JP6926506B2 - Barrier film and wavelength conversion sheet using it - Google Patents

Description

The present invention relates to a barrier film and a wavelength conversion sheet using the barrier film.

Wavelength conversion sheets using phosphors such as quantum dots have high brightness and color reproducibility, and are desired to be used in displays and the like. However, phosphors such as quantum dots are deteriorated by contact with oxygen or moisture. Therefore, the wavelength conversion sheet often adopts a structure in which a barrier film having a gas barrier layer formed on a polymer film is arranged on one or both sides of a phosphor layer containing a phosphor.

For example, in Patent Document 1, barrier films are attached to both sides of a phosphor layer in which quantum dots are dispersed in an acrylic resin and an epoxy resin to prevent oxygen and the like from entering the phosphor layer.

International Publication No. 2014/113562

However, the phosphor layer in which quantum dots, which are an inorganic material as described in Patent Document 1, are dispersed, has poor adhesion to the barrier film, and peeling occurs between the phosphor layer and the barrier film, resulting in fluorescence. The performance of the body layer may deteriorate. For this reason, there is a method of improving the adhesion by providing a primer layer on the barrier film, but peeling may occur when a moisture resistance test is performed. In addition, due to the lack of flexibility of the primer layer, it was not possible to cope with the curing shrinkage of the phosphor layer, and peeling may occur.

The present invention has been made in view of the above-mentioned problems of the prior art, and is in close contact with an adherend such as a phosphor layer even after a moisture resistance test (hence, long-term stability) and after curing of a phosphor layer. It is an object of the present invention to provide a barrier film having excellent properties and a wavelength conversion sheet using the same.

In order to solve the above-mentioned problems, the invention according to claim 1 comprises a gas barrier film and the like.
Disposed on one of the outermost surface consists of at least a metal chelate compound comprising one metal, the cured product of the primer compositions containing silane-coupling agent is selected from the group consisting of water-soluble resin, titanium and zirconium primers With layers,
A wavelength conversion sheet is produced by applying a mixed solution containing a phosphor and a resin material onto the primer layer.
It is a barrier film for a wavelength conversion sheet, which is characterized by being used for manufacturing.

The invention according to claim 2 is the barrier film according to claim 1, wherein the water-soluble resin contains a resin of either polyvinyl alcohol or a polycarboxylic acid.

The invention according to claim 3 is the barrier film according to claim 1 or 2, wherein the metal chelate compound has a hydroxyl group and contains titanium.

The invention according to claim 4 is characterized in that the silane coupling agent has at least one functional group selected from the group consisting of a methacryloyl group, an acryloyl group, an epoxy group, an amino group and a mercapto group. The barrier film according to any one of Items 1 to 3.

The invention according to claim 5 comprises a phosphor layer containing a phosphor and a barrier film according to any one of claims 1 to 4 laminated on at least one surface of the phosphor layer. Prepare,
The barrier film is a wavelength conversion sheet characterized in that the primer layer is provided on the outermost surface on the phosphor layer side.

According to the present invention, the present invention comprises a gas barrier film and a primer layer composed of a water-soluble resin and a metal chelate compound arranged on one of the outermost surfaces and a cured product of a primer composition containing a silane coupling agent. Since the barrier film is used, a barrier film that is stable for a long period of time and has excellent adhesion to an adherend such as a phosphor layer and a wavelength conversion sheet using the same can be obtained.

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

[Barrier film]
The barrier film of the present invention comprises a gas barrier film, a primer layer composed of a cured product of a primer composition containing a water-soluble resin, a metal chelate compound, and a silane coupling agent arranged on one of the outermost surfaces. To be equipped with.

Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings. However, it is not limited to these. In the drawings, the same or corresponding parts are designated by the same reference numerals, and duplicate description will be omitted. Further, the dimensional ratio in the drawing is not limited to the ratio shown in the drawing.

1 to 6 are schematic cross-sectional views showing an embodiment of the barrier film of the present invention. The barrier film 100 shown in FIG. 1 includes a first film 1 which is a gas barrier film, a second film 2 which 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 base material 11, an anchor coat layer 12, and a barrier layer 15 composed of 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 composed of an inorganic thin film layer 23 and a gas barrier coating layer 24. The first film 1 and the second film 2 are bonded to each other via an adhesive layer 5 so that the gas barrier coating layer 14 and the gas barrier coating layer 24 face each other. In the barrier film 100, the primer layer 4 is arranged on the surface of the first film 1 on the side of the first base material 11 in a state of being in contact with the first base material 11, and the mat layer 6 is the first. The film 2 is arranged on the surface of the film 2 on the side of the second base material 21 in contact with the second base material 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, the permeation of water and oxygen can be more sufficiently suppressed. .. Further, by arranging the barrier layers 15 and 25 inside the first and second base materials 11 and 21, the barrier layers 15 and 25 are protected and damage to the barrier layers 15 and 25 is suppressed.

The barrier film 200 shown in FIG. 2 includes a first film 1 which is a gas barrier film, a second film 2 which 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 base material 11, an anchor coat layer 12, and a barrier layer 15 composed of 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 composed of an inorganic thin film layer 23 and a gas barrier coating layer 24. The first film 1 and the second film 2 are bonded to each other via an adhesive layer 5 so that the first base material 11 and the gas barrier coating layer 24 face each other. In the barrier film 200, the primer layer 4 is arranged on the surface of the first film 1 on the gas barrier coating layer 14 side in a state of being in contact with the gas barrier coating layer 14, and the mat layer 6 is a second. The film 2 is arranged on the surface of the film 2 on the side of the second base material 21 in contact with the second base material 21. Since the barrier film 200 having the structure shown in FIG. 2 has two gas barrier films of the first and second films 1 and 2 bonded together, the permeation of water and oxygen can be more sufficiently suppressed. .. Further, by arranging the barrier layer 15 on the primer layer 4 side, that is, at a position closer to the adherend, it is possible to more sufficiently suppress the invasion of water and oxygen into the adherend.

The barrier film 300 shown in FIG. 3 includes a first film 1, a second film 2, a primer layer 4, an adhesive layer 5, and a mat layer 6, which are gas barrier films. Here, the first film 1 includes a first base material 11, an anchor coat layer 12, and a barrier layer 15 in which two layers of an inorganic thin film layer 13 and a gas barrier coating layer 14 are alternately laminated. ing. The second film 2 is composed of only the second base material 21. The first film 1 and the second film 2 are bonded to each other via an adhesive layer 5 so that the gas barrier coating layer 14 and the second base material 21 face each other. In the barrier film 300, the primer layer 4 is arranged on the surface of the first film 1 on the side of the first base material 11 in a state of being in contact with the first base material 11, and the mat layer 6 is the first. The second base material 21 constituting the film 2 of 2 is arranged on the surface opposite to the adhesive layer 5 in a state of being in contact with the second base material 21. In the barrier film 300 having the structure shown in FIG. 3, since the second film 2 is composed of only the second base material 21, the manufacturing process can be simplified and the cost can be reduced, and further, the second film 2 can be reduced. Rigidity can be imparted as needed by changing the thickness of the base material 21. Further, since the barrier layer 15 has a structure in which two layers of the inorganic thin film layer 13 and the gas barrier coating layer 14 are alternately laminated, the gas barrier property can be enhanced.

The barrier film 400 shown in FIG. 4 includes a first film 1 which 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 layers of an inorganic thin film layer 13 and a gas barrier coating layer 14 are alternately laminated. ing. In the barrier film 300, the primer layer 4 is arranged on the surface of the first film 1 on the gas barrier coating layer 14 side in a state of being in contact with the gas barrier coating layer 14, and the mat layer 6 is the first. The film 1 is arranged on the surface of the film 1 on the side of the first base material 11 in contact with the first base material 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. Further, since the barrier layer 15 has a structure in which two layers of the inorganic thin film layer 13 and the gas barrier coating layer 14 are alternately laminated, the gas barrier property can be enhanced.

The barrier film 500 shown in FIG. 5 includes a first film 1 which is a gas barrier film, a second film 2 which is a gas barrier film, a third film 3, a primer layer 4, and an adhesive layer 5. A mat layer 6 is provided. Here, the first film 1 includes a first base material 11, an anchor coat layer 12, and a barrier layer 15 composed of 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 composed of an inorganic thin film layer 23 and a gas barrier coating layer 24. The third film 3 is composed of only the third base material 31. The first film 1 and the second film 2 are bonded to each other via an adhesive layer 5 so that the gas barrier coating layer 14 and the gas barrier coating layer 24 face each other. The second film 2 and the third film 3 are bonded to each other via an adhesive layer 5 so that the second base material 21 and the third base material 31 face each other. In the barrier film 500, the primer layer 4 is arranged on the surface of the first film 1 on the side of the first base material 11 in a state of being in contact with the first base material 11, and the mat layer 6 is the first. The third base material 31 constituting the film 3 of No. 3 is arranged on the surface opposite to the adhesive layer 5 in a state of being in contact with the third base material 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, the permeation of water and oxygen can be more sufficiently suppressed. .. Further, by arranging the barrier layers 15 and 25 inside the first and second base materials 11 and 21, the barrier layers 15 and 25 are protected and damage to the barrier layers 15 and 25 is suppressed. Further, by providing the third film 3, it is possible to reduce the heat wrinkles generated in the first film 1 or the second film 2. Further, the rigidity can be imparted as needed by changing the thickness of the third base material 31.

The barrier film 600 shown in FIG. 6 includes a first film 1, a second film 2, a primer layer 4, an adhesive layer 5, and a mat layer 6, which are gas barrier films. Here, the first film 1 includes a first base material 11, an anchor coat layer 12, and a barrier layer 15 in which two layers of an inorganic thin film layer 13 and a gas barrier coating layer 14 are alternately laminated. ing. The second film 2 is composed of only the second base material 21. The first film 1 and the second film 2 are bonded to each other via an adhesive layer 5 so that the first base material 11 and the second base material 21 face each other. In the barrier film 600, the primer layer 4 is arranged on the surface of the first film 1 on the gas barrier coating layer 14 side in a state of being in contact with the gas barrier coating layer 14, and the mat layer 6 is a second. The second base material 21 constituting the film 2 is arranged on the surface opposite to the adhesive layer 5 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 of only the second base material 21, the manufacturing process can be simplified and the cost can be reduced, and further, the second film 2 can be reduced. Rigidity can be imparted as needed by changing the thickness of the base material 21. Further, since the barrier layer 15 has a structure in which two layers of the inorganic thin film layer 13 and the gas barrier coating layer 14 are alternately laminated, the gas barrier property can be enhanced.

The barrier film having the above-mentioned structure has good gas barrier properties, and excellent adhesion can be obtained by adhering it to an adherend such as a phosphor layer via a primer layer 4. Further, since the primer layer 4 exhibits extremely good adhesion to both the first base material 11 and the gas barrier coating layer 14, peeling in the barrier film is sufficiently suppressed. Therefore, the barrier film having the above-mentioned structure can suppress the invasion of oxygen and water from the interface between the barrier film and the adherend, and can suppress the deterioration of the adherend. From the viewpoint of adhesion, it is more preferable that the primer layer 4 is applied to the first base material 11. When the adhesion between the primer layer 4 and the first base material 11 or the gas barrier coating layer 14 is poor, corona treatment, frame treatment, plasma treatment, or the like is applied to the first base material 11 or the gas barrier coating layer 14. Therefore, the adhesion with the primer layer 4 can be further improved. Alternatively, an easy-adhesion coat layer such as urethane-based, polyester-based, or acrylic-based may be provided.

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

(Base material)
It is desirable that the first, second and third base materials 11, 21, 31 are polymer films. Examples of the material of the polymer film include polyesters such as polyethylene terephthalate, polybutylene terephthalate and polyethylene naphthalate, polyamides such as nylon, polyolefins such as polypropylene and cycloolefin, polycarbonate, triacetyl cellulose and the like. 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 even more preferably a polyethylene terephthalate film. Polyethylene terephthalate film is desirable from the viewpoint of transparency, processing suitability and adhesion. Further, the polyethylene terephthalate film is preferably a biaxially stretched polyethylene terephthalate film from the viewpoint of transparency and gas barrier property.

The polymer film may contain additives such as an antistatic agent, an ultraviolet absorber, a plasticizer and a slip agent, if necessary. Further, the surface of the polymer film may be subjected to corona treatment, frame treatment and plasma treatment. Alternatively, an easy-adhesion coat layer such as urethane-based, polyester-based, or acrylic-based may be provided.

When the first base material 11 and the primer layer 4 are in contact with each other in the barrier film, the first base material 11 preferably has a polar functional group such as a hydroxyl group or a carbonyl group on its surface. When the first base material 11 has a polar functional group such as a hydroxyl group or a carbonyl group on its surface, it is generated by hydrolysis of the polar functional group such as the hydroxyl group and the alkoxysilane of the silane coupling agent in the primer layer 4. It reacts with the silanol group and the adhesion is further improved. Among the above-mentioned polymer films, those having a polar functional group such as a hydroxyl group or a carbonyl group on the surface usually include polyethylene terephthalate film, polybutylene terephthalate film, polyethylene naphthalate film, polyamide film, triacetyl cellulose film, and acrylic. Examples include films and polycarbonate films. When the first base material 11 does not have a polar functional group such as a hydroxyl group or a carbonyl group on its surface, it can be adhered to the primer layer 4 by performing surface treatments such as corona treatment, frame treatment and plasma treatment. Can be further improved. Alternatively, an easy-adhesion coat layer such as urethane-based, polyester-based, or acrylic-based may be provided.

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 5 μm or more and 50 μm or less from the viewpoint of workability and productivity. Is more preferable. When the thickness is 3 μm or more, processing is easy, and when the thickness 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 in order to improve the adhesion between the inorganic thin film layers 13 and 23. Further, the anchor coat layers 12 and 22 may have a barrier property to prevent the permeation of water and oxygen.

The 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, and modified silicone resin. Alternatively, it can be formed using a resin selected from alkyl titanates and the like. The anchor coat layer can be formed by using the above-mentioned resin alone or by using a composite resin in which two or more kinds of the above-mentioned resins are combined.

The anchor coat layers 12 and 22 can be formed by applying the above-mentioned resin-containing solution on the first and second base materials 11 and 21 and drying and curing the solution. Examples of the coating method include 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 it is 500 nm or less, it tends to be possible to form a uniform layer in which the internal stress is sufficiently suppressed.

(Barrier layer)
The barrier layers 15 and 25 are layers provided to further improve the water vapor transmission rate and the oxygen permeability. It is desirable that the barrier layers 15 and 25 have high transparency from an optical point of view. The barrier layers 15 and 25 may be a single layer or a multi-layer, but as shown in FIGS. 1 to 6, it is desirable to have the inorganic thin film layers 13 and 23 and the gas barrier coating layers 14 and 24. Further, when the gas barrier coating layer 14 and the primer layer 4 are in contact with each other as shown in FIGS. 2 and 4, it is desirable that the gas barrier coating layer 14 has a siloxane bond. When 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 in a vacuum. Examples of the vacuum film formation include a physical vapor deposition method and a chemical vapor deposition method. Examples of the physical vapor deposition method include a vacuum deposition method, a sputtering method, and an ion plating method. Examples of the chemical vapor deposition (CVD) method include a thermal CVD method, a plasma CVD (PECVD) method, an optical CVD method, and the like. 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 method for forming the inorganic thin film layers 13 and 23 is preferably a vacuum vapor deposition method, a sputtering method, or a PECVD method. The vacuum vapor deposition method is more preferably a resistance heating vacuum deposition method, an electron beam heating vacuum deposition method, or an induction heating vacuum vapor deposition method, and the sputtering method is a reactive sputtering method or a dual magnetron sputtering method. Is more preferable. From the viewpoint of film homogeneity, the sputtering method is preferable, and from the viewpoint of cost, the vacuum vapor deposition method is preferable and can be selected according to the purpose and application.

Examples of the plasma generation method 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 superimposition method. Can be done.

In vacuum film formation, a metal or an oxide such as silicon, a nitride or a film such as a nitride oxide is usually formed. As the inorganic thin film layers 13 and 23, metals such as aluminum, titanium, copper, indium and tin, oxides thereof (alumina and the like), or films of silicon and silicon oxide are preferable. Further, not only the oxide of metal or silicon but also the nitride or oxide film of metal or silicon may be formed. Further, a film containing a plurality of metals may be formed. The above-mentioned aluminum, titanium, copper, indium, and silicon oxides, nitrides, and nitride oxides are excellent in both transparency and barrier properties. Oxides containing silicon and nitride oxides have high barrier properties and are particularly preferable.

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, a better barrier property tends to be obtained. Further, 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 deterioration of the water vapor barrier property and the oxygen barrier property due to the cracks tends to be suppressed. Further, 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 of the amount of material used and the shortening of the film formation time, which is preferable from the economical viewpoint.

(Gas barrier coating layer)
The gas barrier coating layers 14 and 24 are provided to prevent various secondary damages in the subsequent process and to impart 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. When the gas barrier coating layers 14 and 24 are formed in the atmosphere, they contain, for example, a polar compound such as polyvinyl alcohol, polyvinylpyrrolidone, or ethylene vinyl alcohol, a chlorine-containing compound such as polyvinylidene chloride, and a Si atom. It can be formed by applying a coating liquid containing a compound, a compound containing a Ti atom, a compound containing an Al atom, a compound containing a Zr atom, or the like on the inorganic thin film layers 13 and 23 and drying and curing the mixture.

Specific examples of the coating liquid coating method for 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, a die coater, and the like. Be done.

The compound containing a siloxane bond is preferably formed by reacting a silanol group with, for example, a silane compound. Examples of such a silane compound include a compound represented by the following formula (1).
R ¹ _n (OR ² ) _4-n Si ... (1)
[In the formula, n represents an integer of 0 to 3, and R1 and R2 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. And so on. Polysilazane containing nitrogen may be used.

Further, as the gas barrier coating layers 14 and 24, a material made of a precursor composed of other metal atoms may be used. Examples of the compound containing a Ti atom include a compound represented by the following formula (2).
R ¹ _n (OR ² ) _4-n Ti ... (2)
[In the formula, n represents an integer of 0 to 3, and R1 and R2 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.

Examples of the compound containing an Al atom include a compound represented by the following formula (3).
R ¹ _m (OR ² ) _3-m Al ... (3)
[In the formula, m represents an integer of 0 to 2, and R1 and R2 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)
[In the formula, n represents an integer of 0 to 3, and R1 and R2 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 liquid is cured after coating. The curing method is not particularly limited, and examples thereof include ultraviolet curing and thermosetting. In the case of UV curing, the coating liquid may contain a polymerization initiator and a compound having a double bond. Further, if necessary, heat aging may be performed.

As another method for 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 mediated by phosphorus atoms derived from a phosphorus compound. It is also possible to use a method in which the reaction product obtained by dehydration condensation is used as a gas barrier coating layer. Specifically, a functional group (for example, a hydroxyl group) existing on the surface of an inorganic oxide and a site of a phosphorus compound capable of reacting with the inorganic oxide (for example, a halogen atom directly bonded to a phosphorus atom or a direct bond to a phosphorus atom). The bonded oxygen atom) causes a condensation reaction to bond. In the reaction product, for example, a coating liquid containing an inorganic oxide and a phosphorus compound is applied to the surfaces of the inorganic thin film layers 13 and 23, and the formed coating film is heat-treated so that the particles of the inorganic oxide are made of phosphorus. It is obtained by advancing the reaction of binding via a phosphorus atom derived from a compound. The lower limit of the heat treatment temperature is 110 ° C. or higher, preferably 120 ° C. or higher, more preferably 140 ° C. or higher, and even more preferably 170 ° C. or higher. If 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 heat treatment temperature varies depending on the type of the base material and the like, but is 220 ° C. or lower, and preferably 190 ° C. or lower. The heat treatment can be carried out in air, in a nitrogen atmosphere, in an argon atmosphere, or the like.

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

The coating liquid may further contain a filler, a leveling agent, a defoaming agent, an ultraviolet absorber, an antioxidant, a silane coupling agent, a titanium chelating agent, and the like, if 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 easy. 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 is a first film 1 and a second film 2 in order to bond and laminate the first film 1 and the second film 2. It is provided between and. Further, 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 bond and laminate the second film 2 and the third film 3. It is provided between 3 and 3. As the adhesive layer 5, a general adhesive or an adhesive for a polymer film can be used, and the adhesive layer 5 is appropriately selected according to the surfaces of the first film 1 and the second film 2 on the side to be bonded. Will be done. Examples of the material of 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 of applying the adhesive or the pressure-sensitive adhesive include a gravure coater, a dip coater, a reverse coater, a wire bar coater, a die coater, and the like.

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 the cost increase tends to be suppressed. be.

Further, the first film 1 and the second film 2 or the second film 2 and the third film 3 can be bonded to each other via the adhesive layer 5 and then aged. Aging is carried out, for example, at 20 to 80 ° C. for 1 to 10 days.

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 dispersant and the like, if 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 base material 11 of the first film 1 or on the gas barrier coating layer 14. 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 attached to the adherend.

The primer layer in the barrier film of the present invention is a layer composed of a cured product of a primer composition containing a water-soluble resin, a metal chelate compound, and a silane coupling agent.

As the water-soluble resin, polyvinyl alcohol (PVA) or a polycarboxylic acid such as polyacrylic acid (PAA) or carboxymethyl cellulose (CMC) is preferable from the viewpoint of high reactivity with a metal chelate compound and water resistance. Since PVA has a hydroxyl group, when the metal chelate compound has a hydroxyl group, it is crosslinked by a dehydration reaction to form a film. It is preferable to use PVA having a high degree of saponification in order to increase the cross-linking rate. Since PAA and CMC have a carboxyl group, they are crosslinked to form a film by a dealcohol reaction with a metal chelate compound. When the metal chelate compound does not have a hydroxyl group, the water-soluble resin is crosslinked by an intermolecular force. Further, the water-soluble resin imparts flexibility to the primer layer, and the barrier film and the adherend such as the phosphor layer are brought into close contact with each other by hydrogen bonds.

The silane coupling agent shows high affinity for the adherend and contributes to the improvement of adhesion. That is, the silane coupling agent is hydrolyzed by a metal chelate compound to generate a silanol group in the primer layer, and the silanol group is a polar functional group such as a hydroxyl group on the surface of a base material in contact with the primer layer or a gas barrier coating layer. The reaction contributes to the improvement of adhesion and suppresses the ingress of moisture, oxygen, etc. from the interface between the primer layer and the layer in contact with the primer layer.

The silane coupling agent is not particularly limited, but one having at least one functional group selected from the group consisting of a methacryloyl group, an acryloyl group, an epoxy group, an amino group and a mercapto group is preferable. By using such a silane coupling agent, the barrier film can obtain better adhesion to an adherend such as a phosphor layer. Further, by selecting the functional group of the silane coupling agent, excellent adhesion to various adherends can be obtained. 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 a reactivity or affinity with the functional group. Further, as the silane coupling agent, two or more kinds of silane coupling agents having different functional groups may be used in combination.

Examples of the silane coupling agent having a methacryl group include 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, and 3-methacryloxypropyltriethoxysilane. Can be mentioned. Among these, 3-methacryloxypropylmethyldimethoxysilane and 3-methacryloxypropyltrimethoxysilane are preferable from the viewpoint of reactivity. These can be used alone or in combination of two or more.

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

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 alone or in combination of two or more.

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 can be mentioned. Among these, 3-aminopropyltriethoxysilane and 3-aminopropyltriethoxysilane are preferable from the viewpoint of reactivity. These can be used alone or in combination of two or more.

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. Further, the silane coupling agent having a mercapto group also includes a silane coupling agent in which, for example, a mercapto group is protected with an alkoxysilyl group or the like from the viewpoint of odor. These can be used alone or in combination of two or more.

By using the organometallic compound in combination with the silane coupling agent, it is possible to easily obtain a primer layer having a sufficient thickness to ensure excellent adhesion as compared with the case where the silane coupling agent is used alone. can. At that time, steps such as excessive heating, ultraviolet irradiation, and aging are not always required. 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 improvement in adhesion. Furthermore, the organometallic compound acts as a binder that binds the unreacted silane coupling agents to each other, and prevents tackiness due to the presence of an excessive unreacted silane coupling agent in the primer layer for handling. Can be facilitated.

As the organic metal compound, a metal chelate compound, a metal alkoxide compound and a metal acylate compound are candidates, but from the viewpoint of promoting the reactivity of hydrolysis of the silane coupling agent and controlling the pot life after liquid preparation, the metal chelate compound Is preferable. Further, the metal chelate compound preferably contains at least one metal selected from the group consisting of titanium, zirconium, aluminum and tin. Among these, it is preferable to contain at least one metal selected from the group consisting of titanium, zirconium and aluminum from the viewpoint of the environment, and from the viewpoint of particularly improving the initial adhesion, the group consisting of titanium and zirconium is used. It preferably contains at least one metal of choice.

Examples of the metal chelate compound include titanium lactate ammonium salt, titanium lactate, titanium triethanolaminate, titanium aminoethylaminoetanolate zirconium lactate ammonium salt, zirconium ethyl acetoacetate, zirconium tributoxymonoacetylacetate, and zirconium tetraacetylacetate. Nate, zirconium dibutoxybis (ethyl acetoacetate), zirconium monoacetyl acetonate, titanium diisopropoxybis (acetyl acetonate), titanium tetraacetyl acetonate, titanium diisopropoxybis (ethyl acetoacetate), titanium di-2 -Ethylhexoxybis (2-ethyl-3-hydroxyhexoxide), Titanium Diisopropoxybis (Triethanolaminete), Titanium-1,3-Propanodioxybis (Ethylacetacetate), Titanium Aminoethylamino Ethanolate, Titanium Acetylacetate, Titanium Ethylacetate, Titanium Phosphate Compound, Titanium Octylene Glycolate, Titanium Ethylacetate, Aluminum Trisethylacetate, Aluminumtris Acetylacetate, Aluminum Bisethylacetate Monoacetylacetate And so on.

Among the above-mentioned metal chelate compounds, those having a hydroxyl group are preferable from the viewpoint of compatibility with a water-soluble resin, and water-soluble or alcohol-soluble is preferable, and those having a hydroxyl group are preferable from the viewpoint of reactivity with a water-soluble resin, and further, two or more hydroxyl groups are used. Those are more preferable, and examples thereof include titanium lactate and zirconium lactate ammonium salt. These can be used alone or in combination of two or more.

In the primer composition, the silane coupling agent with respect to 100 (parts by mass) of the water-soluble resin is preferably 1 to 10000, more preferably 10 to 1000. The compounding ratio (parts by mass) of the metal chelate compound to the water-soluble resin 1 (parts by mass) is preferably 1 to 10000, and more preferably 10 to 100. If the amount of the metal chelate compound blended is less than the above range, it may take time to form the primer layer 4 and the effect of suppressing tackiness may be reduced. On the other hand, if the blending amount of the metal chelate 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 the adherend such as the base material 11 and the base material 21 phosphor layer is insufficient. Sex may be reduced.

The primer composition forming the primer layer 4 may contain components other than the above-mentioned silane coupling agent and metal chelate compound. Examples of other components include a diluting solvent, a slip agent, an antifoaming agent, an antistatic agent and the like.

Examples of the diluting solvent include water, methanol, ethanol, isopropyl alcohol, 1-butanol and the like. These can be used alone or in combination of two or more. The blending amount of the diluting solvent is not particularly limited, and it can be used to adjust the solid content from the target coating amount, processing method, and the like.

The primer layer 4 can be formed by applying the above-mentioned primer composition on the first base material 11 or the gas barrier coating layer 14 of the first film 1 and curing it. Examples of the coating method include 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 to 300 seconds.

The thickness of the primer layer 4 is preferably 1 to 1000 nm, more preferably 1 to 200 nm, further preferably 5 to 100 nm, and particularly preferably 10 to 80 nm. When this thickness is 1 nm or more, the film forming property after coating is stable, and good adhesion can be uniformly obtained in the plane. 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 portion of the primer layer 4 (barrier film and phosphor). The invasion of water vapor and oxygen from the layer 7) can be sufficiently suppressed. Further, when the thickness of the primer layer 4 is thin, the curing reaction of the primer layer 4 proceeds faster and the initial adhesion to the adherend becomes better. Further, when the thickness of the primer layer 4 is 200 nm or less, optical interference fringes can be reduced.

(Mat layer)
The mat layer 6 is provided on the surface of the barrier film opposite to the primer layer 4 in order to exert 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, the mat layer 6 preferably has at least an interference fringe prevention function as an optical function. In the present embodiment, a case where the mat layer 6 has at least an interference fringe prevention function will be described.

The mat layer 6 may be composed of a binder resin and fine particles. Then, the surface of the mat layer 6 may have fine irregularities by embedding the fine particles in the binder resin so that a part of the fine particles is exposed from the surface of the mat layer 6. By providing such a mat layer 6 on the surface of the barrier film, the occurrence of interference fringes such as Newton's rings can be more sufficiently prevented, and as a result, a wavelength conversion sheet having high efficiency, high definition, and long life can be obtained. It becomes possible.

The binder resin is not particularly limited, but a resin having excellent optical transparency can be used. More specifically, for example, polyester resin, acrylic resin, acrylic urethane resin, polyester acrylate resin, polyurethane acrylate resin, urethane resin, epoxy resin, polycarbonate resin, polyamide resin, polyimide resin. , Melamine-based resin, thermoplastic resin such as phenol-based resin, thermosetting resin, ionizing radiation curable resin 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 an acrylic resin or a urethane resin because of the wide range of materials, and it is more desirable to use an acrylic resin because of its excellent light resistance and optical characteristics. These are not limited to one type, but a plurality of types can be used in combination.

The fine particles are not particularly limited, but are, for example, inorganic fine particles such as silica, clay, talc, calcium carbonate, calcium sulfate, barium sulfate, titanium oxide, and alumina, as well as styrene resin, urethane resin, and silicone resin. Organic fine particles such as acrylic resin and polyamide resin can be used. Among these, as the fine particles, it is preferable 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 in terms of transmittance. Fine particles with a low index of refraction are expensive, while fine particles with an excessively high index of refraction tend to impair the transmittance. These are not limited to one type, but a plurality of types can be used in combination.

The average particle size of the fine particles is preferably 0.1 to 30 μm, more preferably 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 the average particle size 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 occurrence of interference fringes tend to be further improved, and when it is 30% by mass or less, the brightness is not reduced. ..

The mat layer 6 can be formed by applying a coating liquid containing the above-mentioned binder resin and fine particles on the surfaces of the first film 1, the second film 2 or the third film 3 and drying and curing the mat layer 6. .. Examples of the coating method include 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, more preferably 0.3 to 10 μm. When the thickness of the mat layer 6 is 0.1 μm or more, a uniform film tends to be easily obtained, and an optical function tends to 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 on the surface of the mat layer 6 and the effect of imparting unevenness tends to be easily obtained.

The barrier film of the present embodiment having the configuration described above can be used in applications that require a barrier property regarding the permeation of oxygen and water vapor. For example, a wavelength conversion sheet containing a light emitter used for a backlight for a liquid crystal display. In particular, it can be used as a barrier film for industrial materials such as wavelength conversion sheets containing quantum dot illuminants, organic EL elements, and solar cells.

[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 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. 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. The 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, since the barrier film 100 and the phosphor layer 7 are bonded to each other via the primer layer 4, 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.

(Fluorescent layer)
The phosphor layer 7 is a layer having a wavelength conversion function of emitting light having a different wavelength by irradiation with excitation light, and includes at least one type of phosphor (not shown).

Among the phosphors, nano-sized semiconductors called quantum dots are preferable because they can obtain high wavelength conversion efficiency and are excellent in brightness and color reproducibility as a display. Examples of the quantum dots include those in which the core as a light emitting portion is covered with a shell as a protective film. Examples of the core include cadmium selenide (CdSe) and the like, and examples of the shell include zinc sulfide (ZnS) and the like. Quantum efficiency is improved by covering the surface defects of CdSe particles with ZnS having a large bandgap. Further, the phosphor may have a core double-coated 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. The above phosphors are used in combination of two or more types. Further, a phosphor layer containing only one type of phosphor and a phosphor layer containing only another type of phosphor may be laminated.

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, an ultraviolet curable resin (photocurable resin), or the like can be used. Examples of the thermoplastic resin include cellulose derivatives such as acetyl cellulose, nitro cellulose, acetyl butyl cellulose, ethyl cellulose and methyl cellulose, vinyl acetate and its copolymer, vinyl chloride and its copolymer, and vinylidene chloride and its copolymer. Vinyl resins such as, polyvinyl formal and acetal resins such as polyvinyl butyral, acrylic resins and their copolymers, methacrylic resins and their copolymers and other acrylic resins, polystyrene resins, polyamide resins, linear polyester resins, fluorine. Resins, polycarbonate resins and the like can be used. Examples of the thermosetting resin include epoxy resin, phenol resin, urea melamine resin, polyester resin, silicone resin and the like. Examples of the photocurable resin include photopolymerizable prepolymers such as epoxy acrylate, urethane acrylate, and polyester acrylate. Further, it is also possible to use these photopolymerizable prepolymers as a main component and a monofunctional or polyfunctional monomer as a diluent. Other examples of the photocurable resin include a cured product containing a polyfunctional thiol compound as a main component and reacting with a polyfunctional acrylic compound, a methacrylic compound, an allyl compound and the like.

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

The coating film can be appropriately cured depending on the resin material used. For example, when the resin material is a photocurable resin, the coating film can be cured by curing the photocurable resin by irradiating with ultraviolet rays (UV curing). The photocurable resin may be further thermoset after UV curing.

The wavelength conversion sheet of the present embodiment described above can be used, for example, in a backlight unit. The backlight unit includes, for example, a light source, a light guide plate, a reflector, and a wavelength conversion sheet of the present embodiment. In the backlight unit, the light guide plate and the reflector 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 (the surface direction of the light guide plate). As the light source, for example, a blue light emitting diode element or the like is used.

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

Further, in the barrier films 100, 200, 500 shown in FIGS. 1, 2, 5, and 7, the barrier layers 15 and 25 alternate between the inorganic thin film layers 13 and 23 and the gas barrier coating layers 14 and 24. A plurality of laminated ones may be used. Further, in the barrier films 300, 400, 600 shown in FIGS. 3, 4, and 6, the barrier layers 15 and 25 are the inorganic thin film layers 13, 2.
3 and the gas barrier coating layers 14 and 24 may be laminated one by one.

Further, in the barrier films shown in FIGS. 1 to 7, the orientations of the first film 1 and the second film 2 are not limited to the directions shown in the drawings, and may be arranged in opposite directions.

Further, the barrier films shown in FIGS. 1 to 7 may further include one or more films having the same or different configurations as those of the first to third films shown in each figure. ..

Further, in the wavelength conversion sheet shown in FIG. 7, the pair of barrier films sandwiching the phosphor layer 7 may have different configurations from each other. Further, the mat layer 6 does not necessarily have to be provided on both sides of the wavelength conversion sheet, and may be provided only on one surface.

Hereinafter, the present invention will be described in more detail based on Examples and Comparative Examples, but the present invention is not limited to the following Examples.

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

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

<Example 1>
A polyester resin solution was applied by the bar coat method on the corona discharge-treated surface of a biaxially stretched polyethylene terephthalate film (trade name: P60, thickness: 16 μm, manufactured by Toray Industries, Inc.) whose one side was corona-discharge-treated. An anchor coat layer having a thickness of 100 nm was formed by drying and curing at 80 ° C. for 1 minute.

Using a vacuum vapor deposition apparatus of the electron beam heating type, a silicon oxide material (manufactured by Canon Optron Inc.) and evaporated by electron beam heating under a pressure of 1.5 × 10 -2 ^Pa, an inorganic thin film on the anchor coat layer A SiOx film having a thickness of 80 nm was formed as a layer. The acceleration voltage in the vapor deposition was 40 kV, and the emission current was 0.2 A. On this SiOx film, a coating solution prepared by mixing a hydrolyzate of tetraethoxysilane (containing a siloxane bond) and polyvinyl alcohol 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. As a result, a first film was obtained. Moreover, the second film was produced in the same manner as the first film. The water vapor transmission rate of the first and second films was 0.1 g / (m ² · day).

A pressure-sensitive adhesive (main agent: TPO-3183, curing agent: K-341, manufactured by Saiden Chemical Co., Ltd.) is applied onto the gas barrier coating layer of the first film to form an adhesive layer, and the gas barrier property of the second film is obtained. The surfaces on the coating layer side were bonded together and aged at 25 ° C. for 7 days. As a result, a laminated film in which the first film and the second film were bonded together via an adhesive layer was obtained. The thickness of the adhesive layer was 4 μm.

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

112.73 g of water / methanol = 6/4 solution, 80 g of 5% PVA solution (water / methanol = 6/4) as a water-soluble resin solution, 3-methacryloxypropyltrimethoxysilane (methacryl-based silane coupling agent, Shinetsu) Mix 5.0 g of Kagaku Kogyo Co., Ltd., trade name: KBM-503) and 2.27 g of titanium lactate (manufactured by Matsumoto Fine Chemical Co., Ltd., trade name: Organix TC-310) as a metal chelate compound and stir for 5 minutes. 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 in an oven at 120 ° C. for 2 minutes and cured to a thickness of 70 nm. A primer layer was formed. As a result, a barrier film in the form in which the matte layer was omitted in FIG. 1 was obtained. A total of two barrier films having the same composition were produced.

A coating liquid for forming a phosphor layer was prepared by dispersing a quantum dot illuminant in a UV-curable acrylic compound. This coating liquid 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. ^{The coating film was cured by exposing it to an exposure amount of 1200 mJ / cm 2} using an ultraviolet irradiation device to form a phosphor layer having a wavelength conversion function. As a result, a wavelength conversion sheet having a structure in which the matte layer was omitted in FIG. 7 was obtained.

<Example 2>
A wavelength conversion sheet was obtained in the same manner as in Example 1 except that the water-soluble resin was changed from PVA to polyacrylic acid (PAA).

<Example 3>
A wavelength conversion sheet was obtained in the same manner as in Example 1 except that the water-soluble resin was changed from PVA to carboxymethyl cellulose (CMC).

<Example 4>
A wavelength conversion sheet was obtained in the same manner as in Example 1 except that the metal chelate compound was changed to titanium tetraacetylacetonate (manufactured by Matsumoto Fine Chemicals Co., Ltd., trade name: Organix TC-401) having no hydroxyl group.

<Example 5>
A wavelength conversion sheet was obtained in the same manner as in Example 1 except that the metal chelate compound was changed to a zirconium lactate ammonium salt having only one hydroxyl group (manufactured by Matsumoto Fine Chemical Co., Ltd., trade name: Organix ZC-300).

<Example 6>
The silane coupling agent is 3-glycidoxypropylmethyldimethoxysilane (epoxy-based silane coupling agent, manufactured by Shin-Etsu Chemical Industry Co., Ltd., trade name: KBM-402), and the compounds that disperse quantum dots are epoxy compounds and amine compounds. A wavelength conversion sheet was obtained in the same manner as in Example 1 except that the mixture was changed to the mixture of 1 and heat cured.

<Example 7>
A wavelength conversion sheet was obtained in the same manner as in Example 1 except that the silane coupling agent was an amine-based resin and the resin for dispersing the quantum dots was the same mixture of the epoxy compound and the amine compound as in Example 6.

<Example 8>
A wavelength conversion sheet was obtained in the same manner as in Example 1 except that the resin for dispersing the quantum dots was changed to a mixture of a thiol compound and an allyl compound.

<Example 9>
A wavelength conversion sheet was obtained in the same manner as in Example 1 except that the silane coupling agent was changed to a mercapto-based resin and the resin for dispersing the quantum dots was changed to a mixture of a thiol-based compound and an allyl-based compound.

<Comparative example 1>
A wavelength conversion sheet was obtained in the same manner as in Example 1 except that the primer layer did not contain a water-soluble resin and the metal chelate compound was changed to the same zirconium lactate ammonium salt ZC-300) as in Example 5.

<Comparative example 2>
A wavelength conversion sheet was obtained in the same manner as in Example 6 except that the primer layer did not contain a water-soluble resin and the metal chelate compound was changed to the same zirconium lactate ammonium salt ZC-300) as in Example 5.

<Comparative example 3>
A wavelength conversion sheet was obtained in the same manner as in Example 1 except that the primer layer contained neither a water-soluble resin nor a metal chelate compound.

<Comparative example 4>
A wavelength conversion sheet was obtained in the same manner as in Example 6 except that the primer layer contained neither a water-soluble resin nor a metal chelate compound.

<Comparative example 5>
A wavelength conversion sheet was obtained in the same manner as in Example 1 except that the primer layer did not contain a silane coupling agent.

<Comparative Example 6>
A wavelength conversion sheet was obtained in the same manner as in Example 6 except that the primer layer did not contain a silane coupling agent.

<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 off from the phosphor layer at a speed of 300 mm / min in the direction perpendicular to the glass plate using a Tensilon universal material tester (manufactured by A & D). Then, the strength required for peeling was measured.

<Evaluation of moisture resistance>
Each sample prepared in the same manner as above was stored in a high humidity chamber at 65 ° C. and 95% RH for 500 hours, and then the peel strength was measured by the same method as described above to evaluate the moisture resistance.

<Evaluation of relative brightness>
The wavelength conversion sheets obtained in Examples and Comparative Examples are cut into 10 cm squares, placed on a blue backlight unit, and initial brightness measurement is performed using an ultra-low brightness spectroradiometer SR-UL2 (manufactured by TOPCON). rice field. After storing each sample in a heat circulation oven at 85 ° C. for 500 hours, the brightness was measured by the same method, and the brightness after storage for 500 hours was divided by the initial brightness to obtain a relative brightness evaluation.

Table 1 shows the preparation conditions and evaluation results of each of the above samples.

As is clear from the results shown in Table 1, it was confirmed that the 1 to 6 wavelength conversion sheets of Examples had good adhesion both at the initial stage and after 65 ° C. and 95% 500 hours.

In addition, the following was confirmed.
1) In Example 2, PAA is less likely to react with the metal chelate compound than PVA, so that the peel strength is slightly lower than that in Example 1.
2) In Example 3, since the reaction of CMC with the metal chelate compound is less likely to occur than in PVA and PAA, the peel strength is slightly lower than that in Examples 1 and 2.
3) In Example 4, since the metal chelate compound does not have a hydroxyl group, the PVA and the metal chelate compound are bonded by an intermolecular force, and the peel strength after 65 ° C. 95% 500 h is inferior to that of Example 1. However, since the silane coupling agent binds to the phosphor layer, the peel strength after 65 ° C. 95% 500 hours was improved as compared with Comparative Example 5.
4) In Example 5, since ZC-300 has only one hydroxyl group, there are few cross-linking points, and the initial strength is inferior to that of Example 1. Further, although the peel strength after 65 ° C. 95% 500h is also inferior, the peel strength after 65 ° C. 95% 500h is improved as compared with Comparative Example 5 because the silane coupling agent binds to the phosphor layer.
5) In Examples 6 to 9, the peel strength at the initial stage after 65 ° C. 95% 500 hours was good as in Examples 1 and 2.
6) In Comparative Examples 1 and 2, since the primer layer was not flexible and hardened as compared with Example 1, since it did not contain a water-soluble resin, the peel strength was lowered.
7) In Comparative Examples 3 and 4, since the metal chelate compound was not further contained in Comparative Examples 1 and 2, the primer layer became more inflexible and hard, and the peel strength was lowered.
8) In Comparative Examples 5 and 6, since the silane coupling agent was not contained, the reaction between the silane coupling agent and the phosphor layer disappeared, the peel strength after 65 ° C. 95% 500 hours decreased, and the brightness also decreased.

1 ... 1st film, 2 ... 2nd film, 3 ... 3rd film, 4 ... Primer layer, 5 ... Adhesive layer, 6 ... Matte layer, 7 ... Fluorescent layer, 11 ... 1st substrate, 21 ... 2nd substrate, 31 ... 3rd substrate, 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 (5)

Gas barrier film and
Disposed on one of the outermost surface consists of at least a metal chelate compound comprising one metal, the cured product of the primer compositions containing silane-coupling agent is selected from the group consisting of water-soluble resin, titanium and zirconium primers With layers,
A barrier film for a wavelength conversion sheet, which is used for producing a wavelength conversion sheet by applying a mixed solution containing a phosphor and a resin material on the primer layer. The barrier film according to claim 1, wherein the water-soluble resin contains a resin of either polyvinyl alcohol or a polycarboxylic acid. The barrier film according to claim 1 or 2, wherein the metal chelate compound has a hydroxyl group and contains titanium. Any one of claims 1 to 3, wherein the silane coupling agent has at least one functional group selected from the group consisting of a methacryloyl group, an acryloyl group, an epoxy group, an amino group, and a mercapto group. Barrier film described in. The barrier film according to any one of claims 1 to 4 is provided with a phosphor layer containing a phosphor and a barrier film laminated on at least one surface of the phosphor layer.
The barrier film is a wavelength conversion sheet including the primer layer on the outermost surface on the phosphor layer side.

Images