WO2019035326A1 - Structure multicouche de barrière contre l'humidité - Google Patents

Structure multicouche de barrière contre l'humidité Download PDF

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WO2019035326A1
WO2019035326A1 PCT/JP2018/027807 JP2018027807W WO2019035326A1 WO 2019035326 A1 WO2019035326 A1 WO 2019035326A1 JP 2018027807 W JP2018027807 W JP 2018027807W WO 2019035326 A1 WO2019035326 A1 WO 2019035326A1
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moisture
layer
water
moisture barrier
multilayer structure
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PCT/JP2018/027807
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English (en)
Japanese (ja)
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瞬也 南郷
真平 奥山
美理 八木澤
圭将 高山
芳弘 太田
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東洋製罐グループホールディングス株式会社
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Priority claimed from JP2018082512A external-priority patent/JP2019034539A/ja
Application filed by 東洋製罐グループホールディングス株式会社 filed Critical 東洋製罐グループホールディングス株式会社
Publication of WO2019035326A1 publication Critical patent/WO2019035326A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin

Definitions

  • the present invention relates to a moisture barrier multilayer structure in which a plurality of moisture barrier layers and a moisture trap layer are provided on at least one surface of a plastic substrate.
  • Patent Document 1 It is known to form a moisture barrier layer made of silicon oxide or the like by vapor deposition on the surface of a plastic substrate as a means for improving the properties of various plastic substrates, in particular, the gas barrier property (Patent Document 1) ).
  • the inside of the device has a low moisture atmosphere because it does not like charge leakage.
  • High moisture barrier properties are required for plastic substrates forming the circuit board and the like and films for sealing the circuit board and the like.
  • the formation of the moisture barrier layer described above can not meet such high requirements for moisture barrier properties, and various proposals have been made to improve the moisture barrier properties.
  • Patent Documents 2 to 4 For example, in Patent Documents 2 to 4, according to the present applicant, a water trap layer in which a specific particulate hygroscopic agent is dispersed in a matrix of an ionic polymer is formed on a water barrier layer on a plastic substrate Gas barrier laminates have been proposed.
  • a moisture barrier laminate exhibits high barrier properties to moisture flowing in the thickness direction (planar direction) of the laminate, but a barrier to moisture flowing in from the side surface (end face) thereof. It is hard to say that sex is enough. In addition, the inflow of water from such an end face has not been studied so far.
  • Patent Document 5 discloses a moisture trap layer and a moisture barrier layer in addition to a surface facing a low moisture atmosphere or from the surface Applicants have proposed a structure in which an auxiliary moisture trap layer is provided in an area within 20 ⁇ m.
  • Patent Document 5 can effectively prevent the inflow of water from the end face, thereby ensuring the super barrier property against water, the deterioration of the water trap performance of the water trap layer due to the passage of time Under the present circumstances, it is required to suppress and to develop super barrier properties against water over a longer period of time.
  • JP 2000-255579 A WO2014 / 123197 JP, 2014-168949, A JP, 2014-168950, A JP, 2017-39315, A
  • the object of the present invention is to effectively avoid the deterioration with time of the water trapping performance of the water trapping layer in the water barrier multilayer structure comprising the water barrier layer and the water trapping layer, and to super-barrier the water. It is to be expressed over a long period of time.
  • the performance of the water trapping layer largely depends on the thickness of the organic layer provided between the water trapping layer and the water barrier layer in the multilayer structure.
  • the thickness of the organic layer By controlling the thickness of the organic layer to be thin, it has been found that the performance of the water trap layer can be maintained over a long period of time, and the present invention has been completed.
  • a plurality of moisture barrier layers and a moisture trap layer located between the moisture barrier layers are provided on the side not facing the high moisture atmosphere of the plastic base facing the high moisture atmosphere.
  • a water-barrier multilayer structure in which an organic layer is provided between the water trap layer and a water barrier layer located on the low water atmosphere side with respect to the water trap layer;
  • a moisture barrier multilayer structure is provided, characterized in that the thickness of the layer is in the range of 0.1 ⁇ m to less than 3 ⁇ m.
  • the moisture trap layer is a layer that blocks the permeation of moisture by absorbing moisture, and the moisture barrier layer blocks the permeation of moisture without absorbing moisture (that is, moisture Means a layer).
  • the organic layer is an adhesive layer; (2) The organic layer is made of epoxy resin, acrylic resin or urethane resin (3) The water trap layer is made of a resin containing hygroscopic inorganic particles, a hygroscopic ionic polymer, and a hygroscopic nonionic polymer. (4) It has a structure in which a hygroscopic agent having a lower reaching humidity than that of the matrix is dispersed in a hygroscopic matrix made of an ionic polymer, Is preferred.
  • An important feature of the present invention is that the thickness of the organic layer for bonding the water trap layer and the water barrier layer located on the low water atmosphere side of the water trap layer is set to 0.1 ⁇ m or more and less than 3 ⁇ m. As a result, the deterioration of the performance of the water trap layer in the short term is suppressed, and as a result, it is possible to exhibit the super-water barrier property exhibited by this water-barrier multilayer structure over a long period of time.
  • a multilayer structure having a structure in which a moisture barrier layer and a moisture trap layer are laminated on a plastic substrate
  • a plurality of moisture barrier layers and a plurality of moisture trap layers are provided, respectively.
  • a basic structure in which a water trap layer is sandwiched between barrier layers is adopted, a water barrier layer and a water trap layer are further stacked on such a basic structure, and a super water barrier property is exhibited by such a multilayer structure.
  • Ru Although the moisture absorption performance of the water trapping layer is also important for maintaining the super-water barrier property over a long period of time, the layer adjacent to the water trapping layer is also important.
  • the moisture trap layer absorbs moisture from the outside and stores it, the volume is increased with swelling or chemical change (eg, CaO + H 2 O ⁇ Ca (OH) 2 ) of the hygroscopic material contained in the moisture trap layer.
  • swelling or chemical change eg, CaO + H 2 O ⁇ Ca (OH) 2
  • the moisture barrier layer is directly adjacent to the moisture trap layer, even a slight increase in volume may lead to the generation of defects on the nanometer-order moisture barrier layer.
  • the moisture absorbent itself of the water trap layer is accompanied by a chemical change
  • there is a possibility of causing a defect due to the interaction with the water barrier layer (example: base of Ca (OH) 2 generated by reaction of CaO and water (Due to the destruction of the cross-linked network of the SiOx deposited thin film of the moisture barrier layer).
  • the water-trapping layer is formed between the water-trapping layer and the water-barrier layer so that the water-trapping layer does not adjoin the water barrier layer.
  • An organic layer is formed to reduce the volume change due to swelling associated with moisture absorption.
  • the moisture absorption capacity of the trap layer is limited, and when the moisture absorption amount increases, the moisture absorption capacity gradually decreases, and the moisture transmitted through the moisture trap layer diffuses to the organic layer on the low humidity side. At this time, if the thickness of the organic layer between the moisture trap layer and the moisture barrier layer located on the low moisture atmosphere side is thin, the moisture trapped by the moisture barrier layer on the low humidity side is re-absorbed by the moisture trap layer. This makes it possible to suppress the permeation of water. On the other hand, when the thickness of the organic layer is large, moisture permeates the moisture barrier layer on the low humidity side more quickly than the moisture is re-absorbed by the trap layer, and the moisture shifts to the low humidity atmosphere side.
  • the thickness of the organic layer when the thickness of the organic layer is large, the inflow of water from the end face of the organic layer is not negligible, such water flows into the water trap layer, and more water flows into the water trap layer, resulting in the water trap layer Performance will be reduced in the short term.
  • the thickness of the organic layer as thin as described above, the moisture can be absorbed efficiently by the trap layer, the inflow of moisture from the end face of the organic layer is suppressed, and the performance of the water trap layer is prolonged It has become possible to maintain high levels throughout the
  • Such a moisture barrier laminate of the present invention is effectively used for various devices that resist the ingress of moisture, and is useful as a substrate or sealing layer for various devices, and in particular for organic electroluminescent (organic EL) panels. It applies suitably.
  • the moisture barrier multilayer structure of the present invention comprises a first moisture barrier layer 3, a water trap layer 5 and a second moisture on a plastic substrate 1.
  • the barrier layer 7 is provided in this order, and the first organic layer 9 is provided between the water trap layer 5 and the second water barrier layer 7.
  • the second moisture barrier layer 7 has the second organic layer 10 as a base, and the first organic layer 9 is present at a position facing the moisture barrier layer 7.
  • Such a multilayer structure 11 is positioned on the high humidity atmosphere side (that is, the outer side when attached to a device or the like) on the plastic substrate 1 side, and the second moisture barrier layer 7 is a first moisture barrier.
  • the layer 3 is disposed and used so as to be located on the atmosphere side where the relative humidity is relatively low (that is, the inner side when attached to a device or the like).
  • the moisture flowing in the thickness direction from the outside and flowing in is blocked by the moisture trap layer 5, and the moisture inflow from the end face of the first organic layer 9 is the first organic layer.
  • the thickness of the layer 9 is controlled as much as possible.
  • the plastic substrate 1 is made of thermoplastic resin or thermosetting resin known per se, for example, injection or co-injection molding, extrusion or co-extrusion molding, film or sheet molding, compression molding, injection molding
  • thermoplastic resin or thermosetting resin known per se, for example, injection or co-injection molding, extrusion or co-extrusion molding, film or sheet molding, compression molding, injection molding
  • low-density polyethylene high-density polyethylene, polypropylene, poly 1-butene, poly 4-methyl-1-pentene or ethylene, propylene, from the viewpoint of moldability and cost.
  • Polyolefins such as random or block copolymers of ⁇ -olefins such as -butene and 4-methyl-1-pentene, cyclic olefin copolymers, etc., and ethylene / vinyl acetate copolymer, ethylene / vinyl alcohol copolymer
  • Ethylene-vinyl compound copolymers such as ethylene-vinyl chloride copolymer, polystyrene, Styrenic resins such as lyronitrile-styrene copolymer, ABS, ⁇ -methylstyrene-styrene copolymer, etc., polyvinyl chloride, polyvinylidene chloride, vinyl chloride-vinylidene chloride copolymer, methyl polyacrylate, polymethyl methacrylate Etc., polyamides such as nylon 6, nylon 6-6, nylon 6-10, nylon 11, nylon 12 etc., thermoplastic polyesters such as polyethylene terephthalate (PET), poly
  • the plastic substrate 1 is also preferably formed of a gas barrier resin or the like having an excellent oxygen barrier property such as ethylene / vinyl alcohol copolymer, and is further formed of such a gas barrier resin It may have a multi-layer structure including a plurality of layers.
  • the present invention it is easy to obtain, shows cost, moldability, or shows some barrier property against oxygen and moisture, and it is said that it is suitable as a base of the first moisture barrier layer 3 described later. From the viewpoint, it is more preferable to use a polyester resin represented by polyethylene terephthalate (PET), and an olefin resin represented by polyethylene and polypropylene as the plastic substrate 1.
  • PET polyethylene terephthalate
  • olefin resin represented by polyethylene and polypropylene
  • the second organic layer 10 underlying the second moisture barrier layer 7 is also made of the same resin material as that of the plastic substrate 1, and naturally includes a layer formed of a gas barrier resin. It may have a multilayer structure. From the viewpoint of preventing the inflow of water from the end face, the thickness of the second organic layer 10 is preferably as thin as possible, for example, preferably 100 ⁇ m or less.
  • the first moisture barrier layer 3 and the second moisture barrier layer 7 provided on the inner surface side (opposite the surface facing the high humidity atmosphere) of the plastic substrate 1 so as to sandwich the moisture trap layer 5 are, for example, JP-A-2015-96320 and the like, which are well-known, include inorganic deposited films formed by physical vapor deposition represented by sputtering, vacuum deposition, ion plating, etc. or chemical vapor deposition represented by plasma CVD, eg, oxidation Films made of various metals or metal oxides such as silicon films, silicon oxynitride films, aluminum oxide films, etc., in particular, films can be uniformly formed on surfaces having asperities, not only moisture but also oxygen etc.
  • a resin having a high water vapor barrier property such as polyvinylidene chloride, polysilazane, a polycondensable silane compound (for example, alkoxysilane), a polycondensable alumina compound (for example, Using an organic solvent solution which is contained as an inorganic film forming component such as alkoxy aluminum etc., and in which inorganic fine particles such as silica and alumina are mixed appropriately, this is applied on a predetermined surface and heated to volatilize the organic solvent It is also preferable to use what forms a film.
  • the first moisture barrier layer 3 is formed by vapor deposition using the surface (inner surface side) of the plastic substrate 1 as a base
  • the second moisture barrier layer 7 is a second organic layer 10 is formed by vapor deposition using as a base.
  • the second moisture barrier layer 7 can also be formed using the first organic layer 9 as a base.
  • the base material serving as the base of the moisture barrier layer is disposed in the plasma processing chamber maintained at a predetermined degree of vacuum, and the film forming metal or gas of the compound containing the metal (reactive gas) And plasma treatment chamber, which is shielded by metal walls and depressurized to a predetermined degree of vacuum, using a gas supply pipe, as appropriate, with a carrier gas such as argon, helium, etc.
  • a carrier gas such as argon, helium, etc.
  • a film having a flexible region containing a carbon component at the interface with the base material of the base and a region (high oxidation degree region) excellent in barrier property with high oxidation degree thereon It is preferable to use an organic metal compound, for example, an organic aluminum compound such as trialkylaluminum, or a gas such as an organic titanium compound, an organic zirconium compound, an organic silicon compound from the viewpoint of being able to form Organosilicon compounds are most preferable in that the water barrier layer 3 or 7 having a high barrier property to oxygen can be formed relatively easily and efficiently.
  • organosilicon compounds examples include hexamethyldisilane, vinyltrimethylsilane, methylsilane, dimethylsilane, trimethylsilane, diethylsilane, propylsilane, phenylsilane, methyltriethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane
  • Organic silane compounds such as tetramethoxysilane, tetraethoxysilane, phenyltrimethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, octamethylcyclotetrasiloxane, 1,1,3,3-tetramethyldisiloxane, hexamethyl ester
  • An organic siloxane compound such as disiloxane is used. Besides these, aminosilane, silazane and the like can also be used.
  • the organometallic compounds described above can be used alone or in combination of two or more
  • the plastic substrate 1 or the like to be a base upon vapor deposition Of 10 -2 g / m 2 ⁇ day / atom or less, particularly 10 -3 g / m 2 ⁇ day / atom or less at 40 ° C and 90% RH.
  • the thickness is generally 4 to 500 nm, preferably about 30 to 400 nm, although it varies depending on the ratio of the high oxidation region described above.
  • a plurality of films having a moisture barrier layer may be stacked in order to ensure the water vapor transmission rate described above.
  • An anchor coat layer may be provided between the plastic substrate 1 and the second organic layer 10 and the moisture barrier layer, and between the first organic layer 9 and the moisture trap layer 5 for the purpose of improving adhesion. Good.
  • resins such as thermosetting resin and thermoplastic resin forming the anchor coat layer, both solvent-based and water-based resins can be used.
  • An epoxy resin, an oxazoline group-containing resin, a modified styrene resin, a modified silicon resin, an alkyl titanate and the like can be used alone or in combination of two or more.
  • the moisture trap layer 5 blocks the moisture flowing in the thickness direction with respect to the moisture barrier multilayer structure 11, and any material that exhibits such moisture barrier properties is not particularly limited, and a predetermined resin may be used.
  • physical desiccant such as zeolite or silica gel
  • chemical dispersant such as calcium oxide dispersed
  • hygroscopic non-ionic polymer such as polyvinyl alcohol, water-soluble nylon, polyethylene oxide, etc.
  • the layer may be a layer known per se, but in particular when high barrier properties to moisture are required, for example, an ionic polymer disclosed in JP-A-2015-96320 or the like is used as a matrix, and in this matrix It is preferable to have a structure in which a hygroscopic agent having a lower reaching humidity than that of the ionic polymer is dispersed. Those having such an ionic polymer as a matrix are excellent in water-capturing ability, and moreover deformation such as swelling due to water absorption can be effectively avoided.
  • FIG. 2 shows a typical structure of the water trap layer 5 having the above-mentioned ionic polymer as a matrix.
  • FIG. 2 (a) shows a cationic group (NH 2 group etc.) as an ionic group.
  • a water trap layer having a cationic polymer having a matrix as a matrix is shown in FIG. 2 (b), and an anionic polymer having an anionic group (COONa group, COOH group, etc.) as an ionic group.
  • a water trap layer is shown.
  • the water trap layer 5 having the above-mentioned ionic polymer as a matrix, a trace amount of water flowing through the above-mentioned first water barrier layer 3 is absorbed by this matrix (ionic polymer) .
  • the matrix itself exhibits high hygroscopicity, it absorbs and absorbs water without leakage. By the way, when water is merely absorbed into the matrix, the absorbed water is easily released due to environmental changes such as temperature rise. In addition, the penetration of water widens the space between the polymer molecules forming the matrix, and as a result, the water trapping layer 5 is also swollen.
  • the moisture absorbed in the matrix is more hygroscopic than the matrix (ie, the reaching humidity is lower).
  • the swelling by the absorbed water molecules is effectively suppressed, but the water molecules are trapped in the water trap layer 5, and as a result, the water from the water trap layer 5 Release is also effectively prevented.
  • the moisture trap layer 5 when the moisture trap layer 5 is formed by dispersing the hygroscopic agent in the ionic polymer, it has a dual function of trapping and trapping of moisture as well as high hygroscopic ability. Water can be trapped even in a low humidity atmosphere, without being trapped at a rate sufficiently faster than the rate at which moisture permeates the moisture barrier layer and leaking to the outside to further trap moisture throughout the layer, High moisture barrier properties can be realized.
  • Ionic polymer cationic polymer
  • cationic polymers are cationic groups that can be positively charged in water, such as primary to tertiary amino groups, quaternary ammonium groups, It is a polymer having pyridyl group, imidazole group, quaternary pyridinium and the like in the molecule.
  • Such cationic polymers can form a hygroscopic matrix because the cationic groups have strong nucleophilic action and capture water by hydrogen bonding.
  • the amount of cationic groups in the cationic polymer is generally such that the water absorption coefficient (JIS K-7209-1984) of the hygroscopic matrix to be formed is at least 20%, particularly 30% to 45%, under an atmosphere of 80% RH and 30.degree. It is sufficient if the amount is%.
  • cationic polymers such as allylamine, ethyleneimine, vinylbenzyltrimethylamine, [4- (4-vinylphenyl) -methyl] -trimethylamine, vinylbenzyltriethylamine, etc .; vinylpyridine, vinylimidazole etc. And / or at least one of cationic monomers represented by nitrogen-containing heterocyclic monomers; and salts thereof; optionally polymerizing or copolymerizing with other copolymerizable monomers; If necessary, those obtained by partial neutralization by acid treatment are used.
  • copolymerizable monomers include, but are not limited to, styrene, vinyl toluene, vinyl xylene, ⁇ -methylstyrene, vinyl naphthalene, ⁇ -halogenated styrenes, acrylonitrile, acrolein And methyl vinyl ketone, vinyl biphenyl and the like.
  • a monomer having a functional group capable of introducing a cationic functional group such as styrene, bromobutylstyrene, vinyltoluene, chloromethylstyrene, vinylpyridine, vinyl After polymerization, imidazole, ⁇ -methylstyrene, vinyl naphthalene and the like can be treated to be aminated, alkylated (quaternary ammonium chloride) and the like to obtain a cationic polymer.
  • allylamine is preferable from the viewpoint of film formability and the like.
  • introducing a crosslinked structure into the matrix formed using the above-mentioned cationic polymer improves mechanical stability while reducing the ability to absorb moisture and at the same time improve dimensional stability. It is preferable to That is, when the crosslinked structure is introduced into the hygroscopic matrix, when the matrix absorbs water, the molecules of the cationic polymer are bound to each other by the crosslinking, and the volume change due to swelling (water absorption) The mechanical strength and dimensional stability are improved.
  • the above-mentioned crosslinked structure can be introduced by blending a crosslinking agent in the coating composition for forming the water trap layer 5.
  • the anionic polymer used to form the hygroscopic matrix may be an anionic functional group that can be negatively charged in water, such as a carboxylic acid group, a sulfonic acid group, a phosphonic acid group, or these groups. It is a polymer having a partially neutralized acidic base in the molecule. An anionic polymer having such functional groups can form a hygroscopic matrix because the functional groups capture water by hydrogen bonding.
  • the amount of anionic functional groups in the anionic polymer varies depending on the type of functional group, but the water absorption of the hygroscopic matrix to be formed (JIS K-7209-1984) is 80% humidity as in the case of the cationic polymer described above.
  • the amount may be 20% or more, particularly 30% to 45% in an atmosphere of RH and 30 ° C.
  • anionic polymer having a functional group as described above examples include carboxylic acid monomers such as methacrylic acid, acrylic acid and maleic anhydride; ⁇ -halogenated vinyl sulfonic acid, styrene sulfonic acid, vinyl sulfonic acid and the like Sulfonic acid-based monomers; phosphonic acid-based monomers such as vinyl phosphoric acid; and salts of these monomers; and at least one other anionic monomer represented by Those obtained by polymerizing or copolymerizing with the monomers of (1) and, if necessary, partially neutralizing by alkali treatment are used.
  • carboxylic acid monomers such as methacrylic acid, acrylic acid and maleic anhydride
  • phosphonic acid-based monomers such as vinyl phosphoric acid
  • salts of these monomers and at least
  • copolymerizable monomers include, but are not limited to, styrene, vinyl toluene, vinyl xylene, ⁇ -methylstyrene, vinyl naphthalene, ⁇ -halogenated styrenes, acrylonitrile, acrolein And methyl vinyl ketone, vinyl biphenyl and the like.
  • an ester of the above-mentioned anionic monomer or a monomer having a functional group capable of introducing an anionic functional group such as styrene, vinyl toluene, vinyl
  • An anionic polymer can also be obtained by treatment with hydrolysis, sulfonation, chlorosulfonation, phosphoniumation, etc. after polymerization using xylene, ⁇ -methylstyrene, vinyl naphthalene, ⁇ -halogenated styrenes, etc. .
  • preferred anionic polymers are poly (meth) acrylic acids and their partially neutralized products (e.g. those which are partially Na salts).
  • the present invention it is particularly preferable to introduce a cross-linked structure also in the hygroscopic matrix formed using the above-mentioned anionic polymer, whereby the water trapping ability of the water trapping layer 5 is further enhanced.
  • the dimensional stability is further improved. That is, in the case of the anionic polymer, unlike the cationic polymer, since it is only a supplement of water by hydrogen bonds, the hygroscopicity can be improved by introducing a network structure (crosslinked structure) of a space suitable for moisture absorption into the matrix. It can be greatly enhanced.
  • Such a crosslinked structure is, for example, one having a hydrophobic moiety such as an alicyclic structure in a network structure, whereby the hygroscopic effect of the hydrophilic moiety is further enhanced. Furthermore, by introducing a cross-linked structure into the hygroscopic matrix, when the matrix absorbs water, the molecules of the anionic polymer are mutually constrained by the cross-linking, the volume change due to swelling (water absorption) is suppressed, and the dimensionally stable Improves the quality. Such dimensional stability improvement effect is the same as in the case of the cationic polymer described above.
  • the cross-linked structure described above is introduced by incorporating a cross-linking agent into the coating composition for forming the water trap layer 5, as in the case of the cationic polymer.
  • Hygroscopic agents The hygroscopic agent dispersed in the water trap layer 5 having the above-mentioned ionic polymer as a matrix has a lower reaching humidity than the ionic polymer (cationic or anionic polymer) forming the above-mentioned matrix, and extremely high moisture absorption performance
  • the hygroscopic agent having higher hygroscopicity than the matrix in this manner, the moisture absorbed in the matrix formed by the above-described ionic polymer is immediately captured by the hygroscopic agent, and is absorbed into the matrix of absorbed moisture.
  • the swelling of the water trap layer 5 due to the absorption of water is also effectively suppressed.
  • Those having an ultimate humidity of 6% or less under the conditions are preferably used. That is, if the ultimate humidity of the moisture absorbent is higher than that of the ionic polymer, the moisture absorbed in the matrix is not sufficient and the release of water is likely to occur, so that the water barrier property can not be significantly improved. I will.
  • the moisture absorbent as described above has a water absorption (JIS K-7209-1984) of 50% or more in an atmosphere of humidity 80% RH and temperature 30 ° C., and there are inorganic and organic ones.
  • inorganic hygroscopic agents include zeolite, alumina, activated carbon, clay minerals such as montmorillonite, silica gel, calcium oxide, magnesium sulfate and the like.
  • organic hygroscopic agents include cross-linked products of anionic polymers or their partially neutralized products.
  • anionic polymer examples include carboxylic acid monomers (such as (meth) acrylic acid and maleic anhydride), sulfonic acid monomers (such as halogenated vinyl sulfonic acid, styrene sulfonic acid and vinyl sulfonic acid), and phosphonic acid.
  • carboxylic acid monomers such as (meth) acrylic acid and maleic anhydride
  • sulfonic acid monomers such as halogenated vinyl sulfonic acid, styrene sulfonic acid and vinyl sulfonic acid
  • phosphonic acid examples include carboxylic acid monomers (such as (meth) acrylic acid and maleic anhydride), sulfonic acid monomers (such as halogenated vinyl sulfonic acid, styrene sulfonic acid and vinyl sulfonic acid), and phosphonic acid.
  • phosphonic acid examples include carboxylic acid monomers (such as (meth) acrylic acid and maleic anhydride),
  • a hygroscopic agent having a small particle size is preferable from the viewpoint of increasing the specific surface area and exhibiting high hygroscopicity (for example, the average primary particle size is 100 nm or less, particularly 80 nm or less).
  • Polymeric hygroscopic agents are best. That is, the hygroscopic agent of the organic polymer is very good in dispersibility of the ionic polymer in the matrix and can be uniformly dispersed, and emulsion polymerization, suspension polymerization, etc.
  • the amount of the hygroscopic agent as described above sufficiently exerts the characteristics, and significantly improves the moisture barrier property and suppresses the dimensional change due to swelling, and at the same time, the moisture barrier higher than the barrier exhibited by the moisture barrier layer It sets according to the kind of ionic polymer from a viewpoint of securing property over a long period of time.
  • the water trap layer 5 having the above-mentioned ionic polymer as a matrix and a hygroscopic agent dispersed in this matrix has a water vapor permeability of 10 -5 g, particularly in applications where super moisture barrier properties are required.
  • the super barrier property can be exhibited such as not more than 1 / m 2 / day, but in the case where the matrix is formed of a cationic polymer
  • it is present in an amount of at least 50 parts by weight, in particular 100 to 900 parts by weight, and more preferably 200 to 600 parts by weight, per 100 parts by weight of the ionic polymer in the water trap 5.
  • the matrix is formed of an anionic polymer
  • it is preferably present in an amount of 50 parts by weight or more, particularly 100 to 1300 parts by weight, per 100 parts by weight of the anionic polymer in the water trap layer 5 More preferably, the amount is 150 to 1200 parts by weight.
  • the water trap layer 5 described above uses a coating composition in which a hygroscopic agent and, if necessary, a crosslinking agent are dissolved or dispersed in a predetermined solvent in an ionic polymer to be a matrix, this coating composition is used as a first water It is formed by coating on the barrier layer 3 and drying to remove the solvent, but after such film formation, it is kept under reduced pressure in a dry atmosphere to release the moisture contained in this layer 5 It is necessary.
  • the multilayer structure 11 is manufactured in a state in which the water trap layer 5 contains water, the water reaches a saturated state in a short period of time. It is.
  • composition of the coating composition for forming the water trap layer 5 described above is as described in JP-A-2015-96320 and the like, and when the matrix is formed of a cationic polymer (hereinafter simply referred to as “ The term “cationic matrix” is different from that when it is formed by an anionic polymer (hereinafter simply referred to as “anionic matrix”).
  • the cationic polymer and the hygroscopic agent are used in the ratio described above. That is, the hygroscopic agent is formulated into the coating composition together with the cationic polymer in the amount described above, relative to 100 parts by weight of the cationic polymer.
  • a crosslinking agent for introducing a crosslinked structure into a hygroscopic matrix of a cationic polymer can introduce, for example, a siloxane structure or a polyalicyclic structure in the crosslinked structure, whereby a network of space suitable for moisture absorption Form a structure.
  • the crosslinking agent includes a crosslinkable functional group (eg, an epoxy group) capable of reacting with a cationic group and a functional group (eg, alkoxysilyl) capable of forming a siloxane structure in a crosslinked structure through hydrolysis and dehydration condensation.
  • a crosslinkable functional group eg, an epoxy group
  • a functional group eg, alkoxysilyl
  • Compounds having a group) can be used, and in particular, compounds of the following formula (1): X-SiR 1 n (OR 2 ) 3-n (1)
  • X is an organic group having an epoxy group at the end
  • R 1 and R 2 are each a methyl group, an ethyl group or an isopropyl group
  • n is 0, 1 or 2
  • the silane compound represented by is preferably used.
  • Such a silane compound has an epoxy group and an alkoxysilyl group as functional groups, and the epoxy group undergoes an addition reaction with a functional group (for example, NH 2 ) of the cationic polymer.
  • the alkoxysilyl group forms a silanol group (SiOH group) by hydrolysis, and forms a siloxane structure through condensation reaction to grow, thereby finally forming a crosslinked structure between cationic polymer chains.
  • SiOH group silanol group
  • a crosslinked structure having a siloxane structure is introduced into the matrix of the cationic polymer.
  • the coating composition contains a cationic polymer, it is alkaline, and as a result, the addition reaction between the cationic group and the epoxy group and the dehydration condensation between silanol groups are also rapidly promoted.
  • the organic group X having an epoxy group in the above formula (1) is typically a ⁇ -glycidoxyalkyl group, and examples thereof include ⁇ -glycidoxypropyltrimethoxysilane and ⁇ -glycidoxy.
  • Propylmethyldimethoxysilane is preferably used as the crosslinker.
  • that whose epoxy group in said Formula (1) is an alicyclic epoxy group like an epoxy cyclohexyl group is also suitable as a crosslinking agent.
  • an alicyclic structure when a compound having an alicyclic epoxy group such as ⁇ - (3,4-epoxycyclohexyl) ethyltrimethoxysilane is used as a crosslinking agent, an alicyclic structure, as well as a siloxane structure, may be incorporated in the crosslinked structure of the matrix. Structure is introduced. The introduction of such an alicyclic structure can more effectively exhibit the function of the matrix of forming a network of spaces suitable for moisture absorption.
  • A is a divalent hydrocarbon group having an aliphatic ring, such as a cycloalkylene group
  • the diglycidyl ester represented by can be used as a crosslinking agent.
  • a typical example of such a diglycidyl ester is represented by the following formula (2-1).
  • the diglycidyl ester of Formula (2) does not have an alkoxysilyl group, in order to introduce an alicyclic structure into a crosslinked structure, it forms the network of the space of the space suitable for moisture absorption in a matrix. Is effective.
  • the crosslinking agent mentioned above in an amount of 5 to 60 parts by weight, in particular 15 to 50 parts by weight, per 100 parts by weight of the cationic polymer It is desirable that at least 70% by weight or more, preferably 80% by weight or more of such a crosslinking agent is the silane compound of the formula (1) described above.
  • the amount of the crosslinking agent used is too large, mechanical strength may become brittle and the handling property may be impaired, and when it is formed into a paint, the thickening may be fast and an effective pot life may not be secured.
  • the resistance for example, mechanical strength
  • a severe environment for example, under high humidity
  • the solvent used for the coating composition containing the various components described above is not particularly limited as long as it can be removed by evaporation at a relatively low temperature, for example, alcohols such as methanol, ethanol, propyl alcohol and butanol Solvents, ketone solvents such as acetone and methyl ethyl ketone, mixed solvents of these solvents and water, or aromatic hydrocarbon solvents such as water, benzene, toluene, xylene and the like can be used, but in particular the coating composition
  • alcohols such as methanol, ethanol, propyl alcohol and butanol Solvents, ketone solvents such as acetone and methyl ethyl ketone, mixed solvents of these solvents and water, or aromatic hydrocarbon solvents such as water, benzene, toluene, xylene and the like
  • aromatic hydrocarbon solvents such as water, benzene, toluene, xylene and the like
  • the solvent mentioned above is used in such an amount that the coating composition has a viscosity suitable for coating, but the water absorption rate of the hygroscopic matrix to be formed may be appropriately adjusted to adjust the viscosity of the coating composition.
  • the nonionic polymer can also be blended in an appropriate amount to adjust to As such non-ionic polymer, polyvinyl alcohol, ethylene-propylene copolymer, saturated aliphatic hydrocarbon polymer such as polybutylene, styrene polymer such as styrene-butadiene copolymer, polyvinyl chloride, or These include various comonomers (eg, styrene-based monomers such as vinyltoluene, vinylxylene, chlorostyrene, chloromethylstyrene, ⁇ -methylstyrene, ⁇ -halogenated styrene, ⁇ , ⁇ , ⁇ ′-trihalogenated styrene, etc.) What cop
  • the anionic polymer and the hygroscopic agent are such that the amount of the hygroscopic agent relative to 100 parts by weight of the anionic polymer is in the range described above. Formulated into a coating composition.
  • a crosslinking agent is appropriately blended.
  • a compound having two or more crosslinkable functional groups for example, an epoxy group
  • a compound having two or more crosslinkable functional groups capable of reacting with the ionic group possessed by the anionic polymer
  • G is a glycidyl group
  • A is a divalent hydrocarbon group having an aliphatic ring, such as a cycloalkylene group
  • the diglycidyl ester represented by is preferably used.
  • the epoxy group reacts with the anionic group, and a crosslinked structure including an alicyclic structure by the divalent group A is formed in the matrix.
  • the formation of a crosslinked structure containing such an alicyclic structure results in suppression of swelling.
  • preferred ones are listed above, and in particular, from the viewpoint of being able to form a network structure of a space suitable for moisture absorption, it is represented by the above formula (2-1) Diglycidyl esters are most preferred.
  • the coating composition for such an anionic matrix it is desirable to use the above-mentioned crosslinking agent in an amount of 1 to 50 parts by weight, in particular 10 to 40 parts by weight, per 100 parts by weight of the anionic polymer.
  • the amount of the crosslinking agent used is too large, mechanical strength may become brittle and the handling property may be impaired, and when it is formed into a paint, the thickening may be fast and an effective pot life may not be secured.
  • the resistance for example, mechanical strength
  • a severe environment for example, under high humidity
  • the solvent used for the coating composition containing the various components described above is not particularly limited as long as it can be removed by evaporation at a relatively low temperature, and those mentioned for the coating composition for the cationic matrix The same kind can be used.
  • an alkali for example, sodium hydroxide or the like
  • the alkali can be added to the coating composition for the anion matrix described above for pH adjustment, and for example, the alkali is added so that the pH is about 8 to 12. It is good to do.
  • the solvent mentioned above like the coating composition for the cationic matrix, is used in such an amount that the coating composition has a viscosity suitable for coating, and the hygroscopic matrix formed to adjust the viscosity of the coating composition, or In order to adjust the water absorption of the above to an appropriate range, the nonionic polymers exemplified above can be blended in an appropriate amount.
  • film formation using the above-mentioned coating composition for forming a cationic matrix or for forming an anionic matrix comprises the above-mentioned coating composition It is performed by applying to the first moisture barrier layer 3 and heating to a temperature of about 80 to 160.degree.
  • the heating time depends, for example, on the capacity of the heating device such as a heating oven, but is generally several seconds to several minutes. By this heating, the solvent is removed, and further, the crosslinking agent can react with the ionic polymer to form the water trapping layer 5 in which the crosslinking structure is introduced into the matrix.
  • First organic layer 9 The water trap layer 5 formed as described above is adhered and fixed to the second water barrier layer 7 formed on the second organic layer 10 using an adhesive after the water release process is performed. Thus, the first organic layer 9 is formed between the water trapping layer 5 and the second water barrier layer 7. As understood from the above description, the first organic layer 9 is basically formed of an adhesive, but the invention is not limited to the adhesive, and in principle, the water trapping property is The functional layer may be made of a material exhibiting a function other than (further, water barrier property).
  • a buffer layer and a barrier layer are formed between the water trap layer and the water barrier layer so as not to place the water trap layer and the water barrier layer adjacent to each other, to reduce the volume fluctuation due to swelling due to moisture absorption of the water trap layer.
  • It may be a layer having a function such as a smoothing layer for forming a film, and an organic layer (adhesion to which an inorganic filler or a silane compound is added in order to further improve the barrier property and the adhesion with the inorganic layer, etc. Or the like).
  • the organic material forming the first organic layer 9 include urethane-based resin, polyester-based resin, polyether-based resin, epoxy-based resin, acrylic resin, phenol-based resin, melamine-based resin, and the like. .
  • the thickness t of the first organic layer 9 is set to an extremely thin range of less than 3 ⁇ m, particularly 2.5 ⁇ m or less. That is, if the thickness t is larger than the above range, the trap performance of the permeated water is lowered, and the amount of inflow of water from the end face of the first organic layer 9 is increased. Will disappear.
  • the lower limit of the thickness t of the first organic layer 9 is not particularly limited as long as the moisture trapping layer 5 and the second moisture barrier layer 7 are firmly adhered and fixed by the first organic layer 9, but In practice, it is set to at least 0.1 ⁇ m or more.
  • the adhesive for forming the first organic layer 9 described above there are known pressure-sensitive adhesives and so-called dry laminating adhesives in which an adhesive resin component is dissolved or dispersed in an organic solvent, for example, Urethane-based adhesives, polyester-based adhesives, polyether-based adhesives, epoxy-based adhesives, acrylic-based adhesives and the like can be used.
  • a urethane adhesive and an epoxy adhesive of a dry laminate adhesive are preferable from the viewpoint of low saturated moisture absorption and relatively high moisture barrier properties.
  • the above-mentioned urethane adhesive contains a polyol and a polyisocyanate as a resin component.
  • the polyol component is not limited thereto, but ethylene glycol, propylene glycol, 1,4-butanediol, diethylene glycol, 1,6-hexylene glycol, cyclohexane dimethanol, ethylene oxide adduct of bisphenol A, etc.
  • at least one kind of alcohols such as trimethylolmethane, trimethylolethane, trimethylolpropane and pentaerythritol, etc. are used.
  • polyester polyols for example, pentaerythritol triacrylate etc.
  • hydroxyl group-containing acrylates for example, pentaerythritol triacrylate etc.
  • the polyisocyanate is not limited to this, but is also limited to diphenylmethane diisocyanate (MDI), tolylene diisocyanate (TDI), hexamethylene diisocyanate (HDI), metaxylylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, lysine Mention may be made of at least one of isocyanate, isophorone diisocyanate (IPDI) and polynuclear condensates of these isocyanates.
  • MDI diphenylmethane diisocyanate
  • TDI tolylene diisocyanate
  • HDI hexamethylene diisocyanate
  • metaxylylene diisocyanate tetram
  • the terminal of the above-mentioned polyisocyanate may be blocked by a blocking agent, and as such a blocking agent, alcohols such as methanol, ethanol, lactic acid ester and the like; phenolic hydroxyl group-containing compounds such as phenol and salicylic acid ester Compounds; amides such as ⁇ -caprolactam and 2-pyrrolidone; oximes such as acetone oxime and methyl ethyl ketone oxime; methyl acetoacetate, ethyl acetoacetate, active acetylene compounds such as acetylacetone, dimethyl malonate and diethyl malonate; is there.
  • a blocking agent alcohols such as methanol, ethanol, lactic acid ester and the like
  • phenolic hydroxyl group-containing compounds such as phenol and salicylic acid ester Compounds
  • amides such as ⁇ -caprolactam and 2-pyrrolidone
  • oximes such as
  • the above-mentioned epoxy adhesive preferably contains at least two epoxy groups in the molecule.
  • a resin for example, aliphatic glycidyl ether, bisphenol A type, AD type, S type or F type glycidyl ether, hydrogenated bisphenol A type glycidyl ether, ethylene oxide adduct bisphenol A type glycidyl ether, propylene Oxide adducts Bisphenol A type glycidyl ether, Phenolic novolac resin glycidyl ether, Cresol novolac resin glycidyl ether, Bisphenol A novolac resin glycidyl ether, Naphthalene resin glycidyl ether, Trifunctional (or tetrafunctional) glycidyl ether , Glycidyl ether of dicyclopentadiene phenol resin, diallyl bisphenol A diglycidyl ether, allylated bisphenol A and epichlorohydrin Polycon
  • a curing agent for the above epoxy resin for example, polyurethane having an amino group end, phenol based compound, aliphatic amine, alicyclic amine, aromatic polyamine, polyamide, aliphatic acid anhydride, alicyclic acid anhydride, aroma Group acid anhydrides, dicyandiamides, organic acid dihydrazides, boron trifluoride amine complexes, imidazoles, tertiary amines and the like, and these can be used alone or in combination of two or more.
  • the pressure-sensitive adhesive includes, for example, an acrylic resin, an epoxy resin, an epoxy group-containing acrylic copolymer, a phenol resin, an epoxy resin curing agent, an isobutylene resin, and an epoxy resin curing agent What consists of at least 1 type chosen from an epoxy thermosetting resin is mentioned.
  • the first organic layer 9 made of the above-mentioned dry laminate adhesive is, for example, a first moisture barrier layer 7 formed on the second organic layer 10, and the adhesive is applied and dried. It is formed by pressure bonding to the water trap layer 5 formed on the water barrier layer 3.
  • another layer is provided on the side of the second organic layer 10 opposite to the side on which the second moisture barrier layer 7 is provided. It may be laminated to form a further multilayer structure, which can further improve the moisture barrier properties.
  • a moisture barrier layer may be further formed on the surface of the second organic layer 10.
  • a moisture barrier layer may be generally formed by vapor deposition or coating, as in the case of the moisture barrier layers 3 and 7 described above.
  • a water trap layer or a water barrier layer can be further formed through the above-mentioned water barrier layer, and a water trap layer is directly formed on the second organic layer 10, and a water barrier layer is formed thereon.
  • a moisture trapping layer can also be formed.
  • the moisture barrier layer and the moisture trap layer are formed according to the method described above, but an organic layer or the like may be formed between the moisture trap layer and the moisture barrier layer on the low moisture atmosphere side.
  • the thickness of the organic layer must also be set to the same thickness as that of the first organic layer 9 described above.
  • Such a moisture barrier multilayer structure 11 of the present invention can be suitably used as a film for sealing various electronic devices such as electronic circuits such as organic EL elements, solar cells, electronic papers, etc. Attached to various devices so that the plastic substrate 1 mentioned above is on the high humidity atmosphere side (specifically the atmosphere side) and the second organic layer 10 side is on the low humidity atmosphere side (specifically the device side) It can exhibit excellent moisture barrier properties and can effectively avoid leakage of charges due to moisture and the like, and can also be used to protect, for example, light emitting elements of organic EL and photovoltaic elements of solar cells.
  • a moisture barrier layer of silicon oxide was formed on one side of a 12 ⁇ m thick biaxially stretched PET film using a plasma CVD apparatus.
  • the film forming conditions are shown below.
  • a CVD apparatus having a high frequency power supply with a frequency of 27.12 MHz and a maximum output of 2 kW, a matching box, a metal cylindrical plasma processing chamber with a diameter of 300 mm and a height of 450 mm, and an oil rotary vacuum pump for evacuating the processing chamber was used.
  • a plastic substrate is placed on a parallel flat plate in a processing chamber, and 3 sccm of hexamethyldisiloxane and 45 sccm of oxygen are introduced, a high frequency oscillator is used to oscillate a high frequency with an output of 50 W, film formation is performed for 2 seconds, and an adhesion layer is formed. did.
  • a high frequency was oscillated with an output of 200 W by a high frequency oscillator, film formation was performed for 50 seconds, a moisture barrier layer of silicon oxide was formed, and a moisture barrier layer coated PET film A1 was obtained.
  • the obtained water barrier layer-coated PET film A1 had a water vapor transmission rate of 5 ⁇ 10 ⁇ 2 g / m 2 / day as measured in an atmosphere of 60 ° C. and 90% RH.
  • Example 1 Polyallylamine (PAN-15C, an aqueous solution, 15% solid content, manufactured by Nitto Bod Medical Co., Ltd.) as an ionic polymer was diluted with water to a solid content of 5% by weight to obtain a polymer solution.
  • ⁇ -glycidoxypropyltrimethoxysilane was used as a crosslinker, and it was dissolved in water to a concentration of 5% by weight to prepare a crosslinker solution.
  • the polymer solution and the crosslinker solution are mixed so that 15 parts by weight of ⁇ -glycidoxypropyltrimethoxysilane is contained with respect to 100 parts by weight of polyallylamine, and the mixed solution further contains, as a hygroscopic agent, A crosslinked product of sodium polyacrylate (manufactured by Toyobo Co., Ltd., TAFFIC HU-820E, aqueous dispersion, solid content 13%) is added so as to be 400 parts by weight relative to polyallylamine, and the solid content is 5%.
  • the reaction liquid was adjusted with water and stirred well to prepare a coating solution A for a water trap layer.
  • the coating liquid A obtained above was apply
  • the coated film is heat treated in a box-type electric oven under conditions of a peak temperature of 120 ° C. and a peak temperature holding time of 10 seconds to form a 3 ⁇ m thick water trap layer (corresponding to symbol 5 in FIG. 1) Coating film A1 was obtained.
  • a polyester resin (Toyobo Co., Ltd., Byron GK 880) was dissolved in 2-butanone so that the solid content was 3% by weight, to prepare a coating solution B for the organic layer.
  • the coating solution B was applied to the moisture trap layer of the laminate film A1 obtained above by a bar coater immediately after the formation of the moisture trap layer.
  • the coated film is heat-treated in a box-type electric oven under the conditions of a peak temperature of 120 ° C. and a peak temperature holding time of 10 seconds, and a first organic layer with a thickness of 0.1 ⁇ m (corresponding to symbol 9 in FIG. 1) To obtain a coating film B1.
  • a second moisture barrier layer (symbol 7 in FIG. 1) under the same conditions as the preparation of the moisture barrier layer coated PET film A1. ) was rapidly formed to obtain a multilayer structure.
  • Example 2 The resin base material used for the moisture barrier layer coated PET film A1 is replaced with a 12 ⁇ m biaxially stretched PET film from a 50 ⁇ m thick PET film (Cosmo Shine A4300 manufactured by Toyobo Co., Ltd.), and the moisture barrier layer coated PET film B1 is Created. Next, the coating solution A obtained above was applied to the moisture barrier layer of the moisture barrier layer-coated PET film B1 with a bar coater. The coated film was heat-treated in a box-type electric oven under conditions of a peak temperature of 120 ° C. and a peak temperature holding time of 10 seconds to form a water trap layer with a thickness of 3 ⁇ m, to obtain a coating film A2.
  • the same coating solution B as in Example 1 was used to apply a bar coater on the water trap layer of the above-mentioned coating film A2.
  • the coated film was heat-treated in a box-type electric oven under the conditions of a peak temperature of 120 ° C. and a peak temperature holding time of 10 seconds to form a first organic layer having a thickness of 0.1 ⁇ m to obtain a coating film B2 .
  • a second moisture barrier layer is rapidly formed on the first organic layer of the coating film B2 using a plasma CVD apparatus under the same conditions as the preparation of the moisture barrier layer-coated PET film A1. I got a structure.
  • Example 3 Main material resin (Arakawa Chemical Co., Ltd., DA 105 solid content 35%) and curing agent (Arakawa Chemical Co., Ltd., CL 102 H solid content 40%) are blended so as to have a weight ratio of 5: 2,
  • the coating solution C for the organic layer was prepared by adjusting the solid content to be 20% by weight with butanone.
  • the coating solution C was applied to the moisture barrier layer-coated PET film B1 having a thickness of 50 ⁇ m by a bar coater.
  • the coated film was heat-treated in a box-type electric oven under conditions of a peak temperature of 150 ° C. and a peak temperature holding time of 2 minutes to form an organic layer having a thickness of 1 ⁇ m, whereby a coating film C1 was formed.
  • the coating solution A obtained above was applied onto the organic layer of the coating film C1 by a bar coater.
  • the coated film was heat-treated in a box-type electric oven under the conditions of a peak temperature of 120 ° C. and a peak temperature holding time of 10 seconds to form a water trap layer with a thickness of 3 ⁇ m, to obtain a coating film A3.
  • the coating liquid C was applied by a bar coater immediately after the formation of the water trap layer on the water trap layer of the coating film A3 obtained above.
  • the coated film was heat-treated in a box-type electric oven under conditions of a peak temperature of 150 ° C. and a peak temperature holding time of 2 minutes to form a first organic layer having a thickness of 1 ⁇ m, whereby a coating film C2 was formed.
  • a second moisture barrier layer is rapidly formed on the first organic layer of the coating film C2 using a plasma CVD apparatus under the same conditions as the preparation of the moisture barrier layer coated PET film A1, I got a structure.
  • Example 4 In Example 2, in the glove box adjusted to a nitrogen concentration of 99.95% or more, the moisture is provided via the urethane adhesive having a thickness of 1.8 ⁇ m on the moisture trap layer of the coating film A2.
  • the barrier layer-coated PET film A1 was dry-laminated so that the moisture barrier layer was on the inner side, to obtain a multilayer structure having a layer structure as shown in FIG.
  • the urethane-based adhesive layer having a thickness of 1.8 ⁇ m corresponds to the organic layer.
  • Example 5 As a moisture trap layer, 75 weight parts of a resin component of a calcium oxide-containing LLDPE masterbatch (Omi Chemical Industry Co., Ltd., Bell-CML) as a moisture absorbing material, and a LDPE (Sumitomo Chemical Co., Ltd., Sumikasen) as a matrix resin layer
  • a hygroscopic functional component in this case, calcium oxide
  • a hygroscopic functional component in this case, calcium oxide
  • the moisture barrier layer coated PET film A1 is a moisture barrier via the urethane adhesive having a thickness of 1.8 ⁇ m on both sides of the moisture absorption film D1. It dry-laminated so that a layer might be inside and obtained the multilayer structure.
  • the urethane-based adhesive layer having a thickness of 1.8 ⁇ m corresponds to the organic layer.
  • Example 6 Two vapor-deposited PET films (GL-RD, produced by Letterpress Printing Co., Ltd.) formed by a commercially available PVD method were used, with the moisture barrier layer and the base PET surfaces of the substrate, using the urethane adhesive having a thickness of 1.8 ⁇ m. It dry-laminated and produced moisture barrier film layered product E1. Then, the moisture barrier film laminate E2 in which the moisture barrier layer and the substrate PET surfaces of the moisture barrier film laminate E1 are laminated and the substrate PET surfaces of the moisture barrier film laminate E1 are laminated The moisture barrier film laminate E3 was produced by dry lamination using the above-mentioned urethane adhesive with a thickness of 1.8 ⁇ m.
  • the coating solution D for the organic layer was prepared by adjusting the solid content to be 20% by weight with water.
  • the coating solution D obtained above was applied to both surfaces of the moisture barrier film laminate E3 by a bar coater.
  • the film after application is heat-treated in a box-type electric oven under conditions of peak temperature 150 ° C. and peak temperature holding time 2 minutes to form an organic layer with a thickness of 0.3 ⁇ m on both sides of the inorganic barrier film laminate E3. did.
  • the coating solution A is sequentially applied on the organic layers on both sides of the moisture barrier film laminate E3 by a bar coater, and a peak temperature 120 ° C., peak temperature holding time 10 seconds by a box-type electric oven A heat treatment was performed under the following conditions to obtain a coating film A4 having a water trap layer with a thickness of 3 ⁇ m on both sides.
  • the coating solution C is sequentially applied by a bar coater on the water trap layer formed on both sides of the coating film A4, and a peak temperature of 150 ° C. and a peak temperature holding time of 2 minutes by a box type electric oven It heat-treated on conditions, and created coating film C3 which has a 1-micrometer-thick organic layer on both sides.
  • the moisture barrier film laminate E2 is a moisture barrier layer via the urethane adhesive having a thickness of 1.8 ⁇ m on one side of the coating film C3. Dry lamination was performed so that the inner side was on the inside to obtain a multilayer structure.
  • the urethane-based adhesive layer having a thickness of 1.8 ⁇ m corresponds to the organic layer.
  • Example 7 The coating solution D, the coating solution A, and the coating solution C are sequentially applied on the moisture barrier layer of the inorganic barrier film E2 in the same manner as in Example 6 and heat treatment is performed to form a 1 ⁇ m thick film on one surface of the film. Coating film C4 having an organic layer was produced.
  • the coating film C4 is provided on the moisture barrier layer of the moisture barrier film laminate E1 via the urethane adhesive having a thickness of 1.8 ⁇ m. Dry laminating so that the organic layer side is inside, and further dry laminating the coating film C3 on the PET surface side of the moisture barrier film laminate E1 via the urethane adhesive having a thickness of 1.8 ⁇ m. , I got a multilayer structure. In the multilayer structure of Example 7, the urethane-based adhesive layer having a thickness of 1.8 ⁇ m corresponds to the organic layer.
  • Comparative Example 1 A multilayer structure was obtained in the same manner as in Example 1 except that the thickness of the first organic layer was set to 4 ⁇ m in Example 1.
  • Comparative Example 2 A multilayer structure was obtained in the same manner as in Example 4 except that the thickness of the urethane adhesive was changed to 3 ⁇ m in Example 4. In the multilayer structure of Comparative Example 2, the urethane adhesive layer having a thickness of 3 ⁇ m corresponds to the organic layer.
  • Plastic substrate 3 First moisture barrier layer 5: Moisture trap layer 7: Second moisture barrier layer 9: First organic layer 10: Second organic layer 11: Moisture barrier multilayer structure

Landscapes

  • Laminated Bodies (AREA)

Abstract

La présente invention a pour objet, dans une structure multicouche de barrière contre l'humidité comprenant une couche de barrière contre l'humidité et une couche de piégeage d'humidité, d'éviter efficacement une dégradation des performances de piégeage d'humidité de la couche de piégeage d'humidité en raison de l'écoulement du temps, ce qui permet d'obtenir des propriétés de super-barrière contre l'humidité pendant une longue période. La présente invention concerne une structure multicouche de barrière contre l'humidité (11) pourvue, sur un côté d'un élément de base en plastique (1) qui fait face à une atmosphère à l'humidité élevée, ledit côté ne faisant pas face à l'atmosphère à l'humidité élevée : de couches de barrière contre l'humidité (3, 7); d'une couche de piégeage d'humidité (5) située entre les couches de barrière contre l'humidité (3, 7); et d'une première couche organique (9) servant à relier la couche de piégeage d'humidité (5) et la couche de barrière contre l'humidité (7). La structure multicouche de barrière contre l'humidité (11) est caractérisée en ce que l'épaisseur t de la première couche organique (9) est comprise dans la plage de 0,1 µm ou plus à moins de 3 µm.
PCT/JP2018/027807 2017-08-18 2018-07-25 Structure multicouche de barrière contre l'humidité WO2019035326A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2020183064A (ja) * 2019-05-07 2020-11-12 東洋製罐グループホールディングス株式会社 水分バリア性積層フィルム

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007141685A (ja) * 2005-11-18 2007-06-07 Sumitomo Heavy Ind Ltd 封止構造体及び封止構造体の製造方法
JP2009090633A (ja) * 2007-09-20 2009-04-30 Fujifilm Corp ガスバリアフィルムおよびその製造方法、ならびに、ガスバリアフィルムを用いた電子デバイス
JP2015096320A (ja) * 2013-10-10 2015-05-21 東洋製罐グループホールディングス株式会社 水分バリア性の良好なガスバリア性積層体
WO2016021459A1 (fr) * 2014-08-07 2016-02-11 東洋製罐グループホールディングス株式会社 Stratifié à propriétés de barrière contre l'humidité
JP2017035829A (ja) * 2015-08-10 2017-02-16 東洋製罐グループホールディングス株式会社 水分バリア性積層体

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007141685A (ja) * 2005-11-18 2007-06-07 Sumitomo Heavy Ind Ltd 封止構造体及び封止構造体の製造方法
JP2009090633A (ja) * 2007-09-20 2009-04-30 Fujifilm Corp ガスバリアフィルムおよびその製造方法、ならびに、ガスバリアフィルムを用いた電子デバイス
JP2015096320A (ja) * 2013-10-10 2015-05-21 東洋製罐グループホールディングス株式会社 水分バリア性の良好なガスバリア性積層体
WO2016021459A1 (fr) * 2014-08-07 2016-02-11 東洋製罐グループホールディングス株式会社 Stratifié à propriétés de barrière contre l'humidité
JP2017035829A (ja) * 2015-08-10 2017-02-16 東洋製罐グループホールディングス株式会社 水分バリア性積層体

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2020183064A (ja) * 2019-05-07 2020-11-12 東洋製罐グループホールディングス株式会社 水分バリア性積層フィルム

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