) treatment described later, it is preferably 210 to 375 nm. Use ultraviolet light.

  In the irradiation with ultraviolet rays, it is preferable to set the irradiation intensity and the irradiation time within a range in which the substrate carrying the irradiated metal (M2) -containing layer is not damaged.

For example, when a plastic film is used as the substrate, for example, a 2 kW (80 W / cm × 25 cm) lamp is used, and the strength of the substrate surface is 20 to 300 mW / cm ² , preferably 50 to 200 mW / cm. The distance between the substrate and the ultraviolet irradiation lamp is set so as to be ^2, and irradiation can be performed for 0.1 second to 10 minutes.

  In general, when the substrate temperature during ultraviolet irradiation treatment is 150 ° C. or more, in the case of a plastic film or the like, the properties of the substrate are impaired, such as deformation of the substrate or deterioration of its strength. Become. 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 as the substrate temperature at the time of ultraviolet irradiation, and it can be appropriately set depending on the type of the substrate. Moreover, there is no restriction | limiting in particular in ultraviolet irradiation atmosphere, What is necessary is just to implement in air.

  Examples of such ultraviolet ray generating means include metal halide lamps, high pressure mercury lamps, low pressure mercury lamps, xenon arc lamps, carbon arc lamps, and excimer lamps (single wavelengths of 172 nm, 222 nm, and 308 nm, for example, USHIO INC. Manufactured by MD Excimer Co., Ltd.), UV light laser, and the like, but are not particularly limited. Moreover, when irradiating the generated ultraviolet ray to the metal (M2) -containing layer, from the viewpoint of achieving efficiency improvement and uniform irradiation, the ultraviolet ray from the generation source is reflected by the reflecting plate and then the metal (M2) -containing layer is contained. It is preferred to hit the layer.

  The ultraviolet irradiation can be adapted to both batch processing and continuous processing, and can be appropriately selected depending on the shape of the substrate to be used. For example, in the case of batch processing, a laminate having a metal (M2) -containing layer on the surface can be processed in an ultraviolet baking furnace equipped with the above-described ultraviolet light source. The ultraviolet baking furnace itself is generally known. For example, an ultraviolet baking furnace manufactured by I-Graphics Co., Ltd. can be used. Moreover, when the laminated body which has a metal (M2) content layer on the surface is a elongate film form, it irradiates with an ultraviolet-ray continuously in the drying zone equipped with the above ultraviolet generation sources, conveying this. Can be made into ceramics. The time required for ultraviolet irradiation is generally 0.1 seconds to 10 minutes, preferably 0.5 seconds to 3 minutes, although it depends on the composition and concentration of the substrate and metal (M2) -containing layer used.

(Vacuum ultraviolet irradiation treatment: excimer irradiation treatment)
In the present invention, the most preferable modification treatment method is treatment by vacuum ultraviolet irradiation (excimer irradiation treatment). The treatment by vacuum ultraviolet irradiation uses light energy of 100 to 200 nm, preferably light energy with a wavelength of 100 to 180 nm, which is larger than the interatomic bonding force in the polysilazane compound, and bonds the atoms with only photons called photon processes. This is a method of forming a silicon oxide film 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 by action. In addition, when performing an excimer irradiation process, it is preferable to use heat processing together as mentioned above, and the detail of the heat processing conditions in that case is as having mentioned above.

  The radiation source in the present invention is not limited as long as it generates light having a wavelength of 100 to 180 nm, but is preferably an excimer radiator having a maximum emission at about 172 nm (for example, Xe excimer lamp), and has an emission line at about 185 nm. Low pressure mercury vapor lamps, medium and high pressure mercury vapor lamps having wavelength components of 230 nm or less, and excimer lamps having maximum emission at about 222 nm.

  Among these, 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, it can generate radical oxygen atom species and ozone at a high concentration with a very small amount of oxygen.

  Moreover, it is known that the energy of light having a short wavelength of 172 nm has a high ability to dissociate organic bonds. Due to the high energy possessed by the active oxygen, ozone and ultraviolet radiation, the polysilazane coating can be modified in a short time.

  Since the excimer lamp has high light generation efficiency, it can be turned on with low power. In addition, it does not emit light with a long wavelength that causes a temperature increase due to light, and irradiates energy in the ultraviolet region, that is, with a short wavelength, so that the surface temperature of the object to be fired is suppressed from rising. . For this reason, it is suitable for flexible film materials such as PET that are easily affected by heat.

  Oxygen is necessary for the reaction at the time of ultraviolet irradiation, but since vacuum ultraviolet rays are absorbed by oxygen, the efficiency in the ultraviolet irradiation process is likely to decrease. It is preferable to carry out 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 20000 ppm by volume, more preferably in the range of 50 to 10,000 ppm by volume. Also, the water vapor concentration during the conversion process is preferably in the range of 1000 to 4000 ppm by volume.

  As a gas that satisfies the irradiation atmosphere used at the time of irradiation with vacuum ultraviolet rays, a dry inert gas is preferable, and a dry nitrogen gas is particularly preferable from the viewpoint of cost. The oxygen concentration can be adjusted by measuring the flow rate of oxygen gas and 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 Is more preferable, and it is still more preferable in it being in the range of 50-160 mW / cm < ² >. If it is 1 mW / cm ² or more, sufficient reforming efficiency is obtained, and if it is 10 W / cm ² or less, it is difficult to cause ablation in the coating film and damage the substrate.

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 More preferably within the range of / cm ² . If it is 10 mJ / cm ² or more, the modification can proceed sufficiently. If it is 10,000 mJ / cm ² or less, cracking due to over-reformation and thermal deformation of the substrate are unlikely to occur.

Further, the vacuum ultraviolet light used for the modification may be generated by plasma formed of a gas containing at least one of CO, CO ₂ and CH ₄ . Further, as the gas containing at least one of CO, CO ₂ and CH ₄ (hereinafter also referred to as 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 carbon-containing gas. Examples of the plasma generation method include capacitively coupled plasma.

Moreover, although the film density of a metal (M2) content layer is set appropriately according to the objective, it is preferable to exist in the range of 1.5-2.6 g / cm < ³ >. Within this range, the density of the film becomes higher, and the gas barrier property deterioration and the oxidation deterioration of the film due to humidity hardly occur.

  When the metal (M2) -containing layer has a laminated structure of two or more layers, the metal (M2) -containing layer may consist only of a layer formed by a vacuum film forming method, or only a layer formed by a coating method. Alternatively, a combination of a layer formed by a vacuum film forming method and a layer formed by a coating method may be used.

  Moreover, it is also preferable that a metal (M2) content layer contains a nitrogen atom or a carbon atom from viewpoints, such as stress relaxation property and absorbing an ultraviolet-ray.

<Oxygen deficiency region>
In the functional film of the present invention, the composition in the region where the transition metal (M1) -containing layer and the metal (M2) -containing layer are adjacent (hereinafter also referred to as a mixed region) is (M2) (M1) _x O _y N _z. When expressed by (0.02 <x <50, y> 0, z ≧ 0), it is preferable to satisfy the following formula (1).

(2y + 3z) / (a + bx) <1 Formula (1)
(In the formula (1), a represents the maximum valence of the metal (M2), and b represents the maximum valence of the transition metal (M1).)

  In the region where the transition metal (M1) -containing layer and the metal (M2) -containing layer are adjacent to each other, the oxygen deficiency composition of the composite oxide of the transition metal (M1) and the metal (M2) is more than a predetermined thickness. It represents that it is included.

As described above, the composition of the composite oxide of the transition metal (M1) and the metal (M2) is represented by (M2) (M1) _x O _y N _z . As is clear from this composition, the composite oxide may partially include a nitride structure. Here, the maximum valence of the 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 above composite oxide (including one that is partially nitrided) has a stoichiometric composition, (2y + 3z) / (a + bx) = 1. This formula means that the total number of bonds of transition metal (M1) and metal (M2) is equal to the total number of bonds of O and N, and in this case, transition metal (M1) and metal ( Both M2) are bonded to either O or N. In addition, in this invention, when 2 or more types are used together as a metal (M2), or when 2 or more types are used together as a transition metal (M1), the maximum valence of each element is set to the abundance ratio of each element. The composite valence calculated by performing the weighted average according to is adopted 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 transition metal (M1) and metal (M2). This state is an “oxygen deficiency” of the composite oxide. In the oxygen deficient state, the remaining bonds of the transition metal (M1) and the metal (M2) have a possibility of bonding to each other, and when the metals of the transition metal (M1) and the metal (M2) are directly bonded to each other. It is considered that a denser and higher-density structure is formed than in the case of bonding between metals via O or N, and as a result, gas barrier properties are improved.

The mixed region is a region that satisfies 0.02 <x <50. In this region, since both the transition metal (M1) and the metal (M2) are involved in the direct bonding between the metals, the region satisfying this condition is present in a thickness of a predetermined value or more, so that the gas barrier property is improved. It is thought that it contributes to improvement.
In addition, since it is thought that the closer the abundance ratio of the transition metal (M1) and the metal (M2), the more the gas barrier property can be improved, the mixed region is a region satisfying 0.1 <x <10. It is preferable to include a thickness of 5 nm or more, more preferably include a region satisfying 0.2 <x <5 at a thickness of 5 nm or more, and a region satisfying 0.3 <x <4 to a thickness of 5 nm or more. It is further preferable to contain.

As described above, it has been confirmed that if there is a mixed region satisfying (2y + 3z) / (a + bx) <1.0, the effect of improving the gas barrier property is exhibited. As a maximum value, (2y + 3z) / (a + bx) ≦ 0.9 is preferably satisfied, (2y + 3z) / (a + bx) ≦ 0.85 is more preferable, and (2y + 3z) / (a + bx) ≦ 0. 8 is more preferably satisfied.
Here, the smaller the value of (2y + 3z) / (a + bx) in the mixed region, the higher the gas barrier property, but the greater the absorption in visible light. 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 further preferable.

In the present invention, 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. More preferably, it is more preferably 20 nm or more.

  The functional film having the above-described configuration exhibits a gas barrier property that is very high enough to 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, a functional film is formed by using an oxygen-deficient composition film of a transition metal (M1) compound (oxide) alone, or a metal (M2) compound ( When a functional film is formed by using an oxygen-deficient oxygen deficient composition film alone, the gas barrier property tends to improve as the degree of oxygen deficiency increases, but the gas barrier property is significantly improved. It was not connected. In response, a transition metal (M1) -containing layer containing a compound (oxide) containing a transition metal (M1) as a main component and a metal (M2) containing a compound (oxide) containing a metal (M2) as a main component When the mixed layer is laminated to form a mixed region where the transition metal (M1) and the metal (M2) are present at the same time, and the mixed region has an oxygen deficient composition, the gas barrier increases as the degree of oxygen deficiency increases. It has been found that the properties are further improved.
This is because, as described above, the transition metal (M1) and the metal (M2) are more easily bonded than the transition metal (M1) and the metal (M2). This is probably because a dense and high-density structure is formed in the mixed region by making the region have an oxygen deficient composition.

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

As a method for producing the mixed region described above, a co-evaporation method can be preferably used. The co-evaporation method is preferably a co-sputtering method. The co-sputtering method employed in the present invention includes, for example, a composite target made of an alloy containing both transition metal (M1) and metal (M2), or a composite oxide of transition metal (M1) and metal (M2). It can be a single sputtering using a composite target as a sputtering target. Further, the co-sputtering method in the present invention is multi-source simultaneous sputtering using a plurality of sputtering targets including a single element of transition metal (M1) or its oxide and a single element of metal (M2) or its oxide. Good. Regarding the method for producing these sputtering targets and the method for producing a thin film made of a complex oxide using these sputtering targets, for example, JP 2000-160331 A, JP 2004-068109 A, JP Reference can be made to the description of JP2013-047361A. The film forming conditions for performing the co-evaporation method include the ratio of transition metal (M1) and oxygen in the film forming raw material, the ratio of inert gas to reactive gas during film formation, and the film forming condition. Examples include one or more conditions selected from the group consisting of the gas supply amount, the degree of vacuum during film formation, and the power during film formation, and these film formation conditions (preferably oxygen partial pressure) ) Can be adjusted to form a thin film made of a complex oxide having an oxygen-deficient composition.
That is, by forming the transition metal (M1) -containing layer and the metal (M2) -containing layer using the co-evaporation method as described above, almost all regions in the thickness direction can be mixed regions. For this reason, according to such a method, a desired gas barrier property can be realized by an extremely simple operation of controlling the thickness of the mixed region. In addition, what is necessary is just to adjust the film-forming time at the time of implementing a co-evaporation method, for example, in order to control the thickness of a mixing area | region.

<Organic silicon compound-containing layer (6, 26)>
As shown in FIGS. 1 and 2, the organosilicon compound-containing layer according to the present invention is formed on the side opposite to the base material of the transition metal (M1) -containing layer.
The functional film of the present invention is organic silicon so that the transition metal (M1) contained in the transition metal (M1) -containing layer and the UV curable resin constituting the QD-containing resin layer are bonded via a chemical bond. A compound-containing layer is formed. By adopting such a configuration, a strong bond is formed between the transition metal (M1) -containing layer and the QD-containing resin layer, and as a result, the adhesion between these two layers is improved. The peel strength is improved.

  The thickness of the organosilicon compound-containing layer is preferably 30 nm or less, more preferably 25 nm or less, still more preferably 20 nm or less, and particularly preferably less than 20 nm. In the present invention, the thickness of the organosilicon compound-containing layer is measured by a transmission electron microscope (TEM).

As described above, for example, as shown in FIG. 1, a functional group such as a (meth) acryloyl group is exposed on the exposed surface of the transition metal (M1) -containing layer as a method of thinly forming the organosilicon compound-containing layer. Thus, the method of forming an organosilicon compound content layer is mentioned.
Here, by setting the thickness of the organosilicon compound-containing layer to 30 nm or less, as shown in FIG. 1, the exposed functional groups can be sufficiently oriented on the surface of the organosilicon compound-containing layer, Moreover, the possibility that the organosilicon compound-containing layer is peeled off due to cohesive failure is also reduced. In addition, by adopting such a configuration, it is difficult for water vapor and oxygen to enter from the side surface of the organosilicon compound-containing layer, so that quantum dots (semiconductors) included in the QD-containing resin layer disposed particularly adjacent to each other Nanoparticles) can also be sufficiently prevented from deteriorating.
On the other hand, when the thickness of the organosilicon compound-containing layer exceeds 30 nm, the influence of moisture intrusion from the side surface of the organosilicon compound-containing layer increases in proportion to the thickness. For example, when an organosilicon compound-containing layer made of a silane coupling agent is thickened, it is considered that alkoxysilyl groups in the silane coupling agent are bonded to each other to form siloxane bonds and aggregate. However, the siloxane bond formed here is different from the strong bond in the SiO ₂ film, etc., and is simply connected by a bond between some incomplete functional groups with a random structure. Can cause cleavage. Therefore, when moisture enters the organic silicon compound-containing layer having such a thick film, the siloxane bond existing in the layer is cleaved, and the cohesive failure is promoted. As a result, the adhesiveness under high-temperature and high-humidity conditions decreases, and deterioration of the QD-containing resin layer is caused due to deterioration of gas barrier properties.

Hereinafter, as a preferred embodiment of the present invention, the organic silicon compound-containing layer is formed in detail so that a functional group such as a (meth) acryloyl group is exposed on the exposed surface of the transition metal (M1) -containing layer. explain.
In the present invention, the acryloyl group is an acyl group derived from acrylic acid represented by “CH ₂ ═CH—C (═O) —”, and the methacryloyl group is “CH ₂ ═C (CH ₃ ) —C (═O) — ”, an acyl group derived from methacrylic acid, and“ (meth) acryloyl group ”is a collective name.

As a preferable aspect of this embodiment, the organosilicon compound-containing layer is formed such that the transition metal compound constituting the transition metal (M1) -containing layer and the ultraviolet curable resin constituting the QD-containing resin layer are bonded via a chemical bond. Is formed. By adopting such a configuration, a strong bond is formed between the transition metal (M1) -containing layer and the QD-containing resin layer, and as a result, the adhesion between these two layers is improved. The peel strength is improved.
In the present invention, the peel strength between the transition metal (M1) -containing layer and the QD-containing resin layer is preferably 2 N / 20 mm or more, more preferably 3 N / 20 mm or more, and further preferably 4 N / 20 mm or more. And particularly preferably 5 N / 20 mm or more. In addition, there is no restriction | limiting in particular about the upper limit of peeling strength. Here, as the value of the peel strength, a value measured using a peel tester FGPX-0.5 manufactured by SHIMPO is adopted.

In the organosilicon compound-containing layer shown in FIG. 1, a reactive group (for example, (meth) acryloyl group-containing compound (for example, (meth) acryloyl group-containing silane coupling agent) other than (meth) acryloyl group. ) The alkoxysilyl group in the acryloyl group-containing silane coupling agent) forms a chemical bond (covalent bond) with the constituent material of the transition metal (M1) -containing layer. As a result, the (meth) acryloyl group becomes a transition metal ( M1) It is preferable that an organosilicon compound-containing layer is formed on the surface of the containing layer.
Here, “the functional group such as (meth) acryloyl group is exposed on the surface of the transition metal (M1) -containing layer” means that the surface layer is scraped and measured by pyrolysis gas chromatography. It is possible to confirm by collating.

As described above, the result of the reactive group other than the (meth) acryloyl group of the (meth) acryloyl group-containing compound forming a chemical bond (covalent bond) with the constituent material of the transition metal (M1) -containing layer Examples of the (meth) acryloyl group-containing compound used in the “form in which the (meth) acryloyl group is exposed” include compounds containing a (meth) acryloyl group and an alkoxysilyl group in one molecule.
By using a compound containing a (meth) acryloyl group and an alkoxysilyl group in one molecule as a (meth) acryloyl group-containing compound, the alkoxysilyl moiety contained in the compound forms a bond with the transition metal (M1). can do. As a result, the (meth) acryloyl group contained in the (meth) acryloyl group-containing compound forms a chemical bond with the transition metal (M1) via another atom. By adopting such a configuration, the (meth) acryloyl group can be more firmly connected to the transition metal (M1) -containing layer, and as a result, the ultraviolet curable resin is adjacent to the transition metal (M1) -containing layer. When a layer or the like is provided, there is an advantage that the adhesion at the interface between these two layers can be further improved.

Here, as a compound containing a (meth) acryloyl group and an alkoxysilyl group in one molecule, a silane coupling agent containing a (meth) acryloyl group ((meth) acryloyl group-containing silane coupling agent) is preferably used. . Examples of the (meth) acryloyl group-containing silane coupling agent include 3- (meth) acryloyloxypropyltrimethoxysilane, 3- (meth) acryloyloxypropyltriethoxysilane, 3- (meth) acryloyloxypropylmethyldimethoxysilane, 3 -(Meth) acryloyloxypropylmethyldiethoxysilane, acrylic group-containing alkoxy oligomer and the like.
Examples of commercially available (meth) acryloyl group-containing silane coupling agents include KBM-5103, KBM-502, KBM-503, KBE-502, KBE-503, and KR-513 (manufactured by Shin-Etsu Silicone). It is done. 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 (meth) acryloyl group and alkoxysilyl group in one molecule” other than the (meth) acryloyl group-containing silane coupling agent include, for example, polyorganosilsesquioxy introduced with (meth) acryloyl group. Sun and organic-inorganic hybrid materials such as polysiloxane-modified acrylic resins containing unsaturated double bonds. These materials may be prepared independently with reference to conventionally known knowledge, or commercially available products may be used.

In the above, the organosilicon compound-containing layer is formed such that the transition metal compound constituting the transition metal (M1) -containing layer and the ultraviolet curable resin constituting the QD-containing resin layer are bonded via a chemical bond. The case where the chemical bond is derived from "a compound containing (meth) acryloyl group and alkoxysilyl group in one molecule" has been described as an example, but the functionalities exposed on the surface of the organosilicon compound-containing layer The group is not limited to a (meth) acryloyl group, but may be other functional groups. Examples of such functional groups include polymerizable substituents such as vinyl groups, epoxy groups, styryl groups, isocyanate groups, and amino groups, and mercapto groups.
Examples of such compounds include vinyl group-containing silane coupling agents such as KBM-1003 (manufactured by Shin-Etsu Silicone) and epoxy group-containing silane coupling agents such as KBM-403 (manufactured by Shin-Etsu Silicone).
That is, as a preferred embodiment of the present invention, “a reactive group capable of forming a bond with the transition metal (M1) constituting the transition metal (M1) -containing layer and a raw material for the ultraviolet curable resin constituting the QD-containing resin layer” 1 or 2 or more types selected from the group consisting of an alkoxysilyl group, a (meth) acryloyl group, a vinyl group, and an epoxy group. It is a preferable embodiment that the silane coupling agent contains a functional group (polymerizable substituent).

  Furthermore, as another preferred embodiment of the present invention, for example, on the organosilicon compound layer containing the above-mentioned (meth) acryloyl group-containing silane coupling agent, other than the (meth) acryloyl group-containing silane coupling agent Examples include a form in which a layer containing a material (for example, an acrylic monomer described later) is provided.

As a method of forming the organosilicon compound-containing layer on the surface of the transition metal (M1) -containing layer, a compound capable of forming the organosilicon compound-containing layer (for example, the above-described (meth) acryl group-containing silane coupling agent, etc. 1 reactive group capable of forming a bond with the transition metal compound constituting the transition metal (M1) -containing layer and 1 reactive group capable of forming a bond with the raw material of the ultraviolet curable resin constituting the QD-containing resin layer An example is a method in which a solution obtained by dissolving a compound “) in a molecule”) in an appropriate solvent is applied to the surface of the transition metal (M1) -containing layer and dried.
In this case, examples of the solvent used include toluene, xylene, other high boiling aromatic solvents, ester solvents such as butyl acetate, ethyl acetate, and cellosolve acetate, ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone, and methanol. And alcohol solvents such as ethanol and isopropyl alcohol, and ether solvents such as diethyl ether, dibutyl ether, tetrahydrofuran, dioxane, ethylene glycol monomethyl ether, propylene glycol monomethyl ether diethylene glycol monomethyl ether, and the like.

Examples of materials other than the above-described (meth) acryloyl group-containing silane coupling agent include compounds containing a (meth) acryloyl group.
Examples of the (meth) acryloyl group-containing compound other than the (meth) acryloyl group-containing silane coupling agent include polyol poly (meth) acrylate, epoxy (meth) acrylate, urethane (meth) acrylate, and (meth) acrylic monomer. .

  Polyol poly (meth) acrylate is an ester obtained from polyol and (meth) acrylic acid. The polyol selected here is not particularly limited, and examples thereof include 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 1,5-pentanediol, neopentyl glycol, 3-methyl- 1,5-pentanediol, 1,6-hexanediol, 2-methyl-1,8-octanediol, 1,9-nonanediol, 2-ethyl-2-butyl-1,3-propanediol, 2,4 -Chain aliphatic polyols such as diethyl-1,5-pentanediol, 1,10-decanediol, 1,12-dodecanediol, polyolefin polyol, hydrogenated polyolefin polyol, and more, 1,4-cyclohexane Dimethanol, 1,3-cyclohexanedimethanol, tricyclo [5.2.1.02,6] decanedimeta And polyols having an alicyclic structure such as 2-methylcyclohexane-1,1-dimethanol, and further trimer triol, p-xylylene glycol, bisphenol A ethylene oxide adduct, bisphenol F ethylene oxide addition And polyols having an aromatic ring such as biphenol ethylene oxide adduct, and further polyether polyols such as polyethylene glycol, polypropylene glycol and polytetramethylene glycol, and further, polyhexamethylene adipate, polyhexaethylene Examples include polyester polyols such as methylene succinate and polycaprolactone, and α, ω-poly (1,6-hexylene carbonate) diol, α, ω-poly (3-methyl-1,5-pentylene carbonate). -Bonate) diol, α, ω-poly [(1,6-hexylene: 3-methyl-pentamethylene) carbonate] diol, α, ω-poly [(1,9-nonylene: 2-methyl-1,8-octylene) (Poly) carbonate diols such as carbonate) diol. These may be used alone or in combination of two or more.

  Epoxy (meth) acrylate is a compound obtained by adding (meth) acrylic acid to the terminal epoxy group of an epoxy resin. There is no restriction | limiting in particular as an epoxy resin, For example, a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a novolak type epoxy resin, a glycidyl ester type epoxy resin, a biphenyl type epoxy resin etc. are mentioned. These may be used alone or in combination of two or more.

Urethane (meth) acrylate is a compound obtained by reacting polyol and polyisocyanate with hydroxy group-containing (meth) acrylate, or polyol and isocyanato group-containing (meth) acrylate. The polyol, polyisocyanate, hydroxy group-containing (meth) acrylate and isocyanato group-containing (meth) acrylate are not particularly limited.
The polyol is the same as the polyol used in the polyol poly (meth) acrylate.
Examples of the polyisocyanate include 1,4-cyclohexane diisocyanate, isophorone diisocyanate, methylene bis (4-cyclohexyl isocyanate), 1,3-bis (isocyanatomethyl) cyclohexane, 1,4-bis (isocyanatomethyl) cyclohexane, , 4-tolylene diisocyanate, 2,6-tolylene diisocyanate, diphenylmethane-4,4'-diisocyanate, 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, lysine triisocyanate, lysine diisocyanate, hexamethylene diisocyanate 2,4,4-trimethylhexamethylene diisocyanate, 2,2,4-trimethylhexanemethylene diisocyanate, norbornane diisocyanate, etc. It is. These may be used alone or in combination of two or more.
Examples of the hydroxy group-containing (meth) acrylate include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4- Examples include hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2-hydroxy-3- (o-phenylphenoxy) propyl (meth) acrylate, and 2-hydroxyethyl (meth) acrylamide. . These may be used alone or in combination of two or more.
Examples of the isocyanato group-containing (meth) acrylate include 2-isocyanatoethyl (meth) acrylate. These may be used alone or in combination of two or more.

  The (meth) acrylic monomer is a compound obtained by removing the above polyol poly (meth) acrylate, epoxy (meth) acrylate and urethane (meth) acrylate from the above-mentioned (meth) acryloyl group-containing compound.

  Examples of (meth) acrylic monomers include (meth) acryloyl-containing compounds having a cyclic ether group such as glycidyl (meth) acrylate and tetrahydrofurfuryl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, and di Cyclic fats such as cyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentanylethyl (meth) acrylate, 4-tert-butylcyclohexyl (meth) acrylate Monofunctional (meth) acryloyl group-containing compound having a group, lauryl (meth) acrylate, isononyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isobutyl (meth) acrylic , Tert-butyl (meth) acrylate, isooctyl (meth) acrylate, monofunctional (meth) acryloyl group-containing compounds having a chain aliphatic group such as isoamyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl ( Monofunctional (meth) acryloyl group-containing compound having an aromatic ring such as (meth) acrylate, polyethylene glycol di (meth) acrylate, decanediol di (meth) acrylate, nonanediol di (meth) acrylate, hexanediol di (meth) acrylate , Tricyclodecane dimethanol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaeri Ritorupenta (meth) acrylate, and polyfunctional (meth) acryloyl group-containing compounds such as dipentaerythritol hexa (meth) acrylate. In the present invention, the monofunctional (polyfunctional) (meth) acryloyl group-containing compound is also simply referred to as “monofunctional (polyfunctional) (meth) acrylate compound”.

  Moreover, as a method of exposing the (meth) acryloyl group of the (meth) acryloyl group-containing compound other than the (meth) acryloyl group-containing silane coupling agent, the above (meth) acryloyl group-containing compound is suitable as described above. A method in which a solution dissolved in a solvent is applied to the surface of the organosilicon compound-containing layer and dried is exemplified. At this time, a suitable photopolymerization initiator is added to the solution, and the coating obtained by applying the solution and drying is subjected to a light irradiation treatment, and a part of the (meth) acryloyl group-containing compound. May be polymerized to form a polymerizable polymer. However, if it is completely polymerized, the unreacted (meth) acryloyl group disappears, so the polymerization should not be performed completely.

  The photopolymerization initiator is not particularly limited as long as it is a compound that generates radicals that contribute to the initiation of radical polymerization upon irradiation with light such as near infrared rays, visible rays, and ultraviolet rays. Examples of the photopolymerization initiator include acetophenone, acetophenone benzyl ketal, 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-1,2-diphenylethane-1-one, xanthone, fluorenone, benzaldehyde, fluorene, anthraquinone, tri Phenylamine, carbazole, 3-methylacetophenone, 4-chlorobenzophenone, 4,4'-dimethoxybenzophenone, 4,4'-diaminobenzophenone, benzoin propyl ether, benzoin ethyl ether, benzyldimethyl ketal, 1- (4-isopropylphenyl) ) -2-hydroxy-2-methylpropan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, thioxanthone, diethylthioxanthone, -Isopropylthioxanthone, 2-chlorothioxanthone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholino Phenyl) -butanone-1,4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis- (2,6-dimethoxybenzoyl) ) -2,4,4-trimethylpentylphosphine oxide, oligo (2-hydroxy-2-methyl-1- (4- (1-methylvinyl) phenyl) propanone) and the like. Moreover, a metallocene compound can also be used as a photopolymerization initiator. These photopolymerization initiators can be used alone or in combination of two or more.

  In addition, the said solution may contain a filler for the purpose of slipperiness and winding-up property. Examples of the filler include silica-based inorganic fillers such as quartz, fumed silica, precipitated silica, anhydrous silica, fused silica, crystalline silica, and ultrafine powder amorphous silica, titanium oxide, zinc oxide, zirconium oxide, and niobium oxide. And metal oxide inorganic fillers such as aluminum oxide, cerium oxide, and yttrium oxide. Among these, silica-based inorganic fillers are particularly preferable. In addition, the shape of the filler is preferably spherical, and the particle size is preferably in the range of 10 to 50 μm.

  The content of the (meth) acryloyl group-containing compound is preferably in the range of 80 to 100% by mass with respect to 100% by mass of the solid content contained in the solution obtained by dissolving the (meth) acryloyl group-containing compound in a solvent. Yes, the content of the photopolymerization initiator is preferably in the range of 0 to 5% by mass, and the content of the filler is preferably in the range of 0 to 20% by mass.

<Other parts>
The functional film of the present invention essentially includes a base material, a transition metal-containing layer, and an organosilicon compound-containing layer, but may further include other members. The functional film of the present invention is, for example, a transition metal when a plurality of transition metal (M1) -containing layers and / or metal (M2) -containing layers are present between the substrate and the transition metal (M1) -containing layer. The (M1) -containing layer and / or the metal (M2) -containing layer, or another member may be provided on the surface of the base material on which the transition metal (M1) -containing layer is not formed.
Other members are not particularly limited, and members used for conventional functional films can be used in the same manner or appropriately modified. Specific examples include a base layer (smooth layer, primer layer), an anchor coat layer (anchor layer), a bleed-out prevention layer, a protective layer, a moisture absorption layer, and an antistatic layer functional layer. The other members may be used alone or in combination of two or more. Further, the other member may exist as a single layer or may have a laminated structure of two or more layers.

  Instead of or in addition to the above, the transition metal (M1) -containing layer and / or the metal (M2) -containing layer may exist as a single layer (a layer that can be produced in one step) or two or more layers You may have the laminated structure of. By providing a plurality of layers, the gas barrier property can be further improved. In the latter case, one or more transition metal (M1) -containing layers and / or metal (M2) -containing layers exist as one unit or in a state where two or more of the above units are laminated. You may do it.

(Underlayer (smooth layer, primer layer))
The functional film of the present invention may have an underlayer (smooth layer, primer layer) between the base material and the transition metal (M1) -containing layer, for example. The underlayer is flattened by flattening the rough surface of the substrate on which protrusions and the like exist, or by filling the irregularities and pinholes generated in the transition metal (M1) -containing layer with the protrusions existing on the substrate. Provided for. Such an underlayer may be formed of any material, but preferably includes a carbon-containing polymer, and more preferably includes a carbon-containing polymer. That is, it is preferable that the functional film of the present invention further has an underlayer containing a carbon-containing polymer between the base material and the transition metal (M1) -containing layer.

  The underlayer also contains a carbon-containing polymer, preferably a curable resin. The curable resin is not particularly limited, and the active energy ray curable resin or the thermosetting material obtained by irradiating the active energy ray curable material with an active energy ray such as ultraviolet ray to be cured is heated. The thermosetting resin etc. which are obtained by curing by the above method. The curable resins may be used alone or in combination of two or more.

  As an active energy ray curable material used for forming the underlayer, specifically, UV curable organic / inorganic hybrid hard coat material OPSTAR (registered trademark) series manufactured by JSR Corporation (polymerizable unsaturated group on silica fine particles) And a compound obtained by bonding an organic compound having a compound (a). Further, as thermosetting materials, specifically, TutProm series (Organic polysilazane) manufactured by Clariant, SP COAT heat-resistant clear paint manufactured by Ceramic Coat, Nanohybrid silicone manufactured by Adeka, manufactured by DIC Corporation Unidic (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., Nittobo Co., Ltd. Company-made inorganic / organic nanocomposite material SSG coat, thermosetting urethane resin consisting of acrylic polyol and isocyanate prepolymer, phenol resin, urea melamine resin, epoxy resin, unsaturated polyester resin, silicone resin, polyamidoamine-epichlorohydrin Butter, and the like can be mentioned.

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

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

  Although it does not restrict | limit especially as thickness of a base layer, The inside of the range of 0.1-10 micrometers is preferable.

(Anchor coat layer (anchor layer))
On the surface of the substrate according to the present invention, an anchor coat layer (anchor layer) may be formed as an easy adhesion layer for the purpose of improving adhesiveness (adhesion). As an anchor coat agent used for this anchor coat layer, polyester resin, isocyanate resin, urethane resin, acrylic resin, ethylene vinyl alcohol resin, vinyl modified resin, epoxy resin, modified styrene resin, modified silicon resin, alkyl titanate, etc. One type or two or more types can be used in combination.
A commercially available product may be used as the anchor coating agent. Specifically, a siloxane-based UV curable polymer solution (manufactured by Shin-Etsu Chemical Co., Ltd., 3% isopropyl alcohol solution of “X-12-2400”) can be used.

  The thickness of the anchor coat layer is not particularly limited, but is preferably about 0.5 to 10.0 μm.

(Bleed-out prevention layer)
The functional film of the present invention can further have a bleed-out prevention layer. The bleed-out prevention layer is used for the purpose of suppressing a phenomenon in which unreacted oligomers and the like migrate from the film base material to the surface when the film having the base layer is heated, and contaminate the contact surface. It is provided on the opposite surface of the substrate. The bleed-out prevention layer may basically have the same configuration as the underlayer as long as it has this function.

  Compounds that can be included in the bleed-out prevention layer include polyunsaturated organic compounds having two or more polymerizable unsaturated groups in the molecule, or one polymerizable unsaturated group in the molecule. Hard coat agents such as unitary unsaturated organic compounds can be mentioned.

  The thickness of the bleed-out prevention layer is in the range of 1 to 10 μm, preferably in the range of 2 to 7 μm.

<QD-containing resin layer (light emitting layer) (14)>
Hereinafter, quantum dots (QD), resins, and the like, which are main components of the QD-containing resin layer, will be described.

(Quantum dot)
In general, semiconductor nanoparticles exhibiting a quantum confinement effect with a nanometer-sized semiconductor material are also referred to as “quantum dots”. Such a quantum dot is a small lump within about 10 and several nanometers in which several hundred to several thousand semiconductor atoms are gathered, but when absorbing energy from an excitation source and reaching an energy excited state, the energy of the quantum dot Releases energy corresponding to the band gap.
Therefore, it is known that quantum dots have unique optical characteristics due to the quantum size effect. Specifically, (1) By controlling the size of the particles, various wavelengths and colors can be emitted. (2) The absorption band is wide and fine particles of various sizes can be obtained with a single wavelength of excitation light. It has the characteristics that it can emit light, (3) it has a symmetrical fluorescence spectrum, and (4) it has excellent durability and fading resistance compared to organic dyes.

  The quantum dots contained in the QD-containing resin layer may be known, and can be generated using any method known to those skilled in the art. For example, suitable QDs and methods for forming suitable QDs include US Pat. No. 6,225,198, US 2002/0066401, US Pat. No. 6,207,229, US Pat. No. 6,322,901. Description, US Pat. No. 6,949,206, US Pat. No. 7,572,393, US Pat. No. 7,267,865, US Pat. No. 7,374,807, US Patent Application No. 11/299299, and US Pat. No. 6,861,155 Can be mentioned.

The QD is generated 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, BeS, 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 include but are more than one suitable combination of such semiconductor, and the like.

  In the present invention, 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 be preferably used.

(resin)
Resin can be used for a QD containing resin layer as a binder holding a quantum dot. For example, polycarbonate, polyarylate, polysulfone (including polyethersulfone), polyester such as polyethylene terephthalate, polyethylene naphthalate, polyethylene, polypropylene, cellophane, cellulose diacetate, cellulose triacetate, cellulose acetate Cellulose esters such as pionate and cellulose acetate butyrate, polyvinylidene chloride, polyvinyl alcohol, ethylene vinyl alcohol, syndiotactic polystyrene, norbornene, polymethylpentene, polyether ketone, polyether ketone imide And acrylic resins such as polyamide resins, fluororesins, nylon resins, and polymethyl methacrylate.
The QD-containing resin layer preferably has a thickness in the range of 50 to 200 μm.
The optimum amount of quantum dots in the QD-containing resin layer varies depending on the compound used, but is generally preferably in the range of 15 to 60% by volume.

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto.

<< Production of functional film >>
<Preparation of functional film 101>
(Preparation of base material)
A polyethylene terephthalate (PET) film with a double-sided easy-adhesion layer having a thickness of 125 μm (U34, manufactured by Toray Industries, Inc.) was used as a substrate.

(Formation of underlayer)
JSR Co., Ltd. UV curable organic / inorganic hybrid hard coating material OPSTA Z7501 diluted with butyl acetate to a solid content concentration of 35%, the coating surface side of the substrate so that the dry film thickness is 2 μm After coating with a bar coater, drying was performed at 80 ° C. for 2 minutes as a drying condition. Next, under an air atmosphere, ultraviolet irradiation treatment was performed with a high-pressure mercury lamp under conditions of 700 mW / cm ² and 250 mJ / cm ² to form an underlayer.

(Formation of metal (M2) -containing layer)
A dibutyl ether solution containing 20% 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% dibutyl ether solution of Perhydropolysilazane (Merck Performance Materials LLC, NAX120-20) in a ratio of 4: 1 (mass ratio), and further adjusting the dry film thickness Therefore, a coating solution was prepared by diluting with dibutyl ether to a solid content concentration of 5%.

Then, after apply | coating the coating liquid prepared above with the bar coater on the exposed surface by the side of the base layer of the laminated | multilayer film of a base material and a base layer, it dried for 1 minute at 80 degreeC as drying conditions. Next, the dried coating film was subjected to a vacuum ultraviolet ray irradiation treatment 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 to obtain a metal (M2 ), A 100 nm thick metal (M2) -containing layer made of Si oxynitride containing Si was formed.

(Formation of transition metal (M1) -containing layer)
A transition metal (M1) -containing layer is formed on the metal (M2) -containing layer by a vapor phase method / sputtering (magnetron sputtering apparatus, manufactured by Canon Anelva: Model EB1100 (hereinafter, the same apparatus is used for sputtering)). A film was formed. The used sputtering apparatus can set a plurality of types of targets, and can continuously form a plurality of layers having different metal types while maintaining a predetermined vacuum state.

Here, an oxygen-deficient Nb ₂ O ₅ target was used as the target, Ar and O ₂ were used as process gases, and a transition metal (M1) -containing layer having a thickness of 10 nm was formed by DC sputtering. The sputtering power source power was 5.0 W / cm ² and the film forming pressure was 0.4 Pa. The oxygen partial pressure was 10%. As for the layer thickness, data on the change in the layer thickness with respect to the film formation time is obtained within the range of 100 to 300 nm, the layer thickness formed per unit time is calculated, and then the film is formed so that the set layer thickness is obtained. The layer thickness was adjusted by setting the time. Hereinafter, in the film formation by sputtering, similarly, the film thickness formed per unit time is calculated and the conditions are applied.

(Formation of organosilicon compound-containing layer)
A transition metal obtained by diluting a mercapto group-containing silane coupling agent KBM-803 (manufactured by Shin-Etsu Silicone) with propylene glycol monomethyl ether (PGME) to a solid content concentration of 1% so that the dry film thickness becomes 20 nm. (M1) The exposed surface of the containing layer was coated with a bar coater. Then, the functional film 101 was produced by forming the organosilicon compound containing layer which consists of a mercapto group containing silane coupling agent by drying at 80 degreeC for 1 minute.

<Preparation of functional film 102>
In the production of the functional film 101, in place of KBM-803 which is a silane coupling agent, KBM-903 which is an amino group-containing silane coupling agent (manufactured by Shin-Etsu Silicone Co., Ltd.) is used in the same manner. A film 102 was produced.

<Production of functional film 103>
In the production of the functional film 101, functionalities were similarly obtained except that KBM-5103 (manufactured by Shin-Etsu Silicone Co., Ltd.), which is an acryloyl group-containing silane coupling agent, was used instead of KBM-803, which is a silane coupling agent. A film 103 was produced.

<Preparation of functional film 104>
In the production of the functional film 101, in place of KBM-803 which is a silane coupling agent, KBM-503 (manufactured by Shin-Etsu Silicone Co.) which is a methacryloyl group-containing silane coupling agent is used in the same manner. A film 104 was produced.

<Production of functional film 105>
In the production of the functional film 101, the functionality is the same except that KBM-1003 (manufactured by Shin-Etsu Silicone Co., Ltd.) which is a vinyl group-containing silane coupling agent is used instead of KBM-803 which is a silane coupling agent. A film 105 was produced.

<Preparation of functional film 106>
In the production of the functional film 101, a functional film 106 was produced in the same manner except that KBM-403, which is an epoxy group-containing silane coupling agent, was used instead of KBM-803, which is a silane coupling agent.

<Preparation of functional film 107>
In the production of the functional film 103, the functional film 107 was produced in the same manner except that the organic silicon compound-containing layer was formed as follows.

(Formation of organosilicon compound-containing layer)
KR-513 (acrylic equivalent 210 g / mol, acryloyl group-containing oligomer type silane coupling agent containing acryloyl group and methoxy group) diluted with propylene glycol monomethyl ether (PGME) to a solid content concentration of 1% The applied coating solution was applied to the exposed surface of the transition metal (M1) -containing layer with a bar coater so that the dry film thickness was 100 nm. Then, the organosilicon compound containing layer which consists of the said acryloyl group containing oligomer type silane coupling agent was formed by drying at 80 degreeC for 1 minute.

<Production of functional film 108>
In the production of the functional film 103, except that 1% by mass of ALCH (aluminum ethyl acetoacetate diisopropylate) manufactured by Kawaken Fine Chemical Co., Ltd. was added to PHPS to form a metal (M2) containing layer, A functional film 108 was produced.

<Production of functional film 109>
In the production of the functional film 103, the functional film 109 was produced in the same manner except that the metal (M2) -containing layer was formed as follows.

(Formation of metal (M2) -containing layer)
The obtained laminated film of the base material and the underlayer was placed in a take-up magnetron sputtering apparatus and evacuated to 3 × 10 ⁻⁶ Torr. Thereafter, the laminated film was rolled back, sufficiently degassed, and it was confirmed that there was no fluctuation in moisture pressure even when the laminated film was conveyed. Here, an Al target was used as a sputtering target. Thereafter, an O ₂ / Ar mixed gas (O ₂ / Ar = 30/100 (volume%)) was introduced into the tank at 100 sccm. After maintaining the pressure at 8.0 × 10 ⁻⁴ Torr, the main roll temperature was set to room temperature (25 ° C.), the input power density was set to 1 W / cm ² , and the film speed was Vf = 1.0 m / min. Sputtering was performed to form a metal (M2) -containing layer (composition AlO _1.5 ) having a thickness of 150 nm.

<Preparation of functional film 110>
In the production of the functional film 103, an Fe target is used as a target, Ar and O ₂ are used as process gases, an oxygen partial pressure is set to 20%, and a transition metal (M1) having a thickness of 10 nm is contained by DC sputtering. A functional film 110 was produced in the same manner except that the layer was formed.

<Preparation of functional film 111>
In the production of the functional film 103, the functional film 111 was produced in the same manner except that the transition metal (M1) -containing layer was formed as follows.

(Formation of transition metal (M1) -containing layer)
Nb (n-OC ₃ H ₇ ) ₅ (manufactured by Kojundo Chemical Laboratory Co., Ltd.) was diluted with isopropanol to a solid content concentration of 5% to prepare a coating solution.
Thereafter, the prepared coating solution was applied onto the metal (M2) -containing layer 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 a vacuum ultraviolet ray irradiation treatment using an 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 3.0 J / cm ² to obtain a thickness of 100 nm. The transition metal (M1) -containing layer was formed.

<Preparation of functional film 112>
In the production of the functional film 109, the functional film 112 was produced in the same manner except that the metal (M2) -containing layer was formed using Si as a target.

<Production of functional film 113>
In the production of the functional film 103, instead of forming the transition metal (M1) -containing layer and the metal (M2) -containing layer, a polycrystalline Si target and an Nb target are used as targets, and Ar and O ₂ are used as process gases. Then, the functional film 113 was produced in the same manner except that the dual simultaneous sputtering was performed by the DC method to form the transition metal (M1) -containing layer and the metal (M2) -containing layer. At this time, the sputtering conditions for the polycrystalline Si target, the sputtering conditions for the metal Nb target, and the oxygen partial pressure during DC sputtering are set so that the composition ratio of the transition metal (M1) to the metal (M2) is 1: 1. It was adjusted.

<Production of functional film 114>
In the production of the functional film 112, the functional film 114 was produced in the same manner except that the transition metal (M1) -containing layer was formed as follows.

(Formation of transition metal (M1) -containing layer)
Nb (n-OC ₃ H ₇ ) ₅ (manufactured by Kojundo Chemical Laboratory Co., Ltd.) was diluted with isopropanol to a solid content concentration of 5% to prepare a coating solution.
Thereafter, the prepared coating solution was applied onto the metal (M2) -containing layer 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 a vacuum ultraviolet ray irradiation treatment using an 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 3.0 J / cm ² to obtain a thickness of 100 nm. The transition metal (M1) -containing layer was formed.

<Production of functional film 115>
In the production of the functional film 103, the functional film 115 was produced in the same manner except that the organic silicon compound-containing layer was formed as follows.

(Formation of organosilicon compound-containing layer)
Solid content of 50% by mass of dipentaerythritol hexaacrylate which is a polyfunctional acrylate compound and 50% by mass of KBM-5103 (manufactured by Shin-Etsu Silicone) which is an acryloyl group-containing silane coupling agent is solidified with propylene glycol monomethyl ether (PGME). A coating solution for forming an organosilicon compound-containing layer was prepared by diluting to a partial concentration of 1%.
Next, this organosilicon compound-containing layer forming coating solution was applied to the exposed surface of the transition metal (M1) -containing layer with a bar coater so that the dry film thickness was 100 nm, and then dried at 80 ° C. for 1 minute. Drying was performed.
Next, an organic silicon compound-containing layer was formed by performing an ultraviolet irradiation treatment with a high-pressure mercury lamp under conditions of 500 mW / cm ² and 200 mJ / cm ^{2 in} an air atmosphere.

<Preparation of functional film 116>
In the production of the functional film 103, the functional film 116 was produced in the same manner except that the organic silicon compound-containing layer was formed as follows.

(Formation of organosilicon compound-containing layer)
A coating film obtained by diluting an organic-inorganic hybrid (acrylic resin-silica hybrid) material, COMPOCERAN AC601 (manufactured by Arakawa Chemical Industries, Ltd.) with propylene glycol monomethyl ether (PGME) to a solid content concentration of 1%, has a dry film thickness of 100 nm. It was applied to the exposed surface of the transition metal (M1) -containing layer with a bar coater so that Then, the organic silicon compound containing layer which consists of organic-inorganic hybrid material was formed by drying at 80 degreeC for 1 minute.

<Preparation of functional film 117>
In the production of the functional film 103, a functional film 117 was produced in the same manner except that the metal (M2) -containing layer was not formed.

<Preparation of functional film 118>
In the production of the functional film 108, the functional film 118 was produced in the same manner except that the base material having no underlayer was used instead of the base material (U34) on which the underlayer was formed.

(Preparation of base material)
A polyethylene terephthalate (PET) film with a double-sided easy-adhesion layer having a thickness of 125 μm (UH13, manufactured by Toray Industries, Inc.) was used as a substrate. However, the said base material (UH13) was provided with the high-refractive-index easy-adhesion layer on the single side | surface, and the metal (M2) containing layer formed continuously was provided in the high-refractive-index easy-adhesion layer side.

The functional film 118 was subjected to the following composition analysis.
Specifically, the composition distribution profile was measured in the thickness direction from the surface side (organosilicon compound-containing layer side) of the functional film 118 by XPS analysis. XPS analysis conditions are as follows.

(XPS analysis conditions)
・ Device: QUANTERASXM manufactured by ULVAC-PHI
・ X-ray source: Monochromatic Al-Kα
・ Sputtering ion: Ar (2 keV)
Depth profile: The measurement was repeated at a predetermined thickness interval with a SiO ₂ equivalent sputtering thickness to obtain a depth profile in the thickness direction. The thickness interval was 1 nm (data every 1 nm is obtained in the thickness direction).
Quantification: The background was determined by the Shirley method, and quantified using the relative sensitivity coefficient method from the obtained peak area. 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 mixed region (region where the transition metal (M1) -containing layer and the metal (M2) -containing layer are adjacent) is (M2) (M1) _x O _y N _z (0.02 <x <50, y > 0, z ≧ 0), it was confirmed that the region satisfying the following formula (1) had a thickness of 25 nm in the thickness direction. Here, (M2) is Si and (M1) is Nb. In this region, Al was not detected.

(2y + 3z) / (a + bx) <1 Formula (1)
(In the formula (1), a represents the maximum valence 4 of the metal (M2), and b represents the maximum valence 5 of the transition metal (M1).)

Further, the region satisfying (2y + 3z) / (a + bx) ≦ 0.8 had 6 nm.
The minimum value of (2y + 3z) / (a + bx) in the mixed region of the functional film 118 was 0.63.

<Preparation of functional film 119>
In the production of the functional film 103, a functional film 119 was produced in the same manner except that the transition metal (M1) -containing layer was not formed.

<Preparation of functional film 120>
In the production of the functional film 103, the functional film 120 was produced in the same manner except that the transition metal (M1) -containing layer and the organosilicon compound-containing layer were not formed.

<Preparation of functional film 121>
In the production of the functional film 103, a functional film 121 was produced in the same manner except that the organic silicon compound-containing layer was not formed.

<Preparation of functional film 122>
In the production of the functional film 103, the functional film 122 was produced in the same manner except that the metal (M2) -containing layer, the transition metal (M1) -containing layer, and the organosilicon compound-containing layer were not formed.

<Evaluation>
<Evaluation of water vapor barrier property (WVTR)>
About each produced functional film, the water vapor | steam barrier property after storage for 100 hours in an environment of 60 degreeC and 90% RH was evaluated. The evaluation of water vapor barrier property was carried out using AQUATRAN manufactured by MOCON, measuring the water vapor permeability (g / (m ² · day)) after waiting for the numerical value to stabilize under the conditions of 38 ° C. and 100% RH, and evaluated as follows. Evaluation was made according to criteria.
The evaluation results are shown in Table 1.

Less than 5: 1 × 10 ⁻² (g / (m ² · day)) 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 2 × 10 ⁻¹ (g / (m ² · day)) 1: 2 × 10 ⁻¹ (g / (m ² · day)) or more

<Evaluation of adhesiveness>
First, 3% by mass of a polymerization initiator (BASF Japan, Irgacure 184) is added to 100% by mass of the polyfunctional acrylate compound to pentaerythritol diacrylate, which is a polyfunctional acrylate compound, and resin A is added. Prepared.

  On the other hand, semiconductor nanoparticles (CdSe / ZnS) emitting red and green light were respectively synthesized according to the method described in JP-T 2013-505347. The semiconductor nanoparticles were dispersed in a toluene solvent so 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 solution for forming an acrylic resin-containing light emitting layer in which the content of semiconductor nanoparticles was 1% (solid content).

This acrylic resin-containing light-emitting layer-forming coating solution was applied on each organosilicon compound-containing layer of each functional film thus produced to form a quantum dot (QD) -containing coating film. Subsequently, it arrange | positions so that the organosilicon compound content layer side of the same functional film may touch a quantum dot (QD) containing coating film (a quantum dot (QD) containing coating film was pinched | interposed with two functional films), and 800 mW. An acrylic resin-containing light-emitting layer corresponding to each of the functional films 101 to 122 by curing the quantum dot-containing coating film by applying an ultraviolet irradiation treatment with a high-pressure mercury lamp under the conditions of / cm ² and 300 mJ / cm ² ( A QD sheet for evaluation having a QD-containing resin layer) was produced. In the production of the QD sheet for evaluation corresponding to the functional film 106, a resin A was prepared using Epotech OG-142 (Epotech), which is an epoxy resin, instead of pentaerythritol diacrylate.
The thickness of the cured layer (QD-containing resin layer) of the quantum dot-containing coating film was 100 μm.
However, when the both surfaces of the quantum dot-containing coating film were sandwiched between two functional films and cured, one functional film was peeled off as a release film, and then the following adhesive evaluation was performed.

Subsequently, adhesiveness was evaluated according to the test method described in JIS K 5600-5-6 about each produced QD sheet for evaluation. Specifically, 100 grid-shaped cuts were made using a cutter guide with a gap interval of 1 mm. Next, an 18 mm wide tape (Cello Tape (registered trademark) CT-18 manufactured by Nichiban Co., Ltd.) was applied to the cut surface on the grid, and the 2.0 kg roller was reciprocated 20 times to completely adhere to it. The peeling surface after peeling off rapidly at the peeling angle was observed, the number of cells not peeled off was counted, and evaluated according to the following evaluation criteria.
In the following evaluation criteria, for example, a case in which 90 squares in 100 squares remain without being peeled is described as “90/100”.
The evaluation results are shown in Table 1.

6: 100/100
5: 99/100 to 95/100
4: 94/100 to 80/100
3: 79/100 to 50/100
2: 49/100 to 1/100
1: 0/100

As is clear from Table 1, it can be seen that the functional film of the present invention is superior in water vapor barrier property and adhesiveness as compared with the functional film of the comparative example.
From the above, the transition metal (M1) -containing layer and the organosilicon compound-containing layer are sequentially laminated on the base material to provide a functional film having high adhesion to the QD-containing resin layer. It was confirmed that it was useful.

DESCRIPTION OF SYMBOLS 1, 10 Functional film 2 Base material 4 Transition metal (M1) containing layer 6, 26 Organosilicon compound containing layer 8 Metal (M2) containing layer 12 Quantum dot 14 QD containing resin layer 20, 30 QD sheet

Claims (12)

  A functional film in which a transition metal (M1) -containing layer and an organosilicon compound-containing layer are sequentially laminated on a substrate.   The functional film according to claim 1, wherein the transition metal (M1) is a transition metal selected from the group consisting of Group 5 to 11 elements.   The functional film according to claim 2, wherein the transition metal (M1) is a transition metal selected from the group consisting of Group 5 elements.   The functional film according to any one of claims 1 to 3, wherein the organosilicon compound has a polymerizable substituent.   The functional film according to claim 4, wherein the polymerizable substituent is a substituent selected from the group consisting of an acryloyl group, a methacryloyl group, a vinyl group, and an epoxy group. Between the base material and the transition metal (M1) -containing layer, it has a metal (M2) -containing layer,
The functional film according to any one of claims 1 to 5, wherein the metal (M2) is a metal selected from the group consisting of elements of groups 12 to 14.   The functional film according to claim 6, wherein the metal (M2) is Si.   The functional film according to claim 7, wherein the metal (M2) -containing layer is formed of a film formed by converting a coating film of a polysilazane compound. The composition in the region where the transition metal (M1) -containing layer and the metal (M2) -containing layer are adjacent to each other is expressed as (M2) (M1) _x O _y N _z (0.02 <x <50, y> 0, z ≧ The functional film according to any one of claims 6 to 8, wherein the functional film satisfies the following formula (1) when represented by 0).
(2y + 3z) / (a + bx) <1 Formula (1)
(In the formula (1), a represents the maximum valence of the metal (M2), and b represents the maximum valence of the transition metal (M1).)   The functional film according to any one of claims 1 to 9, wherein the organosilicon compound-containing layer is a film formed by applying a liquid containing a silane coupling agent.   The functional film according to any one of claims 1 to 10, wherein the organosilicon compound-containing layer further contains a polymerizable polymer.   An electronic device comprising the functional film according to any one of claims 1 to 11.

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