JP2019051663A - Barrier film laminate - Google Patents

Abstract

To provide a barrier film laminate having excellent peeling strength when pulling a barrier film in a 180° direction.SOLUTION: A barrier film laminate 10 has: a first barrier film 16a having a first substrate layer 11a and a first barrier layer 14a formed on the first substrate layer 11a; a second barrier film 16b having a second substrate layer 11b and a second barrier layer 14b formed on the second substrate layer 11b; and an adhesion layer 15, where the first barrier film 16a and the second barrier film 16b are laminated through the adhesion layer 15 so that the first barrier layer 14 faces the second barrier layer 14b. The adhesion layer 15 is formed from an adhesive containing an epoxy resin, and a curing agent having an amino group. The epoxy resin contains an open-chain aliphatic bifunctional epoxy resin.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a barrier film laminate.

  In a light emitting unit such as a backlight unit of a liquid crystal display and an electroluminescence light emitting unit, the performance as a light emitter may be deteriorated when a long time elapses when the light emitter comes into contact with oxygen or water vapor. For this reason, in these light emitting units, a barrier film laminate in which a gas barrier film in which a gas barrier layer is formed on a polymer film is laminated via an adhesive layer is often used as a protective film for the light emitter (for example, Patent Documents). 1).

JP 2012-76288 A

  In the barrier film laminate as described above, the gas barrier film has a gas barrier property that suppresses oxygen or water vapor or the like from entering mainly in the thickness direction (lamination direction) from the upper surface (or lower surface) of the barrier film laminate. Since this gas barrier film is laminated, the barrier film laminate can further suppress the intrusion of oxygen or water vapor as compared with the case of a gas barrier film single layer. Even if this occurs, the gas barrier properties of the barrier film laminate are not easily impaired.

  On the other hand, in the barrier film laminate, oxygen or water vapor or the like may enter the surface direction (direction perpendicular to the lamination direction) from the side surface of the barrier film laminate through the adhesive layer, and when the gas barrier film has a defect. The gas barrier property as a gas barrier film laminate may be impaired, and the performance of the light-emitting body to be protected may be deteriorated. For this reason, in a barrier film laminated body, not only a gas barrier film but an adhesive layer may be given a high gas barrier property. Thereby, invasion of oxygen, water vapor, or the like through the adhesive layer can be suppressed, and even when a defect occurs in the barrier film, the gas barrier property as the barrier film laminate is easily maintained.

  However, in the barrier film laminate using such an adhesive layer having gas barrier properties, the peel strength between the barrier films varies depending on the peel angle, and in particular, one barrier film is parallel to the surface direction of the other barrier film. There was a problem that peeling was likely to occur when pulled in the direction of 180 degrees. This invention is made | formed in view of the said situation, and it aims at providing the barrier film laminated body excellent in the peeling strength when a barrier film is pulled in the direction of 180 degree | times.

  The present invention is formed on a first barrier film including a first substrate layer and a first barrier layer formed on the first substrate layer, a second substrate layer, and the second substrate layer. A barrier film laminate comprising a second barrier film including a second barrier layer and an adhesive layer is provided. In the barrier film laminate, the first barrier film and the second barrier film are bonded so that the first barrier layer and the second barrier layer face each other with the adhesive layer interposed therebetween. The first barrier layer includes a first inorganic thin film layer and a first gas barrier coating layer, the second barrier layer includes a second inorganic thin film layer and a second gas barrier coating layer, and the adhesive layer includes And an epoxy resin and a curing agent having an amino group, and the epoxy resin includes a chain aliphatic type bifunctional epoxy resin.

  In a barrier film laminate using an adhesive layer having a gas barrier property, it was confirmed that when one barrier film was pulled in parallel (180-degree direction) to the surface direction of the other barrier film, peeling was confirmed. Was not the adhesive layer / barrier film interface peeling or the cohesive peeling of the adhesive layer, but the cohesive peeling of the base material layer in the vicinity of the barrier layer. The barrier film laminate is a laminate of a large number of layers, and stress generated during and after the production may be accumulated therein. Since an adhesive layer having a gas barrier property is generally hard and often lacks flexibility, it is difficult to disperse the generated stress in a barrier film laminate having such an adhesive layer. is there. As a result, stress concentrates in the vicinity of the barrier layer of the base material layer, and the base material layer is likely to be agglomerated and peeled off, which appears as agglomerated peeling of the base material layer when the barrier film is pulled in the direction of 180 degrees. It is thought that. When the cohesive peeling of the base material layer occurs, the peel strength may decrease. In particular, when a stretched polyethylene terephthalate film was used as the base material layer, it was found that the surface peeled into a layer shape (surface layer peeling), so that the decrease in peel strength tends to become more prominent.

  Therefore, the present inventors give the adhesive layer flexibility by using a chain aliphatic type bifunctional epoxy resin as the epoxy resin used for the adhesive, and peeling when the barrier film is pulled in the direction of 180 degrees. It has been found that a decrease in strength can be suppressed. According to the present invention, since the barrier film laminate includes an adhesive layer formed from the adhesive, the peel strength when the barrier films are pulled in the 180 degree direction (hereinafter referred to as 180 degree peel strength) is excellent. A barrier film laminate can be obtained.

  In the barrier film laminate, the chain aliphatic bifunctional epoxy resin is preferably hexanediol diglycidyl ether. Thereby, the gas barrier property can be further improved while obtaining an excellent 180 degree peel strength between the barrier films.

The ratio (M _E / M _C ) of the epoxy resin content M _{E to} the curing agent content M _C in the adhesive used for forming the adhesive layer is 0.05 to 0.00. 5 is preferable. Thereby, it becomes easy to obtain excellent peel strength between the barrier films.

  The adhesive preferably further contains a silane coupling agent having an amino group. Thereby, there exists a tendency for the peeling strength between barrier films to improve.

In the adhesive that, the ratio of the content of _{M SCA} silane coupling agent having an amino group content _{M E} of the epoxy resin _{(M E /} M _SCA) is a weight ratio, 1.0 or higher Is preferred. Thereby, it becomes easy to improve the peeling strength between barrier films.

  The adhesive preferably further contains a silane coupling agent having an epoxy group. Thereby, there exists a tendency for the peeling strength between barrier films to improve.

The oxygen permeability of the adhesive layer is preferably 1000 cm ³ / (m ² · day · atm) or less at a thickness of 5 μm. Thereby, there exists a tendency for the gas barrier property of a barrier film laminated body to improve further.

  ADVANTAGE OF THE INVENTION According to this invention, the barrier film laminated body excellent in the peeling strength when a barrier film is pulled in the 180 degree | times direction can be provided.

It is a schematic sectional drawing of the barrier film laminated body which concerns on one Embodiment of this invention. It is a schematic sectional drawing of the wavelength conversion sheet obtained using the barrier film laminated body which concerns on one Embodiment of this invention. It is a schematic sectional drawing of the backlight unit obtained using the barrier film laminated body which concerns on one Embodiment of this invention. It is a schematic sectional drawing of the electroluminescent light emission unit obtained using the barrier film laminated body which concerns on one Embodiment of this invention.

  Hereinafter, embodiments of the present invention will be described in detail. In addition, this invention is not limited to the following embodiment.

[Barrier film laminate]
FIG. 1 is a schematic cross-sectional view of a barrier film laminate according to an embodiment of the present invention. In FIG. 1, the barrier film laminate 10 includes a first barrier film 16 a, a second barrier film 16 b, and an adhesive layer 15, and the first barrier film 16 a and the second barrier film 16 b are bonded together via the adhesive layer 15. ing.

  The adhesive layer 15 is formed from an adhesive containing an epoxy resin and a curing agent having an amino group. More specifically, the above-mentioned adhesive is applied and dried on one barrier film, the other barrier film is bonded through the coating film, and these are subjected to aging treatment, whereby the epoxy resin in the coating film and its An adhesive layer is formed through a curing reaction with the curing agent. In other words, the adhesive layer 15 contains a reaction product of an epoxy resin and a curing agent having an amino group. The epoxy resin includes a chain aliphatic type bifunctional epoxy resin. Thereby, the formed adhesive layer 15 has flexibility. When the adhesive layer 15 has flexibility, it is possible to disperse stress generated during and after the manufacture of the barrier film laminate, and to suppress the stress from being applied to a specific portion. Therefore, in the barrier film laminate 10 provided with the adhesive layer 15, an excellent 180 degree peel strength between the barrier films can be obtained.

  In this specification, the chain aliphatic type epoxy resin refers to an epoxy resin having a chain aliphatic hydrocarbon group as a main skeleton, and the main skeleton is, for example, a portion excluding an epoxy group introduction site in the epoxy resin. Point to. The bifunctional epoxy resin refers to an epoxy resin having two epoxy groups as functional groups in the molecule. The chain aliphatic hydrocarbon group is an aliphatic hydrocarbon group having no ring structure (including an aromatic ring and an aliphatic ring).

  A chain aliphatic type bifunctional epoxy resin can be obtained, for example, by allowing epichlorohydrin to act on alkylene diamine, alkylene diol or the like. In this case, in the obtained epoxy resin, the nitrogen atom derived from the amino group of the alkylene diamine or the portion containing the terminal epoxy group from the oxygen atom derived from the hydroxyl group of the alkylene diol is the epoxy group introduction site. Moreover, the part derived from the alkylene group in alkylene diamine or alkylene diol becomes the main skeleton of the epoxy resin.

  Specific examples of the chain aliphatic type bifunctional epoxy resin include hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, ethylene glycol diglycidyl ether, and diethylene glycol diglycidyl ether. Among these, the chain aliphatic type bifunctional epoxy resin is preferably hexanediol diglycidyl ether or neopentyl glycol diglycidyl ether, more preferably hexanediol diglycidyl ether. When the chain aliphatic type bifunctional epoxy resin is hexanediol diglycidyl ether, the gas barrier property of the barrier film laminate tends to be improved.

The said epoxy resin can contain other epoxy resins other than the chain aliphatic type bifunctional epoxy resin in the range which does not impair the effect of this invention. Examples of the other epoxy resins include aromatic epoxy resins, cycloaliphatic epoxy resins, monofunctional epoxy resins, and trifunctional or higher functional epoxy resins. The other epoxy resin can be a tri- or higher functional epoxy resin. If the epoxy resin containing 3 or more functional epoxy resin, 3 ratio content M _E2 bifunctional epoxy resin chain aliphatic type content M _EM functional or more epoxy resin _{(M EM /} M _E2) is The mass ratio of the nonvolatile content is preferably 1.0 or less, more preferably 0.5 or less, and further preferably 0.3 or less. When the adhesive contains a tri- or higher functional epoxy resin in a chain aliphatic type bifunctional epoxy resin with the above-mentioned content below a certain level, the adhesive layer is provided with flexibility and an effect of 180 degree peel strength. There is a tendency that the gas barrier property can be improved without impairing.

  The curing agent having an amino group is not particularly limited as long as it can be mixed with an epoxy resin and cured by heating.

The ratio to the content M _C of the curing agent having an amino group content M _E of the epoxy resin in the adhesive _(M E _/ M _C) is at a weight ratio of non-volatile component, preferably 1.0 or less, More preferably, it is 0.05-0.5, More preferably, it is 0.2-0.5, Most preferably, it is 0.3-0.5. When the adhesive contains the epoxy resin and the curing agent having an amino group within the above range, the adhesion of the barrier film is further easily obtained.

  The adhesive preferably further contains a silane coupling agent, more preferably contains a silane coupling agent having an amino group or an epoxy group, and more preferably contains a silane coupling agent having an amino group. . The silane coupling agent having an amino group preferably further has two or more hydrolyzable functional groups. The silane coupling agent having an epoxy group preferably further has two or more hydrolyzable functional groups.

  Examples of the silane coupling agent having an amino group include N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldiethoxysilane, 3- Aminopropyldimethoxysilane, N-2- (aminoethyl) -3-aminobutylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminohexylmethyldimethoxysilane, N-2- (aminoethyl) -3- Examples include aminooctylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, and the like.

  Examples of the silane coupling agent having an epoxy group include 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltrimethoxysilane, and 3-glycidoxypropyl. Examples include triethoxysilane and 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane.

When the adhesive contains a silane coupling agent having an amino group, the ratio of the content M _E of the epoxy resin to the content M _SCA of the silane coupling agent having an amino group in the adhesive (M _E / M _SCA ) is a mass ratio of the non-volatile content, and is preferably 1.0 or more, and more preferably 2.0 or more. By containing the silane coupling agent having an amino group in the adhesive in the above ratio, the peel strength of the barrier film is easily improved.

In addition, when a silane coupling agent the adhesive agent having an epoxy group, in the adhesive, to the content M _SCE of the silane coupling agent having an epoxy group content M _C of the curing agent having an amino group The ratio (M _C / M _SCE ) is a mass ratio of nonvolatile content, and is preferably 10.0 or more. When the adhesive contains the silane coupling agent having an epoxy group at the above ratio, the peel strength of the barrier film is easily improved.

The oxygen permeability of the adhesive layer 15 is preferably 1000 cm ³ / (m ² · day · atm) or less in the thickness direction at a thickness of 5 μm. The oxygen permeability is more preferably 500 cm ³ / (m ² · day · atm) or less, and further preferably 200 cm ³ / (m ² · day · atm) or less. When the oxygen permeability of the adhesive layer 15 is 1000 cm ³ / (m ² · day · atm) or less, even when the barrier layer has a defect when used in the light emitting unit, It becomes easy to suppress the occurrence of dark spots. The lower limit value of the oxygen permeability is not particularly limited, and is, for example, 0.1 cm ³ / (m ² · day · atm).

  The thickness of the adhesive layer 15 is preferably 0.5 to 20 μm, more preferably 1 to 10 μm, and further preferably 2 to 6 μm. When the thickness of the adhesive layer 15 is 0.5 μm or more, the adhesion between the first barrier film 16a and the second barrier film 16b is easily obtained, and when the thickness is 20 μm or less, the gas barrier property is obtained. Becomes easier to obtain.

  In FIG. 1, the first barrier film 16a includes a first base layer 11a and a first barrier layer 14a formed on the first base layer 11a, and the second barrier film 16b includes a second base layer 11b. And a second barrier layer 14b formed on the second base material layer 11b.

  The 1st base material layer 11a and the 2nd base material layer 11b are layers for controlling breakage in processing, distribution, etc. Examples of the first base material layer 11a and the second base material layer 11b include: polyesters such as polyethylene terephthalate, polybutylene terephthalate and polyethylene naphthalate; polyamides such as nylon; polyolefins such as polypropylene and cycloolefin polymers; polycarbonates; Although a film, such as acetylcellulose, is mentioned, it is not limited to these. The first base material layer 11a and the second base material layer 11b are preferably a polyester film, a polyamide film or a polyolefin film, more preferably a polyester film or a polyamide film, and a polyethylene terephthalate film or a polyethylene naphthalate film. More preferably it is. Moreover, it is preferable that the 1st base material layer 11a and the 2nd base material layer 11b are biaxially stretched. The first base material layer 11a and the second base material layer 11b may be the same or different. When the first base material layer 11a or the second base material layer 11b is a stretched polyethylene terephthalate film, when the first barrier film 16a or the second barrier film 16b is pulled in the 180 degree direction, the first base material layer 11a Alternatively, the surface of the second base material layer 11b may be peeled off in a layered manner (surface peeling), but the barrier film laminate 10 according to the present embodiment includes the adhesive layer 15, and thus the 180 degree peel strength is reduced. Without the occurrence, the stretched polyethylene terephthalate film can sufficiently exhibit its function.

  Although the thickness in particular of the 1st base material layer 11a and the 2nd base material layer 11b is not restrict | limited, It is preferable that they are 3 micrometers or more and 100 micrometers or less, and it is more preferable that they are 5 micrometers or more and 50 micrometers or less.

  A first barrier layer 14a and a second barrier layer 14b are formed on the first substrate layer 11a and the second substrate layer 11b, respectively, via an anchor coat layer (not shown) as necessary. A polyester resin etc. are mentioned as an anchor coat layer, and the thickness of an anchor coat layer is about 0.01-1 micrometer.

  The first barrier film 16a and the second barrier film 16b are bonded together so that the first barrier layer 14a and the second barrier layer 14b face each other. Thereby, more excellent gas barrier properties can be obtained, and the first barrier layer 14a and the second barrier layer 14b can be protected from external force, so that more stable gas barrier properties can be obtained.

  The first barrier film 16a may include two or more first barrier layers 14a, and the second barrier film 16b may include two or more second barrier layers 14b. When the first barrier film 16a includes two or more first barrier layers 14a, the configuration of the plurality of first barrier layers 14a may be the same or different. When the second barrier film 16b includes two or more second barrier layers 14b, the configurations of the plurality of second barrier layers 14b may be the same or different. When using the said barrier film laminated body 10 for a light emitting unit, the barrier film laminated body 10 is arrange | positioned so that the 1st barrier film 16a may contact | connect a light emitter layer. When the barrier film laminate 10 is a barrier film laminate in which the first barrier film 16a and the second barrier film 16b are overlapped, when used in a light emitting unit, the damage of the light emitter layer due to external force is suppressed, and Gas barrier properties can be improved.

  The first barrier layer 14a includes a first inorganic thin film layer 12a and a first gas barrier coating layer 13a, and the first inorganic thin film layer 12a and the first gas barrier coating layer 13a are arranged in this order on the first base material layer 11a. Are stacked. The second barrier layer 14b includes a second inorganic thin film layer 12b and a second gas barrier coating layer 13b, and the second inorganic thin film layer 12b and the second gas barrier coating layer 13b are arranged in this order on the second base material layer 11b. Are stacked.

The first inorganic thin film layer 12a and the second inorganic thin film layer 12b contain an inorganic compound and preferably contain a metal oxide. Examples of the metal oxide include oxides of metals such as aluminum, copper, silver, yttrium, tantalum, silicon, and magnesium. Since the metal oxide is inexpensive and excellent in barrier performance, it is preferably silicon oxide (SiO _x , x is 1.0 to 2.0). When x is 1.0 or more, good gas barrier properties tend to be obtained.

  The formation method of the first inorganic thin film layer 12a and the second inorganic thin film layer 12b is preferably vacuum film formation. Examples of vacuum film formation include physical vapor deposition and chemical vapor deposition. Examples of physical vapor deposition include vapor deposition, sputtering, and ion plating. Examples of the chemical vapor deposition method include a thermal CVD method, a plasma CVD method, and a photo CVD method. From the viewpoint of production cost, the first inorganic thin film layer 12a or the second inorganic thin film layer 12b is preferably an inorganic vapor deposition film layer formed by a vapor deposition method.

  The thickness of the first inorganic thin film layer 12a and the second inorganic thin film layer 12b is preferably 10 to 300 nm, and more preferably 20 to 100 nm. When the thickness of the first inorganic thin film layer 12a and the second inorganic thin film layer 12b is 10 nm or more, there is a tendency that a uniform film is easily obtained and gas barrier properties are easily obtained. On the other hand, when the thickness of the first inorganic thin film layer 12a and the second inorganic thin film layer 12b is 300 nm or less, the first inorganic thin film layer 12a and the second inorganic thin film layer 12b can be kept flexible. There is a tendency that cracks and the like are less likely to occur due to external forces such as bending and tension after film formation.

The first gas barrier coating layer 13a and the second gas barrier coating layer 13b are formed from a composition containing at least one selected from the group consisting of a metal alkoxide represented by the following formula (1) and a hydrolyzate thereof. Is preferred.
M (OR ¹ ) _m (R ² ) _nm (1)

In the above formula (1), a monovalent organic group having 1 to 8 carbon atoms R ¹ and R ² are each independently preferably an alkyl group such as a methyl group, an ethyl group. M represents an n-valent metal atom such as Si, Ti, Al, or Zr. m is an integer of 1 to n. Examples of the metal alkoxide include tetraethoxysilane [Si (OC ₂ H ₅ ) ₄ ], triisopropoxyaluminum [Al (O-iso-C ₃ H ₇ ) ₃ ] and the like. The metal alkoxide is preferably tetraethoxysilane or triisopropoxyaluminum because it is relatively stable in an aqueous solvent after hydrolysis. Examples of the hydrolyzate of the metal alkoxide include silicic acid (Si (OH) ₄ ) that is a hydrolyzate of tetraethoxysilane and aluminum hydroxide (Al (OH) ₃ that is a hydrolyzate of tripropoxyaluminum. ) And the like. These can be used in combination of not only one type but also a plurality of types. Content of the metal alkoxide and its hydrolyzate in the said composition is 10-90 mass%, for example.

  The composition may further contain a hydroxyl group-containing polymer compound. Examples of the hydroxyl group-containing polymer compound include water-soluble polymers such as polyvinyl alcohol, polyvinyl pyrrolidone and starch. The hydroxyl group-containing polymer compound is preferably polyvinyl alcohol from the viewpoint of barrier properties. These can be used in combination of not only one type but also a plurality of types. The content of the hydroxyl group-containing polymer compound in the composition is, for example, 10 to 90% by mass.

  The thickness of the first gas barrier coating layer 13a and the second gas barrier coating layer 13b is preferably 50 to 1000 nm, and more preferably 100 to 500 nm. When the thickness of the first gas barrier coating layer 13a and the second gas barrier coating layer 13b is 50 nm or more, there is a tendency that a sufficient gas barrier property can be obtained, and when the thickness is 1000 nm or less, sufficient flexibility is obtained. There is a tendency to hold.

  In order to exhibit the light scattering function, the barrier film laminate 10 may further include a coating layer (not shown) on the surface on the second barrier film 16b side. When the barrier film laminate 10 includes the coating layer, an interference fringe (moire) prevention function and an antireflection function can be obtained in addition to the light scattering function.

  The barrier film laminate 10 can be suitably used as a protective film for a light emitter (light emitter protective film) that can be deteriorated by contact with oxygen, water vapor, or the like. As said light-emitting body, fluorescent substance, such as a quantum dot, an electroluminescent light-emitting body, etc. are mentioned.

  The manufacturing method of the barrier film laminated body which concerns on this embodiment is demonstrated. First, the first barrier film 16a and the second barrier film 16b are prepared. The method for producing the first barrier film 16a and the second barrier film 16b is as described above. Next, the said adhesive agent is apply | coated on the surface by the side of the 1st barrier layer 14a of the 1st barrier film 16a (or the 2nd barrier layer 14b side of the 2nd barrier film 16b), and a coating film is formed. Examples of the method for applying the adhesive include a reverse gravure coating method. The coating film may be dried as necessary. The drying temperature is about 70 to 130 ° C., and the drying time is about 10 to 60 seconds. Thereafter, the first barrier film 16a and the second barrier film 16b are bonded so that the first barrier layer 14a and the second barrier layer 14b are opposed to each other through the coating film. After the bonding, the coating film is heated and cured, whereby the coating film becomes the adhesive layer 15 and the barrier film laminate 10 can be manufactured. The heating (aging) temperature for curing the coating film is, for example, 40 to 60 ° C., and the heating time is, for example, 1 to 4 days.

[Wavelength conversion sheet]
FIG. 2 is a schematic sectional view of a wavelength conversion sheet obtained using the barrier film laminate according to one embodiment of the present invention. The wavelength conversion sheet is a sheet that can convert some wavelengths of light from the light source of the backlight unit for liquid crystal display. As shown in FIG. 2, the wavelength conversion sheet 20 includes the barrier film laminate 10 described above, a phosphor layer 21 formed on the barrier film laminate 10, and another provided on the phosphor layer 21. The barrier film laminate 10 is schematically configured. The wavelength conversion sheet 20 has a structure in which the phosphor layer 21 is encapsulated (that is, sealed) between the two barrier film laminates 10. In the wavelength conversion sheet 20, a protective film different from the barrier film laminate 10 described above may be used for one barrier film laminate disposed on the light source side of the backlight unit. Moreover, the wavelength conversion sheet 20 does not necessarily have to include a protective film on the light source side. That is, the wavelength conversion sheet 20 may include the barrier film laminate 10 and the phosphor layer 21 formed on the first barrier film 16a of the barrier film laminate 10.

  The phosphor layer 21 contains a resin and a phosphor. The thickness of the phosphor layer 21 is several tens to several hundreds μm. As the resin, for example, a photocurable resin or a thermosetting resin can be used. The phosphor layer 21 preferably includes two types of phosphors composed of quantum dots. Further, the phosphor layer 21 may be a laminate in which two or more phosphor layers containing one kind of phosphor and another kind of phosphor are laminated. Two types of phosphors having the same excitation wavelength are selected. The excitation wavelength is selected based on the wavelength of light emitted from the light source of the backlight unit. The fluorescent colors of the two types of phosphors are different from each other. When a blue light emitting diode (blue LED) is used as the light source, the fluorescent colors are red and green. The wavelength of each fluorescence and the wavelength of light emitted from the light source are selected based on the spectral characteristics of the color filter. The peak wavelength of fluorescence is, for example, 610 nm for red and 550 nm for green.

  Next, the particle structure of the phosphor will be described. As the phosphor, a core-shell type quantum dot having particularly good luminous efficiency is preferably used. The core-shell type quantum dot is obtained by covering a semiconductor crystal core as a light emitting portion with a shell as a protective film. For example, cadmium selenide (CdSe) can be used for the core and zinc sulfide (ZnS) can be used for the shell. The surface yield of CdSe particles is covered with ZnS having a large band gap, so that the quantum yield is improved. Further, the phosphor may be one in which the core is doubly covered with the first shell and the second shell. In this case, CdSe 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 phosphor layer 21 may have a single layer configuration in which all phosphors are dispersed in a single layer, and each phosphor is separately dispersed in a plurality of layers, and a multilayer configuration in which these are laminated is formed. You may have.

  Next, a method for manufacturing the wavelength conversion sheet 20 will be described with reference to FIG. It does not specifically limit as a formation method of the fluorescent substance layer 21, For example, the method described in Japanese translations of PCT publication No. 2013-544018 is mentioned. After dispersing the phosphor in the binder resin and applying the prepared phosphor dispersion on the surface of the barrier film laminate 10 on the first barrier film 16a side, another barrier film laminate 10 is bonded to the application surface, The wavelength conversion sheet 20 can be manufactured by curing the phosphor layer 21.

[Backlight unit]
By using the wavelength conversion sheet 20, a backlight unit is obtained. FIG. 3 is a schematic cross-sectional view of a backlight unit obtained using the barrier film laminate. In FIG. 3, the backlight unit 30 includes a light source 32 and the wavelength conversion sheet 20, and the barrier film laminate 10 is disposed on the light source 32 side and the opposite side across the phosphor layer 21. Specifically, in the backlight unit 30, the light guide plate 34 and the reflection plate 36 are arranged in this order on the surface of the barrier film laminate 10 of the wavelength conversion sheet 20, and the light source 32 is disposed on the side of the light guide plate 34. It is arrange | positioned (the surface direction of the light-guide plate 34).

  The light guide plate 34 and the reflection plate 36 efficiently reflect and guide the light emitted from the light source 32, and a known material is used. As the light guide plate 34, for example, acrylic, polycarbonate, cycloolefin film, or the like is used. For example, the light source 32 is provided with a plurality of blue light emitting diode elements. The light emitting diode element may be a violet light emitting diode or a light emitting diode having a lower wavelength. The light emitted from the light source 32 enters the light guide plate 34 (D1 direction), and then enters the phosphor layer 21 (D2 direction) with reflection and refraction. The light that has passed through the phosphor layer 21 becomes white light by mixing the yellow light generated in the phosphor layer 21 with the light before passing through the phosphor layer 21.

[Electroluminescence light emitting unit]
FIG. 4 is a schematic cross-sectional view of an electroluminescence light emitting unit obtained using the barrier film laminate. The electroluminescence light emitting unit 50 according to this embodiment includes an electroluminescence light emitter layer 56 and a barrier film laminate 10. The electroluminescence light emitting unit 50 includes, for example, a transparent electrode layer 54, an electroluminescence light emitter layer 56 provided on the transparent electrode layer 54, and a dielectric layer 58 provided on the electroluminescence light emitter layer 56. The electrode element including the back electrode layer 60 provided on the dielectric layer 58 is obtained by sandwiching and sealing between the barrier film laminate 10 and the protective film 62. The electroluminescence light emitter layer 56 is formed on the first barrier film 16 a of the barrier film laminate 10.

  EXAMPLES The present invention will be specifically described below with reference to examples, but the scope of the present invention is not limited to these examples.

[Preparation of barrier film laminate]
Example 1
Acrylic polyol and tolylene diisocyanate are mixed so that the number of NCO groups of tolylene diisocyanate is equal to the number of OH groups of acrylic polyol, and ethyl acetate is added so that the total solid content becomes 5% by mass. Diluted. Β- (3,4 epoxy cyclohexyl) trimethoxysilane is further added to the diluted liquid mixture so as to be 5% by mass with respect to the total solid content, and these are mixed to obtain an anchor coat layer composition. Produced.

  On one surface of a biaxially stretched polyethylene terephthalate film (first base material layer, thickness: 25 μm), the anchor coat layer composition is applied by a bar coating method, and dried and cured at 100 ° C. for 1 minute to obtain a thickness. An anchor coat layer having a thickness of 50 nm was formed.

Using an electron beam heating vacuum deposition apparatus, a silicon oxide material (SiO, manufactured by Canon Optron Co., Ltd.) is evaporated by electron beam heating under a pressure of 1.5 × 10 ⁻² Pa. A 30 nm thick SiO _x film (first inorganic thin film layer) was formed. In addition, the acceleration voltage in vapor deposition was 40 kV, and the emission current was 0.2 A.

  Next, 10.4 parts by mass of tetraethoxysilane and 89.6 parts by mass of hydrochloric acid (concentration: 0.1 N) were mixed, and the mixture was stirred for 30 minutes to obtain a hydrolyzed solution of tetraethoxysilane. On the other hand, polyvinyl alcohol was dissolved in a mixed solvent of water / isopropyl alcohol (water / isopropyl alcohol (mass ratio) = 90: 10) to obtain a 3% by mass polyvinyl alcohol solution. 60 parts by mass of a tetraethoxysilane hydrolysis solution and 40 parts by mass of a polyvinyl alcohol solution were mixed to obtain a gas barrier coating composition.

  On the first inorganic thin film layer, the gas barrier coating layer composition was applied and dried to form a first gas barrier coating layer having a thickness of 300 nm. Furthermore, another first inorganic thin film layer having a thickness of 30 nm is formed on the first gas barrier coating layer in the same manner as described above, and another 300 nm thick film is formed on the other first inorganic thin film layer. A first gas barrier coating layer was formed. As described above, the first base material layer, the anchor coat layer, the first inorganic thin film layer, the first gas barrier coating layer, the first inorganic thin film layer, and the first gas barrier coating layer are laminated in this order. One barrier film was obtained.

  On one surface of a biaxially stretched polyethylene terephthalate film (second base material layer, thickness: 25 μm), the anchor coat layer composition is applied by a bar coating method, and dried and cured at 100 ° C. for 1 minute to obtain a thickness. An anchor coat layer having a thickness of 50 nm was formed.

Using an electron beam heating vacuum deposition apparatus, a silicon oxide material (SiO, manufactured by Canon Optron Co., Ltd.) is evaporated by electron beam heating under a pressure of 1.5 × 10 ⁻² Pa. A 30 nm thick SiO _x film (second inorganic thin film layer) was formed. In addition, the acceleration voltage in vapor deposition was 40 kV, and the emission current was 0.2 A.

  On the 2nd inorganic thin film layer, the said gas barrier coating layer composition was apply | coated and dried, and the 2nd gas barrier coating layer which has a thickness of 300 nm was formed. As described above, a second barrier film in which the second base material layer, the anchor coat layer, the second inorganic thin film layer, and the second gas barrier coating layer were laminated in this order was obtained.

  Bifunctional chain aliphatic type epoxy resin main agent (hexanediol diglycidyl ether, manufactured by Mitsubishi Chemical Corporation, trade name: YED-216, nonvolatile content: 100% by mass), 5 parts by mass, curing agent having amino group (Mitsubishi Gas Chemical Co., Ltd., trade name: C-93, nonvolatile content: 65% by mass) 16 parts by mass and an amino group-containing silane coupling agent (N-2- (aminoethyl) -3-aminopropyl 1 part by mass of methyldimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM-602) was dissolved in a solvent consisting of 23 parts by mass of methanol and 47 parts by mass of ethyl acetate to prepare an adhesive. The composition of the adhesive is summarized in Table 1.

  On the surface of the first gas barrier coating layer of the obtained first barrier film, the adhesive is applied using a reverse gravure device, and then dried at 82 ° C. for 1 minute to apply the adhesive coating surface and the second gas barrier coating. The second barrier film was bonded so that the layers face each other, and aging was performed at 50 ° C. for 2 days. As described above, the first barrier film and the second barrier film were bonded together through an adhesive layer having a thickness of 5 μm to produce a barrier film laminate.

(Example 2)
In the preparation of the adhesive, a barrier film laminate was produced in the same manner as in Example 1 except that the compounding amount of the epoxy resin main agent was changed from 5 parts by mass to 1 part by mass. The composition of the adhesive is summarized in Table 1.

(Example 3)
A barrier film laminate was produced in the same manner as in Example 1 except that the content of the epoxy resin main agent was changed from 5 parts by mass to 2.5 parts by mass in the preparation of the adhesive. The composition of the adhesive is summarized in Table 1.

Example 4
In the preparation of the adhesive, the same as in Example 3 except that the epoxy resin main agent was changed to neopentyl glycol diglycidyl ether (manufactured by ADEKA, trade name: ED-523T, nonvolatile content: 100% by mass). Thus, a barrier film laminate was produced. The composition of the adhesive is summarized in Table 1.

(Example 5)
In the preparation of the adhesive, the same as Example 3 except that the amino group-containing silane coupling agent was changed to 3-aminopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM-903). Thus, a barrier film laminate was produced. The composition of the adhesive is summarized in Table 1.

(Example 6)
In the preparation of the adhesive, the silane coupling agent having an amino group is changed to a silane coupling agent having an epoxy group (3-glycidoxypropylmethyldimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM-402). A barrier film laminate was produced in the same manner as in Example 3 except that the change was made. The composition of the adhesive is summarized in Table 1.

(Example 7)
A barrier film laminate was produced in the same manner as in Example 1 except that the amount of the silane coupling agent having an amino group was changed from 1 part by mass to 0.1 part by mass in the preparation of the adhesive. The composition of the adhesive is summarized in Table 1.

(Example 8)
A barrier film laminate was produced in the same manner as in Example 1 except that in the preparation of the adhesive, the amount of the silane coupling agent having an amino group was changed from 1 part by mass to 0.05 part by mass. The composition of the adhesive is summarized in Table 1.

Example 9
A barrier film laminate was prepared in the same manner as in Example 3 except that no silane coupling agent having an amino group was added in the preparation of the adhesive. The composition of the adhesive is summarized in Table 1.

(Example 10)
In the preparation of the adhesive, the epoxy resin-based main component was mixed with 4 parts by mass of hexanediol diglycidyl ether (Mitsubishi Chemical Co., Ltd., trade name: YED-216, nonvolatile content: 100% by mass) and a polyfunctional epoxy resin (Mitsubishi). A barrier film laminate was produced in the same manner as in Example 1, except that the gas chemical was changed to 1 part by mass, trade name: M-100, nonvolatile content: 100% by mass. The composition of the adhesive is summarized in Table 1.

(Comparative Example 1)
Except having changed the epoxy resin main ingredient into 5 mass parts of polyfunctional epoxy resins (Mitsubishi Gas Chemical Co., Ltd., brand name: M-100, non-volatile content: 100 mass%) in preparation of adhesive agent, Example In the same manner as in Example 1, a barrier film laminate was produced. The composition of the adhesive is summarized in Table 2.

(Comparative Example 2)
In the preparation of the adhesive, the epoxy resin-based main component is a bifunctional aromatic epoxy resin (resorcinol diglycidyl ether, manufactured by Nagase ChemteX Corporation, trade name: EX-201, nonvolatile content: 100 mass%) 5 mass A barrier film laminate was produced in the same manner as in Example 1 except that the part was changed to the part. The composition of the adhesive is summarized in Table 2.

(Comparative Example 3)
In the preparation of the adhesive, the epoxy resin-based main agent was used as a bifunctional cycloaliphatic epoxy resin (3 ′, 4′-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate, manufactured by Daicel Corporation, trade name: Celoxide 2021P, nonvolatile content: 100% by mass) A barrier film laminate was produced in the same manner as in Example 1 except that the content was changed to 5 parts by mass. The composition of the adhesive is summarized in Table 2.

[Evaluation of adhesive layer]
(Oxygen permeability)
The adhesive used in Examples and Comparative Examples was applied onto a 70 μm thick CPP (unstretched polypropylene film), and the 70 μm thick CPP was bonded to the adhesive application surface at 50 ° C. for 2 days. Aging was performed. As described above, an oxygen permeability measurement sample (laminated body) in which a CPP having a thickness of 70 μm, an adhesive layer having a thickness of 5 μm, and a CPP having a thickness of 70 μm were laminated in this order was obtained. The obtained sample was placed in a differential pressure type gas permeability measuring apparatus (GTR-30X, manufactured by GTR Tech Co., Ltd.), and the temperature was 40 ° C. and the relative humidity was 0 according to the method described in JIS K7126-1 (Appendix 1). The oxygen permeability of the sample was measured by the differential pressure method at a differential pressure of 101 kPa (1 atm) with oxygen as the test gas in a% environment. Tables 1 and 2 show the measurement results of oxygen permeability. In the measurement method, a film having an oxygen transmission rate higher than that of the adhesive layer (for example, an oxygen transmission rate higher than 1000 cm ³ / (m ² · day · atm)) is used as the film bonded with the adhesive. Thus, the oxygen permeability of the laminate can be regarded as the oxygen permeability of the adhesive layer. That is, in the above measurement method, since the CPP having an oxygen transmission rate of 2500 cm ³ / (m ² · day · atm) is used as the film bonded with the adhesive, 2500 cm ³ / (m ² · day). Atm) The oxygen permeability measurement results of the following samples can be regarded as the oxygen permeability of the adhesive layer.

[Evaluation of barrier film laminate]
(180 degree peel strength and peel mode)
The barrier film laminates obtained in Examples and Comparative Examples were cut into strips having a width of 1 cm, and the first barrier film side of the barrier film laminate was fixed on a glass plate. Using a Tensilon tensile tester (Orientec Co., Ltd.), the second barrier film of the fixed strip-shaped barrier film laminate is fixed at a speed of 300 mm / min in a direction parallel to the glass plate (180 degrees). Then, it peeled off from the 1st barrier film, and the intensity | strength (180 degree peeling strength) required for peeling was measured. The said intensity | strength was measured in the environment of temperature 23 degreeC humidity 65% RH. Furthermore, the peeling surface of the 1st barrier film and the 2nd barrier film was observed visually and microscopically, and the aspect of peeling was evaluated. Tables 1 and 2 show the measurement results of the 180 degree peel strength and the peeled surface.

(90 degree peel strength and peel mode)
The barrier film laminates obtained in Examples and Comparative Examples were cut into strips having a width of 1 cm, and the first barrier film side of the barrier film laminate was fixed on a glass plate. Using a Tensilon tensile tester (Orientec Co., Ltd.), the second barrier film of the fixed strip-shaped barrier film laminate was fixed at a speed of 300 mm / min in a direction perpendicular to the glass plate (90 degrees). Then, it peeled off from the 1st barrier film, and the intensity | strength (90 degree peeling strength) required for peeling was measured. The said intensity | strength was measured in the environment of temperature 23 degreeC humidity 65% RH. Furthermore, the peeling surface of the 1st barrier film and the 2nd barrier film was observed visually and microscopically, and the aspect of peeling was evaluated. Tables 1 and 2 show the 90-degree peel strength and peel surface measurement results.

  In any of the barrier film laminates of Examples 1 to 10 and Comparative Examples 1 to 3, when the second barrier film was peeled in a direction perpendicular (90 degrees) to the first barrier film fixed to the glass plate Good peel strength was obtained. Moreover, in the barrier film laminated body of Examples 1-10, when a 2nd barrier film is peeled in the direction parallel (180 degree | times) with respect to the 1st barrier film fixed to the glass plate, it is the same favorable peeling Strength was obtained. When the 180 degree | times peeling surface of the barrier film laminated body of Examples 1-10 was seen, the aggregation peeling of the contact bonding layer was confirmed. On the other hand, in Comparative Example 1, when the second barrier film was peeled off in a direction parallel to the first barrier film fixed to the glass plate (180 degrees), good peel strength was not obtained. When the peeling surface of the barrier film laminated body of Comparative Examples 1-3 was seen, it was confirmed that the base material layer vicinity of a barrier layer has peeled in the layer form. The reason why such an evaluation result was obtained is that the adhesive layer is hardened by using only an epoxy resin other than the chain aliphatic type bifunctional epoxy resin as the epoxy resin, and during the production of the barrier film laminate, It is conceivable that the stress generated after the production is concentrated on the base material layer. In Example 5, white turbidity was observed when the adhesive was allowed to stand for several hours before application, but the peel strength was not affected.

DESCRIPTION OF SYMBOLS 10 ... Barrier film laminated body, 11a ... 1st base material layer, 11b ... 2nd base material layer, 12a ... 1st inorganic thin film layer, 12b ... 2nd inorganic thin film layer, 13a ... 1st gas barrier coating layer, 13b ... Second gas barrier coating layer, 14a ... first barrier layer, 14b ... second barrier layer, 15 ... adhesive layer, 16a ... first barrier film, 16b ... second barrier film, 20 ... wavelength conversion sheet, 21 ... phosphor Layer, 30 ... back light unit, 50 ... electroluminescence light emitting unit.

Claims (7)

A first barrier film comprising a first substrate layer and a first barrier layer formed on the first substrate layer;
A second barrier film comprising a second substrate layer and a second barrier layer formed on the second substrate layer;
An adhesive layer;
With
The first barrier film and the second barrier film are bonded so that the first barrier layer and the second barrier layer face each other with the adhesive layer interposed therebetween,
The first barrier layer includes a first inorganic thin film layer and a first gas barrier coating layer,
The second barrier layer includes a second inorganic thin film layer and a second gas barrier coating layer,
The barrier film laminate, wherein the adhesive layer is formed from an adhesive containing an epoxy resin and a curing agent having an amino group, and the epoxy resin includes a chain aliphatic type bifunctional epoxy resin.   The barrier film laminate according to claim 1, wherein the chain aliphatic type bifunctional epoxy resin is hexanediol diglycidyl ether. The ratio (M _E / M _C ) of the epoxy resin content M _{E to} the curing agent content M _{C in the} adhesive is 0.05 to 0.5 in terms of mass ratio. Or the barrier film laminated body of 2.   The barrier film laminate according to any one of claims 1 to 3, wherein the adhesive further contains a silane coupling agent having an amino group. Wherein in the adhesive, the ratio to the content _{M SCA} silane coupling agent having an amino group content _{M E} of the epoxy resin _{(M E /} M _SCA) is a mass ratio is 1.0 or more, The barrier film laminate according to claim 4.   The barrier film laminate according to any one of claims 1 to 3, wherein the adhesive further contains a silane coupling agent having an epoxy group. The barrier film laminate according to claim 1, wherein the adhesive layer has an oxygen permeability of 1000 cm ³ / (m ² · day · atm) or less at a thickness of 5 μm.

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