JP2016155262A - Sealing film for electronic member - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a sealing film excellent in transparency, productivity, barrier properties, and adhesiveness to an adhesive layer, as a sealing film for an electronic member such as a quantum dot-containing resin sheet, electronic paper, and an organic EL.SOLUTION: A sealing film for an electronic member has such a structure that a barrier layer and a protective layer are sequentially laminated on a coating layer of a coating film, where the coating film has the coating layer which is formed of at least one or more resins selected from a polyester resin, an urethane resin and an acrylic resin, and a melamine resin, on one surface of a polyester film, and has a film haze of 2.0% or less and an air leakage index of 220,000 seconds or less.SELECTED DRAWING: Figure 1

Description

  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. is there.

  In optical applications, polyester films are widely used mainly for various display applications because of their excellent optical properties.

  On the other hand, as a result of the rapid spread of display displays such as electronic paper and organic EL in recent years, an alternative study to a transparent plastic film has been earnestly promoted as a glass substrate alternative from the viewpoint of weight reduction and flexibility.

  However, when the glass substrate is replaced with a transparent plastic film, the device deteriorates because moisture passes through the transparent plastic film. Therefore, a transparent plastic film having a gas barrier layer is required. However, gas barrier films used for conventional food packaging applications have insufficient moisture barrier properties and it is difficult to suppress deterioration of electronic devices. .

For use in display displays such as electronic paper and organic EL, 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 (see Patent Document 1).

  However, the gas barrier film described in Patent Document 1 has an effect of improving the gas barrier property, but does not consider the adhesion with the adhesive layer. In addition, 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.

Further, a gas barrier film having a water vapor barrier property of 10 ⁻⁶ g / m ² / day level by laminating a flattening 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).

  However, while the gas barrier film described in Example 1 of Patent Document 2 has good gas barrier properties, 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.

  Further, 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 is a tendency to be inferior in transparency.

Moreover, to improve the transparency of the sealing film, it can also be achieved by reducing the lubricant particles contained in the film. However, if the lubricant particles are reduced too much, the air trapped during film winding is difficult to escape, and during sputtering. There was a problem that it took a long time to evacuate, and the productivity was impaired.

  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.

  In Patent Document 5, measures for improving the gas barrier layer by alternately laminating organic layers / inorganic layers are taken, but the gas barrier properties are improved, but the interlayer adhesion at the organic layer / inorganic layer interface is insufficient. is there.

  For various electronic members, a sealing film excellent in transparency, productivity, barrier property and adhesiveness to the adhesive layer is required, but a useful one has not yet been found.

JP 2009-190186 A JP 2007-83644 A JP 2003-231789 A JP 2003-326634 A Japanese Patent No. 4254350

  This invention is made | formed in view of the said situation, The solution subject is transparency, productivity, barrier property, and adhesion as a sealing film for electronic members, such as a quantum dot containing resin sheet, electronic paper, and organic EL. It is providing the sealing film with favorable adhesiveness with respect to a layer.

  As a result of intensive studies in view of the above circumstances, the present inventors have found that the above problem can be easily solved by a sealing film having a specific configuration, and have completed the present invention.

  That is, the gist of the present invention is to have a coating layer formed from at least one resin selected from polyester resin, urethane resin, and acrylic resin and melamine resin on one surface of the polyester film. And a structure in which a barrier layer and a protective layer are sequentially laminated on a coating layer of a coating film having a film haze of 2.0% or less and an air leakage index of 220,000 seconds or less. It exists in the sealing film.

  The sealing film for electronic members of the present invention is excellent in transparency, processing characteristics, barrier properties, and adhesiveness with an adhesive layer, and includes quantum dot-containing resin sheets, electronic paper, organic EL, and the like that require high barrier properties. It is suitable as a sealing film for electronic members, and its industrial value is high.

Typical sectional drawing of the sealing film for electronic members of this invention

  In the present invention, the polyester film may have a single layer structure or a laminated structure. For example, in addition to the two-layer or three-layer structure, the polyester film may have four or more layers as long as the gist of the present invention is not exceeded. There may be, and it is not specifically limited.

  The polyester used for the polyester film in the present invention may be a homopolyester or a copolyester. In the case of a homopolyester, those obtained by polycondensation of an aromatic dicarboxylic acid and an aliphatic glycol are preferred. Examples of the aromatic dicarboxylic acid include terephthalic acid and 2,6-naphthalenedicarboxylic acid, and examples of the aliphatic glycol include ethylene glycol, diethylene glycol, and 1,4-cyclohexanedimethanol. Representative polyester includes polyethylene terephthalate (PET) and the like. On the other hand, 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). 1 type or 2 types or more are mentioned, As a glycol component, 1 type or 2 types or more, such as ethylene glycol, diethylene glycol, propylene glycol, butanediol, 1, 4- cyclohexane dimethanol, neopentyl glycol, is mentioned. In any case, 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.

  In the present invention, it is preferable to blend particles in the polyester layer mainly for the purpose of imparting 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. Examples of the particles include magnesium, kaolin, aluminum oxide, and titanium oxide. Further, 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. Furthermore, 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.

  On the other hand, the shape of the particles to be used 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 | limiting in particular also about the hardness, specific gravity, a color, etc. These series of particles may be used in combination of two or more as required.

  Moreover, the average particle diameter of the particle | grains to be used is 0.01-4 micrometers normally, Preferably it is the range of 1.0-3.5 micrometers. When the average particle size is less than 1.0 μm, the processing characteristics may be insufficient. On the other hand, when it exceeds 3.5 μm, the transparency of the film may be insufficient.

  Furthermore, the particle content in the polyester layer is usually in the range of 0.001 to 5% by weight, preferably 0.015 to 0.080% by weight. When the particle content is less than 0.015% by weight, the slipperiness of the film may be insufficient. On the other hand, when the content exceeds 0.080% by weight, the transparency of the film is insufficient. There are cases.

  The method for adding particles to the polyester layer is not particularly limited, and a conventionally known method can be adopted. For example, it can be added at any stage for producing the polyester constituting each layer, but the polycondensation reaction may proceed preferably after the esterification stage or after the transesterification reaction.

  Also, 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. It is done by methods.

  In addition to the above-described particles, conventionally known fluorescent brighteners, antioxidants, antistatic agents, thermal stabilizers, lubricants, dyes, pigments, and the like are added to the polyester film in the present invention as necessary. be able to.

  The thickness of the polyester film constituting the sealing film of the present invention is not particularly limited as long as it can be formed as a film. In consideration of the mechanical strength, flexibility, transparency and the like of the film substrate, 12 to 125 μm is preferable, and 25 to 100 μm is more preferable.

  The air leakage index of the polyester film having the coating layer constituting the sealing film of the present invention is 220,000 seconds or less, preferably 120,000 seconds or less. When the air leakage index is larger than 220,000 seconds, the processing characteristics are impaired, for example, it takes time for evacuation during sputtering when processing into a sealing film such as a quantum dot-containing resin sheet, electronic paper, or organic EL.

  The film haze of the polyester film having the coating layer constituting the sealing film of the present invention is 2.0% or less, preferably 1.5% or less. When the haze exceeds 2.0%, 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 is poor.

  Next, although the manufacture example of the polyester film in this invention is demonstrated concretely, it is not limited to the following manufacture examples at all.

  First, a method of using the polyester raw material described above and cooling and solidifying a molten sheet extruded from a die with a cooling roll to obtain an unstretched sheet is preferable. In this case, in order to improve the flatness of the sheet, it is necessary to improve the adhesion between the sheet and the rotary cooling drum, and an electrostatic application adhesion method and / or a liquid application adhesion method are preferably employed. Next, 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. Subsequently, the extending | stretching temperature orthogonal to the extending | stretching direction of the 1st step is 70-170 degreeC normally, and a draw ratio is 3.0-3 times normally, Preferably it is 3.5-6 times. Subsequently, 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. In the above-described stretching, 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 also be adopted for the production of the polyester film in the present invention. The simultaneous biaxial stretching method is a method in which the unstretched sheet is usually stretched and oriented in the machine direction and the width direction at 70 to 120 ° C., preferably 80 to 110 ° C., and the stretching ratio is as follows: The area magnification is 4 to 50 times, preferably 7 to 35 times, and more preferably 10 to 25 times. Subsequently, 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. With respect to the simultaneous biaxial stretching apparatus that employs the above-described stretching method, a conventionally known stretching method such as a screw method, a pantograph method, or a linear driving method can be employed.

  Furthermore, a so-called coating stretching method (in-line coating) in which the film surface is treated during the above-described polyester film stretching step can be applied. When a coating layer is provided on a polyester film by a coating stretching method, 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.

  In the polyester film constituting the sealing film in the present invention, in order to improve the adhesion with the barrier layer, at least one resin selected from polyester resin, urethane resin, and acrylic resin, and melamine resin It is an essential requirement that a coating layer be formed from the above.

  In the present invention, the polyester resin constituting the coating layer is defined as a linear polyester having a dicarboxylic acid component and a glycol component as constituent components. Examples of the dicarboxylic acid component 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. Further, together with these components, 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- (β-hydroxyethoxy) benzoic acid. Can be used. The proportion of the unsaturated polybasic acid component or the hydroxycarboxylic acid component is at most 10 mol%, preferably 5 mol% or less.

  As glycol components, ethylene glycol, 1,4-butanediol, neopentyl glycol, diethylene glycol, dipropylene glycol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, xylylene glycol, dimethylolpropionic acid Glycerin, trimethylolpropane, poly (ethyleneoxy) glycol, poly (tetramethyleneoxy) glycol, an alkylene oxide adduct of bisphenol A, an alkylene oxide adduct of hydrogenated bisphenol A, and the like. Two or more of these can be used.

  Among these polyol components, ethylene glycol, bisphenol A ethylene oxide adduct, propylene oxide adduct, and 1,4-butanediol are preferable, and ethylene glycol and bisphenol A ethylene oxide adduct and propylene oxide adduct are more preferable.

  Moreover, in the coating layer which comprises the sealing film in this invention, in order to make water dispersion | distribution or water-solubilization easy, it may contain at least 1 or more types of polyester resins which have a sulfonic acid (salt) group. preferable.

  Examples of the polyester resin having a sulfonic acid (salt) group 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 such as 5-potassium sulfoisophthalic acid, 4-potassium sulfoisophthalic acid, 2-potassium sulfoisophthalic acid, and sodium sulfosuccinic acid, and sulfonic acid amine salt compounds.

  In the polyester resin constituting the coating layer in the present invention, the glass transition temperature (hereinafter sometimes abbreviated as Tg) is preferably 40 ° C. or higher, more preferably 60 ° C. or higher. When 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 acrylic resin used in the present invention is a polymer comprising 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 (possibly 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. Similarly, 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. Similarly, a polymer obtained by polymerizing a polymerizable monomer having a carbon-carbon double bond in another polymer solution or dispersion (in some cases, a polymer mixture) 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 salts thereof; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, monobutylhydroxyfumarate, 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) ac Ruamido, various nitrogen-containing vinyl monomers such as diacetone acrylamide, N- methylol acrylamide or (meth) acrylonitrile. Further, in combination with these, polymerizable monomers as shown below can be copolymerized. Namely, various styrene derivatives such as styrene, α-methylstyrene, divinylbenzene and vinyltoluene, various vinyl esters such as vinyl acetate and vinyl propionate; γ-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.

  In the acrylic resin constituting the coating layer in the present invention, the glass transition temperature is preferably 40 ° C. or higher, more preferably 60 ° C. or higher. When 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.

  In order to improve the adhesion to the barrier layer in the present invention, a urethane resin may be included. Among these, a urethane resin having a polycarbonate structure is preferable.

  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. 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-dimethylol heptane 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.

Examples of the polyisocyanates constituting the urethane resin having a polycarbonate structure in the present invention include aromatic diisocyanates such as tolylene diisocyanate, xylylene diisocyanate, methylene diphenyl diisocyanate, phenylene diisocyanate, naphthalene diisocyanate, and tolidine diisocyanate, α, α, Aliphatic diisocyanates having aromatic rings such as α ', α'-tetramethylxylylene diisocyanate, methylene diisocyanate, propylene diisocyanate, lysine diisocyanate, trimethylhexamethylene diisocyanate, hexamethylene diisocyanate and other aliphatic diisocyanates, cyclohexane diisocyanate, methylcyclohexane diisocyanate , Isophorone diisocyanate And alicyclic diisocyanates such as methylenebis (4-cyclohexylisocyanate), dicyclohexylmethane diisocyanate and isopropylidenedicyclohexyl diisocyanate. These may be used alone or in combination. Among the above isocyanates, 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.

  Examples of the chain extender having two hydroxyl groups include 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. Examples of the chain extender having two amino groups include aromatic diamines such as tolylenediamine, xylylenediamine, and 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, isoprobilitincyclohexyl-4,4′-diamine, 1,4-diaminocyclohexane, 1 , 3-Bisaminomethylcyclohexa And alicyclic diamines such as isophorone diamine.

  The urethane resin used in the present invention may use a solvent as a medium, but preferably uses water as a medium. In order to disperse or dissolve the urethane resin in water, 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. In particular, 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, sulfonic acid, phosphoric acid, phosphonic acid, and quaternary ammonium salt, and a carboxyl group is preferred. As 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. In particular, 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.

  For example, 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. Can do. 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 in the present invention has a glass transition point of preferably 0 ° C. or lower, more preferably −15 ° C. or lower, and further preferably −30 ° C. or lower. When Tg is higher than 0 ° C., easy adhesion may be insufficient. Tg said here refers to the temperature which created the dry film | membrane of the urethane resin and was measured using the differential scanning calorimeter (DSC).

  The melamine resin used in the present invention is not particularly limited. However, melamine, a methylolated melamine derivative obtained by condensing melamine and formaldehyde, or a partially or completely ether obtained by reacting a methylolated melamine with a lower alcohol. And the like, and mixtures thereof 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. As 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, for the purpose of promoting thermal curing of the melamine resin, for example, an acidic catalyst such as p-toluenesulfonic acid can be used in combination.

  The ratio of the acrylic resin in the coating layer which comprises the sealing film in this invention is 10-80 weight% normally, and the ratio of a urethane resin and / or a polyester resin is 10-80 weight% normally. The proportion of the melamine resin is usually 6 to 80% by weight, preferably 10 to 60% by weight.

From coating amount (after drying) a surface of the coating property of the coating layer, usually, 0.005~1g / ^{m 2,} preferably from 0.005 to 0.5 / ^{m 2,} more preferably 0.01 to 0 .2 g / m ² range. When 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. On the other hand, when the coating is thicker than 1 g / m ² , the coating film adhesion and curability of the coating layer itself may be lowered.

  In the present invention, as a method for providing the coating layer on the polyester film, a conventionally known coating method such as reverse gravure coating, direct gravure coating, roll coating, die coating, bar coating, curtain coating, or the like can be used. As for the coating method, there is a description example in “Coating method” published by Yoji Harasaki in 1979.

  Regarding the polyester film in the present invention, a coating layer such as an antistatic layer or an oligomer precipitation preventing layer may be provided on the film surface on which the coating layer is not provided, as long as the gist of the present invention is not impaired.

  The polyester film may be subjected to surface treatment such as corona treatment or plasma treatment in advance.

The barrier layer which comprises the sealing film in this invention is laminated | stacked for the purpose of providing barrier property to a polyester film. As a material of the barrier layer, the barrier property is a desired level. In the present invention, the water vapor permeability measured according to JIS-K7129 B method is 0.01 g / min under the 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 set to m 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. 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, and metals such as aluminum, magnesium, zinc, and tin It is done. These can be used individually by 1 type or in combination of 2 or more types.

  The thickness of the barrier layer is preferably 1 nm to 10 μm, more preferably 10 to 1000 nm, still 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 μm, it is in a saturated state in terms of performance, and it is difficult to expect a barrier effect any more.

  In the present invention, the barrier layer constituting the sealing film may be a single layer or a plurality of layers composed of two or more layers.

Regarding the method for forming the barrier layer, a conventionally known method can be used depending on the material constituting the barrier layer, and can be appropriately selected according to 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.

  In the sealing film in the present invention, it is an essential requirement to provide a protective layer on the barrier 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. In addition, by covering the barrier layer with a protective layer, the barrier layer is protected from being rubbed or scraped by contact with the conveying guide roll during the processing process, and from the organic solvent used in the manufacturing process, and has barrier properties. Can also be maintained.

  The protective layer in the present invention preferably contains an organic compound containing at least one metal element selected from aluminum, titanium, and zirconium in the protective layer.

  Specific examples of the organic compound having an aluminum element include aluminum tris (acetylacetonate), aluminum monoacetylacetonate bis (ethylacetoacetate), aluminum-di-n-butoxide-monoethylacetoacetate, aluminum di- Examples include iso-propoxide-monomethyl acetoacetate.

  Specific examples of the organic compound having a titanium element 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.

  Specific examples of the organic compound having a zirconium element include zirconium acetate, zirconium normal propyrate, zirconium normal butyrate, zirconium tetraacetylacetonate, zirconium monoacetylacetonate, zirconium bisacetylacetonate and the like.

  Among them, 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. It is also described in detail in the “Crosslinking agent handbook” (Yamashita Shinzo, Kaneko East Assistant Editor, Taiseisha, 1990 edition).

  The protective layer in the present invention 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.

Si (X) _d (Y) _e (R ¹ ) _f (1)
[In the above formula, X is an organic group having at least one selected from an epoxy group, a mercapto group, a (meth) acryloyl group, an alkenyl group, a haloalkyl group and an amino group, R ¹ is a monovalent hydrocarbon group, and 1 to 10 carbon atoms, Y is a hydrolyzable group, d is an integer of 1 or 2, e is an integer of 2 or 3, f is an integer of 0 or 1, and d + e + f = 4 ]

  The organosilicon compound represented by the general formula (1) has two hydrolyzable groups Y (D unit source) or three (T unit) capable of forming a siloxane bond by hydrolysis / condensation reaction. Source) can be used.

In the general formula (1), 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.

  In the general formula (1), as the hydrolyzable group Y, conventionally known ones can be used, and the following can be exemplified. Methoxy group, ethoxy group, butoxy group, isopropenoxy group, acetoxy group, butanoxime group, amino group and the like. These hydrolyzable groups may be used alone or in combination. The application 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.

  In the present invention, as the organosilicon compound contained in the protective layer, conventionally known compounds can be used, specifically, vinyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycid. Xylpropylmethyldiethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-acryloxypropyltrimethoxysilane, γ -Aminopropyltriethoxysilane, 5-hexenyltrimethoxysilane, p-styryltrimethoxysilane, trifluoropropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldiisopropenoxysilane Etc. It is possible.

In the present invention, a catalyst may be used in the protective layer for the purpose of promoting hydrolysis / condensation reaction. Specific examples include 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. Organometallic salts such as diacetate, dibutyltin dioctate, dibutyltin diolate, diphenyltin diacetate, dibutyltin oxide, dibutyltin dimethoxide, dibutylbis (triethoxysiloxy) tin, dibutyltin benzylmalate, etc., KF, NH ₄ F, etc. And fluorine element-containing compounds. The above catalysts may be used alone or in combination of two or more.
Among these, organometallic salts are particularly preferable from the viewpoint of good coating film durability, and more preferably a tin catalyst is used from the viewpoint of long-lasting catalytic activity.

  Furthermore, for the purpose of improving the adhesion and slipperiness of the protective layer, inorganic particles may be contained within a range not impairing the gist of the present invention. Specific examples include silica, alumina, kaolin, calcium carbonate, titanium oxide, Barium salt etc. are mentioned.

  Moreover, an antifoamer, a coating property improving agent, 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.

  In the range not exceeding the gist of the present invention, 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 provided in the barrier layer constituting the sealing film of the present invention (after drying) typically, 0.005~1g / ^{m 2,} the range preferably from 0.005 to 0.5 / ^{m 2} It is. When 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. On the other hand, when the coating is applied in excess of 1 g / m ² , problems such as a decrease in slipperiness may occur.

  With the protective layer composed of the above composition, the durability is excellent and the adhesiveness with the adhesive layer is also excellent.

It is an essential requirement that the water vapor permeability of the sealing film in the present invention is 0.01 g / m ² / day or less. Preferably, 0.005 g / m ² / day or less is preferable. In particular, as a sealing film for an electronic member, 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.

  Next, a quantum dot-containing resin sheet will be described as a counterpart to which the sealing film in the present invention is bonded.

  The resin sheet layer containing the quantum dots (sometimes abbreviated as a quantum dot layer) may contain a plurality of quantum dots and a resin. In the present invention, the term “quantum dot” refers to a semiconductor particle having 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.

  When the quantum dot absorbs light from the excitation source and reaches an energy excited state, the quantum dot 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 in various levels of wavelength bands can be obtained.

  For example, 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, and a blue color 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.

  Therefore, various colors including red, green, and blue can be easily obtained from the quantum dots by a quantum size effect. Therefore, it is possible to create colors that emit light at respective wavelengths, and it is also possible to generate and implement white or various colors by mixing red, green, and blue.

  For example, when the light emitted from the light source is blue light, the quantum dot layer may include red quantum dots and green quantum dots. The red quantum dot converts a part of blue light into red light having a wavelength region of 620 to 750 nm, and the green quantum dot converts a part of blue light into green light having a wavelength region of 495 to 570 nm. To do. And the blue light which is not converted into red light and green light permeate | transmits a quantum dot layer as it is. Therefore, in the quantum dot layer, blue light, red light, and green light are emitted to the upper surface, and these lights are mixed to generate white light.

  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. Here, the core includes any one material selected from the group consisting of CdSe, CdTe, CdS, ZnSe, ZnTe, ZnS, HgTe, and HgS, and the shell also includes CdSe, CdTe, CdS, ZnSe, Any one substance selected from the group consisting of ZnTe, ZnS, HgTe, and HgS is included. Furthermore, 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.

  For 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.

  On the other hand, the method of forming the quantum dot layer is as follows.

  A quantum dot-containing resin sheet may be formed by adding a plurality of quantum dots to the resin and applying the resin on the color filter layer using a spin coating method or a printing method.

  Moreover, you may form a quantum dot resin sheet | seat by shape | molding and hardening | curing resin to which the quantum dot was added.

  Furthermore, 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. Here, 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.

  The quantum dot-containing resin sheet obtained in the present invention has a laminate structure in which a sealing film is bonded through an adhesive layer.

Next, the adhesive layer in the present invention will be described below. The pressure-sensitive adhesive layer in the present invention means a layer composed of a material having adhesiveness, and a conventionally known material such as an acrylic pressure-sensitive adhesive or a silicone-based pressure-sensitive adhesive can be used as long as the gist of the present invention is not impaired. it can.
Moreover, in the pasting, a conventionally known pasting method can be adopted.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to a following example, unless the summary is exceeded. The measuring method used in the present invention is as follows.

(1) Measurement of intrinsic viscosity (dl / g) of polyester 1 g of polyester from which other polymer components and pigments incompatible with polyester have been removed are precisely weighed and mixed with phenol / tetrachloroethane = 50/50 (weight ratio). 100 ml of solvent was added and dissolved, and measurement was performed at 30 ° C.

(2) Measurement of average particle diameter (d ₅₀ : μm) Integration (weight basis) 50% in equivalent spherical distribution measured using centrifugal sedimentation type particle size distribution measuring device (SA-CP3 type manufactured by Shimadzu Corporation) Was the average particle size.

(3) Measurement of glass transition temperature (Tg) of polyester resin Using a DSC-II type measuring device manufactured by PerkinElmer, the sample was heated at a heating rate of 10 ° C./min under a nitrogen gas stream at a rate of 10 ° C./min. The segregation start temperature was defined as Tg.

(4) Measurement of air leakage index of polyester film having coating layer The polyester film was measured using a Digibeck smoothness tester DB-2 manufactured by Toyo Seiki under an atmosphere of a temperature of 23 ° C. and a humidity of 50% RH. The pressure of the pressurizer is 100 kPa, and the vacuum vessel is a small vacuum vessel with a volume of 38 ml. The time for 1 ml of air to flow, that is, the time until the pressure in the vessel changes from 50.7 kPa to 48.0 kPa (seconds) And 10 times the obtained number of seconds was taken as the air leakage index. The sample size is 70 mm square, 20 sheets are laminated so that the A2 surface is down, and a hole having a diameter of 5 mm is formed in the center of the laminated film so that air leakage is uniform.
(Productivity criteria)
A: Air leakage index of 120,000 seconds or less (good, particularly satisfactory level)
○: Air leakage index of 120001 seconds or more and 220,000 seconds or less (no problem level)
×: Air leakage index of 220001 seconds or more (practically problematic level)

(5) Haze measurement of polyester film having coating layer Haze of the film was measured with a haze meter “HM-150” manufactured by Murakami Color Research Laboratory Co., Ltd. according to JIS-K-7136.
(Criteria)
A: Haze of 1.5% or less (good, no problem)
○: Haze 1.6 or more and 2.0% or less (although there is no problem, it may be difficult to apply to high-end display devices)
X: Haze 2.1% or more (practical problem level)

(6) Film thickness of barrier layer The film sample piece which laminated | stacked the barrier layer was cut out to the magnitude | size of 1 mm x 10 mm, and was embedded in the epoxy resin for electron microscopes. 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 section where the thin film of this section is not significantly damaged, a transmission electron microscope (manufactured by JEOL, JEM-2010) is used to obtain a 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.

(7) 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.

(8) Refractive index measurement of coating layer and barrier layer For coating layer or barrier layer formed with a coater on a silicon wafer or quartz glass, using a high-speed spectrometer M-2000 (manufactured by JA Woollam), The change in polarization state of the reflected light of the coating layer or the barrier layer was measured at incident angles of 60 degrees, 65 degrees, and 70 degrees, and the refractive index at a wavelength of 550 nm was calculated by the analysis software WVASE32.

(9) Water vapor transmission rate Under the conditions of a temperature of 40 ° C. and a humidity of 90% RH, a water vapor transmission rate measurement device (model name, “Permatran” (registered trademark) W3 / 31, manufactured by MOCON, USA) ) Was measured based on the B method (infrared sensor method) described in JIS K7129 (2000 edition).
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.

<Preparation of coating liquid for forming quantum dot resin sheet>
Using a polyethylene container with a volume of 300 ml, 40% by weight of “OE-6630A / B” (manufactured by Toray Dow Corning Co., Ltd., refractive index 1.53) as a silicone resin, and “CdSe / ZnS 480” (SIGMA) as a quantum dot -Made by ALDRICH: Blue 480 nm), "CdSe / ZnS 530" (made by SIGMA-ALDRICH: Green 53)
0 nm) and “CdSe / ZnS 560” (manufactured by SIGMA-ALDRICH: Yellow 560 nm) were mixed at a ratio of 20% by weight. Then, planetary stirring and defoaming device "
Using a Mazerustar (registered trademark) “KK-400” (manufactured by Kurabo Industries), stirring and defoaming were carried out at 1000 rpm for 20 minutes to obtain a quantum dot-containing resin sheet preparation liquid.

<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, Inc .: 100 μm), heated at 130 ° C. for 5 minutes and dried, and the film thickness (after drying) is 50 μm. The quantum dot resin sheet 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.

<Formation of laminate>
“SD4580” (silicone adhesive manufactured by Toray Dow Corning) was applied to both surfaces of the quantum dot resin sheet and dried by heating at 100 ° C. for 5 minutes to obtain an adhesive layer having a thickness of 25 μm. Furthermore, on the adhesive layer, as the cover film, the sealing film was heat-laminated at 100 ° C. for 3 minutes so that the protective layer surface was bonded to the adhesive layer surface.

(10) Comprehensive evaluation Using the sealing films produced in the examples and comparative examples, comprehensive evaluation was performed according to the following criteria for each evaluation item of transparency, barrier properties, and processing characteristics.
<Criteria>
○: All of transparency, barrier properties, and processing characteristics are ○ (a level that is practically acceptable)
×: At least one of transparency, barrier property, adhesion to the adhesive layer, and luminance unevenness × (practically problematic level)

The polyester used in the examples and comparative examples was prepared as follows.
<Manufacture of polyester>

Production Example 1 (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).

Production Example 2 (Polyester A2)
In the production method of polyester (A1), polyester (A1) was added except that ethyl acid phosphate was added and silica particles having an average particle size of 2.7 μm were added so that the content with respect to the polyester was 0.3% by weight. ) Was used to obtain polyester A2 having an intrinsic viscosity of 0.62 (dl / g).

Production Example 3 (Polyester A3)
In the method for producing polyester (A1), polyester (A1) was used except that after adding ethyl acid phosphate, silica particles having an average particle size of 3.6 μm were added so that the content with respect to polyester was 0.6% by weight. ) To obtain polyester A3 having an intrinsic viscosity of 0.62 (dl / g).

Production Example 4 (Polyester A4)
In the production method of polyester (A1), after adding ethyl acid phosphate, synthetic calcium carbonate particles having an average particle diameter of 1.0 μm were added so that the content with respect to the polyester was 1.0% by weight. A polyester A4 having an intrinsic viscosity of 0.63 (dl / g) was obtained using a method similar to the production method of (A1).

Production Example 5 (Polyester A5)
In the method for producing polyester (A1), after adding ethyl acid phosphate, an ethylene glycol slurry of divinylbenzene / methyl methacrylate copolymer crosslinked particles having an average particle size of 4.4 μm is contained in the polyester in a content of 0.5. A polyester A5 having an intrinsic viscosity of 0.63 (dl / g) was obtained by using the same method as the method for producing the polyester (A1) except that it was added in an amount of% by weight. In addition, the manufacturing method of divinylbenzene / methyl methacrylate copolymer crosslinked particle | grains is as follows. A homogeneous solution of 100 parts of methyl methacrylate, 25 parts of divinylbenzene, 22 parts of ethylvinylbenzene, 1 part of benzoyl peroxide and 100 parts of toluene is dispersed in 700 parts of water, and then stirred at 80 ° C. for 6 hours in a nitrogen atmosphere. Polymerization was carried out while heating. The average particle diameter of the obtained crosslinked polymer granules having ester groups was about 0.1 mm. The produced polymer was washed with demineralized water and extracted twice with 500 parts of toluene to remove a small amount of unreacted monomer linear polymer. Next, the crosslinked polymer particles were pulverized with an attritor and a sand grinder to obtain divinylbenzene / methyl methacrylate copolymer crosslinked particles having an average particle diameter of 4.4 μm and different particle diameters.

Example 1:
Polyester A1 and A2 were blended in proportions of 88% and 12%, respectively, as a surface layer raw material, and polyester A1 as a raw material for an intermediate layer, and fed to two vented extruders at 290 ° C. After melt-extrusion, an amorphous film having a thickness of about 1500 μm 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. Thereafter, a coating solution having the following coating layer composition was coated on one side so that the coating thickness (after drying) was 0.05 g / m 2, the film was guided to a tenter, and stretched 3.8 times in the transverse direction at 100 ° C. Then, heat treatment was performed at 210 ° C. to obtain a polyester film F1 provided with a coating layer having a thickness of 100 μm (thickness ratio = 2.5 μm / 95 μm / 2.5 μm).

  Moreover, the following was used as a composition contained in a coating liquid.

<Water-based polyester resin B>
Tg = 63 ° C
Acid component: terephthalic acid 50 mol%, isophthalic acid 48 mol%, 5-Na sulfoisophthalic acid 2 mol%
Diol component: 50% by mole of ethylene glycol, 50% by mole of neopentyl glycol

<Production conditions for (aqueous polyurethane resin C)>
First, 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. Next, 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. Furthermore, 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.

(Coating layer composition)
Melamine resin A 40% by weight
(Crosslinkable resin of alkylol melamine / urea copolymer DIC's becamine “J101”)
Aqueous polyester resin B 25% by weight,
Aqueous urethane resin C 30% by weight
Colloidal silica (average particle size 70 nm) 5% by weight
The coating solution was diluted with ion exchange water to prepare a coating solution having a solid content concentration of 2% by weight.

<Formation of barrier layer 1>
The following barrier layer 1 was laminated on the coating layer. Specifically, 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—Si (composition ratio Al: Si = 5: 5, manufactured by High Purity Chemical) was used as a target, and DC power of 3 W / cm ² was applied. Moreover, Ar gas was flowed, it was made into the atmosphere of 0.4 Pa, and it formed into a film using DC magnetron sputtering method. At this time, the magnetic field strength was 600 gauss. The center roll temperature was set to 0 ° C., and the oxygen flow rate was controlled using a Speedflo 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 1 having a thickness of 40 nm and a refractive index of 1.52 was deposited.

<Protective layer formation>
Organic compound having aluminum element (A1): 19.5% by weight
Aluminum tris (acetylacetonate)
Organosilicon compound (B1): 80% by weight
γ-Glycidoxypropyltrimethoxysilane catalyst (C1): 0.5% by weight
Dibutyltin dilaurate The coating agent was diluted with a toluene / MEK mixed solvent (mixing ratio was 1: 1) to obtain 4% by weight.

Thereafter, a protective layer comprising the above coating composition is applied on the barrier layer by a reverse gravure coating method so that the coating amount (after drying) is 0.1 g / m ² , heat-treated at 120 ° C. for 30 seconds, and sealed. A stop film was obtained.

Examples 2-5:
In Example 1, it manufactured like Example 1 except having changed an application layer composition and polyester film substrate thickness as shown in the following table 1, 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 6:
In 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 2>
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. Moreover, Ar gas was flowed, it was made into the atmosphere of 0.4 Pa, and it formed into a film using DC magnetron sputtering method. At this time, the magnetic field strength was 600 gauss. The center roll temperature was set to 0 ° C., and the oxygen flow rate was controlled using a Speedflo 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 32 nm was formed on the coating layer. In the obtained sealing film, since the difference in refractive index between the barrier layer 2 (refractive index 1.61) and the protective layer (refractive index: 1.43) was large, the result was slightly inferior in transparency.

Comparative Examples 1-4:
In Example 1, it manufactured like Example 1 except having changed an application layer composition and polyester film substrate thickness as shown in the following table 1, 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.

Comparative Example 5:
In 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.

Comparative Example 6:
In Example 1, it manufactured similarly to Example 1 except having changed the structure of the application layer into the application 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.

  The characteristic of each sealing film obtained by the said Example and comparative example is shown to the following Tables 1-3.

  The sealing film for electronic members of the present invention is particularly excellent in transparency, water vapor barrier property and processing characteristics, and is used for electronic members such as quantum dot-containing resin sheets, electronic paper, and organic EL, which require high water vapor barrier properties. It can be suitably used as a film.

DESCRIPTION OF SYMBOLS 10 Laminated body 11 Quantum dot containing resin sheet 12 1st polyester film 13 1st application layer 14 1st barrier layer 15 1st protective layer 22 2nd polyester film 23 2nd application layer 24 2nd barrier layer 25 2nd protective layer 31 First sealing film 32 Second sealing film 41 First adhesive layer 42 Second adhesive layer

Claims (2)

One surface of the polyester film has a coating layer formed of at least one resin selected from polyester resin, urethane resin, and acrylic resin and a melamine resin, and has a film haze of 2.0% A sealing film for an electronic member having a constitution in which a barrier layer and a protective layer are sequentially laminated on a coating layer of a coating film having an air leakage index of 220,000 seconds or less. The electronic member sealing film according to claim 1, wherein the electronic member is a quantum dot-containing resin sheet.