Patent Application
20220105713
The present invention relates to a laminate film and a laminate, and a wavelength conversion sheet, a backlight unit and an electroluminescent light-emitting unit.
In light-emitting units, such as backlight units of liquid crystal displays and electroluminescent light-emitting units, emitters or phosphors may come into contact with oxygen or moisture for a long time and may be impaired in their performance as emitters or phosphors. Therefore, these light-emitting units use a laminate film made up of a polymer film which is provided with a gas barrier layer, with an adhesive or the like being coated thereto to serve as a packaging material or a protective material for the emitters, phosphors, or the like.
However, the laminate films mentioned above cannot achieve intimate contact between the layers configuring the laminate film, and thus may have difficulty in achieving sufficient gas barrier properties. In this regard, PTL 1, for example, proposes configuring a laminate having barrier properties, using terminal hydroxyl group-containing (meth)acrylate as a material of an organic layer to thereby improve intimate contact between an adhesive layer that contains an epoxy-based adhesive and the organic layer.
According to one aspect of the present invention, a laminate film includes a barrier film and an adhesion-enhancing layer formed on the barrier film and having a thickness in a range of from 0.01 μm to 1 μm. The adhesion-enhancing layer includes polyisocyanate and a polymer including a group having a reactive carbon-carbon double bond and a plurality of hydroxyl groups.
A more complete appreciation of the invention and many of the attendant advantages thereof will be readily obtained as the same becomes better understood by reference to the following detailed description when considered in connection with the accompanying drawings, wherein:
The embodiments will now be described with reference to the accompanying drawings, wherein like reference numerals designate corresponding or identical elements throughout the various drawings.
Embodiments of the present invention will hereinafter be described in details. It should be noted that the present invention should not be construed as being limited to the embodiments below.
In
In the laminate film 20 of the present embodiment, the moisture impermeable layer 4 may be formed on the first polymer film 2 via an anchor coat layer (not shown). Moreover, the second polymer film 8 may be disposed on the moisture impermeable layer 4 without the tackifier layer or adhesive layer 6 interposed therebetween. Moreover, the adhesion-enhancing layer 10 may be formed on the second polymer film 8 via an anchor coat layer (not shown).
The laminate film 20 of the present embodiment can be favorably used as a protective film for emitters or phosphors. In terms of favorably using the laminate film 20 as a protective film for emitters or phosphors, the laminate film 20 preferably has a total light transmittance of 80% or more, and more preferably 85% or more.
The first polymer film 2 is a layer for preventing the occurrence of breakage during processing, distribution, and the like. Examples of the material for the first polymer film 2 include, but are not limited to: polyesters such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate; polyamides such as nylon; polyolefins such as polypropylene and cycloolefin; polycarbonates; triacetyl cellulose; and the like. The first polymer film 2 is preferably a polyester film, a polyamide film, or a polyolefin film, more preferably a polyester film or a polyamide film, and further preferably a polyethylene terephthalate film. Moreover, the first polymer film 2 is preferably biaxially oriented.
The first polymer film 2 may include, as needed, additives such as an antistatic agent, an ultraviolet absorbing agent, a plasticizer, and a lubricant. Moreover, the first polymer film 2 may have a corona-treated, flame-treated, or plasma-treated surface.
The thickness of the first polymer film 2 is not particularly limited, but is preferably in the range of 3 μm or more to 100 μm or less, and more preferably 5 μm or more to 50 μm or less.
The moisture impermeable layer 4 serves to prevent entry of moisture into a light-emitting unit. The moisture impermeable layer 4 may be a single-layer or multilayer. The moisture impermeable layer 4 is preferably transparent. In terms of transparency, the moisture impermeable layer 4 is preferably formed by vacuum deposition.
The moisture impermeable layer 4 is formed on the first polymer film 2 via an anchor coat layer, as needed. The anchor coat layer may be a polyester resin or the like with a thickness approximately in the range of 0.01 to 10 μm. The method of forming the moisture impermeable layer 4 is not particularly limited, but in terms of further enhancing moisture impermeability, vacuum deposition is preferable. Examples of vacuum deposition include physical vapor deposition, chemical vapor deposition, and the like. Non-limiting examples of physical vapor deposition include vacuum vapor deposition, sputtering, ion plating, and the like. Non-limiting examples of chemical vapor deposition (CVD) include thermal CVD, plasma-enhanced CVD, optical CVD, and the like.
The method of forming the moisture impermeable layer 4 is preferably vacuum deposition, sputtering, or plasma-enhanced CVD, and more preferably resistance heating vacuum vapor deposition, electron beam heating vacuum deposition, induction heating vacuum deposition, reactive sputtering, dual magnetron sputtering, or plasma-enhanced chemical vapor deposition (PECVD). The method of forming the moisture impermeable layer 4 may be sputtering in terms of moisture impermeability, and may be vacuum deposition in terms of cost, and thus can be selected according to usage.
Examples of the method of generating plasma in sputtering and plasma-enhanced CVD can include methods based on DC (direct current), RF (radio frequency), MF (medium frequency), DC pulse, RF pulse, and DC+RF superimposition, and the like.
In the case of sputtering, a negative potential gradient is generated at a target that is a negative electrode, and Ar+ ions, which have received potential energy, impinge on the target. When plasma is generated, but no negative self-bias potential is generated, sputtering cannot be performed. Accordingly, MW (micro wave) plasma, which does not generate self-bias, is not suitable for sputtering. PECVD, however, can use MW plasma because PECVD uses vapor-phase reactions in the plasma to advance the process of chemical reaction and deposition and enable film formation without self-bias.
In the case of vacuum deposition, a metal or oxide film is generally formed, and thus a metal film such as of aluminum, titanium, copper, indium or tin, an oxide film of any of these metals (alumina or the like), or an oxide film of silicon is usually formed. Moreover, a film such as of a nitride may be formed, besides the metal or oxide film. Alternatively, a film that contains a plurality of metals may be formed. The moisture impermeable layer 4 preferably includes a layer of an oxide, nitride, or oxynitride having atoms of at least one substance selected from the group consisting of aluminum, titanium, copper, indium, and silicon, because these substances are superior in both of transparency and moisture impermeability. The moisture impermeable layer 4 more preferably includes a layer of a silicon oxide or an oxynitride, because these substances are much superior in moisture impermeability.
The moisture impermeable layer 4 formed by vacuum deposition preferably has a thickness in the range of 5 nm or more to 100 nm or less. If the moisture impermeable layer 4 formed by vacuum deposition has a thickness of 5 nm or more, moisture barrier properties are likely to be obtained. If the moisture impermeable layer 4 formed by vacuum deposition has a thickness of 100 nm or less, generation of cracks due to cure shrinkage is likely to be minimized, and thus moisture barrier properties are likely to be prevented from being deteriorated due to the cracks. The moisture impermeable layer 4 with a thickness of 1,000 nm or less is preferable in terms of economic aspect, i.e. reducing cost, which is ascribed to reduction in the amount of materials to be used, the time taken for film formation, and the like.
The moisture impermeable layer 4 can also be formed in atmospheric air. If the moisture impermeable layer 4 is formed in atmospheric air, an oxide film such as of metal can be formed by using, for example, a coating liquid containing: a compound that contains chlorine such as polyvinylidene chloride; and a compound that contains atoms such as of Si, Ti, Al, and Zr. The moisture impermeable layer 4 may also be formed by combining a layer formed in vacuum and a layer formed in atmospheric air.
Specifically, as the method of applying the coating liquid in forming the moisture impermeable layer 4 in atmospheric air, mention can be made of gravure coating, dip coating, reverse coating, wire bar coating, die coating, or the like.
The compound that contains Si atoms may be a silane compound, for example. The oxide film is preferably formed by reaction of a silanol group contained in the silane compound. Such a silane compound includes a compound expressed by Formula (1) below.
R1n(OR2)4-nSi (1)
In Formula (1), n is an integer 0 to 3, and R1 and R2 are each a hydrocarbon group, and preferably an alkyl group having a carbon number 1 to 4. Examples of the compound expressed by Formula (1) include tetramethoxy silane, tetraethoxy silane, tetrapropoxy silane, tetrabutoxy silane, methyltrimethoxy silane, methyltriethoxy silane, dimethyldimethoxy silane, and dimethyldiethoxy silane, and the like. Polysilazane that contains nitrogen may also be used.
Examples of the compound that contains Ti atoms include a compound expressed by Formula (2) below.
R1n(OR2)4-nTi (2)
In Formula (2), n is an integer 0 to 3, and R1 and R2 are each a hydrocarbon group, and preferably an alkyl group having a carbon number 1 to 4. Examples of the compound expressed by Formula (2) include tetramethoxy titanium, tetraethoxy titanium, tetraisopropoxy titanium, tetrabutoxy titanium, and the like.
Examples of compounds that contain Al atoms include compounds expressed by Formula (3) below.
R1n(OR2)4-nAl (3)
In Formula (3), n is an integer 0 to 3, and R1 and R2 are each a hydrocarbon group, and preferably an alkyl group having a carbon number 1 to 4. Examples of the compound expressed by Formula (3) include tetramethoxy aluminum, tetraethoxy aluminum, tetraisopropoxy aluminum, tetrabutoxy aluminum, and the like.
Examples of compounds that contain Zr atoms include compounds expressed by Formula (4) below.
R1n(OR2)4-nZr (4)
In Formula (4), n is an integer 0 to 3, and R1 and R2 are each a hydrocarbon group, and preferably an alkyl group having a carbon number 1 to 4. Examples of the compound expressed by Formula (4) include tetramethoxy zirconium, tetra ethoxy zirconium, tetraisopropoxy zirconium, tetrabutoxy zirconium, and the like. In Formulas (1) to (4), R1, R2, and n are independent of one another.
If the moisture impermeable layer 4 is formed in atmospheric air, the coating liquid mentioned above is applied, followed by curing. The curing method is not particularly limited, but examples thereof include ultraviolet curing, thermal curing, and the like. In the case of ultraviolet curing, the coating liquid may contain a polymerization initiator, and a compound that has a double bond. As needed, the coating liquid may be heat aged.
If the moisture impermeable layer 4 is formed in atmospheric air, the moisture impermeable layer 4 may be a reaction product of dehydration condensation of inorganic oxide particles such as of magnesium, calcium, zinc, aluminum, silicon, titanium, or zirconium via phosphorus atoms derived from a phosphorus compound. Specifically, a functional group (e.g., hydroxyl group) that is present on a surface of the inorganic oxide, and a portion of the phosphorus compound that can react with the inorganic oxide (e.g., halogen atoms directly bonded to phosphorus atoms, or oxygen atoms directly bonded to phosphorus atoms) cause a condensation reaction for bonding. The reaction product can be obtained, for example, by applying a coating liquid that contains the inorganic oxide and the phosphorus compound to a surface of a base material, followed by heat treating the applied film to advance the reaction of mutually bonding inorganic oxide particles via phosphorus atoms derived from the phosphorus compound. The lower limit temperature of the heat treatment is 110° C., preferably 120° C., more preferably 140° C., and even more preferably 170° C. A low heat treatment temperature makes it difficult to obtain a satisfactory reaction speed and lowers productivity. A preferable upper limit heat treatment temperature depends on the base material, and the like, but is 220° C., and is preferably 190° C. The heat treatment can be performed in air, a nitrogen atmosphere, an argon atmosphere, or the like.
If the moisture impermeable layer 4 is formed in atmospheric air, the coating liquid mentioned above may further contain a resin, as long as coagulation or the like does not occur in the coating liquid. Specific examples of the resin include acrylic resins, polyester resins, polyvinyl alcohols, polyvinyl pyrrolidone, and the like. The coating liquid preferably contains, among these resins, a resin having high compatibility with other materials contained in the coating liquid.
The coating liquid may further contain, as needed, a filler, a leveling agent, an antifoaming agent, an ultraviolet absorbing agent, and an antioxidant, and, separately from these agents, a silane coupling agent, a titanium chelating agent, and the like.
The thickness of the moisture impermeable layer 4 formed in atmospheric air is preferably in the range of 50 nm to 1,000 nm, and more preferably 100 nm to 800 nm. If the moisture impermeable layer 4 formed in atmospheric air has a thickness of 50 nm or more, film formation is likely to be easier. If the moisture impermeable layer 4 formed in atmospheric air has a thickness of 1,000 nm or less, fracture or curling is likely to be reduced.
The moisture impermeable layer 4 may also be a multilayer film including a layer formed by vacuum deposition, and a layer formed of a coating liquid. The multilayer film can be ensured to have a structure in which layers formed by vacuum deposition and layers formed of a coating liquid are alternately laminated to further improve barrier properties.
To improve adhesion with the tackifier layer or adhesive layer 6, or improve bending resistance of the moisture impermeable layer 4, a coating layer may be formed on the moisture impermeable layer 4. If the coating layer is formed on the moisture impermeable layer 4 formed by vacuum deposition, the coating layer is preferably formed by using, for example, a homopolymer of acrylic acid or methacrylic acid, such as PAA (polyacrylic acid) and PMAA (polymethacrylic acid), or a copolymer obtained by copolymerizing monomers that contain acrylic acid or methacrylic acid, such as EAA (ethylene acrylic acid copolymer) or EMAA (ethylene methacrylic acid copolymer), in terms of improving intimate contact between the tackifier layer or adhesive layer 6 and the coating layer.
The second polymer film 8 is disposed on the moisture impermeable layer 4 via the tackifier layer or adhesive layer 6 as needed. Non-limiting examples of the second polymer film 8 include: polyesters such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate; polyamides such as nylon; polyolefins such as polypropylene and cycloolefin; polycarbonates; triacetyl cellulose; and the like. The second polymer film 8 is preferably a polyester film or a polyamide film, and more preferably a polyethylene terephthalate film. The second polymer film 8 is preferably biaxially oriented.
The second polymer film 8 may contain, as needed, additives such as an antistatic agent, an ultraviolet absorbing agent, a plasticizer, and a lubricant. The second polymer film 8 may have a corona-treated, flame-treated, or plasma-treated surface.
The thickness of the second polymer film 8 is not particularly limited, but preferably in the range of 3 μm or more to 100 μm or less, and more preferably 5 μm or more to 50 μm or less.
The tackifier layer or adhesive layer 6 is preferably formed by coating a solution of an tackifier/adhesive onto the moisture impermeable layer 4, and bonding the second polymer film 8 to the coated surface. As the tackifier or the adhesive (tackifier/adhesive), one generally used as a tackifier/adhesive for a polymer film can be used, and thus is appropriately selected in conformity with the surface of the moisture impermeable layer 4. Examples of the tackifier/adhesive include polyester tackifiers/adhesives, acrylic tackifiers/adhesives, rubber tackifiers/adhesives, phenolic tackifiers/adhesives, urethane tackifiers/adhesives, and the like.
The method of coating a solvent of the tackifier/adhesive includes gravure coating, dip coating, reverse coating, wire bar coating, die coating, or the like.
The tackifier layer or adhesive layer 6 preferably has a thickness in the range of 1 μm or more to 20 μm or less. If the thickness of the tackifier layer or adhesive layer 6 is 1 μm or more, adhesion is likely to be obtained, and if 20 μm or less, a poor-quality surface or cost increase is likely to be reduced. Bonding of the second polymer film 8 to the surface coated with the solution of the tackifier/adhesive is followed by aging. Aging is performed at 20 to 80° C. for 1 to 10 days, for example.
The tackifier/adhesive may also contain, as needed, a curing agent, an antistatic agent, a silane coupling agent, an ultraviolet absorbing agent, an antioxidant, a leveling agent, a dispersant, and the like.
In the laminate film 20, the barrier film 11 may also be optionally configured as shown in Configurational Examples 1 to 10 described below. With reference to
The barrier film 11 has a basic configuration made up of at least the first polymer film 2 and the moisture impermeable layer 4.
The method of forming the moisture impermeable layer 4 is not particularly limited, but, in terms of further enhancing moisture impermeability, the layer is preferably formed by vacuum deposition with which a closely-packed film can be formed.
The moisture impermeable layer 4 can also be formed in atmospheric air. If the moisture impermeable layer 4 is formed in atmospheric air, the coating liquid that contains, for example, a compound that contains chlorine such as polyvinylidene chloride, and a compound that contains atoms such as of Si, Ti, Al, Zr, and the like is used to form an oxide film, thereby providing a moisture impermeable layer.
The moisture impermeable layer 4 may be formed on the first polymer film 2 via an anchor coat layer.
A sealing layer (not shown) may further be formed on the moisture impermeable layer 4. By preventing damage to the moisture impermeable layer 4, moisture impermeability is further improved. If the sealing layer is formed on the moisture impermeable layer 4, the sealing layer is preferably formed by use of, for example, a homopolymer of acrylic acid or methacrylic acid, such as PAA (polyacrylic acid) or PMAA (polymethacrylic acid), or a copolymer obtained by copolymerizing monomers that contain acrylic acid or methacrylic acid, such as EAA (ethylene acrylic acid copolymer) or EMAA (ethylene methacrylic acid copolymer).
The moisture impermeable layer 4 may also be a multilayer film made up of a moisture impermeable layer formed by vacuum deposition, and a moisture impermeable layer formed with a coating liquid in atmospheric air.
The moisture impermeable layer 4 may be a multilayer film obtained by alternately laminating moisture impermeable layers formed by vacuum deposition, and moisture impermeable layers formed with a coating liquid in atmospheric air. With the moisture impermeable layer 4 having a structure of the aforementioned multilayer film, barrier properties are further improved.
Adopting the configuration obtained by laminating a moisture impermeable layer formed by vacuum deposition, with a (meth)acrylate resin layer (Configurational Example 6), or the configuration obtained by sandwiching a moisture impermeable layer formed by vacuum deposition with acrylate resin layers (Configurational Example 7), moisture impermeability of the moisture impermeable layer 4 is improved. In particular, moisture impermeability is further improved by flash depositing or coating a cross-linkable functional (meth)acrylate onto a moisture impermeable layer, and forming cross-links by an electron beam or heat and providing a configuration in which (meth)acrylate resin layers are alternately laminated with moisture impermeable layers (Configurational Example 8).
As another configuration, a solution of a tackifier may be coated onto the moisture impermeable layer 4 so as to bond the second polymer film 8 to the applied film. The second polymer film 8 can be bonded to the moisture impermeable layer 4 via the tackifier layer or adhesive layer 6 to thereby prevent damage to the moisture impermeable layer 4, and further improve moisture impermeability.
A second moisture impermeable layer (not shown) may further be formed on the second polymer film 8, with which moisture impermeability can be further improved. If the second moisture impermeable layer is formed on the second polymer film 8, the second moisture impermeable layer is preferably configured to be disposed on the tackifier layer side.
The adhesion-enhancing layer 10 is formed on the second polymer film 8 (on the barrier film 11). The adhesion-enhancing layer 10 contains a polymer that contains a group having a reactive carbon-carbon double bond and two or more hydroxyl groups, and polyisocyanate. The adhesion-enhancing layer 10 may further contain a monomer that contains a group having a reactive carbon-carbon double bond and a hydroxyl group, described below. The reactive carbon-carbon double bond refers to a radically or cationically polymerizable carbon-carbon double bond. The group having a reactive carbon-carbon double bond is preferably a group having an ethylenically-unsaturated double bond, more preferably a styryl group, a (meth)acryloyl group, or the like, for example, and even more preferably an acryloyl group. If the group having a reactive carbon-carbon double bond is an acryloyl group, reactivity is likely to be improved, and better intimate contact is likely to be achieved.
The polymer that contains a group having a reactive carbon-carbon double bond and two or more hydroxyl groups can be obtained by polymerizing monomers that contain a group having a reactive carbon-carbon double bond. The aforementioned monomers may be of one kind, or may be of two or more kinds. When the monomers used for producing a polymer are of one kind, the aforementioned monomers contain a group having a reactive carbon-carbon double bond and a group having a hydroxyl group. When the monomers used for producing the polymer are of two or more kinds, the aforementioned monomers can be a combination of monomers that contain a group having a reactive carbon-carbon double bond and a hydroxyl group, with monomers that contain a group having a reactive carbon-carbon double bond.
The aforementioned monomers that contain a group having a reactive carbon-carbon double bond are preferably monomers that contain a (meth)acryloyl group, or monomers that contain a styryl group, and more preferably monomers that contain a (meth)acryloyl group. Examples of the monomers that contain a (meth)acryloyl group include (meth)acrylic acid, alkyl (meth)acrylate, urethane (meth)acrylate, epoxy (meth)acrylate, and the like. The carbon number of an alkyl group of the alkyl (meth)acrylate is 1 to 5, for example. The monomers that contain a group having a reactive carbon-carbon double bond and a hydroxyl group are preferably monomers that contain a (meth)acryloyl group and a hydroxyl group, or monomers that contain a styryl group and a hydroxyl group, and more preferably monomers that contain a (meth)acryloyl group and a hydroxyl group. The monomers that contain a (meth)acryloyl group and a hydroxyl group include (meth)acrylic acid, hydroxyalkyl (meth)acrylate, pentaerythritol triacrylate, and the like. The carbon number of an alkyl group in the hydroxyalkyl (meth)acrylate is 1 to 5, for example.
The aforementioned polymer may be obtained by polymerizing monomers alone, or may be obtained by polymerizing an acrylic prepolymer obtained in advance with a monomer. The acrylic prepolymer is a polymer obtained by polymerizing acrylic monomers such as acrylic acid, methacrylic acid, and glycidyl (meth)acrylate, i.e. obtained by polymerizing acrylic monomers of at least one kind that contain a hydroxyl group. Examples of the acrylic monomers that contain a hydroxyl group include hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, N-methylolacrylamide, and the like. The acrylic prepolymer preferably has a weight-average molecular weight in the range of 5,000 to 10,000.
When the aforementioned polymer is obtained by ultraviolet irradiation, monomers are polymerized in the presence of a photopolymerization initiator. Examples of such a photopolymerization initiator include acetophenones, benzoins, benzophenones, phosphine oxides, ketals, anthraquinones, thioxanthones, and the like.
Monomers may also be polymerized, as needed, in the presence of a photosensitizer, such as n-butylamine, triethylamine or poly-n-butylphosphine, an antistatic agent, a silane coupling agent, an ultraviolet absorbing agent, an antioxidant, a leveling agent, a dispersant, or the like.
As a raw material of the polyisocyanate, mention can be made of tolylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, or the like. The polyisocyanate may also be a prepolymer obtained by permitting isocyanates to react with each other, or a prepolymer obtained by reaction of isocyanate with alcohol. The content of the polyisocyanate in the adhesion-enhancing layer 10 is preferably in the range of 1 to 100 parts by mass, and more preferably 3 to 60 parts by mass, relative to 100 parts by mass of the polymer that contains a group having a reactive carbon-carbon double bond and two or more hydroxyl groups.
The adhesion-enhancing layer 10 is obtained, for example, by applying an adhesive containing a polymer that contains a group having a reactive carbon-carbon double bond and two or more hydroxyl groups, and polyisocyanate onto the second polymer film 8 (on the barrier film 11), and drying the applied film. The aforementioned adhesive preferably contains a polymer that contains a group having a reactive carbon-carbon double bond and two or more hydroxyl groups, polyisocyanate, and a solvent that dissolves the aforementioned polymer and the polyisocyanate. The solvent that can be used includes, for example, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl acetate, butyl acetate, methanol, ethanol, isopropyl alcohol, butanol, and the like.
When the aforementioned adhesive contains a solvent, the adhesive preferably has a solid content in the range of 0.5 to 30 mass %, and more preferably 1 to 10 mass %, with respect to the total amount of the adhesive.
Examples of the method of coating the adhesive onto the second polymer film 8 (on the barrier film 11) include gravure coating, dip coating, reverse coating, wire bar coating, die coating, and the like. The applied film is dried by heating at 50 to 250° C. for 1 second to 20 minutes, for example.
The thickness of the adhesion-enhancing layer 10 obtained as described above is in the range of 0.01 μm or more to 1 μm or less. The thickness of the adhesion-enhancing layer 10 is preferably 0.02 μm or more, more preferably 0.05 μm or more, and even more preferably 0.1 μm or more. When the adhesion-enhancing layer 10 has a thickness of 0.01 μm or more, intimate contact is likely to be improved. The thickness of the adhesion-enhancing layer 10 is preferably 0.8 μm or less, and more preferably 0.5 μm or less. When the adhesion-enhancing layer 10 has a thickness of 1 μm or less, the adhesion-enhancing layer 10 is unlikely to be influenced by the stress from outside, and intimate contact is likely to be improved.
An adhesion-enhancing layer containing the polymer that contains a group having a reactive carbon-carbon double bond and two or more hydroxyl groups, and polyisocyanate may further be formed on a surface of the first polymer film 2 opposite from the surface where the moisture impermeable layer 4 is formed.
The laminate 30 of the present embodiment may also be obtained, for example, by bonding the resin film 22 to a surface of the adhesion-enhancing layer 10 of the laminate film 20, followed by light irradiation and/or heating. Due to light irradiation or heating, hydroxyl groups in the polymer react with isocyanate groups in the polyisocyanate in the adhesion-enhancing layer 10, thereby forming a urethane bond, so that the adhesion-enhancing layer 10 turns into the cured adhesive layer 10′. The laminate 30 according to the present embodiment may also be obtained, for example, by forming a resin layer on a surface of the adhesion-enhancing layer 10 of the laminate film 20, followed by light irradiation and/or heating. In this case, due to light irradiation or heating, the reaction mentioned above occurs in the adhesion-enhancing layer, while the resin layer is cured to serve as the resin film 22. It should be noted that the resin layer is obtained, for example, by coating and drying a liquid resin composition which is curable by light irradiation or heating (curable liquid resin composition).
Resins that can be used for the resin film 22 are not particularly limited, but include, for example, thermoplastic resins, and cured products such as of thermoplastic resins, thermosetting resins, electron beam curable resins, ultraviolet curable resins, and the like. Therefore, when the resin film 22 is obtained by curing a resin layer, the curable liquid resin composition may contain at least one resin selected from the group consisting of thermosetting resins, electron beam curable resins, and ultraviolet curable resins. The thermoplastic resins include a polyester resin, an acrylic resin, an acrylic urethane resin, a polyester acrylate resin, a polyurethane acrylate resin, a urethane resin, a polycarbonate resin, and the like. The thermosetting resins include an epoxy resin, a melamine resin, a phenolic resin, and the like. The resin used for the resin film 22 is preferably an acrylic resin or a cured epoxy resin, in terms of exhibiting good light resistance or optical properties.
The resin film 22 (or the curable liquid resin composition) may include fine particles, for example. The resin film 22 may have a surface with microscopic asperities caused by the fine particles being exposed. When the laminate 30 including the resin film 22, whose surface is provided with the asperities, is used for a light-emitting unit, generation of Newton's rings is likely to be prevented.
The fine particles contained in the resin film 22 are not particularly limited, but can include, for example, inorganic fine particles of silica, clay, talc, calcium carbonate, calcium sulfate, barium sulfate, titanium oxide, alumina, and the like, and organic fine particles of a styrene resin, a urethane resin, a silicone resin, an acrylic resin, and the like. The fine particles can be used singly or in combination of two or more.
The resin film 22 is preferably an optical film. When the resin film 22 is an optical film, optical functions can be imparted to the light-emitting unit. The optical functions are not particularly limited, but include functions such as of interference fringe (moire) prevention, antireflection, and dispersion. In terms of imparting optical functions to the resin film 22, the resin used for the resin film 22 preferably has good optical transparency.
Light irradiation can be conducted, for example, using a metal halide lamp, a high-pressure mercury lamp, or the like. Heating can be conducted at 50 to 250° C. for 1 second to 20 minutes, for example.
Using the laminate film 20 and the laminate 30, a wavelength conversion sheet can be provided.
In
The wavelength conversion sheet 100 of the present embodiment can be obtained, for example, by preparing two laminate films 20, forming a wavelength conversion layer 13 on an adhesion-enhancing layer 10 in one of the laminate films 20, bonding the other of the laminate films 20 such that the adhesion-enhancing layer 10 and the wavelength conversion layer 13 face each other, and curing the adhesion-enhancing layers 10.
The wavelength conversion layer 13 is an emitter layer that converts energy from outside into light energy to emit light by excitation light being incident thereon. The wavelength conversion layer 13 is obtained by sandwiching and hermetically sealing a phosphor layer by a pair of laminate films 20, with the respective first polymer films 2 being located inside, and sealing, as needed, a space between the phosphor layer and the laminate films 20 with a sealing resin. The wavelength conversion layer 13 has a thickness in the range of 10 to 500 μm, for example.
The phosphor layer contains a resin and phosphors. As the resin, a photocurable resin or a thermosetting resin can be used, for example. The phosphors may have cores serving as light-emitting portions and shells covering the respective cores and serving as protective films. The cores can be served such as by cadmium selenide (CdSe), for example, and the shells can be served such as by zinc sulfide (ZnS), for example. Surface defects of CdSe particles are covered with ZnS having a large band gap to thereby improve quantum efficiency. The phosphors may have cores doubly covered with respective first shells and second shells. In this case, CsSe can be used for the cores, zinc selenide (ZnSe) can be used for the first shells, and ZnS can be used for the second shells. Two or more types of phosphors are combined and used. Alternatively, a phosphor layer containing only one type of phosphors may be laminated with another phosphor layer containing only one type of phosphors. As the two types of phosphors, those having the same excitation wavelength are selected. The excitation wavelength is selected based on the wavelength of the light radiated from a light-emitting diode light source. The two types of phosphors have fluorescent colors different from each other. The fluorescent colors are red and green. The wavelengths of fluorescences, and the wavelength of the light radiated from the light-emitting diode light source are selected based on spectral characteristics of the color filter. The peak wavelength of fluorescence is 610 nm for red, and 550 nm for green, for example. The phosphors are preferably quantum dots. The phosphors have a mean particle size in the range of 1 nm to 20 nm, for example.
In the wavelength conversion sheet 100 of the present embodiment, the cured laminate film 20′a only needs to include the barrier film 11a and the cured adhesive layer 10′a formed on the barrier film 11a, and cured laminate film 20′b only needs to include the barrier film 11b and the cured adhesive layer 10′b formed on the barrier film 11b. Similarly to the laminate film 20, the configurations of the barrier films 11a and 11b are not limited to the ones shown in
When the wavelength conversion sheet 100 is prepared using the laminate 30, the wavelength conversion sheet 100 can be obtained, for example, by preparing two laminates 30, forming a wavelength conversion layer 13 on the first polymer film 2 in one of the laminates 30, and bonding the other of the laminates 30 thereto such that the first polymer film 2 and the wavelength conversion layer 13 face each other. The wavelength conversion layer 13 is obtained by sandwiching and hermetically sealing a phosphor layer by the pair of laminates 30, with the first polymer films 2 being located inside, and sealing, as needed, a space between the phosphor layer and each of the laminates 30 with a sealing resin.
The sealing resin that can be used includes, for example, a thermoplastic resin, a thermosetting resin, an ultraviolet curable-type resin, or the like. The thermoplastic resin that can be used includes, for example: cellulose derivatives such as acetyl cellulose, nitro cellulose, acetyl butyl cellulose, ethyl cellulose, and methyl cellulose; vinyl resins such as vinyl acetate and copolymers thereof, vinyl chloride and copolymers thereof, and vinylidene chloride and copolymers thereof; acetal resins such as polyvinyl formal and polyvinyl butyral; acrylic resins such as an acrylic resin and copolymers thereof, a methacrylic resin and copolymers thereof; a polystyrene resin; a polyamide resin; a linear polyester resin; a fluorine resin; a polycarbonate resin; or the like. As the thermosetting resin, mention can be made of a phenolic resin, a urea melamine resin, a polyester resin, a silicone resin, or the like. As the photocurable resin, mention can be made of a photopolymerizable prepolymer such as epoxy acrylate, urethane acrylate, and polyester acrylate. These photopolymerizable prepolymers may be used as main components, and a monofunctional or polyfunctional monomer may be used as a diluent.
Using the laminate film 20 and the laminate 30, a light-emitting unit can be provided. An example of the light-emitting unit obtained by using the laminate film 20 and the laminate 30 will be described below.
The light guiding layer 36 and the reflecting layer 38 efficiently reflect and guide the light radiated from the light-emitting diode light source 40. Known materials are used for these layers. As the light guiding layer 36, for example, a film such as of acryl, polycarbonate, or cycloolefin, is used.
The light-emitting diode light source 40 includes a plurality of light-emitting diodes that emit blue light. These light-emitting diodes may also be violet light-emitting diodes, or light-emitting diodes of a shorter wavelength. The light radiated from the light-emitting diode light source 40 enters the light guiding layer 36 (in a D1 direction), and then, being reflected and refracted, for example, enters the wavelength conversion layer 13 (in a D2 direction). While passing through the wavelength conversion layer 13, the light is mixed with yellow light of a wide wavelength range generated in the wavelength conversion layer 13 and becomes white light.
The electrode layer, the electroluminescent light-emitting layer, and the dielectric layer can be formed, for example, by deposition, sputtering, and the like. The sealant layer that can be used includes an acid-modified, polyolefin resin obtained by graft-modifying a polyolefin resin with an acid, the resins mentioned above as sealing resins, or the like.
The present invention will be specifically described by way of examples. However, the scope of the present invention should not be construed as being limited to these examples.
Using bar coating, a polyester resin solution was coated onto a corona discharge treated surface of a biaxially-oriented polyethylene terephthalate film (first polymer film 2, trade name: P60, thickness: 12 μm, manufactured by TORAY INDUSTRIES, INC.), followed by drying and curing at 80° C. for 1 minute, thereby forming an anchor coat layer with a thickness of 100 nm.
Using an electron beam heating vacuum deposition device, a silicon oxide material (SiO, manufactured by Canon Optron Inc.) was evaporated by electron beam heating under a pressure of 1.5×10−2 Pa, thereby forming an SiO film (moisture impermeable layer 4) with a thickness of 80 nm on the anchor coat layer. The deposition was conducted by applying an accelerating voltage of 40 kV and an emission current of 0.2 A.
An adhesive (trade name: TAKELAC A525, manufactured by Mitsui Chemicals, Inc.) was coated onto the moisture impermeable layer 4. Then, the moisture impermeable layer 4 was bonded, via the adhesive, to a corona discharge treated surface of a biaxially-oriented polyethylene terephthalate film (second polymer film 8, trade name: FE2001, thickness: 25 μm, manufactured by FUTAMURA CHEMICAL CO., LTD.), followed by aging at 50° C. for 2 days. The adhesive layer 6 after bonding had a thickness of 5 μm.
A mixed solution was prepared by mixing 70 parts by mass of acrylic resin (weight-average molecular weight: 30,000) obtained by polymerizing 35 parts by mass of acrylic acid, 35 parts by mass of hydroxyethyl acrylate, and 30 parts by mass of n-butyl acrylate, with parts by mass of an isocyanurate form of hexamethylene diisocyanate (trade name: Desmodur N3300, manufactured by Sumika Bayer Urethane Co., Ltd.), and the mixed solution was coated onto the second polymer film 8. The coated liquid was dried to form an adhesion-enhancing layer 10 with a thickness of 0.2 μm, thereby obtaining a laminate film 20.
An epoxy sheet (the optical film 22, trade name: XNR5516Z, manufactured by Nagase ChemteX Corporation) was bonded to the adhesion-enhancing layer 10 of the laminate film 20 thus obtained. The laminate film bonded with the epoxy sheet was irradiated with UV (ultraviolet rays) at an exposure of 6 J/cm2, followed by baking at 80° C. for 60 minutes, thereby obtaining a laminate 30.
Using bar coating, a polyester resin solution was coated onto a biaxially-oriented polyethylene terephthalate film (first polymer film 2, trade name: A4100, thickness: 50 μm, manufactured by TOYOBO CO., LTD.), followed by drying and curing at 80° C. for 1 minute, thereby forming an anchor coat layer with a thickness of 100 nm.
Using a resistance heating vacuum deposition device, an aluminum material (trade name: 4N, manufactured by Kojundo Chemical Lab. Co., Ltd.) was evaporated by heating under a pressure of 3.0×10−2 Pa to form an AlOx film with a thickness of 10 nm on the anchor coat layer. The deposition was conducted by applying an accelerating voltage of 50 kV and an emission current of 0.5 A.
A mixed liquid obtained by mixing a hydrolysate of tetraethoxy silane and polyvinyl alcohol at a mass ratio of 1/1 was coated onto the AlOx film by bar coating, followed by drying and curing at 120° C. for 1 minute, thereby forming an SiOx film with a thickness of 400 nm. The multilayer film including the AlOx film and the SiOx film and formed on the anchor coat layer in this way was used as a moisture impermeable layer 4.
An adhesive (trade name: TAKELAC A525, manufactured by Mitsui Chemicals, Inc.) was coated onto the moisture impermeable layer 4. Then, the moisture impermeable layer 4 was bonded, via the adhesive, to a corona discharge treated surface of a biaxially-oriented polyethylene terephthalate film (second polymer film 8, trade name: FE2001, thickness: 25 μm, manufactured by FUTAMURA CHEMICAL CO., LTD.), followed by aging at 50° C. for 2 days. The adhesive layer 6 after bonding had a thickness of 5 μm.
A mixed solution was prepared by mixing 70 parts by mass of acrylic resin (weight-average molecular weight: 30,000) obtained by polymerizing 35 parts by mass of acrylic acid, 35 parts by mass of hydroxyethyl acrylate, and 30 parts by mass of n-butyl acrylate, with 30 parts by mass of an isocyanurate form of hexamethylene diisocyanate (trade name: Desmodur N3300, manufactured by Sumika Bayer Urethane Co., Ltd.), and the mixed solution was coated onto the second polymer film 8. The coated liquid was dried to form an adhesion-enhancing layer 10 with a thickness of 0.2 μm, thereby obtaining a laminate film 20.
An epoxy sheet (optical film 22, trade name: XNR5516Z, manufactured by Nagase ChemteX Corporation) was bonded to the adhesion-enhancing layer 10 of the laminate film 20 thus obtained. The laminate film bonded with the epoxy sheet was irradiated with UV (ultraviolet rays) at an exposure of 6 J/cm2, followed by baking at 80° C. for 60 minutes, thereby obtaining a laminate 30.
Using bar coating, a polyester resin solution was coated onto a corona discharge treated surface of a biaxially-oriented polyethylene terephthalate film (first polymer film, trade name: P60, thickness: 12 μm, manufactured by TORAY INDUSTRIES, INC.), followed by drying and curing at 80° C. for 1 minute, thereby forming an anchor coat layer with a thickness of 100 nm.
Using an electron beam heating vacuum deposition device, a silicon oxide material (SiO, manufactured by Canon Optron Inc.) was evaporated by electron beam heating under a pressure of 1.5×10−2 Pa to form an SiO film (moisture impermeable layer) with a thickness of 80 nm on the anchor coat layer. The deposition was conducted by applying an accelerating voltage of 40 kV and an emission current of 0.2 A.
An adhesive (trade name: TAKELAC A525, manufactured by Mitsui Chemicals, Inc.) was coated onto the moisture impermeable layer. Then, the moisture impermeable layer was bonded, via the adhesive, to a corona discharge treated surface of a biaxially-oriented polyethylene terephthalate film (second polymer film, trade name: FE2001, thickness: 25 μm, manufactured by FUTAMURA CHEMICAL CO., LTD.), followed by aging at 50° C. for 2 days. The adhesive layer after bonding had a thickness of 5 μm.
An acrylic resin (weight-average molecular weight: 30,000) was obtained by polymerizing 35 parts by mass of acrylic acid, 35 parts by mass of hydroxyethyl acrylate, and 30 parts by mass of n-butyl acrylate to prepare a solution of the acrylic resin. The solution was coated onto the second polymer film, followed by drying to form an adhesion-enhancing layer with a thickness of 0.2 μm, thereby obtaining a laminate film.
An epoxy sheet (optical film, trade name: XNR5516Z, manufactured by Nagase ChemteX Corporation) was bonded to the adhesion-enhancing layer of the laminate film thus obtained. The laminate film bonded with the epoxy sheet was irradiated with UV (ultraviolet rays) at an exposure of 6 J/cm2, followed by baking at 80° C. for 60 minutes, thereby obtaining a laminate.
Using bar coating, a polyester resin solution was coated onto a biaxially-oriented polyethylene terephthalate film (first polymer film, trade name: A4100, thickness: 50 μm, manufactured by TOYOBO CO., LTD.), followed by drying and curing at 80° C. for 1 minute, thereby forming an anchor coat layer with a thickness of 100 nm.
Using a resistance heating vacuum deposition device, an aluminum material (trade name: 4N, manufactured by Kojundo Chemical Lab. Co., Ltd.) was evaporated by heating under a pressure of 3.0×10−2 Pa, with oxygen being introduced, thereby forming an AlOx film with a thickness of 10 nm on the anchor coat layer. The deposition was conducted by applying an accelerating voltage of 50 kV and an emission current of 0.5 A.
A mixed liquid obtained by mixing a hydrolysate of tetraethoxy silane with polyvinyl alcohol at a mass ratio of 1/1 was coated onto the AlOx film by bar coating, followed by drying and curing at 120° C. for 1 minute, thereby forming an SiOx film with a thickness of 400 nm. The multilayer film including the AlOx film and the SiOx film and formed on the anchor coat layer in this way was used as a moisture impermeable layer.
An adhesive (trade name: TAKELAC A525, manufactured by Mitsui Chemicals, Inc.) was coated onto the moisture impermeable layer. Then, the moisture impermeable layer was bonded, via the adhesive, to a corona discharge treated surface of a biaxially-oriented polyethylene terephthalate film (second polymer film, trade name: FE2001, thickness: 25 μm, manufactured by FUTAMURA CHEMICAL CO., LTD.), followed by aging at 50° C. for 2 days. The adhesive layer after bonding had a thickness of 5 μm.
A mixed solution was prepared so as to contain 70 parts by mass of polyester urethane resin (trade name: UR1350, manufactured by TOYOBO CO., LTD.) and 30 parts by mass of an isocyanurate form of hexamethylene diisocyanate, and the solution was coated onto the second polymer film. The coated liquid was dried to form an adhesion-enhancing layer with a thickness of 0.2 μm, thereby obtaining a laminate film.
An epoxy sheet (optical film, trade name: XNR5516Z, manufactured by Nagase ChemteX Corporation) was bonded to the adhesion-enhancing layer of the laminate film thus obtained. The laminate film bonded with the epoxy sheet was irradiated with UV (ultraviolet rays) at an exposure of 6 J/cm2, followed by baking at 80° C. for 60 minutes, thereby obtaining a laminate.
An adhesive (trade name: TAKELAC A525, manufactured by Mitsui Chemicals, Inc.) was coated onto a corona discharge treated surface of a biaxially-oriented polyethylene terephthalate film (first polymer film, trade name: P60, thickness: 12 μm, manufactured by TORAY INDUSTRIES, INC.). Then, the biaxially-oriented polyethylene terephthalate film was bonded, via the adhesive, to a corona discharge treated surface of a biaxially-oriented polyethylene terephthalate film (second polymer film, trade name: FE2001, thickness: 25 μm, manufactured by FUTAMURA CHEMICAL CO., LTD.), followed by aging at 50° C. for 2 days. The adhesive layer after bonding had a thickness of 5 μm.
A mixed solution was prepared by mixing 70 parts by mass of acrylic resin (weight-average molecular weight: 30,000) obtained by polymerizing 35 parts by mass of acrylic acid, 35 parts by mass of hydroxyethyl acrylate, and 30 parts by mass of n-butyl acrylate, with parts by mass of an isocyanurate form of hexamethylene diisocyanate (trade name: Desmodur N3300, manufactured by Sumika Bayer Urethane Co., Ltd.), and the mixed solution was coated onto the second polymer film. The coated liquid was dried to form an adhesion-enhancing layer with a thickness of 0.2 μm, thereby obtaining a laminate film.
An epoxy sheet (optical film, trade name: XNR5516Z, manufactured by Nagase ChemteX Corporation) was bonded to the adhesion-enhancing layer of the laminate film thus obtained. The laminate film bonded with the epoxy sheet was irradiated with UV (ultraviolet rays) at an exposure of 6 J/cm2, followed by baking at 80° C. for 60 minutes, thereby obtaining a laminate.
Using bar coating, a polyester resin solution was coated onto a biaxially-oriented polyethylene terephthalate film (first polymer film, trade name: A4100, thickness: 50 μm, manufactured by TOYOBO CO., LTD.), followed by drying and curing at 80° C. for 1 minute, thereby forming an anchor coat layer with a thickness of 100 nm.
Using a resistance heating vacuum deposition device, an aluminum material (trade name: 4N, manufactured by Kojundo Chemical Lab. Co., Ltd.) was evaporated by heating under a pressure of 3.0×10−2 Pa to form an AlOx film with a thickness of 10 nm on the anchor coat layer. The deposition was conducted by applying an accelerating voltage of 50 kV and an emission current of 0.5 A.
A mixed liquid obtained by mixing a hydrolysate of tetraethoxy silane with polyvinyl alcohol at a mass ratio of 1/1 was coated onto the AlOx film by bar coating, followed by drying and curing at 120° C. for 1 minute, thereby forming an SiOx film with a thickness of 400 nm. The multilayer film including the AlOx film and the SiOx film and formed on the anchor coat layer in this way was used as a moisture impermeable layer.
An adhesive (trade name: TAKELAC A525, manufactured by Mitsui Chemicals, Inc.) was coated onto the moisture impermeable layer. Then, the moisture impermeable layer was bonded, via the adhesive, to a corona discharge treated surface of a biaxially-oriented polyethylene terephthalate film (trade name: FE2001, thickness: 25 μm, manufactured by FUTAMURA CHEMICAL CO., LTD.), followed by aging at 50° C. for 2 days. The adhesive layer after bonding had a thickness of 5 μm.
A mixed solution was prepared by mixing 70 parts by mass of acrylic resin (weight-average molecular weight: 30,000) obtained by polymerizing 35 parts by mass of acrylic acid, 35 parts by mass of hydroxyethyl acrylate, and 30 parts by mass of n-butyl acrylate, with parts by mass of an isocyanurate form of hexamethylene diisocyanate (trade name: Desmodur N3300, manufactured by Sumika Bayer Urethane Co., Ltd.), and the mixed solution was coated onto the second polymer film. The coated liquid was dried to form an adhesion-enhancing layer with a thickness of 2 μm, thereby obtaining a laminate film.
An epoxy sheet (optical film, trade name: XNR5516Z, manufactured by Nagase ChemteX Corporation) was bonded to the adhesion-enhancing layer of the laminate film thus obtained. The laminate film bonded with the epoxy sheet was irradiated with UV (ultraviolet rays) at an exposure of 6 J/cm2, followed by baking at 80° C. for 60 minutes, thereby obtaining a laminate.
The moisture impermeability of the laminate films obtained in Examples 1 and 2 and Comparative Examples 1 to 4 were evaluated by measuring moisture permeability using a method in conformance with the infrared sensor method of JIS K 7129. For the measurement of moisture permeability, a moisture permeability measurement device (trade name: Permatran, manufactured by MOCON Inc.) was used. The temperature of a permeation cell was set to 40° C., the relative humidity of a high-humidity chamber was set to 90% RH, and the relative humidity of a low-humidity chamber was set to 0% RH. Table 1 shows measurements of moisture permeability.
The total light transmittance was measured for each of the laminate films obtained in Examples 1 and 2 and Comparative Examples 1 to 4 using a hazemeter device (trade name: NDH2000, manufactured by NIPPON DENSHOKU INDUSTRIES Co., LTD). Table 1 shows measurements of total light transmittance.
According to an adhesion evaluation test method which is in conformance with the cross-cut method of JIS K 5600-5-6 (ISO2409), the adhesion-enhancing layers of the laminate films obtained in Examples 1 and 2 and Comparative Examples 1 to 4 were each cut into a 1 mm-square lattice pattern, and a cellophane tape was attached to the adhesion-enhancing layer. After the cellophane tapes were peeled off from the respective adhesion-enhancing layers, intimate contact was evaluated according to the criteria below. Table shows evaluations of intimate contact between the adhesion-enhancing layer and the second polymer film.
A: The adhesion-enhancing layer did not peel off from the second polymer film (Classes 0 to 2 of JIS K 5600-5-6).
B: The adhesion-enhancing layer peeled off from the second polymer film (Classes 3 to 5 of JIS K 5600-5-6).
The laminates obtained in Examples 1 and 2 and Comparative Examples 1 to 4 were each cut into a strip of 1 cm width, and the epoxy sheet (optical film) side of each strip of the laminate was fixed onto a glass plate. Using a TENSILON universal testing machine (manufactured by A&D Company, Limited), the fixed laminate film strips of the laminates were each peeled off from the epoxy sheet in a direction perpendicular to the glass plate at a speed of 300 mm/minute, to measure the strength required for peeling. The intimate contact between the optical film and the adhesion-enhancing layer was evaluated according to the criteria below. Table 1 shows evaluations of intimate contact between the optical film and the adhesion-enhancing layer.
A: The peel strength was 2N/cm or more.
B: The peel strength was less than 2N/cm.
As shown in Table 1, in the laminate films and the laminates of Examples 1 and 2, good moisture impermeability and good intimate contact were achieved. In contrast, in the laminate film and the laminate of Comparative Example 1 not using polyisocyanate to form the adhesion-enhancing layer, intimate contact was not sufficiently achieved between the adhesion-enhancing layer and the second polymer film, and between the optical film and the adhesion-enhancing layer. In the laminate of Comparative Example 2 using a polyester urethane resin having no reactive carbon-carbon double bond to form the adhesion-enhancing layer, intimate contact was not sufficiently achieved between the optical film and the adhesion-enhancing layer. The laminate film of Comparative Example 3 not including the moisture impermeable layer could not achieve sufficient moisture impermeability. In the laminate of Comparative Example 4 including the adhesion-enhancing layer with a thickness exceeding 1 μm, intimate contact was not sufficiently achieved between the optical film and the adhesion-enhancing layer.
To prepare the wavelength conversion sheet shown in
Using an electron beam heating vacuum deposition device, a silicon oxide material (manufactured by Canon Optron Inc.) was evaporated by electron beam heating under a pressure of 1.5×10−2 Pa to form an SiOx film with a thickness of 40 nm on the anchor coat layer 3a. The deposition was conducted by applying an accelerating voltage of 40 kV and an emission current of 0.2 A.
A mixed liquid prepared by mixing a hydrolysate of tetraethoxy silane with polyvinyl alcohol at a mass ratio of 1/1 was coated onto the SiOx film by bar coating, followed by drying and curing at 120° C. for 1 minute, thereby forming an SiOx film with a thickness of 400 nm. Further, through a similar procedure, an SiOx film with a thickness of 40 nm was formed by vacuum deposition, and then an SiOx film with a thickness of 400 nm was formed by coating. The multilayer film thus formed on the anchor coat layer and included two alternations of vacuum deposited SiOx films and coated SiOx films was used as the moisture impermeable layer 4a.
An adhesive (trade name: TAKELAC A525, manufactured by Mitsui Chemicals, Inc.) was coated onto the moisture impermeable layer 4a to form the tackifier layer 6a. The moisture impermeable layer 4a was bonded, via the adhesive, to a corona discharge treated surface of a biaxially-oriented polyethylene terephthalate film (second polymer film 8a, trade name: FE2001, thickness: 25 μm, manufactured by FUTAMURA CHEMICAL CO., LTD.), followed by aging at 50° C. for 2 days, thereby obtaining the first barrier film 11a. The adhesive layer 6a after bonding had a thickness of 5 μm.
A mixed solution was prepared by mixing 70 parts by mass of acrylic resin (weight-average molecular weight: 30,000) obtained by polymerizing 35 parts by mass of acrylic acid, 35 parts by mass of hydroxyethyl acrylate, and 30 parts by mass of n-butyl acrylate, with 30 parts by mass of an isocyanurate form of hexamethylene diisocyanate (trade name: Desmodur N3300, manufactured by Sumika Bayer Urethane Co., Ltd.), and the mixed solution was coated onto a surface of the second polymer film 8a of the first barrier film 11a. The coated liquid was dried to form a first adhesion-enhancing layer 10a with a thickness of 0.2 μm. In this way, a first laminate film 20a was formed, with the first adhesion-enhancing layer 10a being formed on the first barrier film 11a.
With a method similar to that of the first barrier film 11a, a second barrier film 11b was prepared in which a first polymer film 2b, an anchor coat layer 3b, a moisture impermeable layer 4b, an adhesive layer 6b, and a second polymer film 8b were laminated in this order. Moreover, a second adhesion-enhancing layer 10b with a thickness of 0.2 μm was formed on a surface of the second polymer film 8b of the second barrier film 11b by a method similar to that of the first adhesion-enhancing layer 10a. In this way, a second laminate film 20b was prepared, with the second adhesion-enhancing layer 10b being formed on the second barrier film 11b.
A material obtained as follows was dropped onto the first adhesion-enhancing layer 10a on the first barrier film 11a. Specifically, the material was obtained by dispersing quantum dot emitters, having cores of cadmium selenide (CdSe) and shells of zinc sulfide (ZnS), into a thermosetting epoxy resin. Then, the second adhesion-enhancing layer 10b on the second barrier film 11b was brought into contact with the dropped material. Using a laminator, the first and second barrier films 11a and 11b were laminated with each other via the dropped material, such that the dropped material became a uniform film.
The resultant laminate was aged at room temperature for 24 hours to thereby cure the epoxy resin and form a wavelength conversion layer 13 between the first and second barrier films 11a and 11b, thereby providing a wavelength conversion sheet 100. In this case, the wavelength conversion layer 13 had a thickness of 100 μm.
A wavelength conversion sheet was prepared similarly to Example 3, except that the wavelength conversion layer was formed between the second polymer film of the first barrier film and the second polymer film of the second barrier film, without providing the first and second adhesion-enhancing layers.
(Intimate Contact with Emitter Layer)
The wavelength conversion sheets obtained in Example 3 and Comparative Example 5 were each cut into a strip of 1 cm width, and a first barrier film side of each strip of the wavelength conversion sheet was fixed onto a glass plate. Using a TENSILON universal testing machine (manufactured by A&D Company, Limited), the second barrier film of each fixed strip of wavelength conversion sheet was peeled off from the wavelength conversion layer, i.e. an emitter layer, in a direction perpendicular to the glass plate at a speed of 300 mm/minute, to measure the strength required for peeling. The intimate contact between the second barrier film and the emitter layer was evaluated according to the criteria below.
A: The peel strength was 1N/cm or more.
B: The peel strength was less than 1N/cm.
The wavelength conversion sheets obtained in Example 3 and Comparative Example 5 were placed in an oven at 85° C. for 1,000 hours. Using each of the 1,000-hour lapsed wavelength conversion sheets, the backlight unit shown in
The wavelength conversion sheets obtained in Example 3 and Comparative Example 5 were each used for preparing the backlight unit shown in
Table 2 shows evaluations of intimate contact between the adhesion-enhancing layer and the emitter layer, long-term reliable appearance, and long-term reliable light-emitting efficiency.
As shown in Table 2, in the wavelength conversion sheet of Example 3, good intimate contact was achieved, and thus the backlight unit prepared with the wavelength conversion sheet mentioned above achieved good long-term reliability. In contrast to this, in the wavelength conversion sheet of Comparative Example 5, sufficient intimate contact could not be achieved, and thus the backlight unit prepared with the wavelength conversion sheet mentioned above caused peeling of the first and second barrier films from the wavelength conversion layer during the long-term reliability test. Therefore, the quantum dot emitters became inactive, and the blue light from the light source was recognized in the backlight unit prepared with the stored wavelength conversion sheet. This means that the blue light from the light source was not converted by the wavelength conversion layer (i.e., did not become white light). Accordingly, it can be determined that light emission from the wavelength conversion layer was significantly decreased. The difference is due to the presence/absence of the adhesion-enhancing layer.
According to the studies conducted by the present inventors, intimate contact has by no means been sufficiently achieved if the laminate having barrier properties described in PTL 1 is used. An aspect of the present invention is to provide a laminate film and a laminate that can improve intimate contact and achieve good moisture impermeability, and to provide a wavelength conversion sheet, a backlight unit and an electroluminescent light-emitting unit, obtained using the laminate film and the laminate.
An embodiment of the present invention is a laminate film including a barrier film and an adhesion-enhancing layer formed on the barrier film. In the laminate film; the adhesion-enhancing layer contains a polymer that contains a group having a reactive carbon-carbon double bond and two or more hydroxyl groups, and polyisocyanate; and the adhesion-enhancing layer has a thickness in a range of 0.01 μm or more to 1 μm or less. In the laminate film, the above configuration of the adhesion-enhancing layer improves intimate contact of the laminate film and imparts good moisture impermeability.
In the laminate film, in terms of versatility and reactivity, the group having a reactive carbon-carbon double bond is preferably an acryloyl group.
In the laminate film, it is preferable that the barrier film includes a first polymer film and a moisture impermeable layer formed on the first polymer film, and the adhesion-enhancing layer is formed on the moisture impermeable layer side of the barrier film. With the barrier film having the above configuration, sufficient moisture impermeability is easily obtained.
In the laminate film, it is preferable that the moisture impermeable layer includes a layer of an oxide, nitride, or oxynitride having atoms of at least one substance selected from a group consisting of aluminum, titanium, copper, indium, and silicon. With the moisture impermeable layer having the above configuration, both of transparency and moisture impermeability are easily obtained.
In the laminate film, it is preferable that the barrier film further includes a second polymer film disposed on the moisture impermeable layer, and the adhesion-enhancing layer is formed on the second polymer film. With the barrier film having the above configuration, breakage is further reduced during processing, distribution, and the like.
The laminate film preferably has a total light transmittance of 80% or more. With the total light transmittance of 80% or more, the laminate film can be favorably used for a light-emitting unit. Further, the laminate film is preferably used for protecting phosphors.
Another embodiment of the present invention is a laminate including a cured laminate film obtained by curing the adhesion-enhancing layer of the laminate film described above, and a resin film formed on a cured adhesion-enhancing layer side surface of the cured laminate film.
A still another embodiment of the present invention is a wavelength conversion sheet including a wavelength conversion layer, and a pair of protective films respectively formed on both surfaces of the wavelength conversion layer. In the wavelength conversion sheet, at least one of the protective films is a cured laminate film obtained by curing the adhesion-enhancing layer of the laminate film described above. The wavelength conversion sheet of the present invention improves intimate contact with the wavelength conversion layer, and maintains good appearance and light-emitting efficiency after long-term storage at a high temperature.
A yet another embodiment of the present invention is a backlight unit including a light-emitting diode light source and the wavelength conversion sheet described above. The backlight unit using the laminate film described above prevents external oxygen or moisture from contacting the wavelength conversion layer, and enables long-term use of a backlight without deterioration of the phosphors.
A yet another embodiment of the present invention is an electroluminescent light-emitting unit including an electroluminescent light-emitting layer, and a cured laminate film obtained by curing the adhesion-enhancing layer of the laminate film described above. The electroluminescent light-emitting unit using the laminate film prevents external oxygen or moisture from contacting the electroluminescent light-emitting layer, and enables long-term use of the electroluminescent light-emitting unit without deterioration of the electroluminescent light-emitting layer.
The present invention provides embodiments as a laminate film and a laminate that can improve intimate contact and obtain good moisture impermeability, and provides a wavelength conversion sheet, a backlight unit, and an electroluminescent light-emitting unit, which are all obtained using the laminate film and the laminate.
2, 2a, 2b: First polymer film, 3a, 3b: Anchor coat layer, 4, 4a, 4b: Moisture impermeable layer, 6, 6a, 6b: Tackifier layer or adhesive layer, 8, 8a, 8b: Second polymer film, 10, 10a, 10b: Adhesion-enhancing layer, 10′, 10′a, 10′b: Cured adhesive layer, 11, 11a, 11b: Barrier film, 13: Wavelength conversion layer, 20: Laminate film, 20′, 20′a, 20′b: Cured laminate film, 22: Resin film, 30: Laminate, 36: Light guiding layer, 38: Reflecting layer, 40: Light-emitting diode light source, 50: Backlight unit, 52: Sealant layer, 54: Transparent electrode layer, 56: Electroluminescent light-emitting layer, 58: Dielectric layer, 60: Back surface electrode layer, 70: Electroluminescent light-emitting unit.
Obviously, numerous modifications and variations of the present invention are possible in light of the above teachings. It is therefore to be understood that within the scope of the appended claims, the invention may be practiced otherwise than as specifically described herein.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2014-150811 | Jul 2014 | JP | national |
| 2015-062254 | Mar 2015 | JP | national |
The present application is a continuation of U.S. application Ser. No. 15/412,869, filed Jan. 23, 2017, which is a continuation of International Application No. PCT/JP2015/071110, filed Jul. 24, 2015, which is based upon and claims the benefits of priority to Japanese Application No. 2014-150811, filed Jul. 24, 2014, and Japanese Application No. 2015-062254, filed Mar. 25, 2015. The entire contents of all of the above applications are incorporated herein by reference.
| Number | Date | Country | |
|---|---|---|---|
| Parent | 15412869 | Jan 2017 | US |
| Child | 17451020 | US | |
| Parent | PCT/JP2015/071110 | Jul 2015 | US |
| Child | 15412869 | US |
