JP2017177668A - Barrier film and method for producing the same, and wavelength conversion sheet and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a barrier film having excellent adhesion to an adherend.SOLUTION: A barrier film comprises a gas barrier film, and a primer layer that is disposed on one outermost surface and comprises a cured product of a primer composition that contains at least one organic metal compound selected from the group consisting of metal chelate compounds, metalalkoxide compounds and metal acylate compounds, and a silane coupling agent.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a barrier film and a manufacturing method thereof, and a wavelength conversion sheet and a manufacturing method thereof.

  A wavelength conversion sheet using a phosphor such as a quantum dot has high luminance and color reproducibility, and is desired to be used for a display or the like. However, phosphors such as quantum dots deteriorate due to contact with oxygen or moisture. Therefore, the wavelength conversion sheet often employs a structure in which a barrier film in which a gas barrier layer is formed on a polymer film is disposed on one or both surfaces of a phosphor layer containing a phosphor.

  For example, in Patent Document 1, barrier films are bonded to both surfaces of a phosphor layer in which quantum dots are dispersed in an acrylic resin and an epoxy resin, thereby preventing entry of oxygen or the like into the phosphor layer.

International Publication No. 2014/113562

  However, the phosphor layer in which quantum dots, which are inorganic materials as described in Patent Document 1, are dispersed has poor adhesion to the barrier film, and there is a risk of peeling between the phosphor layer and the barrier film. there were. Moreover, in the optical laminate, not only the wavelength conversion sheet, but peeling of the barrier film has a great effect on the performance degradation, and therefore, improvement in the adhesion between the barrier film and the adherend is required.

  The present invention has been made in view of the above-described problems of the prior art, and has a barrier film excellent in adhesion to an adherend such as a phosphor layer, a manufacturing method thereof, a wavelength conversion sheet, and a manufacturing method thereof. The purpose is to provide.

  To achieve the above object, the present invention provides a gas barrier film and at least one organometallic compound selected from the group consisting of a metal chelate compound, a metal alkoxide compound, and a metal acylate compound disposed on one outermost surface. And a primer layer comprising a cured product of a primer composition containing a silane coupling agent.

  According to the barrier film, the phosphor layer is provided via the primer layer by providing a primer layer made of a cured product of the primer composition containing the specific organometallic compound and the silane coupling agent on one outermost surface. By adhering to an adherend such as the above, excellent adhesion to the adherend can be obtained. This is because the silane coupling agent exhibits high affinity for the adherend, thereby improving the adhesion. In addition, the silane coupling agent generates a silanol group in the primer layer by hydrolysis, and this silanol group contributes to improvement in adhesion by reacting with a polar functional group such as a hydroxyl group on the surface of the layer in contact with the primer layer, It is possible to prevent moisture and oxygen from entering from the interface between the primer layer and the layer in contact therewith. In addition, the combined use of an organometallic compound and a silane coupling agent facilitates a primer layer having a sufficient thickness to ensure excellent adhesion compared to the case where the silane coupling agent is used alone. Can get to. At that time, processes such as excessive heating, ultraviolet irradiation, and aging are not necessarily required. In addition, the organometallic compound is incorporated into the bond between the silane coupling agents, and contributes to the formation of a stronger primer layer and the accompanying adhesion. Furthermore, the organometallic compound serves as a binder that bonds unreacted silane coupling agents together, and prevents tackiness due to the presence of excess unreacted silane coupling agent in the primer layer. Can be made easier. From these things, the said barrier film can acquire the outstanding adhesiveness with respect to adherends, such as a fluorescent substance layer.

  In the barrier film, the organometallic compound preferably contains at least one metal selected from the group consisting of aluminum, zirconium, titanium, and tin. By using such an organometallic compound, the barrier film can obtain better adhesion to an adherend such as a phosphor layer and good handling properties in which stickiness is suppressed.

  In the barrier film, the silane coupling agent is selected from the group consisting of vinyl group, epoxy group, styryl group, methacryl group, acrylic group, amino group, isocyanurate group, ureido group, mercapto group, sulfide group and isocyanate group. It is preferable to have at least one functional group. By using such a silane coupling agent, the barrier film can obtain better adhesion to an adherend such as a phosphor layer. Moreover, the adhesiveness outstanding with respect to various to-be-adhered bodies can be acquired by selection of the functional group of a silane coupling agent. In particular, when a functional group is present on the surface of the adherend, better adhesion can be obtained by selecting and using a silane coupling agent having a functional group having reactivity or affinity with the functional group.

  In the barrier film, the primer layer preferably has a thickness of 1 to 1000 nm. When the thickness of the primer layer is within the above range, better adhesion between the barrier film and the adherend can be obtained, and moisture and oxygen can be sufficiently prevented from entering from the end of the primer layer.

  The present invention also includes a phosphor layer containing a phosphor and the barrier film of the present invention laminated on at least one surface of the phosphor layer, and the barrier film is the outermost layer on the phosphor layer side. A wavelength conversion sheet comprising the primer layer on the surface is provided.

  According to the wavelength conversion sheet, a barrier film and a phosphor layer are laminated through a primer layer made of a cured product of a primer composition containing a specific organometallic compound and a silane coupling agent. And excellent phosphor layer adhesion can be obtained.

  The present invention also provides a method for producing a barrier film comprising a gas barrier film and a primer layer disposed on one outermost surface, wherein the metal chelate compound, the metal alkoxide compound, and the metal acylate are formed on the gas barrier film. A method for producing a barrier film, comprising applying a primer composition containing at least one organometallic compound selected from the group consisting of compounds and a silane coupling agent and curing the primer composition to form the primer layer. provide.

  According to the said manufacturing method, the barrier film excellent in adhesiveness and handling properties with adherends, such as a fluorescent substance layer, can be manufactured easily. The primer layer is not sufficiently cured with the silane coupling agent alone, resulting in stickiness and easy handling. However, the primer layer further contains an organometallic compound to promote curing and reduce stickiness and improve handling. it can.

  The present invention further includes a phosphor layer containing a phosphor, a gas barrier film laminated on at least one surface of the phosphor layer, and a barrier layer disposed on the outermost surface on the phosphor layer side. And at least one organometallic compound selected from the group consisting of a metal chelate compound, a metal alkoxide compound and a metal acylate compound on the gas barrier film, and a silane A method for producing a wavelength conversion sheet, comprising: applying a primer composition containing a coupling agent; curing the primer composition to form the primer layer; and laminating the phosphor layer and the barrier film. provide.

  According to the said manufacturing method, the wavelength conversion sheet excellent in the adhesiveness of a barrier film and a fluorescent substance layer can be manufactured easily.

  ADVANTAGE OF THE INVENTION According to this invention, the barrier film excellent in adhesiveness with adherends, such as a fluorescent substance layer, its manufacturing method, a wavelength conversion sheet, and its manufacturing method can be provided.

It is a schematic cross section which shows one Embodiment of the barrier film of this invention. It is a schematic cross section which shows one Embodiment of the barrier film of this invention. It is a schematic cross section which shows one Embodiment of the barrier film of this invention. It is a schematic cross section which shows one Embodiment of the barrier film of this invention. It is a schematic cross section which shows one Embodiment of the barrier film of this invention. It is a schematic cross section which shows one Embodiment of the barrier film of this invention. It is a schematic cross section which shows one Embodiment of the wavelength conversion sheet of this invention.

  Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the drawings. In the drawings, the same or corresponding parts are denoted by the same reference numerals, and redundant description is omitted. Further, the dimensional ratios in the drawings are not limited to the illustrated ratios.

[Barrier film]
The barrier film of the present invention includes a gas barrier film, at least one organometallic compound selected from the group consisting of a metal chelate compound, a metal alkoxide compound, and a metal acylate compound disposed on one outermost surface of the barrier film, and And a primer layer made of a cured product of a primer composition containing a silane coupling agent. Hereinafter, preferred embodiments of the barrier film of the present invention will be described with reference to the drawings.

  1 to 6 are schematic cross-sectional views showing an embodiment of the barrier film of the present invention. A barrier film 100 shown in FIG. 1 includes a first film 1 that is a gas barrier film, a second film 2 that is a gas barrier film, a primer layer 4, an adhesive layer 5, and a mat layer 6. Here, the first film 1 includes a first substrate 11, an anchor coat layer 12, and a barrier layer 15 including an inorganic thin film layer 13 and a gas barrier coating layer 14. The second film 2 includes a second base material 21, an anchor coat layer 22, and a barrier layer 25 including an inorganic thin film layer 23 and a gas barrier coating layer 24. The 1st film 1 and the 2nd film 2 are bonded together through the contact bonding layer 5 so that the gas-barrier coating layer 14 and the gas-barrier coating layer 24 may oppose. In the barrier film 100, the primer layer 4 is disposed on the surface of the first film 1 on the first base material 11 side in contact with the first base material 11, and the mat layer 6 On the surface of the second film 2 on the second substrate 21 side, the film 2 is disposed in contact with the second substrate 21. Since the barrier film 100 having the structure shown in FIG. 1 has two gas barrier films of the first and second films 1 and 2 bonded together, it can sufficiently suppress the transmission of moisture and oxygen. . Further, the barrier layers 15 and 25 are disposed on the inner side of the first and second base materials 11 and 21, so that the barrier layers 15 and 25 are protected and damage to the barrier layers 15 and 25 is suppressed.

  A barrier film 200 shown in FIG. 2 includes a first film 1 that is a gas barrier film, a second film 2 that is a gas barrier film, a primer layer 4, an adhesive layer 5, and a mat layer 6. Here, the first film 1 includes a first substrate 11, an anchor coat layer 12, and a barrier layer 15 including an inorganic thin film layer 13 and a gas barrier coating layer 14. The second film 2 includes a second base material 21, an anchor coat layer 22, and a barrier layer 25 including an inorganic thin film layer 23 and a gas barrier coating layer 24. The 1st film 1 and the 2nd film 2 are bonded together through the contact bonding layer 5 so that the 1st base material 11 and the gas-barrier coating layer 24 may oppose. In the barrier film 200, the primer layer 4 is disposed on the surface of the first film 1 on the gas barrier coating layer 14 side in contact with the gas barrier coating layer 14, and the mat layer 6 On the surface of the film 2 on the second substrate 21 side, the film 2 is disposed in contact with the second substrate 21. Since the barrier film 200 having the structure shown in FIG. 2 has two gas barrier films, the first and second films 1 and 2, which are bonded together, it can sufficiently suppress the permeation of moisture and oxygen. . In addition, the barrier layer 15 is disposed on the primer layer 4 side, that is, at a position closer to the adherend, whereby moisture and oxygen can be more sufficiently prevented from entering the adherend.

  The barrier film 300 shown in FIG. 3 includes a first film 1 that is a gas barrier film, a second film 2, a primer layer 4, an adhesive layer 5, and a mat layer 6. Here, the first film 1 includes a first base material 11, an anchor coat layer 12, and a barrier layer 15 in which two inorganic thin film layers 13 and two gas barrier coating layers 14 are alternately laminated. ing. The second film 2 is composed only of the second base material 21. The 1st film 1 and the 2nd film 2 are bonded together through the contact bonding layer 5 so that the gas-barrier coating layer 14 and the 2nd base material 21 may oppose. In the barrier film 300, the primer layer 4 is disposed on the surface of the first film 1 on the first base material 11 side in contact with the first base material 11, and the mat layer 6 The second base material 21 constituting the second film 2 is disposed on the surface opposite to the adhesive layer 5 in a state in contact with the second base material 21. Since the barrier film 300 having the structure shown in FIG. 3 comprises the second film 2 only with the second base material 21, the manufacturing process can be simplified and the cost can be reduced. By changing the thickness of the substrate 21, rigidity can be imparted as necessary. Moreover, since the barrier layer 15 has a structure in which the inorganic thin film layers 13 and the gas barrier coating layers 14 are alternately laminated, the gas barrier property can be improved.

  A barrier film 400 shown in FIG. 4 includes a first film 1 that is a gas barrier film, a primer layer 4, and a mat layer 6. Here, the first film 1 includes a first base material 11, an anchor coat layer 12, and a barrier layer 15 in which two inorganic thin film layers 13 and two gas barrier coating layers 14 are alternately laminated. ing. In the barrier film 300, the primer layer 4 is disposed on the surface of the first film 1 on the gas barrier coating layer 14 side so as to be in contact with the gas barrier coating layer 14. On the surface of the film 1 on the first substrate 11 side, the film 1 is disposed in contact with the first substrate 11. Since the barrier film 400 having the structure shown in FIG. 4 does not include the second film 2 and the adhesive layer 5, the manufacturing process can be simplified, the cost can be reduced, and the thickness can be reduced. Moreover, since the barrier layer 15 has a structure in which the inorganic thin film layers 13 and the gas barrier coating layers 14 are alternately laminated, the gas barrier property can be improved.

  The barrier film 500 shown in FIG. 5 is a first film 1 that is a gas barrier film, a second film 2 that is a gas barrier film, a third film 3, a primer layer 4, an adhesive layer 5, A mat layer 6. Here, the first film 1 includes a first substrate 11, an anchor coat layer 12, and a barrier layer 15 including an inorganic thin film layer 13 and a gas barrier coating layer 14. The second film 2 includes a second base material 21, an anchor coat layer 22, and a barrier layer 25 including an inorganic thin film layer 23 and a gas barrier coating layer 24. The third film 3 is composed only of the third base material 31. The 1st film 1 and the 2nd film 2 are bonded together through the contact bonding layer 5 so that the gas-barrier coating layer 14 and the gas-barrier coating layer 24 may oppose. The 2nd film 2 and the 3rd film 3 are bonded together through the contact bonding layer 5 so that the 2nd base material 21 and the 3rd base material 31 may oppose. In the barrier film 500, the primer layer 4 is disposed on the surface of the first film 1 on the first base material 11 side in contact with the first base material 11, and the mat layer 6 The third substrate 31 constituting the third film 3 is disposed on the surface opposite to the adhesive layer 5 in contact with the third substrate 31. Since the barrier film 500 having the structure shown in FIG. 5 has two gas barrier films of the first and second films 1 and 2 bonded together, it can more sufficiently suppress the permeation of moisture and oxygen. . Further, the barrier layers 15 and 25 are disposed on the inner side of the first and second base materials 11 and 21, so that the barrier layers 15 and 25 are protected and damage to the barrier layers 15 and 25 is suppressed. Furthermore, wrinkles can be prevented from occurring in the barrier film 500 by providing the third film 3. Moreover, rigidity can also be provided as needed by changing the thickness of the third substrate 31.

  A barrier film 600 shown in FIG. 6 includes a first film 1 that is a gas barrier film, a second film 2, a primer layer 4, an adhesive layer 5, and a mat layer 6. Here, the first film 1 includes a first base material 11, an anchor coat layer 12, and a barrier layer 15 in which two inorganic thin film layers 13 and two gas barrier coating layers 14 are alternately laminated. ing. The second film 2 is composed only of the second base material 21. The 1st film 1 and the 2nd film 2 are bonded together through the contact bonding layer 5 so that the 1st base material 11 and the 2nd base material 21 may oppose. In the barrier film 600, the primer layer 4 is disposed on the surface of the first film 1 on the gas barrier coating layer 14 side in contact with the gas barrier coating layer 14, and the mat layer 6 On the surface opposite to the adhesive layer 5 of the second base material 21 constituting the film 2, the second base material 21 is disposed in contact with the second base material 21. In the barrier film 600 having the structure shown in FIG. 6, since the second film 2 is composed only of the second base material 21, the manufacturing process can be simplified and the cost can be reduced. By changing the thickness of the substrate 21, rigidity can be imparted as necessary. Moreover, since the barrier layer 15 has a structure in which the inorganic thin film layers 13 and the gas barrier coating layers 14 are alternately laminated, the gas barrier property can be improved.

  The barrier film having the above-described configuration has excellent gas barrier properties, and can be bonded with an adherend such as a phosphor layer via the primer layer 4 to obtain excellent adhesion. Moreover, since the primer layer 4 exhibits extremely good adhesion to both the first base material 11 and the gas barrier coating layer 14, the occurrence of peeling in the barrier film is sufficiently suppressed. Therefore, the barrier film having the above-described configuration can suppress oxygen and moisture from entering from the interface between the barrier film and the adherend, and can suppress deterioration of the adherend. From the viewpoint of adhesion, the primer layer 4 is more preferably applied to the first substrate 11. When the adhesion between the primer layer 4 and the first base material 11 or the gas barrier coating layer 14 is poor, the corona treatment, the flame treatment, the plasma treatment, or the like is applied to the first base material 11 or the gas barrier coating layer 14. Thus, the adhesion with the primer layer 4 can be further improved.

  Hereinafter, each layer constituting the barrier film will be described in detail.

(Base material)
The first, second and third substrates 11, 21, 31 are desirably polymer films. Examples of the material for the polymer film include polyesters such as polyethylene terephthalate, polybutylene terephthalate and polyethylene naphthalate; polyamides such as nylon; polyolefins such as polypropylene and cycloolefin; polycarbonates; and triacetyl cellulose. It is not limited to. The polymer film is preferably a polyester film, a polyamide film or a polyolefin film, more preferably a polyester film or a polyamide film, and still more preferably a polyethylene terephthalate film. The polyethylene terephthalate film is desirable from the viewpoints of transparency, processing suitability, and adhesion. The polyethylene terephthalate film is preferably a biaxially stretched polyethylene terephthalate film from the viewpoints of transparency and gas barrier properties.

  The polymer film may contain additives such as an antistatic agent, an ultraviolet absorber, a plasticizer, and a slip agent as necessary. The surface of the polymer film may be subjected to corona treatment, flame treatment and plasma treatment.

  In the barrier film, when the first substrate 11 and the primer layer 4 are in contact with each other, the first substrate 11 preferably has a polar functional group such as a hydroxyl group or a carbonyl group on the surface. Occurs when the first base material 11 has a polar functional group such as a hydroxyl group or a carbonyl group on its surface, so that the polar functional group such as a hydroxyl group and the alkoxysilane of the silane coupling agent in the primer layer 4 are hydrolyzed. The improved silanol group reacts to improve the adhesion. Among the polymer films described above, those having a polar functional group such as a hydroxyl group or a carbonyl group on the surface are usually polyethylene terephthalate film, polybutylene terephthalate film, polyethylene naphthalate film, polyamide film, triacetyl cellulose film, acrylic A film, a polycarbonate film, etc. are mentioned. Moreover, when the 1st base material 11 does not have polar functional groups, such as a hydroxyl group and a carbonyl group, the adhesiveness with the primer layer 4 is given by performing the surface treatment of corona treatment, flame treatment, and plasma treatment. Can be further improved.

  The thicknesses of the first, second and third base materials 11, 21, 31 are not particularly limited, but are preferably 3 μm or more and 100 μm or less, and are 5 μm or more and 50 μm or less from the viewpoint of workability and productivity. It is more preferable. If the thickness is 3 μm or more, processing is easy, and if it is 100 μm or less, the productivity of the barrier film per lot can be increased.

(Anchor coat layer)
The anchor coat layers 12 and 22 are provided between the first and second base materials 11 and 21 and the inorganic thin film layers 13 and 23 in order to improve the adhesion. Moreover, the anchor coat layers 12 and 22 may have a barrier property that prevents permeation of moisture and oxygen.

  Anchor coat layers 12 and 22 are, for example, polyester resin, isocyanate resin, urethane resin, acrylic resin, polyvinyl alcohol resin, ethylene vinyl alcohol resin, vinyl modified resin, epoxy resin, oxazoline group-containing resin, modified styrene resin, modified silicone resin. Alternatively, it can be formed using a resin selected from alkyl titanate and the like. The anchor coat layer can be formed using the above-described resin alone or using a composite resin in which two or more of the above-described resins are combined.

  The anchor coat layers 12 and 22 can be formed by applying a solution containing the above-described resin onto the first and second substrates 11 and 21 and drying and curing the solution. Examples of the coating method include a coating method using a gravure coater, a dip coater, a reverse coater, a wire bar coater, a die coater, and the like.

  The thickness of the anchor coat layers 12 and 22 is preferably in the range of 5 to 500 nm, and more preferably in the range of 10 to 100 nm. Here, when the thickness is 5 nm or more, the adhesion between the first and second base materials 11 and 21 and the inorganic thin film layers 13 and 23 and the barrier property against moisture and oxygen tend to be improved. When the thickness is 500 nm or less, there is a tendency that a uniform layer in which internal stress is sufficiently suppressed can be formed.

(Barrier layer)
The barrier layers 15 and 25 are layers provided for further improving the water vapor permeability and the oxygen permeability. The barrier layers 15 and 25 are preferably highly transparent from an optical viewpoint. Although the barrier layers 15 and 25 may be a single layer or a multilayer, it is desirable to have the inorganic thin film layers 13 and 23 and the gas barrier coating layers 14 and 24 as shown in FIGS. 2 and 4, when the gas barrier coating layer 14 and the primer layer 4 are in contact with each other, it is desirable that the gas barrier coating layer 14 has a siloxane bond. Since the gas barrier coating layer 14 has a siloxane bond, the adhesion between the gas barrier coating layer 14 and the primer layer 4 is further improved.

  The barrier layers 15 and 25 may be formed in the air or formed in a vacuum. Examples of vacuum film formation include physical vapor deposition and chemical vapor deposition. Examples of physical vapor deposition include vacuum vapor deposition, sputtering, and ion plating. Examples of the chemical vapor deposition (CVD) method include a thermal CVD method, a plasma CVD (PECVD) method, and a photo CVD method. The film forming method may be different between the inorganic thin film layers 13 and 23 and the gas barrier coating layers 14 and 24.

(Inorganic thin film layer)
The formation method of the inorganic thin film layers 13 and 23 is preferably a vacuum deposition method, a sputtering method, or a PECVD method. The vacuum deposition method is preferably a resistance heating type vacuum deposition method, an electron beam heating type vacuum deposition method, or an induction heating type vacuum deposition method, and the sputtering method is a reactive sputtering method or a dual magnetron sputtering method. Is more preferable. The sputtering method is preferable from the viewpoint of film homogeneity, and the vacuum evaporation method is preferable from the viewpoint of cost, and can be selected according to the purpose and application.

  Examples of plasma generation methods in the sputtering method and the PECVD method include a DC (Direct Current) method, an RF (Radio Frequency) method, an MF (Middle Frequency) method, a DC pulse method, an RF pulse method, and a DC + RF superposition method. Can do.

  In the vacuum film formation, a film of metal, oxide such as silicon, nitride, or nitride oxide is usually formed. As the inorganic thin film layers 13 and 23, metals such as aluminum, titanium, copper, indium and tin, or oxides thereof (alumina and the like), or silicon and silicon oxide films are preferable. In addition to a metal or silicon oxide, a metal or silicon nitride or nitride oxide film may be formed. In addition, a film containing a plurality of metals may be formed. The above-mentioned aluminum, titanium, copper, indium, silicon oxide, nitride, and nitride oxide are excellent in both transparency and barrier properties. An oxide containing silicon and an oxide nitride are particularly preferable because of their high barrier properties.

  The thickness of the inorganic thin film layers 13 and 23 formed by vacuum film formation is preferably 5 nm or more and 100 nm or less. When the thickness of the inorganic thin film layers 13 and 23 is 5 nm or more, there is a tendency that better barrier properties can be obtained. Moreover, when the thickness of the inorganic thin film layers 13 and 23 is 100 nm or less, the occurrence of cracks tends to be suppressed, and the decrease in water vapor barrier property and oxygen barrier property due to cracks tends to be suppressed. Furthermore, when the thickness of the inorganic thin film layers 13 and 23 is 100 nm or less, the cost can be reduced due to the reduction in the amount of material used and the shortening of the film formation time.

(Gas barrier coating layer)
The gas barrier coating layers 14 and 24 are provided to prevent various secondary damages in a later process and to provide high barrier properties. The gas barrier coating layers 14 and 24 may contain a siloxane bond. The gas barrier coating layers 14 and 24 can also be formed in the atmosphere. In the case where the gas barrier coating layers 14 and 24 are formed in the air, for example, a polar compound such as polyvinyl alcohol, polyvinyl pyrrolidone, ethylene vinyl alcohol, a compound containing chlorine such as polyvinylidene chloride, and Si atoms are included. It can be formed by applying a coating solution containing a compound, a compound containing Ti atoms, a compound containing Al atoms, a compound containing Zr atoms, etc. on the inorganic thin film layers 13 and 23 and drying and curing them.

  Specific examples of the application method of the coating liquid when forming the gas barrier coating layers 14 and 24 in the atmosphere include a coating method using a gravure coater, a dip coater, a reverse coater, a wire bar coater, and a die coater. It is done.

The compound containing a siloxane bond is preferably formed, for example, by using a silane compound and reacting a silanol group. As such a silane compound, the compound represented by following formula (1) is mentioned.
R ¹ _n (OR ² ) _4-n Si (1)
[Wherein, n represents an integer of 0 to 3, R ¹ and R ² each independently represent a hydrocarbon group, preferably an alkyl group having 1 to 4 carbon atoms. ]

  Examples of the compound represented by the above formula (1) include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, methyltrimethoxysilane, methyltriethoxysilane, dimethyldimethoxysilane, and dimethyldiethoxysilane. Etc. Polysilazane containing nitrogen may be used.

Moreover, you may use the material made from the precursor which consists of another metal atom for the gas-barrier coating layers 14 and 24. FIG. As a compound containing Ti atom, the compound represented by following formula (2) is mentioned, for example.
R ¹ _n (OR ² ) _4-n Ti (2)
[Wherein, n represents an integer of 0 to 3, R ¹ and R ² each independently represent a hydrocarbon group, preferably an alkyl group having 1 to 4 carbon atoms. ]

  Examples of the compound represented by the above formula (2) include tetramethoxytitanium, tetraethoxytitanium, tetraisopropoxytitanium, and tetrabutoxytitanium.

As a compound containing Al atom, the compound represented by following formula (3) is mentioned, for example.
R ¹ _m (OR ² ) _3-m Al (3)
[Wherein, m represents an integer of 0 to 2, R ¹ and R ² each independently represent a hydrocarbon group, preferably an alkyl group having 1 to 4 carbon atoms. ]

  Examples of the compound represented by the above formula (3) include trimethoxyaluminum, triethoxyaluminum, triisopropoxyaluminum, and tributoxyaluminum.

Examples of the compound containing a Zr atom include a compound represented by the following formula (4).
R ¹ _n (OR ² ) _4-n Zr (4)
[Wherein, n represents an integer of 0 to 3, R ¹ and R ² each independently represent a hydrocarbon group, preferably an alkyl group having 1 to 4 carbon atoms. ]

  Examples of the compound represented by the above formula (4) include tetramethoxyzirconium, tetraethoxyzirconium, tetraisopropoxyzirconium, and tetrabutoxyzirconium.

  When the gas barrier coating layers 14 and 24 are formed in the atmosphere, the coating solution is cured after coating. The curing method is not particularly limited, and examples thereof include ultraviolet curing and thermal curing. In the case of UV curing, the coating solution may contain a polymerization initiator and a compound having a double bond. Moreover, you may heat-age as needed.

  As another method of forming the gas barrier coating layers 14 and 24 in the atmosphere, particles of inorganic oxides such as magnesium, calcium, zinc, aluminum, silicon, titanium, and zirconium are connected via phosphorus atoms derived from a phosphorus compound. It is also possible to use a method in which a reaction product obtained by dehydration condensation is used as a gas barrier coating layer. Specifically, a functional group (for example, a hydroxyl group) present on the surface of the inorganic oxide and a phosphorus compound site capable of reacting with the inorganic oxide (for example, a halogen atom directly bonded to the phosphorus atom or a direct bond to the phosphorus atom) A bonded oxygen atom) causes a condensation reaction to bond. For example, the reaction product is obtained by applying a coating solution containing an inorganic oxide and a phosphorus compound to the surfaces of the inorganic thin film layers 13 and 23 and heat-treating the formed coating film so that the particles of the inorganic oxide become phosphorous. It can be obtained by advancing the reaction of bonding via a phosphorus atom derived from a compound. The minimum of the temperature of heat processing is 110 degreeC or more, It is preferable that it is 120 degreeC or more, It is more preferable that it is 140 degreeC or more, It is still more preferable that it is 170 degreeC or more. When the heat treatment temperature is low, it becomes difficult to obtain a sufficient reaction rate, which causes a decrease in productivity. The preferable upper limit of the temperature of the heat treatment varies depending on the kind of the base material and the like, but is 220 ° C. or lower, and preferably 190 ° C. or lower. The heat treatment can be performed in air, under a nitrogen atmosphere, or under an argon atmosphere.

  When the gas barrier coating layers 14 and 24 are formed in the atmosphere, the coating solution may further contain a resin as long as it does not aggregate. Specific examples of the resin include acrylic resins and polyester resins. The coating solution preferably contains a resin having high compatibility with other materials in the coating solution among these resins.

  The coating solution may further contain a filler, a leveling agent, an antifoaming agent, an ultraviolet absorber, an antioxidant, a silane coupling agent, a titanium chelating agent, and the like as necessary.

  The thickness of the gas barrier coating layers 14 and 24 formed in the atmosphere is preferably 50 nm to 2000 nm, more preferably 100 nm to 1000 nm in terms of the film thickness after curing. When the thickness of the gas barrier coating layers 14 and 24 formed in the atmosphere is 50 nm or more, film formation tends to be facilitated. When the thickness of the gas barrier coating layers 14 and 24 formed in the atmosphere is 2000 nm or less, cracking or curling tends to be suppressed.

(Adhesive layer)
As shown in FIGS. 1 to 3 and 5 to 6, the adhesive layer 5 has a first film 1 and a second film 2 for laminating and laminating the first film 1 and the second film 2. Between. In addition, when the barrier film has a third film as shown in FIG. 5, the second film 2 and the third film are laminated in order to laminate the second film 2 and the third film 3 together. 3 is provided. As the adhesive layer 5, a general polymer film adhesive or pressure-sensitive adhesive can be used, and it is appropriately selected according to the surfaces of the first film 1 and the second film 2 to be bonded. Is done. Candidate materials for the adhesive layer 5 include epoxy-based, polyester-based, acrylic-based, rubber-based, phenol-based, and urethane-based adhesives or pressure-sensitive adhesives.

  Examples of the method for applying the adhesive or the pressure-sensitive adhesive include coating methods using a gravure coater, a dip coater, a reverse coater, a wire bar coater, and a die coater.

  The thickness of the adhesive layer 5 is preferably 1 μm or more and 20 μm or less. When the thickness of the adhesive layer 5 is 1 μm or more, sufficient adhesiveness tends to be obtained, and when it is 20 μm or less, the total thickness of the barrier film can be reduced and cost increase can be suppressed. is there.

  Moreover, after bonding the 1st film 1 and the 2nd film 2 or the 2nd film 2 and the 3rd film 3 through the contact bonding layer 5, it can age. Aging is performed at 20 to 80 ° C. for 1 to 10 days, for example.

  The adhesive layer 5 may contain a curing agent, an antistatic agent, a silane coupling agent, an ultraviolet absorber, an antioxidant, a leveling agent, a dispersing agent, and the like as necessary.

(Primer layer)
The primer layer 4 is a layer provided to improve the adhesion between the barrier film and an adherend such as a phosphor layer. The primer layer 4 is provided on the first substrate 11 or the gas barrier coating layer 14 of the first film 1. The primer layer 4 is provided on one outermost surface of the barrier film, and the surface of the barrier film on the primer layer 4 side is bonded to the adherend.

  The primer layer 4 is a layer made of a cured product of a primer composition containing at least one organometallic compound selected from the group consisting of a metal chelate compound, a metal alkoxide compound, and a metal acylate compound, and a silane coupling agent. .

  The silane coupling agent is not particularly limited, but is selected from the group consisting of vinyl group, epoxy group, styryl group, methacryl group, acrylic group, amino group, isocyanurate group, ureido group, mercapto group, sulfide group and isocyanate group. Those having at least one functional group are preferred. These functional groups are preferably selected according to the components of the adherend. For example, when the adherend contains an epoxy resin, it is possible to use a silane coupling agent having at least one functional group selected from the group consisting of an amino group, a mercapto group, a sulfide group, an epoxy group, and a ureido group. From the viewpoint of sex. When the adherend contains an acrylic resin, a silane coupling having at least one functional group selected from the group consisting of an amino group, a mercapto group, a sulfide group, an epoxy group, a methacryl group, an isocyanate group, and an isocyanurate group It is preferable to use an agent from the viewpoint of adhesion. Moreover, as a silane coupling agent, you may use in combination of 2 or more types of silane coupling agents from which a functional group differs.

  Examples of the silane coupling agent having a vinyl group include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, vinylmethyldimethoxysilane, and 3-acryloxypropyl. Among these, vinyltrimethoxysilane and vinylmethyldimethoxysilane are preferable from the viewpoint of reactivity. These can be used individually by 1 type or in combination of 2 or more types.

  Examples of the silane coupling agent having an epoxy group include 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3- Examples thereof include glycidoxypropylmethyldiethoxysilane and 3-glycidoxypropyltriethoxysilane. Among these, 3-glycidoxypropylmethyldimethoxysilane and 3-glycidoxypropyltrimethoxysilane are preferable from the viewpoint of reactivity. These can be used individually by 1 type or in combination of 2 or more types.

  Examples of the silane coupling agent having a styryl group include p-styryltrimethoxysilane.

  Examples of the silane coupling agent having a methacryl group include 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, and 3-methacryloxypropyltriethoxysilane. Is mentioned. Among these, from the viewpoint of reactivity, 3-methacryloxypropylmethyldimethoxysilane and 3-methacryloxypropyltrimethoxysilane are preferable. These can be used individually by 1 type or in combination of 2 or more types.

  Examples of the silane coupling agent having an acrylic group include 3-acryloxypropyltrimethoxysilane.

  Examples of the silane coupling agent having an amino group include N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, and 3-amino. Propyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N- (vinylbenzyl) ) -2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride and the like. Among these, 3-aminopropyltriethoxysilane and 3-aminopropyltriethoxysilane are preferable from the viewpoint of reactivity. These can be used individually by 1 type or in combination of 2 or more types.

  Examples of the silane coupling agent having an isocyanurate group include tris- (trimethoxysilylpropyl) isocyanurate.

  Examples of the silane coupling agent having a ureido group include 3-ureidopropyltriethoxysilane.

  Examples of the silane coupling agent having a mercapto group include 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane. Among these, 3-mercaptopropyltrimethoxysilane is preferable from the viewpoint of reactivity. The silane coupling agent having a mercapto group also includes, for example, a silane coupling agent in which a mercapto group is protected with an alkoxysilyl group or the like from the viewpoint of odor. These can be used individually by 1 type or in combination of 2 or more types.

  Examples of the silane coupling agent having a sulfide group include bis (triethoxysilylpropyl) tetrasulfide and 3-octanoylthio-1-propyltriethoxysilane. Among these, bis (triethoxysilylpropyl) tetrasulfide is preferable from the viewpoint of reactivity. These can be used individually by 1 type or in combination of 2 or more types.

  Examples of the silane coupling agent having an isocyanate group include 3-isocyanatopropyltriethoxysilane and 3-isocyanatepropyltrimethoxysilane. Among these, 3-isocyanatopropyltrimethoxysilane is preferable from the viewpoint of reactivity. These can be used individually by 1 type or in combination of 2 or more types.

  As the organometallic compound, at least one selected from the group consisting of a metal chelate compound, a metal alkoxide compound, and a metal acylate compound is used. Of these, metal chelate compounds and metal alkoxide compounds are preferred in terms of promoting the reactivity of hydrolysis. The organometallic compound preferably contains at least one metal selected from the group consisting of aluminum, zirconium, titanium, and tin. Among these, from the environmental aspect, the organometallic compound preferably contains at least one metal selected from the group consisting of aluminum, zirconium, and titanium. Further, from the viewpoint of particularly improving initial adhesion, zirconium And at least one metal selected from the group consisting of titanium, and from the viewpoint of particularly improving the adhesion after aging, at least one metal selected from the group consisting of zirconium and aluminum is included. From the viewpoint of improving the adhesion at both the initial stage and after aging, it is particularly preferable to contain zirconium.

  Examples of the metal chelate compound include zirconium ethyl acetoacetate, zirconium tributoxy monoacetyl acetonate, zirconium tetraacetyl acetonate, zirconium dibutoxy bis (ethyl acetoacetate), zirconium monoacetyl acetonate, titanium diisopropoxy bis (acetyl). Acetonate), titanium tetraacetylacetonate, titanium diisopropoxybis (ethyl acetoacetate), titanium di-2-ethylhexoxybis (2-ethyl-3-hydroxyhexoxide), titanium diisopropoxybis (tri Ethanolaminate), titanium-1,3-propanedioxybis (ethyl acetoacetate), titanium aminoethylamino ethanolate, titanium acetylacetonate, tita Ethyl acetoacetate, titanium phosphate compound, titanium octylene glycolate, titanium ethyl acetoacetate, aluminum tris ethylacetoacetate, aluminum tris acetylacetonate, aluminum bis ethylacetoacetate monoacetylacetonate, and the like. Among these, from the viewpoint of solubility in organic solvents, zirconium tributoxy monoacetylacetonate, zirconium tetraacetylacetonate, zirconium dibutoxybis (ethylacetoacetate), titanium diisopropoxybis (ethylacetoacetate), titanium Di-2-ethylhexoxybis (2-ethyl-3-hydroxyhexoxide), titanium diisopropoxybis (triethanolaminate), titanium-1,3-propanedioxybis (ethylacetoacetate), titanium Aminoethylaminoethanolate, titanium diisopropoxybis (acetylacetonate), titanium tetraacetylacetonate, and aluminum bisethylacetoacetate monoacetylacetonate are preferred. These can be used individually by 1 type or in combination of 2 or more types.

  Examples of the metal alkoxide compound include zirconium tetranormal propoxide, normal propyl zirconate, normal butyl zirconate, titanium tetranormal butoxide, titanium butoxide dimer, titanium tetra-2-ethylhexoxide, titanium tetraisopropoxide, and tartar. Examples include Liamyl titanate, tetratertiary butyl titanate, tetraisopropyl titanate, tetranormal butyl titanate, butyl titanate dimer, tetraoctyl titanate, tetraisopropyl titanate, tetrastearyl titanate, aluminum isopropoxide, and aluminum secondary butoxide. Among these, from the viewpoint of solubility in an organic solvent, zirconium tetranormal propoxide, titanium tetranormal butoxide, titanium butoxide dimer, titanium tetra-2-ethylhexoxide, titanium tetraisopropoxide, tertiary amyl titanate, Tetra tert-butyl titanate and aluminum trisecondary butoxide are preferred. These can be used individually by 1 type or in combination of 2 or more types.

  Examples of the metal acylate compound include a zirconium octylate compound, zirconium stearate, titanium isostearate and the like. These can be used individually by 1 type or in combination of 2 or more types.

  Among the organometallic compounds described above, it is preferable to use a metal chelate compound from the viewpoint of controlling the pot life after preparation.

  The number of carbon atoms of the organometallic compound is preferably 2 to 120, and more preferably 6 to 72. When the carbon number is within the above range, the pot life after the preparation is easily controlled.

  In the primer composition, the compounding ratio (mass ratio) of the silane coupling agent and the organometallic compound is preferably 100: 1 to 1: 100, and more preferably 10: 1 to 1:10. When the amount of the organometallic compound is less than the above range, it takes time to form the primer layer 4 and the effect of suppressing tackiness may be reduced. On the other hand, when the amount of the organometallic compound is larger than the above range, the silane coupling agent of the primer layer 4 after film formation becomes insufficient, and the adhesion to an adherend such as a phosphor layer may be lowered. .

  The primer composition for forming the primer layer 4 may contain components other than the silane coupling agent and the organometallic compound described above. Examples of other components include a diluting solvent, a slip agent, an antifoaming agent, and an antistatic agent.

  Examples of the diluent solvent include toluene, methyl ethyl ketone, ethyl acetate, butyl acetate, hexane, 1-butanol, isopropyl alcohol, and water. These can be used individually by 1 type or in combination of 2 or more types. Although the compounding quantity of a dilution solvent is not specifically limited, Usually, it is 0-99.9 mass% on the basis of the whole primer composition, Preferably, it is 70-98 mass%. If the dilution solvent is small, the reactivity increases and the coating liquid may be gelled. If the dilution solvent is too large, the price of the coating liquid increases.

  The primer layer 4 can be formed by applying the above-described primer composition onto the first substrate 11 or the gas barrier coating layer 14 of the first film 1 and curing it. Examples of the coating method include a coating method using a gravure coater, a dip coater, a reverse coater, a wire bar coater, a die coater, and the like. Curing can be performed, for example, at 80 to 150 ° C. for 15 seconds to 300 seconds.

  The thickness of the primer layer 4 is preferably 1 to 1000 nm, more preferably 1 to 200 nm, still more preferably 5 to 100 nm, and particularly preferably 10 to 80 nm. When the thickness is 1 nm or more, the film formability after coating is stable, and good adhesion can be obtained uniformly in the surface. On the other hand, when the thickness is 1000 nm or less, the primer layer 4 can be prevented from becoming brittle and stable adhesion to the phosphor layer 7 can be obtained, and the end of the primer layer 4 (barrier film and phosphor) Invasion of water vapor and oxygen from between the layers 7) can be sufficiently suppressed. In addition, the thinner the primer layer 4, the faster the curing reaction of the primer layer 4 and the better the initial adhesion to the adherend. Furthermore, when the thickness of the primer layer 4 is 200 nm or less, optical interference fringes can also be reduced.

(Matte layer)
The mat layer 6 is provided on the surface of the barrier film opposite to the primer layer 4 in order to exhibit one or more optical functions and antistatic functions. Here, the optical function is not particularly limited, and examples thereof include an interference fringe (moire) prevention function, an antireflection function, and a diffusion function. Among these, it is preferable that the mat layer 6 has at least an interference fringe preventing function as an optical function. In the present embodiment, a case where the mat layer 6 has at least an interference fringe preventing function will be described.

  The mat layer 6 may include a binder resin and fine particles. Then, fine irregularities may be formed on the surface of the mat layer 6 by embedding the fine particles in the binder resin so that some of the fine particles are exposed from the surface of the mat layer 6. By providing such a mat layer 6 on the surface of the barrier film, generation of interference fringes such as Newton rings can be more sufficiently prevented, and as a result, a highly efficient, high-definition, long-life wavelength conversion sheet is obtained. It becomes possible.

  Although it does not specifically limit as binder resin, Resin excellent in optical transparency can be used. More specifically, for example, polyester resins, acrylic resins, acrylic urethane resins, polyester acrylate resins, polyurethane acrylate resins, urethane resins, epoxy resins, polycarbonate resins, polyamide resins, polyimide resins. Thermoplastic resins such as melamine resins and phenol resins, thermosetting resins, ionizing radiation curable resins, and the like can be used. In addition to the organic resin, a silica binder can also be used. Among these, it is desirable to use acrylic resins and urethane resins because of the wide range of materials, and it is more desirable to use acrylic resins because of excellent light resistance and optical characteristics. These can be used in combination of not only one type but also a plurality of types.

  The fine particles are not particularly limited. For example, in addition to inorganic fine particles such as silica, clay, talc, calcium carbonate, calcium sulfate, barium sulfate, titanium oxide, and alumina, styrene resin, urethane resin, silicone resin, Organic fine particles such as acrylic resin and polyamide resin can be used. Among these, as the fine particles, it is preferable in terms of transmittance to use fine particles having a refractive index of 1.40 to 1.55 made of silica, acrylic resin, urethane resin, polyamide resin or the like. Fine particles with a low refractive index are expensive, while fine particles with a refractive index that is too high tend to impair the transmittance. These can be used in combination of not only one type but also a plurality of types.

  The average particle size of the fine particles is preferably from 0.1 to 30 μm, and more preferably from 0.5 to 10 μm. When the average particle size of the fine particles is 0.1 μm or more, an excellent interference fringe prevention function tends to be obtained, and when it is 30 μm or less, the transparency tends to be further improved.

  The content of the fine particles in the mat layer 6 is preferably 0.5 to 30% by mass, more preferably 3 to 10% by mass based on the total amount of the mat layer 6. When the content of the fine particles is 0.5% by mass or more, the light diffusion function and the effect of preventing the generation of interference fringes tend to be further improved, and when the content is 30% by mass or less, the luminance is not reduced. .

  The mat layer 6 can be formed by applying the above-described coating solution containing the binder resin and fine particles on the surface of the first film 1, the second film 2, or the third film 3 and drying and curing the coating liquid. . Examples of the coating method include a coating method using a gravure coater, a dip coater, a reverse coater, a wire bar coater, a die coater, and the like.

  The thickness of the mat layer 6 is preferably 0.1 to 20 μm, and more preferably 0.3 to 10 μm. When the thickness of the mat layer 6 is 0.1 μm or more, there is a tendency that a uniform film can be easily obtained and the optical function can be sufficiently obtained. On the other hand, when the thickness of the mat layer 6 is 20 μm or less, when fine particles are used for the mat layer 6, the fine particles are exposed to the surface of the mat layer 6, and the unevenness imparting effect tends to be easily obtained.

  The barrier film of this embodiment having the above-described configuration can be used for applications that require barrier properties relating to the transmission of oxygen and water vapor. For example, a wavelength conversion sheet containing a light emitter used in a backlight for liquid crystal In particular, it can be used as a barrier film for industrial materials such as a wavelength conversion sheet, an organic EL device, and a solar cell containing a quantum dot light emitter.

[Wavelength conversion sheet]
Next, the wavelength conversion sheet of the present invention using the barrier film will be described. The wavelength conversion sheet of the present invention comprises a phosphor layer containing a phosphor, and the barrier film of the present invention laminated on at least one surface of the phosphor layer. The primer layer is provided on the outermost surface on the phosphor layer side. FIG. 7 is a schematic cross-sectional view showing an embodiment of the wavelength conversion sheet of the present invention. A wavelength conversion sheet 800 shown in FIG. 7 has a structure in which a phosphor layer 7 having a wavelength conversion function including a phosphor is sandwiched between a pair of barrier films 100. The pair of barrier films 100 and the phosphor layer 7 are laminated so that the primer layer 4 is in contact with the phosphor layer 7. In the wavelength conversion sheet 800 having such a configuration, the barrier film 100 and the phosphor layer 7 are bonded to each other with the primer layer 4 interposed therebetween, so that excellent adhesion can be obtained. The barrier film 100 may be the barrier film 200, the barrier film 300, or the barrier film 400 described above.

(Phosphor layer)
The phosphor layer 7 is a layer having a wavelength conversion function of emitting light of different wavelengths when irradiated with excitation light, and includes at least one kind of phosphor (not shown).

  Among phosphors, a nano-sized semiconductor called a quantum dot is preferable because high wavelength conversion efficiency is obtained and luminance and color reproducibility as a display are excellent. Examples of the quantum dots include those in which a core as a light emitting portion is covered with a shell as a protective film. Examples of the core include cadmium selenide (CdSe), and examples of the shell include zinc sulfide (ZnS). Quantum efficiency is improved by covering surface defects of CdSe particles with ZnS having a large band gap. In addition, the phosphor may be one in which a core is doubly covered with a first shell and a second shell. In this case, CsSe can be used for the core, zinc selenide (ZnSe) can be used for the first shell, and ZnS can be used for the second shell. Two or more kinds of the phosphors are used in combination. Moreover, the fluorescent substance layer containing only one kind of fluorescent substance and the fluorescent substance layer containing only another kind of fluorescent substance may be laminated | stacked.

  The quantum dots are dispersed in a resin material for sealing. As the resin material (sealing resin), for example, a thermoplastic resin, a thermosetting resin, and an ultraviolet curable resin (photocurable resin) can be used. Examples of the thermoplastic resin include cellulose derivatives such as acetylcellulose, nitrocellulose, acetylbutylcellulose, ethylcellulose, and methylcellulose; vinyl acetate and copolymers thereof, vinyl chloride and copolymers thereof, and vinylidene chloride and copolymers thereof. Acetal resins such as polyvinyl formal and polyvinyl butyral; Acrylic resins and copolymers thereof, Acrylic resins such as methacrylic resins and copolymers; Polystyrene resins; Polyamide resins; Linear polyester resins; Fluorine Resin; and polycarbonate resin etc. can be used. Examples of the thermosetting resin include an epoxy resin, a phenol resin, a urea melamine resin, a polyester resin, and a silicone resin. Examples of the photocurable resin include photopolymerizable prepolymers such as epoxy acrylate, urethane acrylate, and polyester acrylate. Further, these photopolymerizable prepolymers can be the main components, and monofunctional or polyfunctional monomers can be used as diluents.

  The phosphor layer 7 is formed separately by applying a mixed solution containing a phosphor, a resin material, and a solvent as necessary on the primer layer 4 of the barrier film to form a coating film. It can be formed by laminating a single barrier film so that the primer layer 4 faces the phosphor layer 7 and curing the coating film.

  Curing of the coating film can be appropriately performed according to the resin material used. For example, when the resin material is a photocurable resin, the coating film can be cured by curing (UV curing) the photocurable resin by irradiation with ultraviolet rays. The photocurable resin may be further thermally cured after UV curing.

  The wavelength conversion sheet of this embodiment mentioned above can be used for a backlight unit, for example. The backlight unit includes, for example, a light source, a light guide plate, a reflection plate, and the wavelength conversion sheet of the present embodiment. In the backlight unit, the light guide plate and the reflection plate are arranged in this order on one surface of the wavelength conversion sheet, and the light source is arranged on the side of the light guide plate (surface direction of the light guide plate). For example, a blue light emitting diode element or the like is used as the light source.

[Manufacturing method of barrier film and wavelength conversion sheet]
Next, an embodiment of the method for producing the barrier film and the wavelength conversion sheet of the present invention will be described. The method for producing a barrier film of the present embodiment is a method for producing a barrier film comprising a gas barrier film and a primer layer disposed on one outermost surface, wherein the metal chelate compound is formed on the gas barrier film, It has the process of apply | coating and hardening the primer composition containing the at least 1 type of organometallic compound selected from the group which consists of a metal alkoxide compound and a metal acylate compound, and a silane coupling agent, and forming the said primer layer. Also, the wavelength conversion sheet manufacturing method of the present embodiment includes a phosphor layer containing a phosphor, a gas barrier film laminated on at least one surface of the phosphor layer, and the outermost surface on the phosphor layer side. A barrier film having a primer layer disposed on the gas barrier film, wherein the gas barrier film has at least a metal chelate compound, a metal alkoxide compound, and a metal acylate compound. Applying a primer composition containing a kind of organometallic compound and a silane coupling agent and curing to form the primer layer; and laminating the phosphor layer and the barrier film; Have. In the present embodiment, the surface of the gas barrier film forming the primer layer is the first substrate 11 in the barrier films 100, 300, and 500 shown in FIGS. 1, 3, and 5, and FIGS. The barrier films 200, 400, and 600 shown in FIG.

  When manufacturing the barrier film 100 shown in FIG. 1 and the wavelength conversion sheet 800 shown in FIG. 7 using the barrier film 100, it can be manufactured, for example, by the following procedure. The method for forming each layer is as described above. First, the 1st film 1 and the 2nd film 2 are produced, respectively. That is, the anchor coat layer 12 is formed on the first base material 11, and the inorganic thin film layer 13 and the gas barrier coating layer 14 are sequentially formed thereon to produce the first film 1. The second film 2 can be similarly produced.

  By applying an adhesive or a pressure-sensitive adhesive on the gas barrier coating layer 14 of the obtained first film 1 and bonding it to the surface of the second film 2 on the gas barrier coating layer 24 side, aging is performed. A laminated film in which the first film 1 and the second film 2 are bonded together through the adhesive layer 5 is obtained. Bonding can be performed using a general laminating apparatus. The adhesive or pressure-sensitive adhesive may be applied on the gas barrier coating layer 24 of the second film 2.

  Primer containing at least one organometallic compound selected from the group consisting of a metal chelate compound, a metal alkoxide compound and a metal acylate compound, and a silane coupling agent on the first substrate 11 of the obtained laminated film The primer layer 4 is formed by applying and curing the composition. Further, the mat layer 6 is formed on the second base material 21 of the laminated film. The order of forming the primer layer 4 and the mat layer 6 is not particularly limited. Further, the mat layer 6 may be formed on the second base 21 of the second film 2 in advance before the first film 1 and the second film 2 are bonded together. Furthermore, the primer layer 4 may be formed on the first substrate 11 of the first film 1 in advance before the first film 1 and the second film 2 are bonded together. Thereby, the barrier film 100 is obtained. Two barrier films 100 are produced.

  Next, on the primer layer 4 of one barrier film 100, a mixed liquid containing a phosphor, a resin material, and, if necessary, a solvent is applied to form a coating film, on which the other barrier film 100 is coated. The primer layer 4 side is bonded together, and the coating film is cured to form the phosphor layer 7. By the above method, it is possible to obtain the wavelength conversion sheet 800 of the present embodiment that has good gas barrier properties and excellent adhesion between the barrier film 100 and the phosphor layer 7.

  The preferred embodiments of the present invention have been described in detail above. However, the technical scope of the present invention is not limited to the above-described embodiments, and various modifications can be made without departing from the spirit of the present invention. It is.

  For example, in the barrier film shown in FIGS. 1 to 7, the mat layer 6 and the anchor coat layers 12 and 22 may not be provided.

  In addition, in the barrier films 100, 200, and 500 shown in FIGS. 1, 2, 5, and 7, the barrier layers 15 and 25 are composed of the inorganic thin film layers 13 and 23 and the gas barrier coating layers 14 and 24 alternately. A plurality of stacked layers may be used. In the barrier films 300, 400, and 600 shown in FIGS. 3, 4, and 6, the barrier layers 15 and 25 are formed by laminating the inorganic thin film layers 13 and 23 and the gas barrier coating layers 14 and 24 one by one. It may be.

  Moreover, in the barrier film shown in FIGS. 1-7, the direction of the 1st film 1 and the 2nd film 2 is not limited to the direction shown in figure, You may arrange | position in the reverse direction.

  Moreover, in addition to the 1st-3rd film shown to each figure, the barrier film shown in FIGS. 1-7 may further have one or more films which have the structure similar to or different from them. .

  In the wavelength conversion sheet shown in FIG. 7, the pair of barrier films sandwiching the phosphor layer 7 may have different structures. Further, the mat layer 6 is not necessarily provided on both surfaces of the wavelength conversion sheet, and may be provided only on one surface.

  EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example and a comparative example, this invention is not limited to a following example.

  In the following examples and comparative examples, the water vapor transmission rate was measured by using a water vapor transmission rate measuring device (trade name: Permatran, manufactured by MOCON) by an infrared sensor method according to JIS K7129, and the temperature of the transmission cell was 40. The relative humidity of the high humidity chamber was 90% RH, and the relative humidity of the low humidity chamber was 0% RH.

  Moreover, in the following examples and comparative examples, the thickness of the primer layer was measured by observing a sample cross section with a transmission electron microscope (TEM).

[Example 1]
On one side of the biaxially stretched polyethylene terephthalate film (trade name: P60, thickness: 16 μm, manufactured by Toray Industries, Inc.) subjected to corona discharge treatment, a polyester resin solution is applied by a bar coating method. An anchor coat layer having a thickness of 100 nm was formed by drying and curing at 80 ° C. for 1 minute.

A silicon oxide material (manufactured by Canon Optron Co., Ltd.) is evaporated by electron beam heating under a pressure of 1.5 × 10 ⁻² Pa using an electron beam heating type vacuum deposition apparatus, and an inorganic thin film is formed on the anchor coat layer. A SiOx film having a thickness of 80 nm was formed as a layer. In addition, the acceleration voltage in vapor deposition was 40 kV, and the emission current was 0.2 A. On this SiOx film, a coating solution in which a tetraethoxysilane hydrolyzate (containing a siloxane bond) and polyvinyl alcohol are mixed at a mass ratio of 1: 1 is applied by a bar coating method and dried and cured at 120 ° C. for 1 minute. A gas barrier coating layer having a thickness of 400 nm was formed. This obtained the 1st film. Moreover, the 2nd film was produced like the 1st film. The water vapor permeability of the first and second films was 0.1 g / (m ² · day).

  On the gas barrier coating layer of the first film, an adhesive (main agent: TPO-3183, curing agent: K-341, manufactured by Seiden Chemical Co., Ltd.) is applied to form an adhesive layer, and the gas barrier property of the second film The surfaces on the coating layer side were bonded together and aging was performed at 25 ° C. for 7 days. Thereby, the laminated | multilayer film by which the 1st film and the 2nd film were bonded together through the contact bonding layer was obtained. The thickness of the adhesive layer was 4 μm.

  A primer layer was formed on the polyethylene terephthalate film (first substrate) of the first film in the obtained laminated film by the following method.

  1.0 part by mass of 3-glycidoxypropylmethyldimethoxysilane (epoxy silane coupling agent, manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM-402) and zirconium tetraacetylacetonate (zirconium chelate, Matsumoto Fine Chemical Co., Ltd.) Manufactured, trade name: Orgatics ZC-700) 1.0 part by mass and 22.2 parts by mass of toluene as a diluent solvent were mixed to prepare a primer composition. The obtained primer composition was applied onto the first substrate of the first film using a wire bar (# 3), dried at 120 ° C. for 30 seconds to be cured, and a primer layer having a thickness of 70 nm was formed. Formed.

  Further, on a polyethylene terephthalate film (second base material) of the second film, 100 parts by mass of an acrylic polyol resin (manufactured by DIC, trade name: Acrydic A-814), an isocyanate curing agent (manufactured by DIC) , Trade name: Vernock DN-980, hexamethylene diisocyanate compound) 8.5 parts by mass, fine particles (polyurethane, average particle size 2 μm) 10 parts by mass, solvent (ethyl acetate) 70 parts by mass, dried by heating and cured. Thus, a mat layer having a thickness of 3 μm was formed. This obtained the barrier film. Two barrier films having the same structure were produced.

Fluorescence in which a quantum dot light emitter having a core of cadmium selenide (CdSe), a shell of zinc sulfide (ZnS), and a particle diameter of 6 nm is dispersed in an acrylic resin (trade name: Hitaloid 7927-15, manufactured by Hitachi Chemical Co., Ltd.) A body layer forming coating solution was prepared. This coating solution was applied onto the primer layer of one barrier film to form a coating film, and the primer layer of the other barrier film was bonded thereto. The said coating film was hardened by exposing with the exposure amount of 1200 mJ / cm < ² > using an ultraviolet irradiation device, and the fluorescent substance layer which has a wavelength conversion function was formed. This obtained the wavelength conversion sheet which has the structure shown in FIG. At this time, the thickness of the phosphor layer was 100 μm.

[Example 2]
A wavelength conversion sheet was obtained in the same manner as in Example 1 except that the primer layer was formed by the following method.

  1.0 part by mass of 3-methacryloxypropyltrimethoxysilane (methacrylic silane coupling agent, manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM-503) and zirconium tetraacetylacetonate (zirconium chelate, manufactured by Matsumoto Fine Chemical Co., Ltd.) , Trade name: ORGATICS ZC-700) 1.0 part by mass and 22.2 parts by mass of toluene as a diluent solvent were mixed to prepare a primer composition. The obtained primer composition was applied onto the first substrate of the first film using a wire bar (# 3), dried at 120 ° C. for 30 seconds to be cured, and a primer layer having a thickness of 70 nm was formed. Formed.

[Example 3]
A wavelength conversion sheet was obtained in the same manner as in Example 1 except that the phosphor layer was formed by the following method.

In a mixture in which an epoxy compound (Epic Resins, trade name: RM12B4791A) and an amine compound (Epic Resins, trade name: RM12B4791B) are mixed at a mass ratio of 2: 1, the core is cadmium selenide (CdSe), A coating solution for forming a phosphor layer was prepared, in which the shell was zinc sulfide (ZnS) and a quantum dot light emitter having a particle diameter of 6 nm was dispersed. This coating solution was applied onto the primer layer of one barrier film to form a coating film, and the primer layer of the other barrier film was bonded thereto. The coating film was exposed at an exposure amount of 2100 mJ / cm ² using an ultraviolet irradiation device, and then heat-cured at 110 ° C. for 15 minutes to form a phosphor layer having a wavelength conversion function. This obtained the wavelength conversion sheet which has the structure shown in FIG. At this time, the thickness of the phosphor layer was 100 μm.

[Comparative Example 1]
A wavelength conversion sheet was obtained in the same manner as in Example 1 except that the primer layer was formed by the following method.

  Mixing 2.0 parts by mass of 3-glycidoxypropylmethyldimethoxysilane (epoxy silane coupling agent, manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM-402) and 18.9 parts by mass of toluene as a diluent solvent Thus, a primer composition was prepared. The obtained primer composition was applied onto the first substrate of the first film using a wire bar (# 3), dried at 120 ° C. for 30 seconds to be cured, and a primer layer having a thickness of 70 nm was formed. Formed.

[Comparative Example 2]
A wavelength conversion sheet was obtained in the same manner as in Example 1 except that the primer layer was formed by the following method.

  2.0 parts by mass of 3-methacryloxypropyltrimethoxysilane (methacrylic silane coupling agent, manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM-503) and 18.9 parts by mass of toluene as a diluent solvent were mixed. A primer composition was prepared. The obtained primer composition was applied onto the first substrate of the first film using a wire bar (# 3), dried at 120 ° C. for 30 seconds to be cured, and a primer layer having a thickness of 70 nm was formed. Formed.

[Comparative Example 3]
A wavelength conversion sheet was obtained in the same manner as in Comparative Example 1 except that the phosphor layer was formed by the following method.

In a mixture in which an epoxy compound (Epic Resins, trade name: RM12B4791A) and an amine compound (Epic Resins, trade name: RM12B4791B) are mixed at a mass ratio of 2: 1, the core is cadmium selenide (CdSe), A coating solution for forming a phosphor layer was prepared, in which the shell was zinc sulfide (ZnS) and a quantum dot light emitter having a particle diameter of 6 nm was dispersed. This coating solution was applied onto the primer layer of one barrier film to form a coating film, and the primer layer of the other barrier film was bonded thereto. The coating film was exposed at an exposure amount of 2100 mJ / cm ² using an ultraviolet irradiation device, and then heat-cured at 110 ° C. for 15 minutes to form a phosphor layer having a wavelength conversion function. This obtained the wavelength conversion sheet which has the structure shown in FIG. At this time, the thickness of the phosphor layer was 100 μm.

<Evaluation of peel strength>
The wavelength conversion sheets obtained in Examples and Comparative Examples were cut into strips having a width of 1 cm, and the cut wavelength conversion sheets were fixed on a glass plate. The primer layer of the fixed strip-shaped wavelength conversion sheet is peeled from the phosphor layer at a speed of 300 mm / min in a direction perpendicular to the glass plate using a Tensilon universal material testing machine (manufactured by A & D). Then, the strength required for peeling was measured. The measurement results are shown in Table 1.

<Evaluation of blocking>
The barrier film having the primer layer obtained in Examples and Comparative Examples was cut into 10 cm square, and the matte surface and the primer surface were overlapped so that the constant load type permanent strain tester CO-201 (tester industry) The product was subjected to blocking evaluation by storing it in a 60 ° C. thermal circulation oven for 1 week under a weight of 1N. Table 1 shows the evaluation results of the presence or absence of visual blocking.

<Relative luminance evaluation>
The wavelength conversion sheets obtained in Examples and Comparative Examples are cut into 10 cm squares, placed on a blue backlight unit, and initial luminance measurement is performed using an ultra-low luminance spectroradiometer SR-UL2 (manufactured by TOPCON). It was. The sample was stored in a heat-circulating oven at 85 ° C. for 500 hours, and then the luminance was measured by the same method. The luminance after storage for 500 hours was divided by the initial luminance to obtain a relative luminance evaluation. The measurement results are shown in Table 1.

  As is clear from the results shown in Table 1, it was confirmed that the wavelength conversion sheets of Examples 1 to 3 have excellent adhesion and excellent handling properties.

  DESCRIPTION OF SYMBOLS 1 ... 1st film, 2 ... 2nd film, 3 ... 3rd film, 4 ... Primer layer, 5 ... Adhesive layer, 6 ... Matte layer, 7 ... Phosphor layer, 11 ... 1st base material, 21 ... 2nd base material, 31 ... 3rd base material, 12, 22 ... anchor coat layer, 13, 23 ... inorganic thin film layer, 14, 24 ... gas barrier coating layer, 15, 25 ... barrier layer, 100, 200, 300, 400, 500, 600 ... barrier film, 800 ... wavelength conversion sheet.

Claims (7)

A gas barrier film;
From the cured product of the primer composition containing at least one organometallic compound selected from the group consisting of a metal chelate compound, a metal alkoxide compound, and a metal acylate compound, and a silane coupling agent, disposed on the outermost surface A primer layer,
A barrier film comprising:   The barrier film according to claim 1, wherein the organometallic compound contains at least one metal selected from the group consisting of aluminum, zirconium, titanium, and tin.   The silane coupling agent is at least one selected from the group consisting of vinyl group, epoxy group, styryl group, methacryl group, acrylic group, amino group, isocyanurate group, ureido group, mercapto group, sulfide group and isocyanate group. The barrier film of Claim 1 or 2 which has a functional group.   The barrier film as described in any one of Claims 1-3 whose thickness of the said primer layer is 1-1000 nm. A phosphor layer containing a phosphor, and the barrier film according to any one of claims 1 to 4 laminated on at least one surface of the phosphor layer,
The barrier film is a wavelength conversion sheet comprising the primer layer on the outermost surface on the phosphor layer side. A method for producing a barrier film comprising a gas barrier film and a primer layer disposed on one outermost surface,
On the gas barrier film, a primer composition containing at least one organometallic compound selected from the group consisting of metal chelate compounds, metal alkoxide compounds and metal acylate compounds, and a silane coupling agent is applied and cured. A method for producing a barrier film, comprising the step of forming the primer layer. A phosphor layer containing a phosphor, and a barrier film having a gas barrier film laminated on at least one surface of the phosphor layer and a primer layer disposed on the outermost surface on the phosphor layer side. A method for producing a wavelength conversion sheet, comprising:
On the gas barrier film, a primer composition containing at least one organometallic compound selected from the group consisting of metal chelate compounds, metal alkoxide compounds and metal acylate compounds, and a silane coupling agent is applied and cured. Forming the primer layer,
Laminating the phosphor layer and the barrier film;
The manufacturing method of the wavelength conversion sheet | seat which has these.

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