WO2016098504A1 - Film d'étanchéité pour éléments électroniques - Google Patents

Film d'étanchéité pour éléments électroniques Download PDF

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Publication number
WO2016098504A1
WO2016098504A1 PCT/JP2015/082144 JP2015082144W WO2016098504A1 WO 2016098504 A1 WO2016098504 A1 WO 2016098504A1 JP 2015082144 W JP2015082144 W JP 2015082144W WO 2016098504 A1 WO2016098504 A1 WO 2016098504A1
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Prior art keywords
layer
sealing film
film
weight
resin
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PCT/JP2015/082144
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English (en)
Japanese (ja)
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公裕 井崎
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三菱樹脂株式会社
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Priority claimed from JP2014258134A external-priority patent/JP6634675B2/ja
Priority claimed from JP2015003727A external-priority patent/JP2016128245A/ja
Application filed by 三菱樹脂株式会社 filed Critical 三菱樹脂株式会社
Priority to CN201580068125.0A priority Critical patent/CN107107575B/zh
Priority to KR1020197020521A priority patent/KR102138756B1/ko
Priority to KR1020177014545A priority patent/KR20170085058A/ko
Publication of WO2016098504A1 publication Critical patent/WO2016098504A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/26—Layered products comprising a layer of synthetic resin characterised by the use of special additives using curing agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/42—Layered products comprising a layer of synthetic resin comprising condensation resins of aldehydes, e.g. with phenols, ureas or melamines
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/724—Permeability to gases, adsorption
    • B32B2307/7242—Non-permeable
    • B32B2307/7246—Water vapor barrier

Definitions

  • the present invention relates to a sealing film for an electronic member such as a quantum dot-containing resin sheet, electronic paper, and organic EL, which is excellent in transparency, barrier properties, and adhesiveness with an adhesive layer, and requires high water vapor barrier properties. .
  • polyester films are widely used mainly for various display applications because of their excellent optical properties.
  • a water vapor permeability of 0.02 g is provided by providing a cured resin layer made of a polymer and a gas barrier layer made of silicon nitride oxide on at least one side of a plastic film.
  • a gas barrier film of / m 2 / day has been proposed (Patent Document 1).
  • gas barrier film described in Patent Document 1 has an effect of improving gas barrier properties, it does not consider the adhesion to the adhesive layer.
  • a gas barrier film using silicon nitride oxide as a gas barrier layer has a high refractive index of the gas barrier layer, a refractive index difference with the protective layer is increased, and the transmittance may be reduced.
  • Patent Document 2 a gas barrier film having a water vapor barrier property of 10 ⁇ 6 g / m 2 / day level by laminating a planarizing layer, a gas barrier layer, and a protective layer on a base film by an atmospheric pressure plasma CVD method has been proposed ( Patent Document 2).
  • the protective layer made of an inorganic polymer made of TEOS as a raw material by the atmospheric pressure CVD method does not necessarily have adhesion to the adhesive layer. Not enough.
  • Patent Document 3 a gas barrier laminate film (Patent Document 3) in which a composite film of polyvinyl alcohol and an inorganic layered compound is laminated as a protective layer of the gas barrier film has been proposed, but when used for a display body such as a display, the appearance is whitish, There was a tendency to be inferior in transparency. Furthermore, although a gas barrier laminate film (Patent Document 4) having a configuration in which a sol-gel layer is provided as a protective layer has been proposed, the surface hardness is good, but the flexibility and adhesion to the adhesive layer may be inferior. is there.
  • Patent Document 5 measures for improving the gas barrier layer are taken by alternately laminating organic layers / inorganic layers, but the gas barrier property is improved, but the interlayer adhesion at the organic layer / inorganic layer interface is insufficient. there were.
  • This invention is made
  • the gist of the present invention is a sealing film in which a coating layer, a barrier layer, and a protective layer are sequentially laminated on one side of a polyester film, and the coating layer is selected from a polyester resin, an acrylic resin, and a urethane resin. Containing at least one binder resin and at least one cross-linking agent selected from oxazoline compounds, melamine resins, and isocyanate compounds, according to JIS-K7129B method, temperature 40 ° C., humidity 90 It exists in the sealing film for electronic members characterized by the water vapor permeability
  • the sealing film for electronic members of the present invention is excellent in transparency, barrier properties, and adhesiveness with an adhesive layer, and is used for electronic members such as quantum dot-containing resin sheets, electronic paper, and organic EL that require high barrier properties. It is suitable as a sealing film, and its industrial value is high.
  • FIG. 1 is a schematic cross-sectional view showing a laminate according to an embodiment of the present invention.
  • the polyester film may have a single layer structure or a laminated structure.
  • the polyester film may have a multilayer structure of four layers or more as long as it does not exceed the gist of the present invention other than the two-layer or three-layer structure. There is no particular limitation.
  • the polyester may be a homopolyester or a copolyester.
  • a homopolyester those obtained by polycondensation of an aromatic dicarboxylic acid and an aliphatic glycol are preferred.
  • the aromatic dicarboxylic acid include terephthalic acid and 2,6-naphthalenedicarboxylic acid
  • examples of the aliphatic glycol include ethylene glycol, diethylene glycol, and 1,4-cyclohexanedimethanol.
  • Representative polyester includes polyethylene terephthalate (PET) and the like.
  • examples of the dicarboxylic acid component of the copolyester include isophthalic acid, phthalic acid, terephthalic acid, 2,6-naphthalenedicarboxylic acid, adipic acid, sebacic acid, and oxycarboxylic acid (eg, P-oxybenzoic acid).
  • examples of the glycol component include one or more types such as ethylene glycol, diethylene glycol, propylene glycol, butanediol, 1,4-cyclohexanedimethanol, neopentyl glycol and the like.
  • the polyester referred to in the present invention refers to a polyester that is usually 60 mol% or more, preferably 80 mol% or more of polyethylene terephthalate or the like which is an ethylene terephthalate unit.
  • the polyester film it is preferable to mix particles for the main purpose of imparting easy slipperiness.
  • the kind of the particle to be blended is not particularly limited as long as it is a particle capable of imparting slipperiness.
  • Specific examples thereof include silica, calcium carbonate, magnesium carbonate, barium carbonate, calcium sulfate, calcium phosphate, and phosphoric acid.
  • the particles include magnesium, kaolin, aluminum oxide, and titanium oxide.
  • the heat-resistant organic particles described in JP-B-59-5216, JP-A-59-217755 and the like may be used.
  • examples of other heat-resistant organic particles include thermosetting urea resins, thermosetting phenol resins, thermosetting epoxy resins, benzoguanamine resins, and the like.
  • precipitated particles obtained by precipitating and finely dispersing a part of a metal compound such as a catalyst during the polyester production process can also be used.
  • the shape of the particles is not particularly limited, and any of a spherical shape, a block shape, a rod shape, a flat shape, and the like may be used. Moreover, there is no restriction
  • the average particle diameter of the particles is usually in the range of 0.01 to 3 ⁇ m, preferably 0.01 to 1 ⁇ m.
  • the average particle diameter is less than 0.01 ⁇ m, the particles are likely to aggregate and dispersibility may be insufficient.
  • the average particle diameter exceeds 3 ⁇ m, the surface roughness of the film becomes too rough and There may be a problem when a release layer is applied in the process.
  • the content of the particles is usually in the range of 0.001 to 5% by weight, preferably 0.005 to 3% by weight.
  • the particle content is less than 0.001% by weight, the slipperiness of the film may be insufficient.
  • the content exceeds 5% by weight, the transparency of the film is insufficient. There is.
  • the method for adding particles to the polyester film is not particularly limited, and a conventionally known method can be adopted.
  • it can be added at any stage of producing the polyester constituting each layer, but preferably a polycondensation reaction may be carried out after the esterification stage or after the transesterification reaction.
  • a method of blending a slurry of particles dispersed in ethylene glycol or water with a vented kneading extruder and a polyester raw material, or a blending of dried particles and a polyester raw material using a kneading extruder is done by methods.
  • the thickness of the polyester film is not particularly limited as long as it can be formed as a film. In consideration of the mechanical strength, flexibility, transparency, etc. of the film substrate, the thickness is preferably 12 to 125 ⁇ m, more preferably 25 to 100 ⁇ m.
  • polyester film The production example of the polyester film will be specifically described, but is not limited to the following production example.
  • the polyester raw material described above is used and the molten sheet extruded from the die is cooled and solidified with a cooling roll to obtain an unstretched sheet is preferable.
  • a method in which the polyester raw material described above is used and the molten sheet extruded from the die is cooled and solidified with a cooling roll to obtain an unstretched sheet is preferable.
  • an electrostatic application adhesion method and / or a liquid application adhesion method are preferably employed.
  • the obtained unstretched sheet is stretched in the biaxial direction. In that case, first, the unstretched sheet is stretched in one direction by a roll or a tenter type stretching machine.
  • the stretching temperature is usually 70 to 120 ° C., preferably 80 to 110 ° C., and the stretching ratio is usually 2.5 to 7 times, preferably 3.0 to 6 times.
  • the stretching temperature orthogonal to the first-stage stretching direction is usually 70 to 170 ° C., and the draw ratio is usually 3.0 to 7 times, preferably 3.5 to 6 times.
  • heat treatment is performed at a temperature of 180 to 270 ° C. under tension or under relaxation within 30% to obtain a biaxially oriented film.
  • a method in which stretching in one direction is performed in two or more stages can be employed. In that case, it is preferable to carry out so that the draw ratios in the two directions finally fall within the above ranges.
  • the simultaneous biaxial stretching method can be adopted for the production of the polyester film.
  • the simultaneous biaxial stretching method is a method in which the unstretched sheet is usually stretched and oriented simultaneously in the machine direction and the width direction in a state where the temperature is controlled at 70 to 120 ° C, preferably 80 to 110 ° C.
  • the area magnification is 4 to 50 times, preferably 7 to 35 times, and more preferably 10 to 25 times.
  • heat treatment is performed at a temperature of 170 to 250 ° C. under tension or under relaxation within 30% to obtain a stretched oriented film.
  • conventionally known stretching methods such as a screw method, a pantograph method, and a linear drive method can be employed.
  • a so-called coating stretching method for treating the film surface during the above-described polyester film stretching step can be performed.
  • coating stretching method in-line coating
  • coating can be performed simultaneously with stretching and the thickness of the coating layer can be reduced according to the stretching ratio, producing a film suitable as a polyester film. it can.
  • the polyester film has at least one binder resin selected from polyester resin, acrylic resin, and urethane resin, melamine resin, oxazoline group-containing resin, and isocyanate compound to improve adhesion to the barrier layer.
  • a coating layer containing at least one kind of crosslinking agent selected from the inside is formed.
  • the polyester resin is defined as a linear polyester having a dicarboxylic acid component and a glycol component as constituent components.
  • Dicarboxylic acid components include terephthalic acid, isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, 4,4-diphenyldicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, adipic acid, sebacic acid, phenylindanedicarboxylic acid, A dimer acid etc. can be illustrated. Two or more of these components can be used.
  • a small proportion of unsaturated polybasic acids such as maleic acid, fumaric acid, itaconic acid and the like, and hydroxycarboxylic acids such as p-hydroxybenzoic acid and p- ( ⁇ -hydroxyethoxy) benzoic acid, etc.
  • the proportion of the unsaturated polybasic acid component or the hydroxycarboxylic acid component is at most 10 mol%, preferably 5 mol% or less.
  • glycol component examples include ethylene glycol, 1,4-butanediol, neopentyl glycol, diethylene glycol, dipropylene glycol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, xylylene glycol, dimethylolpropionic acid.
  • ethylene glycol and bisphenol A ethylene oxide adducts and propylene oxide adducts and 1,4-butanediol are preferred, and ethylene glycol and bisphenol A ethylene oxide adducts and propylene oxide adducts are more preferred.
  • the coating layer which comprises the sealing film in this invention in order to make water dispersion or water-solubilization easy, it may contain at least 1 or more types of polyester resin which has a sulfonic acid (salt) group. preferable.
  • polyester resin having a sulfonic acid (salt) group examples include 5-sodium sulfoisophthalic acid, 5-ammonium sulfoisophthalic acid, 4-sodium sulfoisophthalic acid, 4-methylammonium sulfoisophthalic acid, 2-sodium sulfoisophthalic acid, Preferable examples include sulfonic acid alkali metal salt compounds or sulfonic acid amine salt compounds such as 5-potassium sulfoisophthalic acid, 4-potassium sulfoisophthalic acid, 2-potassium sulfoisophthalic acid, and sodium sulfosuccinic acid.
  • the glass transition temperature (hereinafter sometimes abbreviated as Tg) is preferably 40 ° C. or higher, more preferably 60 ° C. or higher.
  • Tg is less than 40 ° C., for the purpose of improving adhesiveness, when the coating thickness of the coating layer is increased, problems such as easy blocking may occur.
  • An acrylic resin is a polymer composed of a polymerizable monomer having a carbon-carbon double bond, as typified by acrylic and methacrylic monomers. These may be either a homopolymer or a copolymer. Moreover, the copolymer of these polymers and other polymers (for example, polyester, polyurethane, etc.) is also included. For example, a block copolymer or a graft copolymer. Furthermore, a polymer (in some cases, a mixture of polymers) obtained by polymerizing a polymerizable monomer having a carbon-carbon double bond in a polyester solution or a polyester dispersion is also included.
  • a polymer (in some cases, a mixture of polymers) obtained by polymerizing a polymerizable monomer having a carbon-carbon double bond in a polyurethane solution or polyurethane dispersion is also included.
  • a polymer (in some cases, a polymer mixture) obtained by polymerizing a polymerizable monomer having a carbon-carbon double bond in another polymer solution or dispersion is also included.
  • the polymerizable monomer having a carbon-carbon double bond is not particularly limited, but representative compounds such as acrylic acid, methacrylic acid, crotonic acid, itaconic acid, fumaric acid, maleic acid, and citraconic acid.
  • Various carboxyl group-containing monomers and their salts 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, monobutylhydroxyl fumarate, monobutylhydroxy
  • Various hydroxyl-containing monomers such as itaconate; various (meth) acrylic such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, lauryl (meth) acrylate Acid esters; (meth) a Riruamido, various nitrogen-containing vinyl monomers such as diacetone acrylamide, N- methylol acryl
  • polymerizable monomers as shown below can be copolymerized. That is, various styrene derivatives such as styrene, ⁇ -methylstyrene, divinylbenzene and vinyltoluene, various vinyl esters such as vinyl acetate and vinyl propionate; ⁇ -methacryloxypropyltrimethoxysilane, vinyltrimethoxysilane, Various silicon-containing polymerizable monomers such as methacryloyl silicon macromer; phosphorus-containing vinyl monomers; vinyl chloride, biliden chloride, vinyl fluoride, vinylidene fluoride, trifluorochloroethylene, tetrafluoroethylene, chlorotrifluoroethylene And various vinyl halides such as hexafluoropropylene; and various conjugated dienes such as butadiene.
  • styrene derivatives such as styrene, ⁇ -methylstyrene, divinylbenzene and vinyl
  • the glass transition temperature (hereinafter sometimes abbreviated as Tg) is preferably 40 ° C. or higher, more preferably 60 ° C. or higher.
  • Tg is less than 40 ° C., for the purpose of improving adhesiveness, when the coating thickness of the coating layer is increased, problems such as easy blocking may occur.
  • the urethane resin is preferably a urethane resin having a polycarbonate structure.
  • the urethane resin having a polycarbonate structure refers to a urethane resin in which one of the polyols, which are main components of the urethane resin, is a polycarbonate polyol.
  • Polycarbonate polyols are obtained from a polyhydric alcohol and a carbonate compound by a dealcoholization reaction.
  • the polyhydric alcohols include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, trimethylolpropane, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, , 5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, , 10-decanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 3,3-dimethylolheptane, and the like.
  • Examples of the carbonate compound include dimethyl carbonate, diethyl carbonate, diphenyl carbonate, and ethylene carbonate.
  • Examples of the polycarbonate-based polyols obtained from these reactions include poly (1,6-hexylene) carbonate, poly (3- And methyl-1,5-pentylene) carbonate.
  • polyisocyanates constituting the urethane resin having a polycarbonate structure include aromatic diisocyanates such as tolylene diisocyanate, xylylene diisocyanate, methylene diphenyl diisocyanate, phenylene diisocyanate, naphthalene diisocyanate, and tolidine diisocyanate, ⁇ , ⁇ , ⁇ ′, Aliphatic diisocyanates having an aromatic ring such as ⁇ '-tetramethylxylylene diisocyanate, methylene diisocyanate, propylene diisocyanate, lysine diisocyanate, trimethylhexamethylene diisocyanate, hexamethylene diisocyanate and other aliphatic diisocyanates, cyclohexane diisocyanate, methylcyclohexane diisocyanate, isophorone diisocyanate , Mechi Nbisu (4-cyclohexyl isocyan
  • aliphatic isocyanates or alicyclic isocyanates are more preferable than aromatic isocyanates from the viewpoint of improving adhesion to the active energy ray-curable coating material and preventing yellowing due to ultraviolet rays.
  • a chain extender may be used when synthesizing the urethane resin, and the chain extender is not particularly limited as long as it has two or more active groups that react with an isocyanate group. Alternatively, a chain extender having two amino groups can be mainly used.
  • chain extender having two hydroxyl groups examples include aliphatic glycols such as ethylene glycol, propylene glycol, butanediol and pentanediol, aromatic glycols such as xylylene glycol and bishydroxyethoxybenzene, neopentyl glycol and neopentyl.
  • aliphatic glycols such as ethylene glycol, propylene glycol, butanediol and pentanediol
  • aromatic glycols such as xylylene glycol and bishydroxyethoxybenzene
  • neopentyl glycol and neopentyl examples include glycols such as ester glycols such as glycol hydroxypivalate.
  • chain extender having two amino groups examples include aromatic diamines such as tolylenediamine, xylylenediamine, diphenylmethanediamine, ethylenediamine, propylenediamine, hexanediamine, 2,2-dimethyl-1,3- Propanediamine, 2-methyl-1,5-pentanediamine, trimethylhexanediamine, 2-butyl-2-ethyl-1,5-pentanediamine, 1,8-octanediamine, 1,9-nonanediamine, 1,10- Aliphatic diamines such as decane diamine, 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane, dicyclohexylmethanediamine, isopropylidine cyclohexyl-4,4′-diamine, 1,4-diaminocyclohexane, 1 , 3-Bisaminomethylcyclohexane Alicyclic diamines such as isophorone diamine,
  • Urethane resin may use a solvent as a medium, but preferably uses water as a medium.
  • a forced emulsification type using an emulsifier there are a forced emulsification type using an emulsifier, a self-emulsification type in which a hydrophilic group is introduced into the urethane resin, and a water-soluble type.
  • a self-emulsification type in which an ionic group is introduced into the skeleton of a urethane resin to form an ionomer is preferable because of excellent storage stability of the liquid and water resistance, transparency, and adhesion of the resulting coating layer.
  • examples of the ionic group to be introduced include various groups such as a carboxyl group, a sulfonic acid, a phosphoric acid, a phosphonic acid, a quaternary ammonium salt, and the carboxyl group is preferable.
  • a method for introducing a carboxyl group into a urethane resin various methods can be taken in each stage of the polymerization reaction. For example, there are a method of using a carboxyl group-containing resin as a copolymer component during prepolymer synthesis, and a method of using a component having a carboxyl group as one component such as polyol, polyisocyanate, and chain extender.
  • a method in which a desired amount of carboxyl groups is introduced using a carboxyl group-containing diol depending on the amount of this component charged is preferred.
  • dimethylolpropionic acid, dimethylolbutanoic acid, bis- (2-hydroxyethyl) propionic acid, bis- (2-hydroxyethyl) butanoic acid, and the like are copolymerized with a diol used for polymerization of a urethane resin.
  • the carboxyl group is preferably in the form of a salt neutralized with ammonia, amine, alkali metal, inorganic alkali or the like. Particularly preferred are ammonia, trimethylamine and triethylamine.
  • the urethane resin having a polycarbonate structure has a glass transition point (hereinafter sometimes referred to as Tg) of preferably 0 ° C. or lower, more preferably ⁇ 15 ° C. or lower, and further preferably ⁇ 30 ° C. or lower.
  • Tg glass transition point
  • easy adhesion may be insufficient.
  • Tg said here refers to the temperature which created the dry film
  • the oxazoline compound is a compound having an oxazoline group in the molecule, and is particularly preferably a polymer containing an oxazoline group, and can be prepared by polymerization of an addition polymerizable oxazoline group-containing monomer alone or with another monomer.
  • Addition-polymerizable oxazoline group-containing monomers include 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2-oxazoline, 2-vinyl-5-methyl-2-oxazoline, 2-isopropenyl-2-oxazoline, Examples thereof include 2-isopropenyl-4-methyl-2-oxazoline, 2-isopropenyl-5-ethyl-2-oxazoline, and the like, and one or a mixture of two or more thereof can be used. Of these, 2-isopropenyl-2-oxazoline is preferred because it is easily available industrially.
  • the other monomer is not particularly limited as long as it is a monomer copolymerizable with an addition polymerizable oxazoline group-containing monomer.
  • alkyl (meth) acrylate (alkyl groups include methyl, ethyl, n-propyl, isopropyl, (Meth) acrylic acid esters such as n-butyl group, isobutyl group, t-butyl group, 2-ethylhexyl group, cyclohexyl group); acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid, styrene
  • Unsaturated carboxylic acids such as sulfonic acid and its salts (sodium salt, potassium salt, ammonium salt, tertiary amine salt, etc.); Unsaturated nitriles such as acrylonitrile, methacrylonitrile; (meth) acrylamide, N-alky
  • the content of the oxazoline group contained in the oxazoline compound is usually 0.5 to 10 mmol / g, preferably 1 to 9 mmol / g, more preferably 3 to 8 mmol / g, still more preferably 4 to 6 mmol in terms of the amount of the oxazoline group. / G. Use in the above range is preferable for improving the coating strength.
  • the melamine resin is not particularly limited, but melamine, a methylolated melamine derivative obtained by condensing melamine and formaldehyde, a compound partially or completely etherified by reacting a methylolated melamine with a lower alcohol, and These mixtures can be used.
  • the melamine resin may be either a monomer or a condensate composed of a dimer or higher multimer, or a mixture thereof.
  • the lower alcohol used for the etherification methyl alcohol, ethyl alcohol, isopropyl alcohol, n-butanol, isobutanol and the like can be preferably used.
  • the functional group has an imino group, a methylol group, or an alkoxymethyl group such as a methoxymethyl group or a butoxymethyl group in one molecule, and an imino group type methylated melamine, a methylol group type melamine, or a methylol group type methylated group.
  • Melamine fully alkyl methylated melamine and the like can be used. Of these, methylolated melamine is most preferred. Furthermore, an acidic catalyst such as p-toluenesulfonic acid can be used in combination for the purpose of promoting the thermosetting of the melamine resin.
  • the isocyanate compound is a compound having an isocyanate derivative structure typified by isocyanate or blocked isocyanate.
  • isocyanates include aromatic isocyanates such as tolylene diisocyanate, xylylene diisocyanate, methylene diphenyl diisocyanate, phenylene diisocyanate, and naphthalene diisocyanate, and aromatic rings such as ⁇ , ⁇ , ⁇ ′, ⁇ ′-tetramethylxylylene diisocyanate.
  • Aliphatic isocyanates such as aliphatic isocyanate, methylene diisocyanate, propylene diisocyanate, lysine diisocyanate, trimethylhexamethylene diisocyanate, hexamethylene diisocyanate, cyclohexane diisocyanate, methylcyclohexane diisocyanate, isophorone diisocyanate, methylene bis (4-cyclohexyl isocyanate), isopropylidene dicyclohexyl diisocyanate
  • Alicyclic isocyanates such as bets are exemplified. Reaction products of these isocyanates with various polymers and compounds may be used.
  • polymers and derivatives such as burettes, isocyanurates, uretdiones, and carbodiimide modified products of these isocyanates are also included. These may be used alone or in combination.
  • isocyanates aliphatic isocyanates or alicyclic isocyanates are more preferable than aromatic isocyanates in order to avoid yellowing due to ultraviolet rays.
  • the blocking agent When used in the state of blocked isocyanate, the blocking agent includes, for example, bisulfites, phenolic compounds such as phenol, cresol, and ethylphenol, and alcohols such as propylene glycol monomethyl ether, ethylene glycol, benzyl alcohol, methanol, and ethanol.
  • active methylene compounds such as dimethyl malonate, diethyl malonate, methyl acetoacetate, ethyl acetoacetate and acetylacetone, mercaptan compounds such as butyl mercaptan and dodecyl mercaptan, lactam compounds such as ⁇ -caprolactam and ⁇ -valerolactam , Amine compounds such as diphenylaniline, aniline, ethyleneimine, acetanilide, acid amide compounds of acetic acid amide, formaldehyde, acetal Examples include oxime compounds such as dooxime, acetone oxime, methyl ethyl ketone oxime, and cyclohexanone oxime, and these may be used alone or in combination of two or more.
  • the isocyanate compound in the present invention may be used alone or as a mixture or combination with various polymers.
  • a mixture or a combined product with a polyester resin or a polyurethane resin may be used.
  • the ratio of each component in the coating layer is as follows.
  • the proportion of the polyester resin is usually 10 to 80% by weight, preferably 20 to 60% by weight
  • the proportion of the acrylic resin is usually 10 to 60% by weight, preferably 20 to 50% by weight
  • the proportion of the urethane resin is usually 10%.
  • the proportion of oxazoline compound is usually 20-80 wt%, preferably 40-80 wt%
  • the proportion of melamine resin is usually 6-80 wt%, preferably 10
  • the proportion of the isocyanate compound is generally 6 to 80% by weight, preferably 10 to 60% by weight.
  • the coating layer is formed by applying a coating solution and drying, and the coating amount (after drying) is usually 0.005 to 1 g / m 2 , preferably 0.005 from the viewpoint of coating properties.
  • the range is from -0.5 g / m 2 , more preferably from 0.01 to 0.2 g / m 2 .
  • the coating amount (after drying) is less than 0.005 g / m 2 , the coating property may be less stable and it may be difficult to obtain a uniform coating film.
  • the coating is thicker than 1 g / m 2 , the coating film adhesion and curability of the coating layer itself may be lowered.
  • a coating layer such as an antistatic layer or an oligomer precipitation preventing layer may be provided on the film surface not provided with a coating layer as long as the gist of the present invention is not impaired.
  • polyester film may be subjected to surface treatment such as corona treatment or plasma treatment in advance.
  • the barrier layer is laminated for the purpose of imparting barrier properties to the polyester film.
  • the barrier property is at a desired level.
  • the water vapor permeability measured according to the JIS-K7129B method is 0.01 g / m under measurement conditions of a temperature of 40 ° C. and a humidity of 90% RH. There is no particular limitation as long as it can be 2 / day or less.
  • Examples of the material for the barrier layer include silicon compounds such as polysilazane compounds, polycarbosilane compounds, polysilane compounds, polyorganosiloxane compounds, and tetraorganosilane compounds, silicon oxide, silicon oxynitride, aluminum oxide, aluminum oxynitride, and magnesium oxide.
  • silicon compounds such as polysilazane compounds, polycarbosilane compounds, polysilane compounds, polyorganosiloxane compounds, and tetraorganosilane compounds, silicon oxide, silicon oxynitride, aluminum oxide, aluminum oxynitride, and magnesium oxide.
  • Inorganic oxides such as zinc oxide, indium oxide, and tin oxide
  • inorganic nitrides such as silicon nitride and aluminum nitride
  • inorganic oxynitrides such as silicon oxynitride
  • metals such as aluminum, magnesium, zinc, and tin It is done. These can be used individually by 1
  • the thickness of the barrier layer is usually 1 nm to 10 ⁇ m, preferably 10 nm to 5 ⁇ m, more preferably 20 to 500 nm, and particularly preferably 50 to 200 nm. If the thickness of the barrier layer is less than 1 nm, the barrier effect may be insufficient. On the other hand, when it exceeds 10 ⁇ m, it is in a saturated state in terms of performance, and it is difficult to expect a barrier effect any more.
  • the barrier layer may have a single layer structure or a plurality of layers composed of two or more layers.
  • the method for forming the barrier layer can be a conventionally known method depending on the material constituting the barrier layer, and can be appropriately selected depending on the purpose. For example, a method in which the barrier layer material is formed on a polyester film by vapor deposition, sputtering, ion plating, thermal CVD, plasma CVD, or the like, or a solution in which the barrier layer material is dissolved in an organic solvent Is applied to a polyester film, and plasma ion implantation is performed on the obtained coating film.
  • Examples of ions implanted by plasma ion implantation include rare gases such as argon, helium, neon, krypton, and xenon, ions such as fluorocarbon, hydrogen, nitrogen, oxygen, carbon dioxide, chlorine, fluorine, and sulfur; gold, Examples include ions of metals such as silver, copper, platinum, nickel, palladium, chromium, titanium, molybdenum, niobium, tantalum, tungsten, and aluminum.
  • the protective layer By coating the protective layer on the barrier layer, the coating liquid for forming the protective layer penetrates evenly into the minute defects existing in the barrier layer, and the defective portion of the barrier layer can be repaired by thermosetting. Become.
  • the barrier layer by covering the barrier layer with a protective layer, it is rubbed or scraped due to contact with the guide roller for conveyance during the processing step, and also protects the barrier layer from the organic solvent used in the manufacturing step, It is also possible to maintain barrier properties.
  • organic compound having an aluminum element examples include aluminum tris (acetylacetonate), aluminum monoacetylacetonate bis (ethylacetoacetate), aluminum-di-n-butoxide-monoethylacetoacetate, aluminum-di -Iso-propoxide-monomethyl acetoacetate and the like are exemplified.
  • organic compound having titanium element examples include titanium orthoesters such as tetranormal butyl titanate, tetraisopropyl titanate, butyl titanate dimer, tetra (2-ethylhexyl) titanate, tetramethyl titanate; titanium acetylacetonate, Examples thereof include titanium chelates such as titanium tetraacetylacetonate, polytitanium acetylacetonate, titanium octylene glycolate, titanium lactate, titanium triethanolamate, and titanium ethylacetoacetate.
  • titanium orthoesters such as tetranormal butyl titanate, tetraisopropyl titanate, butyl titanate dimer, tetra (2-ethylhexyl) titanate, tetramethyl titanate
  • titanium acetylacetonate examples thereof include titanium chelates such as titanium tetraacetylacetonate, polytitanium acetylace
  • organic compound having a zirconium element examples include, for example, zirconium acetate, zirconium normal propylate, zirconium normal butyrate, zirconium tetraacetylacetonate, zirconium monoacetylacetonate, zirconium bisacetylacetonate and the like.
  • an organic compound having a chelate structure is preferable with respect to an organic compound containing a metal element selected from aluminum and zirconium, particularly in terms of good adhesion performance.
  • a metal element selected from aluminum and zirconium particularly in terms of good adhesion performance.
  • it is specifically described in “Crosslinking agent handbook” (Yamashita Shinzo, Kaneko Tosuke ed., Taiseisha Co., Ltd., 1990 edition).
  • the protective layer is preferably used in combination with an organosilicon compound represented by the following general formula (1) in order to protect the barrier layer and improve the adhesion to the adhesive layer.
  • the organosilicon compound represented by the general formula (1) has two hydrolyzable groups Y (D unit source) or three (T units) capable of forming a siloxane bond by hydrolysis / condensation reaction. Source) can be used.
  • the monovalent hydrocarbon group R 1 has 1 to 10 carbon atoms, and is particularly preferably a methyl group, an ethyl group, or a propyl group.
  • hydrolyzable group Y conventionally known ones can be used, and the following can be exemplified.
  • These hydrolyzable groups may be used alone or in combination.
  • the use of a methoxy group or an ethoxy group is particularly preferable because it can impart good storage stability to the coating material and has suitable hydrolyzability.
  • organosilicon compound examples include vinyltrimethoxysilane, ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -glycidoxypropylmethyldiethoxysilane, ⁇ - (3,4-epoxycyclohexyl) ethyltrimethoxysilane, ⁇ -mercaptopropyltrimethoxysilane, ⁇ -methacryloxypropyltrimethoxysilane, ⁇ -acryloxypropyltrimethoxysilane, ⁇ -aminopropyltriethoxysilane, 5-hexenyltrimethoxysilane, p-styryltrimethoxysilane, tri Examples include fluoropropyltrimethoxysilane, ⁇ -glycidoxypropyltriethoxysilane, ⁇ -glycidoxypropylmethyldiisopropenoxysilane, and the like.
  • a catalyst may be used in combination for the purpose of promoting hydrolysis / condensation reaction.
  • organic acids such as acetic acid, butyric acid, maleic acid and citric acid
  • inorganic acids such as hydrochloric acid, nitric acid, phosphoric acid and sulfuric acid
  • basic compounds such as triethylamine, tetrabutyl titanate, dibutyltin dilaurate and dibutyltin.
  • Organic metal salts such as diacetate, dibutyltin dioctate, dibutyltin diolate, diphenyltin diacetate, dibutyltin oxide, dibutyltin dimethoxide, dibutylbis (triethoxysiloxy) tin, dibutyltin benzylmalate, etc., fluorine such as KF and NH4F Examples thereof include element-containing compounds.
  • the above catalysts may be used alone or in combination of two or more. Among them, organometallic salts are particularly preferable from the viewpoint that the coating film durability is good, and it is more preferable to use a tin catalyst because the catalytic activity is sustainable for a long time.
  • the urethane resin is a resin obtained by reacting an isocyanate compound with a diol or a polyol compound.
  • the isocyanate compound include aromatic polyisocyanate, aliphatic polyisocyanate, alicyclic polyisocyanate, and aliphatic polyisocyanate, and a diisocyanate compound is usually used.
  • aromatic diisocyanate examples include tolylene diisocyanate (2,4- or 2,6-tolylene diisocyanate or a mixture thereof) (TDI), phenylene diisocyanate (m-, p-phenylene diisocyanate or a mixture thereof), 4,4 '-Diphenyl diisocyanate, 1,5-naphthalene diisocyanate (NDI), diphenylmethane diisocyanate (4,4'-, 2,4'-, or 2,2'-diphenylmethane diisocyanate or mixtures thereof) (MDI) 4,4′-toluidine diisocyanate (TODI), 4,4′-diphenyl ether diisocyanate, and the like.
  • TDI tolylene diisocyanate (2,4- or 2,6-tolylene diisocyanate or a mixture thereof)
  • TDI phenylene diisocyanate
  • Examples of the araliphatic diisocyanate include xylylene diisocyanate (1,3- or 1,4-xylylene diisocyanate or a mixture thereof) (XDI), tetramethylxylylene diisocyanate (1,3- or 1,4- Tetramethylxylylene diisocyanate or a mixture thereof (TMXDI), ⁇ , ⁇ ′-diisocyanate-1,4-diethylbenzene, and the like.
  • XDI xylylene diisocyanate (1,3- or 1,4-xylylene diisocyanate or a mixture thereof)
  • TXDI tetramethylxylylene diisocyanate
  • ⁇ , ⁇ ′-diisocyanate-1,4-diethylbenzene and the like.
  • alicyclic diisocyanate examples include 1,3-cyclopentene diisocyanate, cyclohexane diisocyanate (1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate), 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate (iso Holo isocyanate, IPDI), methylene bis (cyclohexyl isocyanate) (4,4′-, 2,4′- or 2,2′-methylene bis (cyclohexyl isocyanate)) (hydrogenated MDI), methylcyclohexane diisocyanate (methyl-2, 4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate), bis (isocyanate methyl) cyclohexane (1,3- or 1,4-bis (isocyanate) Tomechiru) cyclohexane or mixtures
  • aliphatic diisocyanate examples include trimethylene diisocyanate, 1,2-propylene diisocyanate, butylene diisocyanate (tetramethylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate), Examples include hexamethylene diisocyanate, pentamethylene diisocyanate, 2,4,4- or 2,2,4-trimethylhexamethylene diisocyanate, and 2,6-diisocyanate methyl caffeate.
  • alkylene glycol can be suitably used from the viewpoint of gas barrier properties.
  • alkylene glycol include carbon numbers such as ethylene glycol, propylene glycol, trimethylene glycol, 1,3-butanediol, 1,4-butanediol, pentanediol, hexanediol, neopentylglycol, heptanediol, and octanediol.
  • a low molecular weight glycol such as an alkylene glycol having a linear or branched chain of 2 to 10 and a (poly) oxyalkylene glycol having 2 to 4 carbon atoms can be used. These diol components can be used alone or in combination of two or more.
  • aromatic diols such as bisphenol A, bisbidoxetyl terephthalate, catechol, resorcin, hydroquinone, 1,3- or 1,4-xylylenediol, hydrogenated biswaenol A, hydrogenated xylylenediol
  • a low molecular weight diol component such as cycloaliphatic diol such as cyclohexanediol or cyclohexane may be used in combination.
  • a tri- or higher functional polyol component for example, a polyol component such as glycerin, trimethylolethane, or trimethylolpropane can be used in combination.
  • the polyol component preferably contains a polyol component having 2 to 8 carbon atoms.
  • the protective layer may contain inorganic particles for the purpose of improving adhesion and slipperiness, as long as the gist of the present invention is not impaired.
  • specific examples include silica, alumina, kaolin, calcium carbonate, oxidation Examples include titanium and barium salts.
  • an antifoaming agent a coating property improver, a thickener, an organic lubricant, organic polymer particles, an antioxidant, a UV absorber foaming agent, a dye, and the like may be contained as necessary.
  • only one type of organic solvent may be used for the purpose of improving dispersibility, improving film forming property, etc., and two or more types may be used as appropriate.
  • the coating amount of the protective layer (after drying) is usually in the range of 0.005 to 1 g / m 2 , preferably 0.005 to 0.5 g / m 2 .
  • the coating amount (after drying) is less than 0.005 g / m 2 , the uniformity of the coating thickness may be insufficient, and the protective function as a protective layer may be insufficient.
  • problems such as a decrease in slipperiness may occur.
  • the protective layer composed of the above composition has good durability and excellent adhesion to the adhesive layer. Depending on the product configuration, it may be possible to directly bond with the quantum dot-containing resin sheet without an adhesive layer.
  • the total light transmittance is preferably 86% or more, more preferably 89% or more.
  • the total light transmittance is less than 86%, when used as a sealing film for a quantum dot-containing resin sheet, electronic paper, organic EL, etc., the transparency of the device is lowered and the visibility may be inferior.
  • the water vapor permeability of the sealing film of the present invention is 0.01 g / m 2 / day or less.
  • 0.005 g / m 2 / day or less is preferable.
  • 0.005 g / m 2 / day or less is desired, and when the range is exceeded, moisture gradually enters the device during long-term use of the device, and the device deteriorates. It tends to happen easily.
  • the resin sheet layer containing quantum dots may contain a plurality of quantum dots and resins.
  • a quantum dot means a semiconductor particle of a predetermined size having a quantum confinement effect. It is preferable to use a quantum dot having a diameter generally in the range of 1 to 10 nm.
  • the quantum dot When the quantum dot absorbs light from the excitation source and reaches an energy excited state, it emits energy corresponding to the energy band gap of the quantum dot. Therefore, by adjusting the size of the quantum dots or the composition of the substance, the energy band gap can be adjusted, and energy of various levels of wavelength bands can be obtained.
  • a red color is emitted when the quantum dot size is 55 to 65 mm
  • a green color is emitted when the quantum dot size is 40 to 50 mm
  • a blue color is emitted when the quantum dot size is 20 to 35 mm.
  • the yellow color has an intermediate size between the quantum dots emitting red and the quantum dots emitting green. It can be seen that the size of the quantum dot gradually changes from about 65 mm to about 20 mm by changing the spectrum depending on the wavelength of light from red to blue, and there may be a slight difference in this value.
  • the quantum dot layer may include red quantum dots and green quantum dots.
  • the red quantum dots convert part of blue light into red light having a wavelength range of 620 to 750 nm
  • the green quantum dots convert part of blue light into green light having a wavelength range of 495 to 570 nm.
  • the quantum dots may be synthesized by a chemical wet method.
  • the chemical wet method is a method of growing particles by putting a precursor substance in an organic solvent.
  • Examples of the quantum dots include II-VI group compounds such as CdSe, CdTe, CdS, ZnSe, ZnTe, ZnS, HgTe, and HgS.
  • the quantum dots may have a core / shell structure.
  • the core includes any one material selected from the group consisting of CdSe, CdTe, CdS, ZnSe, ZnTe, ZnS, HgTe, and HgS
  • the shell also includes CdSe, CdTe, CdS, ZnSe, Any one substance selected from the group consisting of ZnTe, ZnS, HgTe, and HgS is included.
  • a III-V group compound such as InP may be used.
  • the organic ligand substituted on the surface of the quantum dot includes pyridine, mercaptoalcohol, thiol, phosphine, phosphine oxide, and the like, and plays a role of stabilizing the unstable quantum dot after synthesis.
  • Examples of commercially available quantum dots include various quantum dots manufactured by SIGMA-ALDRICH.
  • the resin containing quantum dots it is preferable to use a substance that does not absorb the wavelength of light emitted mainly from the light source. Specifically, epoxy, silicone, acrylic polymer, glass, carbonate polymer, or a mixture thereof may be used. When the resin has elasticity, it can also contribute to improving the durability of the liquid crystal display device against external impact.
  • the method of forming the quantum dot layer is as follows.
  • Quantum dot-containing resin sheets may be formed by adding a plurality of quantum dots to the resin and applying the resin to the top of the color filter layer using a spin coating method or a printing method.
  • the quantum dot resin sheet may be formed by molding and curing a resin to which quantum dots are added.
  • a quantum dot layer may be formed by injecting an organic solution, dispersing a plurality of quantum dots therein, and curing the organic solution.
  • the organic solution may include at least one of toluene, chloroform, and ethanol.
  • the organic solution does not absorb blue wavelengths. In this case, since the reaction between the quantum dot ligand and the organic solution does not occur, there is an advantage that the lifetime and efficiency of the quantum dot layer are increased.
  • Quantum dot-containing resin sheet has a laminate structure in which a sealing film is bonded through an adhesive layer.
  • the adhesive layer means a layer composed of an adhesive material, and conventionally known materials such as an acrylic adhesive and a silicone adhesive can be used. In pasting, a conventionally known pasting method can be adopted.
  • the measuring method used in the present invention is as follows.
  • Tg Glass transition temperature
  • a sample film piece was cut into a size of 1 mm ⁇ 10 mm and embedded in an epoxy resin for an electron microscope. This was fixed to a sample holder of an ultramicrotome, and a cross-sectional thin section parallel to the short side of the embedded sample piece was produced. Next, in a portion where the thin film of this section is not significantly damaged, a transmission electron microscope (manufactured by JEOL, JEM-2010) is used to photograph at an acceleration voltage of 200 kV and a bright field at an observation magnification of 10,000 times. The film thickness was determined from the photograph taken.
  • Refractive index measurement of protective layer and polyester film According to JIS K 7142-1996 5.1 (Method A), the refractive index was measured with an Abbe refractometer using sodium D line as a light source.
  • Refractive index measurement of coating layer and barrier layer For the coating layer or barrier layer formed on a silicon wafer or quartz glass with a coater, using a high-speed spectrometer M-2000 (manufactured by JA Woollam), the polarization state change of the reflected light of the coating layer or barrier layer Were measured at an incident angle of 60 degrees, 65 degrees, and 70 degrees, and the refractive index at a wavelength of 550 nm was calculated by analysis software WVASE32.
  • Water vapor transmission rate JISK7129 using a water vapor transmission rate measuring device (model name, “Permatran” (registered trademark) W3 / 31) manufactured by MOCON, USA, under the conditions of a temperature of 40 ° C. and a humidity of 90% RH. It was measured based on the B method (infrared sensor method) described in (2000 version). Two test pieces were cut out from one sample, each test piece was measured once, and the average value of the two measured values was taken as the value of the water vapor transmission rate of the sample.
  • polyester used in the examples and comparative examples was prepared as follows. ⁇ Manufacture of polyester>
  • polyester A1 100 parts of dimethyl terephthalate, 60 parts of ethylene glycol and 0.09 part of magnesium acetate tetrahydrate are placed in a reactor, the temperature is raised by heating, methanol is distilled off, transesterification is performed, and 4 hours are required from the start of the reaction. The temperature was raised to 230 ° C. to substantially complete the transesterification reaction. Next, after adding 0.04 part of ethylene glycol slurry ethyl acid phosphate and 0.03 part of antimony trioxide, the temperature reached 280 ° C. and the pressure reached 15 mmHg in 100 minutes. It was 0.3 mmHg. After 4 hours, the system was returned to normal pressure to obtain polyester A1 having an intrinsic viscosity of 0.61 (dl / g).
  • polyester A2 In the method for producing polyester (A1), polyester (A1) was used except that after adding ethyl acid phosphate, silica particles having an average particle diameter of 2.3 ⁇ m were added so that the content with respect to polyester was 0.2% by weight. ) was used to obtain polyester A2 having an intrinsic viscosity of 0.62 (dl / g).
  • Example 1 Manufacture of sealing film F1
  • the raw materials blended at a ratio of 85% and 15% respectively for polyesters A1 and A2 were used as surface layer materials, and 100% of the raw materials were used as intermediate layer materials and supplied to two extruders with vents at 290 ° C.
  • an amorphous film having a thickness of about 1500 ⁇ m was obtained by cooling and solidifying on a cooling roll having a surface temperature set to 40 ° C. using an electrostatic application adhesion method. This film was stretched 3.5 times in the machine direction at 85 ° C.
  • a polyester polyol comprising 664 parts by weight of terephthalic acid, 631 parts by weight of isophthalic acid, 472 parts by weight of 1,4-butanediol, and 447 parts by weight of neopentyl glycol was obtained.
  • 321 parts by weight of adipic acid and 268 parts by weight of dimethylolpropionic acid were added to the obtained polyester polyol to obtain a pendant carboxyl group-containing polyester polyol A.
  • 160 parts by weight of hexamethylene diisocyanate was added to 1880 parts by weight of the polyester polyol A to obtain an aqueous polyurethane resin aqueous coating material.
  • Block polyisocyanate obtained by adding 58.9 parts by weight of n-butanol, maintaining the reaction solution temperature at 80 ° C. for 2 hours, and then adding 0.86 parts by weight of 2-ethylhexyl acid phosphate.
  • the coating solution was diluted with ion exchange water to prepare a coating solution having a solid content concentration of 2% by weight.
  • barrier layer 1 An active energy ray curable resin composed of the following active energy ray curable resin composition is applied to the coating layer surface of the obtained coated film with a # 16 wire bar, dried at 80 ° C. for 1 minute to remove the solvent, and then irradiated with ultraviolet rays.
  • the barrier layer 1 having a thickness (after drying) of 5 ⁇ m was provided by irradiating ultraviolet rays from the machine with a metal halide lamp 120 w / cm so that the integrated light amount was 180 mJ / cm 2 .
  • ⁇ Active energy ray curable resin composition A mixed coating solution of 72 parts by weight of dipentaerythritol acrylate, 18 parts by weight of 2-hydroxy-3-phenoxypropyl acrylate, 1 part by weight of a photopolymerization initiator (Irgacure 651, manufactured by Ciba Specialty Chemicals), and 200 parts by weight of methyl ethyl ketone.
  • a photopolymerization initiator Irgacure 651, manufactured by Ciba Specialty Chemicals
  • the center roll temperature was set to 0 ° C., and the oxygen flow rate was controlled using a Speedflow manufactured by Gencoa so that the discharge voltage during sputtering was constant. At this time, the discharge voltage is set to 50% when the discharge voltage when only Ar gas is supplied is 100%, and when the discharge voltage is 50% when Ar gas and O 2 gas are supplied at 50 sccm. did. As described above, the barrier layer 2 having a thickness of 40 nm and a refractive index of 1.52 was deposited.
  • the protective layer 1 composed of the above coating composition is applied on the barrier layer 2 by a reverse gravure coating method so that the coating amount (after drying) is 0.1 g / m 2, and heat treatment is performed at 120 ° C. for 30 seconds. After that, a sealing film was obtained.
  • the obtained sealing film was bonded to both surfaces of the quantum dot-containing resin sheet by the following procedure to obtain a laminate.
  • ⁇ Quantum dot resin sheet formation> Using a slit die coater, a sheet-forming resin solution is applied on a polyester film (Diafoil T100 type manufactured by Mitsubishi Plastics Co., Ltd .: 100 ⁇ m), heated at 130 ° C. for 5 minutes, and dried to obtain a film thickness (after drying). A quantum dot resin sheet having a thickness of 50 ⁇ m was obtained. The obtained quantum dot resin sheet was uniformly applied on the base film, pinholes were not seen, and the film thickness uniformity was good.
  • a polyester film Diafoil T100 type manufactured by Mitsubishi Plastics Co., Ltd .: 100 ⁇ m
  • a quantum dot resin sheet having a thickness of 50 ⁇ m was obtained.
  • the obtained quantum dot resin sheet was uniformly applied on the base film, pinholes were not seen, and the film thickness uniformity was good.
  • Example 2 to Example 12 In Example 1, it manufactured like Example 1 except having changed application layer composition and polyester film base material thickness as shown in the following Table 1 and Table 2, and obtained the sealing film. Then, the sealing film and the quantum dot containing resin sheet were bonded together through the adhesion layer, and the laminated body was obtained.
  • Example 1 it manufactured similarly to Example 1 except having changed the structure of the barrier layer into the following barrier layer 2, and obtained the sealing film. Then, the sealing film and the quantum dot containing resin sheet were bonded together through the adhesion layer, and the laminated body was obtained.
  • ⁇ Formation of barrier layer 3> A gas barrier layer made of aluminum oxide was formed. At this time, it was carried out after confirming that the water pressure in the vacuum chamber before sputtering was 1 ⁇ 10 ⁇ 4 Pa. As sputtering conditions, Al (manufactured by Technofine) was used as a target, and DC power of 3 W / cm 2 was applied.
  • Examples 16-18 A sealing film was obtained in the same manner as in Example 1 except that the protective layer composition was changed to protective layer 2 in Example 1 and the adhesive layer was changed to an acrylic adhesive layer. Then, the sealing film and the quantum dot containing resin sheet were bonded together through the adhesion layer, and the laminated body was obtained.
  • ⁇ Protection layer 2 formation> Main agent: WPB-341 (Mitsui Chemicals) Curing agent: WD-725 (Mitsui Chemicals)
  • (Acrylic adhesive layer composition) A solution of an acrylic copolymer having a weight average molecular weight of 600,000 (polystyrene equivalent) by copolymerizing butyl acrylate (100 parts by weight, acrylic acid 6 parts by weight) in ethyl acetate by a conventional method (solid content 30% by weight) ) To 100 parts by weight (solid content) of the acrylic copolymer, 6 parts by weight of tetrad C (manufactured by Mitsubishi Gas Chemical) as an epoxy crosslinking agent was added to obtain an acrylic adhesive layer composition.
  • tetrad C manufactured by Mitsubishi Gas Chemical
  • Example 19 A sealing film was obtained in the same manner as in Example 1 except that the substrate thickness was changed to 50 ⁇ m in Example 1. Then, the sealing film and the quantum dot containing resin sheet were bonded together through the adhesion layer, and the laminated body was obtained.
  • Example 20 In Example 1, it manufactured similarly to Example 1 except having changed the barrier layer structure into 1 layer structure only of the barrier layer 1, and obtained the sealing film. Then, the sealing film and the quantum dot containing resin sheet were bonded together through the adhesion layer, and the laminated body was obtained.
  • Example 21 In Example 1, it manufactured like Example 1 except changing a barrier layer composition into one layer composition only of barrier layer 2, and obtained a sealing film. Then, the sealing film and the quantum dot containing resin sheet were bonded together through the adhesion layer, and the laminated body was obtained.
  • Example 22 A sealing film was obtained in the same manner as in Example 1 except that the raw material composition of the polyester film was changed in Example 1. Then, the sealing film and the quantum dot containing resin sheet were bonded together through the adhesion layer, and the laminated body was obtained.
  • Example 23 In Example 1, it manufactured similarly to Example 1 except not providing an application layer in the surface opposite to the surface which provides a barrier layer, and obtained the sealing film. Then, the sealing film and the quantum dot containing resin sheet were bonded together through the adhesion layer, and the laminated body was obtained.
  • Example 24 In Example 1, except that the type of the adhesive layer is changed to the acrylic adhesive layer described in Example 16, it is heated and dried at 100 ° C. for 5 minutes in the same manner as in Example 1 to obtain an acrylic adhesive layer having a thickness of 25 ⁇ m. Then, the sealing film and the quantum dot containing resin sheet were bonded together, and the laminated body was obtained.
  • Example 1 it manufactured similarly to Example 1 except having changed the structure of the application layer into the application layer 5, and obtained the sealing film. Then, the sealing film and the quantum dot containing resin sheet were bonded together through the adhesion layer, and the laminated body was obtained.
  • Example 2 it manufactured similarly to Example 1 except having changed the structure of the application layer into the application layer 10, and obtained the sealing film. Then, the sealing film and the quantum dot containing resin sheet were bonded together through the adhesion layer, and the laminated body was obtained.
  • Example 1 it manufactured similarly to Example 1 except having changed the structure of the application layer into the application layer 15, and obtained the sealing film. Then, the sealing film and the quantum dot containing resin sheet were bonded together through the adhesion layer, and the laminated body was obtained.
  • Example 1 it manufactured similarly to Example 1 except not providing an application layer, and obtained the sealing film. Then, the sealing film and the quantum dot containing resin sheet were bonded together through the adhesion layer, and the laminated body was obtained.
  • Example 1 it manufactured similarly to Example 1 except not providing a barrier layer, and obtained the sealing film. Then, the sealing film and the quantum dot containing resin sheet were bonded together through the adhesion layer, and the laminated body was obtained.
  • Example 1 it manufactured similarly to Example 1 except not providing a protective layer, and obtained the sealing film. Then, the sealing film and the quantum dot containing resin sheet were bonded together through the adhesion layer, and the laminated body was obtained.
  • Tables 1 to 5 show the properties of the sealing films obtained in the above examples and comparative examples.
  • the sealing film for electronic members of the present invention is particularly excellent in transparency, water vapor barrier properties and adhesiveness with an adhesive layer, and is an electron such as a quantum dot-containing resin sheet, electronic paper, and organic EL, which requires high water vapor barrier properties. It is suitable as a sealing film for members, and its industrial value is high.

Landscapes

  • Laminated Bodies (AREA)

Abstract

L'invention concerne un film d'étanchéité pour éléments électroniques, tels qu'une feuille de résine contenant des points quantiques, un papier électronique et un dispositif électroluminescent organique, ledit film présentant de bonnes caractéristiques en termes de transparence, de propriétés de barrière et d'adhérence à une couche adhésive. Le film d'étanchéité pour éléments électroniques, selon l'invention, possède une couche de revêtement, une couche barrière et une couche de protection stratifiées en séquence sur une surface d'un film de polyester, la couche de revêtement contenant au moins une résine de liant sélectionnée parmi les résines polyester, les résines uréthane et les résines (méth)acryliques. Ce film d'étanchéité pour éléments électroniques présente un taux de transmission de la vapeur d'eau de 0,01 g/m2/jour ou moins, mesuré à une température de 40 °C et à une humidité de 90 % d'humidité relative selon la norme JIS-K7129B.
PCT/JP2015/082144 2014-12-20 2015-11-16 Film d'étanchéité pour éléments électroniques WO2016098504A1 (fr)

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CN201580068125.0A CN107107575B (zh) 2014-12-20 2015-11-16 电子部件用密封膜
KR1020197020521A KR102138756B1 (ko) 2014-12-20 2015-11-16 전자 부재용 밀봉 필름
KR1020177014545A KR20170085058A (ko) 2014-12-20 2015-11-16 전자 부재용 밀봉 필름

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JP2014-258133 2014-12-20
JP2014258134A JP6634675B2 (ja) 2014-12-20 2014-12-20 電子部材用封止フィルム
JP2014-258134 2014-12-20
JP2014258133 2014-12-20
JP2015-003727 2015-01-10
JP2015003727A JP2016128245A (ja) 2015-01-10 2015-01-10 電子部材用封止フィルム

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JP2016128246A (ja) * 2015-01-10 2016-07-14 三菱樹脂株式会社 電子部材用封止フィルム
CN106374028A (zh) * 2016-08-31 2017-02-01 张家港康得新光电材料有限公司 量子点膜及其制备方法
KR20180132667A (ko) * 2016-03-31 2018-12-12 도판 인사츠 가부시키가이샤 배리어 필름 및 그 제조 방법, 파장 변환 시트 및 그 제조 방법, 그리고, 광학 적층체 및 그 제조 방법
US20200006603A1 (en) * 2014-12-26 2020-01-02 Ns Materials Inc. Wavelength converting member and method of producing the same

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WO2016098504A1 (fr) * 2014-12-20 2016-06-23 三菱樹脂株式会社 Film d'étanchéité pour éléments électroniques
TWI798343B (zh) 2018-03-12 2023-04-11 美商陶氏有機矽公司 可固化聚矽氧組成物及其經固化產物
JP7179581B2 (ja) * 2018-10-26 2022-11-29 住友化学株式会社 組成物、フィルム、積層構造体、発光装置及びディスプレイ
CN110499118A (zh) * 2019-07-30 2019-11-26 云谷（固安）科技有限公司 屏幕保护膜及其制造方法、电子设备
CN112768614A (zh) * 2020-12-28 2021-05-07 华灿光电（浙江）有限公司 量子点发光二极管及其制备方法

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KR20180132667A (ko) * 2016-03-31 2018-12-12 도판 인사츠 가부시키가이샤 배리어 필름 및 그 제조 방법, 파장 변환 시트 및 그 제조 방법, 그리고, 광학 적층체 및 그 제조 방법
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CN106374028A (zh) * 2016-08-31 2017-02-01 张家港康得新光电材料有限公司 量子点膜及其制备方法

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KR20170085058A (ko) 2017-07-21
CN107107575B (zh) 2020-07-28

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