WO2016125397A1 - Sealing film for electronic members - Google Patents

Abstract

Provided, as a sealing film for electronic members such as a quantum dot-containing resin sheet, an electronic paper and an organic EL, is a sealing film which has good transparency, barrier properties and processing characteristics. A sealing film for electronic members, which has a configuration wherein a barrier layer and a protective layer are sequentially laminated on a coating layer of a coated film wherein one surface of a polyester film has a roughness (Rt) of 100 nm or more and the other surface is provided with a coating layer that is formed from a coating liquid containing a crosslinking agent composed of a melamine resin or an oxazoline resin and at least one resin selected from among polyester resins, urethane resins and acrylic resins, said coated film having a film haze of 2.0% or less. This sealing film for electronic members has a water vapor transmission rate (as measured at a temperature of 40°C and at a humidity of 90%RH in accordance with JIS-K7129 B) of 0.01 g/m²/day or less.

Description

Sealing film for electronic parts

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 property and adhesion to an electronic member, 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 as an alternative to a glass base material has been earnestly promoted 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, while the 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. 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 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).

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.

In order to improve the transparency of the sealing film, measures to reduce the lubricant particles contained in the film are taken, but if the lubricant particles are reduced too much, for example, a decrease in winding workability during processing of laminating the barrier layer, etc. There is a problem of impairing processing characteristics.

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, a measure for improving the gas barrier property by alternately laminating an organic layer / inorganic layer is taken, but the gas barrier property is improved, but the interlayer adhesion at the organic layer / inorganic layer interface is not good. It is enough.

Although it is in a situation where a sealing film excellent in transparency, barrier properties, and adhesion to the electronic member is required for various electronic members, 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, barrier property, and adhesion | attachment with respect to an electronic member as sealing films for electronic members, such as a quantum dot containing resin sheet, electronic paper, and organic EL. It is in providing a sealing film with favorable property.

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

That is, the gist of the present invention is that the roughness (Rt) of one surface of the polyester film is 100 nm or more, and at least one selected from polyester resin, urethane resin, and acrylic resin on the other surface. A barrier layer on the coating layer of the coating film having a coating layer formed from a coating solution containing at least one kind of resin and a crosslinking agent comprising a melamine resin or an oxazoline resin, and having a film haze of 2.0% or less The film has a structure in which a protective layer is sequentially laminated, and the water vapor permeability of the film (measured in accordance with JIS-K7129 B method at a temperature of 40 ° C. and a humidity of 90% RH) is 0. It exists in the sealing film for electronic members characterized by being below 0.01g / m < ² > / day.

The sealing film for electronic members of the present invention is excellent in transparency, barrier properties, and adhesiveness with electronic members, 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.

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

The sealing film for electronic members of the present invention has a configuration in which a barrier layer and a protective layer are sequentially laminated on a coating layer of a coating film having a polyester film as a base material.

The polyester film may have a single layer structure or a laminated structure. For example, 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. 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). One or two or more types can be mentioned, and 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. 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 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. 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 about the hardness, specific gravity, a color, etc. These series of particles may be used in combination of two or more as required.

The average particle size of the particles used is usually in the range of 0.01 to 4 μm, preferably 1.0 to 3.5 μm. When the average particle size is less than 1.0 μm, the slipperiness is insufficient, so the processing characteristics may be insufficient. On the other hand, when it exceeds 3.5 μm, the transparency of the film is insufficient. There is a case.

The particle content 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 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, 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-mentioned particles, conventionally known fluorescent whitening agents, antioxidants, antistatic agents, thermal stabilizers, lubricants, dyes, pigments and the like can be added to the polyester film as necessary. .

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 and the like of the film substrate, it is preferably 12 to 125 μm, more preferably 25 to 100 μm.

The surface roughness (Rt) of one surface of the polyester film is usually 100 nm or more, preferably 300 nm or more. When Rt is less than 100 nm, when processing into a sealing film used for a quantum dot-containing resin sheet, electronic paper, organic EL, or the like, processing characteristics such as reduction in winding workability may be impaired.
In addition, one surface of the polyester film in which the surface roughness (Rt) is defined means a surface opposite to a surface on which a coating layer, a barrier layer, and a protective layer are sequentially laminated.

The haze of the coated film is usually 2.0% or less, preferably 1.5% or less. When the haze is 2.1% or more, when used as a sealing film for a quantum dot-containing resin sheet, electronic paper, organic EL, or the like, the transparency of the device is lowered and the visibility may be inferior.

Next, a production example of the polyester film will be specifically described, but is not limited to the following production example.

First, 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. 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. Next, 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. Subsequently, heat treatment is performed at a temperature of 180 to 270 ° C. under tension or 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.

Also, 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 usually 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) for treating the film surface during the above-described polyester film stretching step can be performed. 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.

The coated film in the present invention is a crosslinking agent comprising at least one resin selected from polyester resins, urethane resins, and acrylic resins, and a melamine resin or an oxazoline resin for improving adhesion to the barrier layer. The coating layer formed from the coating liquid containing these.

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. In addition to 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, etc. 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.

Examples of the glycol component include 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 such polyol components, 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.

Also, it is preferable to contain at least one polyester resin having a sulfonic acid (salt) group in order to facilitate water dispersion or water solubility.

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 or sulfonic acid amine salt compounds such as 5-potassium sulfoisophthalic acid, 4-potassium sulfoisophthalic acid, 2-potassium sulfoisophthalic acid, and sodium sulfosuccinic acid.

In the polyester resin, 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.

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 (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 (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 acrylamide or (meth) acrylonitrile. Further, in combination with these, polymerizable monomers as shown below can be copolymerized. That is, 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, 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.

Urethane resin is used to improve the adhesion to the barrier layer. From this viewpoint, 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. 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.

Examples of the 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, α, α, α ′, Aliphatic diisocyanates having an aromatic ring such as α'-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 isocyanate), dicyclohexylmethane diisocyanate, alicyclic diisocyanates such as isopropylidene dicyclohexyl diisocyanates. 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, 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. 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.

In addition, 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. 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 glass transition point of the urethane resin having the polycarbonate structure is usually 0 ° C. or lower, preferably −15 ° C. or lower, more 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 measured using the differential scanning calorimeter (DSC).

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.

Further, 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, 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 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. For example, 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-alkyl ( (Meth) acrylamide, N, N-dialkyl (meth) acrylamide, Examples of the alkyl group include unsaturated amides such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, 2-ethylhexyl, cyclohexyl, etc .; vinyl acetate Vinyl esters such as vinyl propionate; vinyl ethers such as methyl vinyl ether and ethyl vinyl ether; α-olefins such as ethylene and propylene; halogen-containing α, β-unsaturated monomers such as vinyl chloride and vinylidene chloride; styrene, An α, β-unsaturated aromatic monomer such as α-methylstyrene can be used, and one or more of these monomers can be used.

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, particularly 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 ratio of the resin in the coating solution is usually 10 to 80% by weight, preferably 10 to 60% by weight as the ratio to the total nonvolatile components, and the ratio of the crosslinking agent in the coating solution is the ratio to the total nonvolatile components, Usually 6 to 80% by weight, preferably 10 to 60% by weight.

The coating amount (after drying) of the coating solution is usually 0.005 to 1 g / m ² , preferably 0.005 to 0.5 g / m ² , more preferably 0.01 to 0. The range is ² g / m ² . 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.

As a coating method, conventionally known coating methods such as reverse gravure coating, direct gravure coating, roll coating, die coating, bar coating, and curtain coating can be used. As for the coating method, there is an example described in “Coating Method” Tsuji Shoten published by Yuji Harasaki in 1979.

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. 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 of this invention is laminated | stacked for the purpose of providing barrier property to a polyester film. As a material for the barrier layer, the barrier property is at a desired level. In the present invention, 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. Preferably it is 0.005 g / 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, metals such as aluminum, magnesium, zinc and tin Can be mentioned. These can be used individually by 1 type or in combination of 2 or more types.

The thickness of the barrier layer is usually 1 nm to 10 μm, preferably 10 to 1000 nm, more preferably 20 to 500 nm, 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.

The barrier layer may have a single layer structure 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 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.

In addition to protecting the barrier layer, the protective layer contains an active energy ray-curable resin that can be cured by irradiation with active energy rays in order to improve adhesion when directly bonding with the quantum dot-containing resin sheet. Is preferred. More preferably, the active energy ray-curable resin is preferably a compound having an acrylate structure.

A compound having an acrylate structure has a weight average molecular weight (Mw) of 5000 by gel permeation chromatography (GPC) measurement in accordance with a polymer compound safety evaluation flow scheme (November 1985, sponsored by the Chemical Substances Council). As described above, it is preferably defined as a polymer compound of 10,000 or more and having a film-forming property.

Specific examples of the compound having an acrylate structure include methyl acrylate, ethyl acrylate, isopropyl acrylate, isobutyl acrylate, epoxy acrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, trimethylol propane triacrylate, dimethylol tricyclodecane diacrylate, tetra Methylene glycol tetraacrylate, 2-hydroxy-1,3-diacryloxypropane, 2,2-bis [4- (acryloxymethoxy) phenyl] propane, 2,2-bis [4- (acryloxyethoxy) phenyl] Examples include propane, dicyclopentenyl acrylate, tricyclodecanyl acrylate, tris (acryloxyethyl) isocyanurate, and urethane acrylate. The These may be used individually by 1 type and may use 2 or more types together. Furthermore, what used the said acrylate as the methacrylate may be used together, may be used individually by 1 type, and may use 2 or more types together.
In addition, “Technical Information Association” issued on December 21, 2010, “How to select and use functional acrylates” has a description about specific examples.

Specific examples of photopolymerization initiators used for curing a compound having an acrylate structure include 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, 2- Hydroxy-2-methyl-1-phenyl-1-propan-1-one, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy -1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] phenyl} -2-methyl-propan-1-one, 2-methyl-1- (4-methylthiophenyl) -2 -Morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2- (dimethylamino ) -2 - [(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone and the like. Examples of the acylphosphine oxide photopolymerization initiator include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, and the like. Examples of titanocene photopolymerization initiators include bis (η5-2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium Is mentioned. Examples of the oxime ester polymerization initiator include 1.2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], ethanone, 1- [9-ethyl-6- (2 -Methylbenzoyl) -9H-carbazol-3-yl]-, 1- (0-acetyloxime), oxyphenylacetic acid, 2- [2-oxo-2-phenylacetoxyethoxy] ethyl ester, 2- (2-hydroxy And ethoxy) ethyl ester. These photoinitiators may be used individually by 1 type, and may use 2 or more types together.

Regarding the amount of the active energy ray curable resin and the photopolymerization initiator in the protective layer, it is preferable to mix 1 to 6 parts by weight of the photopolymerization initiator with respect to 100 parts by weight of the active energy ray curable resin. When the photopolymerization initiator is out of the range, it may be difficult to obtain a protective layer having desired performance.

Hereinafter, another embodiment in which an organic compound containing at least one metal element selected from aluminum, titanium, and zirconium is contained in the protective layer will be exemplified.

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 and the like.

Specific examples of the organic compound having 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, for example, zirconium acetate, zirconium normal propylate, 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 from the viewpoint of particularly good adhesion performance. It is also described in detail in the “Crosslinking agent handbook” (Yamashita Shinzo, Kaneko Tosuke Editor Taiseisha Co., Ltd., 1990 edition).

In addition, when the protective layer is bonded to the quantum dot-containing resin sheet through the adhesive layer as well as protecting the barrier layer, the organosilicon compound represented by the following general formula (1) is used to improve the adhesion. It is preferable to use together.

Si (X) d (Y) e (R1) 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.

As the above organosilicon compound, conventionally known compounds can be used. Specifically, vinyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β -(3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-acryloxypropyltrimethoxysilane, γ-aminopropyltriethoxysilane, 5 Examples include -hexenyltrimethoxysilane, p-styryltrimethoxysilane, trifluoropropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldiisopropenoxysilane, and the like.

A catalyst may be used in combination with the protective layer for the purpose of promoting hydrolysis and condensation reactions. 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.

Further, the protective layer may contain inorganic particles for the purpose of improving its adhesion and slipperiness within the range not impairing the gist of the present invention. Specific examples include silica, alumina, kaolin, calcium carbonate, oxidation. Examples include titanium and barium salts.

In addition, 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.

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 (after drying) when the protective layer is applied is usually 0.005 to 5 g / m ² , preferably 0.005 to 1 g / m ² . 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 it coats exceeding 5 g / m < ² >, malfunctions, such as a slipperiness fall, may arise.

The protective layer composed of the above composition has good durability and excellent adhesion to the adhesive layer.

In the present invention, it is an essential requirement that the water vapor transmission rate of the sealing film 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, the quantum dot-containing resin sheet as a counterpart material to which the sealing film of the present invention is bonded is described.

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

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 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 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.

Therefore, various colors including red, green, and blue can be easily obtained from the quantum dots by a quantum size effect. Accordingly, it is possible to create colors that emit light at respective wavelengths, and it is also possible to generate and realize 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 dots convert part of blue light into red light having a wavelength range of 620 to 750 nm, and the green quantum dots convert part of blue light into green light having a wavelength range 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, or 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, mercapto alcohol, thiol, phosphine, phosphine oxide, and the like, and plays a role in stabilizing unstable quantum dots after synthesis. Examples of commercially available quantum dots include various quantum dots manufactured by SIGMA-ALDRICH.

Also, 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. Preferably, an active energy ray curable resin is preferable similarly to the protective layer of the sealing film, and more preferably, the active energy ray curable resin is a compound having an acrylate structure.

The method for 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 on top of the color filter layer using a spin coating method or a printing method.

Further, the quantum dot resin sheet may be formed by molding and curing a resin to which quantum dots are 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.

In this invention, it is set as the laminated body structure which bonded the quantum dot containing resin sheet and the sealing film through the adhesion layer, or the laminated body structure which bonded the quantum dot containing resin sheet and the sealing film directly. I can do it.

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

Regarding the sealing film laminating method, the method of directly laminating the quantum dot-containing resin sheet and the protective layer of the encapsulating film eliminates the need for an adhesive layer in terms of product configuration and improves productivity by simplifying the manufacturing process. Is preferable in that it can be achieved.

A method in which the quantum dot-containing resin composition is applied onto the protective layer of the sealing film at a predetermined coating amount and dried, and then the protective layer surface of the sealing film and the surface of the quantum dot-containing resin sheet are bonded together is employed. Moreover, about hardening of a quantum dot containing resin composition, it can be hardened by irradiating an active energy ray after apply | coating and drying on the protective layer of a sealing film previously. Furthermore, an active energy ray can also be irradiated by the film laminated body structure which bonded the sealing film on both surfaces of the quantum dot containing resin sheet. A laminate structure can also be obtained by combining the above methods. Specifically, as pre-curing, after pre-applying and drying on the protective layer of the sealing film and then irradiating active energy rays, it is activated again as main curing in the state of the laminate structure as the final structure. Energy rays can also be irradiated. Preferably, as described above, by irradiating the active energy ray at least twice or more, it becomes possible to obtain a film laminate having stronger adhesion.

A preferred range of accumulated light quantity at the time of the active energy rays, the total amount of time of an active energy ray in the process of manufacturing film laminate ^is in the range of 400mJ / cm 2 ~ 1800mJ / cm 2. When the integrated light quantity is less than 400 mJ / cm ² , a coating film having desired performance may not be obtained. On the other hand, when it exceeds 1800 mJ / cm ² , the integrated light quantity is already in a saturated state, and for example, a remarkable characteristic improvement effect such as adhesiveness cannot be expected.

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 were removed was precisely weighed, 100 ml of a mixed solvent of phenol / tetrachloroethane = 50/50 (weight ratio) was added and dissolved, and measurement was performed at 30 ° C.

(2) Measurement of average particle diameter (d50: μm):
The value of 50% of integration (weight basis) in the equivalent spherical distribution measured using a centrifugal sedimentation type particle size distribution measuring apparatus (SA-CP3 type manufactured by Shimadzu Corporation) was defined as the average particle diameter.

(3) Glass transition temperature (Tg) measurement of polyester resin:
Using a DSC-II type measuring device manufactured by PerkinElmer, Inc., the sample was heated at a rate of temperature increase of 10 ° C./min under a nitrogen stream, and the baseline start temperature of the baseline was defined as Tg.

(4) Measurement of the roughness (Rt) of the polyester film surface:
Rt was measured according to JIS B0601-1994 using a surface roughness measuring machine (SE3500 type) manufactured by Kosaka Laboratory. The measurement length was 2.5 mm.
(Machining characteristics criteria)
A: Rt 300 nm or more (good, level with no particular problem)
B: Rt 101 nm or more and less than 300 nm (no problem level)
C: Rt 100 nm or less (practically problematic level)

(5) Haze measurement of a film in which a coating layer is laminated on a polyester film (transparency substitution evaluation):
The haze of the sample film was measured with a haze meter “HM-150” manufactured by Murakami Color Research Laboratory Co., Ltd. according to JIS-K-7136.
(Transparency criteria)
A: Haze 1.5% or less (good, level with no particular problem)
B: Haze 1.6 or more and 2.0% or less (although it is a problem-free level, it may be difficult to apply for high-end display devices)
C: Haze 2.1% or more (practical problem level)

(6) Barrier layer thickness:
A film sample piece on which the barrier layer was laminated 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.

(7) Measuring the refractive index of the barrier layer:
For a barrier layer formed on a silicon wafer or quartz glass with a coater, a high-speed spectrometer M-2000 (manufactured by JA Woollam) was used to change the polarization state of the reflected light of the barrier layer at an incident angle of 60 degrees, Measurements were made at 65 degrees and 70 degrees, and the refractive index at a wavelength of 550 nm was calculated by analysis software WVASE32.

(8) Water vapor transmission rate (barrier property substitution evaluation):
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. Thereafter, the determination was made according to the following criteria.
(Criteria)
A: 0.005 g / m ² / day or less. (Practical, no problem level)
B: Beyond ^{0.005g / m 2 / day, 0.01g} / m 2 / day or less. (Practical level that may cause problems)
C: Exceeds 0.01 g / m ² / day. (Practical problem level)

(9) Adhesiveness between sealing film and quantum dot-containing resin sheet:
Using each of the laminates obtained in Examples and Comparative Examples, the feeling of peeling when peeling one sealing film from the laminate was determined according to the following criteria.
(Criteria)
A: The sealing film and the quantum dot-containing resin sheet are firmly bonded and difficult to peel off. (Practical, no problem level)
B: The sealing film and the quantum dot-containing resin sheet can be peeled off. (Practical problem level)

(10) Overall evaluation:
Using the sealing films produced in Examples and Comparative Examples, overall evaluation was performed according to the following criteria for each evaluation item of transparency, adhesiveness, and barrier property.
<Criteria>
A: Transparency, adhesion, and barrier properties are all judged as A (a level that causes no problem in practical use)
B: Among transparency, adhesiveness, and barrier properties, adhesiveness is A determination, and at least one of the remaining items includes B determination. (Practical level that may cause problems)
C: Among transparency, adhesiveness, and barrier properties, the adhesiveness is B determination, or at least one of the remaining items includes C determination. (Practical problem 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 3.8 times in the lateral direction at 100 ° C. It was stretched and heat treated 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 the coating solution.

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

<Production conditions for (aqueous polyurethane resin)>
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.

<Production conditions for (aqueous acrylic resin)>
A mixture of 40 parts by weight of ethyl acrylate, 30 parts by weight of methyl methacrylate, 20 parts by weight of methacrylic acid and 10 parts by weight of glycidyl methacrylate was solution-polymerized in ethyl alcohol, and heated while adding water after polymerization to remove ethyl alcohol. The pH was adjusted to 7.5 with aqueous ammonia to obtain an aqueous acrylic resin aqueous paint.

(Coating layer 1 composition)
I: Melamine resin 40% by weight
(Alkyrol melamine / urea copolymer crosslinkable resin DIC's becamine "J101")
II: 25% by weight of aqueous polyester resin
III: 30% by weight of aqueous urethane resin
IV: Oxazoline group-containing polymer (Nippon Shokubai "Epocross WS-500" oxazoline group amount 4.5 mmol / g)
0% by weight
V: Water-based acrylic resin 0% by weight
VI: 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>
Next, a barrier layer 1 coating solution having the following composition is coated on the coating layer so that the coating amount (after drying) is 5 g / m ² , heat-treated at 150 ° C. for 1 minute, The barrier layer 1 was formed by irradiating with ultraviolet rays at 450 mJ / cm ² (one 80 w / cm high-pressure mercury lamp × 18 cmH × 5 m / min × 2 Pass).
<Barrier layer 1 coating solution composition>
Active energy ray curable resin (pentaerythritol triacrylate / 2-hydroxyethyl acrylate = 95/5 (mixing ratio)) 95% by weight
Photopolymerization initiator (Irgacure 184: Ciba Specialty Chemicals) 5% by weight
The composition was diluted to 10% by weight with methyl ethyl ketone solvent.

<Formation of barrier layer 2>
The following barrier layer 2 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 was set to 50% when the discharge voltage when only Ar gas was supplied was 100%, and when the discharge voltage was 50% when Ar gas and O2 gas were supplied at 50 sccm. . As described above, the barrier layer 2 having a thickness of 40 nm and a refractive index of 1.52 was deposited.

<Formation of protective layer 1>
In Example 1, a protective layer composition comprising the following protective layer was applied so that the coating amount (after drying) was 5 g / m ² , heat-treated at 150 ° C. for 1 minute, and then with an integrated light amount of 450 mJ / cm ² (80 w The protective layer 1 was formed by irradiating with ultraviolet rays so as to be 1 / cm high-pressure mercury lamp × 18 cmH × 5 m / min × 2 Pass.
<Protective layer 1 coating composition>
Active energy ray curable resin (pentaerythritol triacrylate / 2-hydroxyethyl acrylate = 80/20 (mixing ratio)) 95% by weight
Photopolymerization initiator (Irgacure 184: Ciba Specialty Chemicals) 5% by weight
The composition was diluted to 10% by weight with methyl ethyl ketone solvent.

《Lamination of quantum dot resin sheet and sealing film》
Using a sealing film as a support, a coating solution for forming a quantum dot resin sheet composed of the following composition is applied to the surface of the protective layer so that the coating amount (after drying) is 50 g / m ² and heat-treated at 150 ° C. for 3 minutes. After that, it is sealed as a cover film after being irradiated with ultraviolet rays using an ultraviolet irradiator so that the integrated light quantity becomes 1700 mJ / cm ² (one 80 w / cm high-pressure mercury lamp × 13 cmH × 1.5 m / min × 4 Pass). Affix the stop film.
Next, from the film surface side where the protective layer of the sealing film bonded later is not provided, the integrated light amount becomes 900 mJ / cm ² (one 80 w / cm high-pressure mercury lamp × 18 cmH × 5 m / min × 4 Pass). Thus, the film laminated body which has the structure of sealing film / quantum dot containing resin sheet / sealing film was obtained by irradiating with ultraviolet rays.

<Preparation of coating liquid for forming quantum dot resin sheet>
Using a polyethylene container having a volume of 300 ml, pentaerythritol triacrylate / 2-hydroxyethyl acrylate / isodecyl acrylate = 75/20/5 (mixing ratio) as an active energy ray-curable resin was diluted to 10% by weight with a methyl ethyl ketone solvent. 80% by weight of the composition, 5% by weight of photopolymerization initiator (Irgacure 184: manufactured by Ciba Specialty Chemicals), “CdSe / ZnS480” (manufactured by SIGMA-ALDRICH: Blue 480 nm), “CdSe / ZnS 530” as quantum dots (Manufactured by SIGMA-ALDRICH: Green 530 nm) and “CdSe / ZnS 560” (manufactured by SIGMA-ALDRICH: Yellow 560 nm) were mixed at a ratio of 5% by weight. Thereafter, using a planetary stirring and defoaming apparatus “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 solution.

Example 2 to Example 5:
In Example 1, it manufactured like Example 1 except having changed polyester as shown in following Table 1, and obtained the sealing film. Then, it carried out similarly to Example 1, and bonded the sealing film and the quantum dot containing resin sheet directly, and obtained the film laminated body.

Example 6:
In Example 1, it manufactured similarly to Example 1 except having changed the structure of the barrier layer 2 into the following barrier layer 3, and obtained the sealing film. Then, the sealing film and the quantum dot containing resin sheet were directly bonded together, and the film 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. 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 was set to 50% when the discharge voltage when only Ar gas was supplied was 100%, and when the discharge voltage was 50% when Ar gas and O2 gas were supplied at 50 sccm. . As described above, the barrier layer 3 having a film thickness of 32 nm and a refractive index of 1.61 was formed on the coating layer.

Example 7:
In Example 1, after changing the protective layer composition to the following protective layer 2 composition to obtain a sealing film, the quantum dot-containing resin sheet composition was changed, and the sealing film and the quantum dot-containing resin were interposed via the adhesive layer. The sheets were pasted together.

<Protective layer 2 composition>
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. Thereafter, the sealing film and the quantum dot-containing resin sheet are bonded together via the adhesive layer, and the film laminate has a configuration of sealing film / adhesive layer / quantum dot-containing resin sheet / adhesive layer / sealing film. Got.

<Preparation of coating liquid for forming quantum dot resin sheet>
Using a polyethylene container with a capacity 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 / ZnS480” (SIGMA- ALDRICH: Blue 480 nm), “CdSe / ZnS 530” (SIGMA-ALDRICH: Green 530 nm), “CdSe / ZnS 560” (SIGMA-ALDRICH: Yellow 560 nm) were mixed at a ratio of 20% by weight. Thereafter, using a planetary stirring and defoaming apparatus “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 solution.

<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 film 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.

Example 8:
In Example 1, it manufactured like Example 1 except not providing barrier layer 1, and a film layered product was obtained.

Example 9:
In Example 1, it manufactured like Example 1 except having changed an application layer composition into composition of application layer 2, and obtained a film layered product.

Example 10:
In Example 1, it manufactured like Example 1 except having changed an application layer composition into composition of application layer 3, and obtained a film layered product.

Comparative Examples 1 to 4:
In Example 1, it manufactured like Example 1 except having changed polyester as shown in following Table 1, and obtained the sealing film. Thereafter, similarly, the sealing film and the quantum dot-containing resin sheet were directly bonded to obtain a film laminate.

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 directly bonded together, and the film laminated body was obtained.

Comparative Example 6:
In 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 directly bonded together, and the film laminated body was obtained.

Comparative Example 7:
In Example 1, it manufactured like Example 1 except changing an application layer composition into composition of application layer 4, and a film layered product was obtained.

Tables 1 to 4 show the properties of the sealing films obtained in the above examples and comparative examples.

 

 

 

Table 4 shows the characteristics 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, adhesiveness and water vapor barrier properties, and is used for sealing 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 2nd barrier layer 22 2nd polyester film 23 2nd application layer 24 1st barrier layer 25 2nd barrier layer 31 First sealing film 32 Second sealing film 41 First protective layer 42 Second protective layer

Claims (7)

1. The roughness (Rt) of one surface of the polyester film is 100 nm or more, and at least one resin selected from polyester resin, urethane resin, and acrylic resin on the other surface, and a melamine resin Alternatively, a barrier layer and a protective layer are sequentially laminated on a coating layer of a coating film having a coating layer formed of a coating solution containing a crosslinking agent composed of an oxazoline resin and having a film haze of 2.0% or less. A water vapor permeability of the film (measured in accordance with JIS-K7129 B method under measurement conditions of a temperature of 40 ° C. and a humidity of 90% RH) of 0.01 g / m ² / day or less The sealing film for electronic members characterized by the above-mentioned.
2. The ratio of the resin in the coating liquid is 10 to 80% by weight as a ratio to the total nonvolatile components, and the ratio of the crosslinking agent in the coating liquid is 6 to 80% by weight as a ratio to the total nonvolatile components. Sealing film for electronic members.
3. The sealing film for electronic members according to claim 1 or 2, wherein the protective layer contains an active energy ray-curable resin.
4. The encapsulating film for an electronic member according to claim 3, wherein the active energy ray curable resin is a compound having an acrylate structure.
5. The electronic member sealing film according to any one of claims 1 to 4, wherein the electronic member is a quantum dot-containing resin sheet.
6. 6. A film laminate, wherein the electronic member sealing film according to claim 1 is directly bonded to the surface of the quantum dot-containing resin sheet.
7. The film laminate according to claim 6, wherein the quantum dot-containing resin sheet contains an active energy ray-curable resin.

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