JP2019084747A - Laminate film having moisture-barrier properties - Google Patents

Abstract

To provide a moisture-barrier laminate film having a moisture trap layer containing an inorganic barrier layer and an ionic polymer which effectively prevents cracking during heat-drying to release moisture from the moisture trap layer.SOLUTION: There is provided a moisture-barrier laminate film 10 which comprises a plastic film (A) having an inorganic barrier layer (A1) on its surface and a moisture trap layer (B), wherein a (meth)acrylic coating (C) is provided between the inorganic barrier layer (A1) and the moisture trap layer (B), the moisture trap layer (B) is formed using the (meth)acrylic coating (C) as a substrate and the (meth)acrylic coating (C) contains at least one functional group selected from the group consisting of an epoxy group, a silanol group and an isocyanate group.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a laminated film having an inorganic barrier layer and a water trap layer and having excellent water barrier properties.

  It is known to form an inorganic 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) ).

  By the way, various electronic devices developed and put into practice in recent years, such as organic electroluminescence (organic EL), solar cells, touch panels, electronic paper, etc. High moisture barrier properties are required for films that seal substrates and circuit boards. In the formation of the inorganic barrier layer described above, various proposals for improving the moisture barrier property have been made because the high requirements for the moisture barrier property can not be met.

  For example, in the patent documents 2 to 4, by the applicant, a water trap layer in which a specific particulate hygroscopic agent is dispersed in a matrix of an ionic polymer is formed on an inorganic barrier layer on a plastic substrate A gas barrier laminate film has been proposed.

As described above, various laminated films having a layer configuration in which an inorganic barrier layer and a water trap layer (such as a moisture absorption layer or a water absorption layer) are combined have been proposed to highly enhance the moisture barrier property. When the water trap layer is formed by direct application on the inorganic barrier layer, the film itself of the water trap layer is cracked due to volumetric shrinkage during heating and drying, resulting in deterioration of the barrier property and deterioration of the film appearance. There's a problem. In addition, there is also a problem that the adhesion to the inorganic barrier layer is weak, and film peeling (delamination) tends to occur.
The adhesion to the inorganic barrier layer can also be improved by long-term heating at a temperature of 100 ° C. or higher after the formation of the water trap layer, but long-term heating at high temperatures only greatly reduces productivity. Or, there is a possibility that the plastic film underlying the inorganic barrier layer may be deformed, and furthermore, the above-described cracking of the water trap layer may be promoted. Therefore, it is required to improve the adhesion between the water trap layer and the inorganic barrier layer without heating for a long time at high temperature.

  However, the problem of cracking during heat drying of the water trap layer and the adhesion between the water trap layer and the inorganic barrier layer have not been studied in detail until now.

JP 2000-255579 A WO2014 / 123197 JP, 2014-168949, A JP, 2014-168950, A

  Accordingly, an object of the present invention is to provide a moisture barrier laminate film comprising a plastic film (A) having an inorganic barrier layer (A1) on its surface and a moisture trap layer (B), comprising: a plastic film (A) and a moisture trap It is providing the moisture barrier laminated film excellent in the adhesiveness of a layer (B).

According to the present invention, a moisture barrier laminate film comprising a plastic film (A) having an inorganic barrier layer (A1) on its surface and a moisture trap layer (B),
A (meth) acrylic coating (C) is provided between the inorganic barrier layer (A1) and the water trapping layer (B), and the water trapping layer (B) comprises the (meth) acrylic coating (C) is formed as a base, and
The moisture-barrier laminate film is provided, wherein the methacrylic coating (C) contains at least one functional group selected from the group consisting of an epoxy group, a silanol group and an isocyanate group.

In the moisture barrier laminate film of the present invention, the following embodiment is suitably adopted.
(1) The water trap layer (B) contains a hygroscopic polymer.
(2) The water trap layer (B) has a structure in which a hygroscopic agent having a lower reaching humidity than that of the matrix is dispersed in a hygroscopic matrix of an ionic polymer.
(3) The ionic polymer contained in the water trap layer (B) is a cationic polymer.
(4) A protective layer (D) is provided between the inorganic barrier layer (A1) and the (meth) acrylic coating (C).
(5) At least one member selected from the group consisting of a water-soluble polymer (D1), an organoalkoxysilane or a hydrolyzate thereof, a metal alkoxide and a hydrolyzate thereof and a phosphorus compound as the protective layer (D) Containing the component (D2).
Such a moisture barrier laminate film of the present invention is suitably used as a sealing material for electronic devices.

According to the present invention, the (meth) acrylic resin particles and the curing agent having at least one functional group selected from the group consisting of an epoxy group, a silanol group and an isocyanate group are further dissolved or dispersed in a solvent. A (meth) acrylic coating composition for forming an undercoat layer of a water trap layer, comprising the coating composition of the present invention is provided.
In the (meth) acrylic coating composition of the present invention,
(1) The (meth) acrylic resin particles have a weight average molecular weight (Mw) of 20,000 or more,
(2) The (meth) acrylic resin particles have a particle diameter of 0.02 to 3 μm,
(3) Containing an isocyanate compound as the curing agent in an amount of 1 to 50 parts by weight per 100 parts by weight of the (meth) acrylic resin particles,
Or (4) containing a silane coupling agent as the curing agent in an amount of 0.1 to 50 parts by weight per 100 parts by weight of the (meth) acrylic resin particles,
Is preferred.

The moisture barrier laminate film of the present invention has a basic structure in which a moisture trap layer (B) is provided on the inorganic barrier layer (A1) present on the surface of the plastic film (A). However, it has an important feature in that a (meth) acrylic coating (C) serving as a base of the water trapping layer is present between the water trapping layer and the inorganic barrier layer. That is, the (meth) acrylic coating has a (meth) acrylic polymer or a cured product thereof as a matrix resin (film forming component), and the (meth) acrylic coating (C) has an epoxy group And at least one functional group selected from the group consisting of silanol groups and isocyanate groups.
In the present invention, since the water trapping layer (C) is formed with such (meth) acrylic coating (C) as a base, the water trapping layer (B) is strengthened by the (meth) acrylic coating (C) In this case, the stress generated in the water trapping layer during the heating and drying of the water is effectively relieved, and as a result, the cracking of the water trapping layer is effectively prevented.

For example, as shown in the experimental examples described later, adhesion is obtained when the coating composition for the water trap layer is applied directly to the surface of the inorganic barrier layer without using the (meth) acrylic coating (C) as the base. Is about 0.2 N / 15 mm. On the other hand, according to the present invention, a (meth) acrylic coating (C) is provided on the surface of the inorganic barrier layer, and the (meth) acrylic coating (C) is provided as a base of the water trap layer (B). The adhesion is greatly improved to a level of about 1 N / 15 mm.
Thus, when the adhesion of the water trap layer is improved, the water trap layer (B) is firmly held on the inorganic barrier layer through the (meth) (meth) acrylic coating (C), Peeling is effectively prevented.

  Thus, in the moisture barrier laminate film of the present invention, the cracking of the moisture trapping layer (B) is effectively avoided, the performance of the moisture trapping layer is sufficiently exhibited, and the excellent moisture barrier properties are stably exhibited. In addition, the water trap layer (B) is held with high adhesion even without long-time heat treatment at a temperature of 100 ° C. or higher. Therefore, high productivity can be secured, which is extremely industrially advantageous.

The figure which shows an example of the layer structure of the moisture barrier property laminated | multilayer film of this invention. The figure which shows the structure of the water trap layer (B) in the water-barrier laminated | multilayer film of FIG. The figure which shows the other example of the layer structure of a moisture barrier property laminated film.

The moisture barrier laminate film of the present invention generally indicated by 10 in FIG. 1 has a plastic film (A) as a substrate, and an inorganic barrier layer (a surface on which the plastic film (A) is formed) A1) is formed, and on the inorganic barrier layer (A1), a water trap layer (B) is provided with a (meth) acrylic coating (C) as a base. That is, on the inorganic barrier layer (A1) on the surface of the plastic film (A), a (meth) acrylic coating (C) and a water trap layer (B) are formed in this order.
In the plastic film (A), a protective layer (D) may be provided on the inorganic barrier layer (A1). That is, the (meth) acrylic coating layer (C) may be laminated directly on the inorganic barrier layer (A1) or, as shown in FIG. 3, suitably on the inorganic barrier layer (A1) It may be laminated on the provided protective layer (D).

<Plastic film (A)>
This film (A) is to be a base of the inorganic barrier layer (A1), and is usually injection or coinjection molding, extrusion or coextrusion molding using a thermoplastic or thermosetting resin according to its form. , Film or sheet molding, compression moldability, casting polymerization, and the like.

In general, thermoplastic resins are preferred from the viewpoint of moldability, cost and the like.
Examples of such thermoplastic resins are low density polyethylene, high density polyethylene, polypropylene, poly 1-butene, poly 4-methyl-1-pentene or ethylene, propylene, 1-butene, 4-methyl-1-pentene And polyolefins such as random or block copolymers of α-olefins with one another, cyclic olefin copolymers, etc., and ethylene / vinyl acetate copolymer, ethylene / vinyl alcohol copolymer, ethylene / vinyl chloride copolymer etc. Styrene-based resins such as ethylene / vinyl compound copolymer, polystyrene, acrylonitrile / styrene copolymer, ABS, α-methylstyrene / styrene copolymer, polyvinyl chloride, polyvinylidene chloride, vinyl chloride / vinylidene chloride copolymer , Poly (methyl acrylate), poly (methacrylate) Polyvinyl compounds such as chill, polyamides such as nylon 6, nylon 6-6, nylon 6-10, nylon 11, nylon 12, etc., thermoplastic polyesters such as polyethylene terephthalate (PET), polybutylene terephthalate, polyethylene naphthalate (PEN), Polycarbonate, polyphenylene oxide, and others, polyimide resin, polyamide imide resin, polyether imide resin, fluorine resin, allyl resin, polyurethane resin, cellulose resin, polysulfone resin, polyether sulfone resin, ketone resin, amino resin or poly It is formed of biodegradable resin such as lactic acid. Furthermore, these blends, or those obtained by appropriately modifying these resins by copolymerization (for example, acid-modified olefin resins) may be used.

  The plastic film (A) is also preferably formed of a gas barrier resin or the like excellent in oxygen barrier properties such as ethylene / vinyl alcohol copolymer, and is further formed of such a gas barrier resin It may have a multi-layered structure including the above layers.

  In the present invention, from the viewpoint of easy availability, cost, moldability, or barrier property against oxygen to some extent, and further, suitable as a base of the inorganic barrier layer (A1) described later, 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 film (A).

  The thickness in particular of such a plastic film (A) is not restrict | limited, According to a use, it should just have appropriate thickness.

<Inorganic barrier layer (A1)>
Furthermore, the inorganic barrier layer (A1) provided on the surface of the above-mentioned plastic film (A) may be one known in, for example, JP-A-2015-96320 and the like, and may be used for sputtering, vacuum evaporation, ion plating, etc. Inorganic vapor deposition films formed by physical vapor deposition represented by a representative method, chemical vapor deposition represented by a plasma CVD, etc., for example, films formed by various metals or metal oxides, can ensure high oxygen barrier properties. The plastic film (A) by plasma CVD in that it is suitable in that it is suitable, and in particular, it can be uniformly deposited on a surface having irregularities and exhibits excellent barrier properties against not only oxygen but also moisture. It is preferable to form as a base.

  In addition, the vapor deposition film by plasma CVD arrange | positions the plastic film (A) used as the foundation | substrate of an inorganic barrier layer (A1) in the plasma processing chamber hold | maintained at predetermined | prescribed vacuum degree, The film which forms a film or the compound containing this metal Gas (reactive gas) and oxidizing gas (usually oxygen or NOx gas), together with a carrier gas such as argon and helium, using a gas supply pipe, shielded by metal walls and depressurized to a predetermined degree of vacuum In this state, glow discharge is generated by microwave electric field or high frequency electric field, and plasma is generated by the electric energy, and the decomposition reaction product of the above compound is deposited on the surface of plastic film A. It can be obtained by depositing the film.

  Generally from the viewpoint of forming a film having a flexible region containing a carbon component at the interface with the base material of the base as the above-mentioned reaction gas and having thereon a region excellent in barrier property with a high degree of oxidation. 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, and in particular, an inorganic barrier layer (A1) having a high barrier property to oxygen. Organosilicon compounds are most preferred in that they can be formed relatively easily and efficiently.

Examples of such organosilicon compounds are 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 thickness of the above-mentioned inorganic barrier layer (A1) also varies depending on the application of the gas barrier laminate film 10 and the level of the required barrier property, but generally, a plastic substrate (A And the like, and a thickness such that a water vapor transmission rate of 10 ⁻¹ g / m ² · day / atom or less, in particular 10 ⁻² g / m ² · day / atom or less can be ensured. Although depending on the ratio occupied by the high oxidation degree region described above, the thickness may generally be about 4 to 500 nm, particularly about 30 to 400 nm.

  Furthermore, the above-mentioned inorganic barrier layer (A1) can also be formed on a plastic film (A) by coating etc. irrespective of methods such as vapor deposition. That is, although the inorganic barrier layer (A1) formed by the coating has lower properties such as oxygen barrier property as compared with the one formed by the above-mentioned vapor deposition etc., depending on the degree of the barrier property against oxygen etc required. And may be formed by coating.

  The inorganic barrier layer (A1) formed by coating includes polysilazane, a polycondensable silane compound (such as alkoxysilane), and a polycondensable alumina compound (such as alkoxyaluminum) as a film forming component. Typically, an organic solvent solution in which inorganic fine particles such as silica and alumina are mixed is applied to a predetermined surface, heated, and the organic solvent is volatilized to form a film.

<Water trap layer (B)>
The moisture trap layer (B) blocks moisture flowing in the thickness direction with respect to the moisture barrier laminated film 10, and any material that exhibits such moisture barrier properties is not particularly limited, and a predetermined one may be used. Hygroscopic inorganic particles such as physical desiccant such as zeolite and silica gel, or chemical desiccant such as calcium oxide dispersed in resin layer, and moisture absorption such as polyvinyl alcohol, water-soluble nylon, polyethylene oxide, etc. It may be a layer known per se, such as a non-ionic polymer having a property.
In particular, when a high barrier property to moisture is required, for example, an ionic polymer disclosed in JP-A-2015-96320 or the like is used as a matrix, and moisture absorption achieved in this matrix is lower than that of the ionic polymer. Those having a structure in which the agent is dispersed are preferred. Those having such an ionic polymer as a matrix are excellent in water-capturing ability, and by trapping the water in the dispersed hygroscopic agent, deformation such as swelling due to water absorption can be effectively avoided. It is.

Ionic polymers;
The ionic polymers used in the present invention include the following cationic polymers and anionic polymers.

The cationic polymer is a polymer having a cationic group which can be positively charged in water, for example, a primary to tertiary amino group, quaternary ammonium group, pyridyl group, imidazole group, quaternary pyridinium and the like in the molecule. is there. 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 5% or more, particularly 30% to 45% under an atmosphere of humidity 80% RH and 30 ° C. It is sufficient if the amount is%.

Moreover, as cationic polymers, amine monomers 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.
Such cationic polymers are described in detail in JP-A-2015-96320 and the like, and the details thereof are omitted, but generally, polyallylamine is preferable from the viewpoint of film formability and the like.

On the other hand, the anionic polymer is 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 an acidic base in which these groups are partially neutralized. It is a polymer possessed in it. 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 5% or more, particularly 30% to 45% in an atmosphere of RH and 30 ° C.

Examples of the anionic polymer having a functional group as described above include carboxylic acid monomers such as methacrylic acid, acrylic acid and maleic anhydride; α-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.
Such an anionic polymer is also described in detail in JP-A-2015-96320 and the like, and the details thereof are omitted, but generally, poly (meth) acrylic acid and its partially neutralized product (for example Part is Na salt).

Structure of water trap layer (B);
Referring to FIG. 2 (a) or (b), in the water trap layer (B), a hygroscopic agent having a lower reaching humidity than the ionic polymer (cationic or anionic polymer) forming the above matrix It is preferred that it is blended.
By dispersing 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. As well as being able to effectively exhibit the moisture absorption capacity of water even in an extremely low humidity atmosphere, the swelling of the water trap layer (B) due to the absorption of water is effectively suppressed.

  As the high hygroscopic hygroscopic agent as described above, one having an ultimate humidity of at most 80% RH and a temperature of 30 ° C. under an environmental condition of at most 6%, provided that the ultimate humidity is lower than that of the ionic polymer Is 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. Also, even if the ultimate humidity is lower than that of the ionic polymer, if the ultimate humidity measured under the above conditions is higher than the above range, for example, trapping of water in a low humidity atmosphere becomes insufficient, and the moisture barrier property May not be able to fully

The moisture absorbent as described above generally 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.
Examples of inorganic hygroscopic agents include zeolite, alumina, activated carbon, clay minerals such as montmorillonite, silica gel, calcium oxide, magnesium sulfate and the like.
Examples of organic hygroscopic agents include cross-linked products of anionic polymers or their partially neutralized products. Examples of the anionic polymer 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. Listed are those obtained by polymerizing or copolymerizing with at least one kind of an anionic monomer represented by an acid monomer (vinyl phosphate etc.) and a salt of these monomers, etc. be able to. Organic hygroscopic agents are effective especially in applications where transparency is required. For example, fine particles of crosslinked poly (meth) acrylate Na are a typical organic moisture absorbent.

In the present invention, 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. as a polymerization method for producing it By adopting this, it is possible to make the particle shape into a fine and uniform spherical shape, and by blending this to a certain extent or more, it becomes possible to secure extremely high transparency.
Further, in the case of an organic fine hygroscopic agent, not only the above-mentioned reaching humidity is extremely low, and not only high hygroscopicity is exhibited, but also the volume change due to swelling can be extremely reduced by crosslinking, thus suppressing the volume change. It is most suitable for reducing the humidity of the environmental atmosphere to an absolute or near absolute dryness condition.
As fine particles of such an organic hygroscopic agent, for example, crosslinked polyacrylic acid Na fine particles (average particle diameter: about 70 nm) in the form of a colloidal dispersion (pH = 10.4) manufactured by TOYOBO CO., LTD. It is marketed under the trade name.

In the present invention, the amount of the hygroscopic agent as described above sufficiently exerts the characteristics and effectively suppresses the dimensional change due to the remarkable improvement of the moisture barrier property and the swelling, and at the same time, the barrier exhibited by the inorganic barrier layer (A1) It is set according to the type of ionic polymer from the viewpoint of securing water barrier property higher than the property over a long period of time.
For example, the water trap layer (B) described above exhibits super barrier properties such that the water vapor transmission rate is 10 ⁻⁵ g / m ² / day or less, particularly in applications where super moisture barrier properties are required. The thickness is set to a certain thickness (for example, 1 μm or more, particularly about 2 to 20 μm), but when the matrix is formed of a cationic polymer, per 100 parts by weight of the ionic polymer in the water trapping layer (B) Preferably, it is present in an amount of 50 parts by weight or more, in particular 100 to 900 parts by weight, and more preferably 200 to 600 parts by weight. When 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 B, More preferably, the amount is 150 to 1200 parts by weight.

Further, in the water trap layer (B) having the above-mentioned structure, it is preferable that a crosslinked structure is introduced into the ionic polymer. That is, when a crosslinked structure is introduced into the ionic polymer, when water is absorbed, the molecules of the cationic polymer are mutually constrained by the crosslinking, and the volume change due to swelling (water absorption) is suppressed, the machine This improves the mechanical strength and dimensional stability.
Such a crosslinked structure can be introduced by blending a crosslinking agent in the coating composition for forming the water trap layer (B). Especially in the case of anionic polymers, unlike cationic polymers, since they only capture water by hydrogen bonding, their hygroscopicity can be greatly increased by introducing a network structure (crosslinked structure) of a space suitable for moisture absorption into the matrix. It can be enhanced.

  The crosslinking agent for introducing such a crosslinked structure is slightly different in the case of introducing a crosslinked structure in the cationic polymer and in the case of introducing a crosslinked structure in the anionic polymer.

The crosslinking agent for the cationic polymer includes a crosslinkable functional group capable of reacting with the cationic group (for example, an epoxy group) and a functional group capable of forming a siloxane structure in a crosslinked structure through hydrolysis and dehydration condensation (for example, , Compounds having an alkoxysilyl group) can be used, and in particular, compounds of the following formula (1):
X-SiR ¹ _n (OR ² ) _3-n (1)
In the formula, X is an organic group having an epoxy group at the end,
R ¹ and R ² are each methyl, ethyl or isopropyl
And
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. On the other hand, 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. Thereby, a crosslinked structure having a siloxane structure is introduced into the matrix of the cationic polymer.
Moreover, the cationic polymer is alkaline, and as a result, when the coating composition containing the cationic polymer is applied to form the water trap layer B, the addition reaction between the cationic group and the epoxy group or the dehydration condensation between silanol groups It is also promoted rapidly and can easily introduce a crosslinked structure.

In the present invention, the organic group X having an epoxy group in the above formula (1) is typically a γ-glycidoxyalkyl group, and examples thereof include γ-glycidoxypropyltrimethoxysilane and γ-glycidoxy. Propylmethyldimethoxysilane is preferably used as the crosslinker.
Moreover, 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. For example, when a compound having an alicyclic epoxy group such as .beta .- (3,4-epoxycyclohexyl) ethyltrimethoxysilane is used as a crosslinking agent, an alicyclic structure may be used together with the siloxane structure 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.

Furthermore, in order to introduce an alicyclic structure into the above-mentioned crosslinked structure, a compound having a plurality of epoxy groups and an alicyclic group, for example, the following formula (2):
G-O (C = O) -A- (C = O) O-G (2)
In the formula, G is a glycidyl group,
A is a divalent hydrocarbon group having an aliphatic ring, such as a cycloalkylene group
is there,
The diglycidyl ester represented by can be used as a crosslinking agent. Typical of such diglycidyl esters are represented by the following formula (2-1).

  That is, although 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 crosslinker mentioned above is preferably used in an amount of 5 to 60 parts by weight, in particular 15 to 50 parts by weight, based on 100 parts by weight of the cationic polymer, at least 70% by weight, preferably 80% by weight of such crosslinkers. It is desirable that the weight% or more is the silane compound of the formula (1) described above.

Moreover, as a crosslinking agent for introduce | transducing a crosslinked structure into anionic polymer, it has 2 or more of crosslinkable functional groups (for example, epoxy group) which can react with the ionic group which anionic polymer has. The compounds can be used and the formula (2) mentioned also for coating compositions for cationic matrices:
G-O (C = O) -A- (C = O) O-G (2)
In the formula, G is a glycidyl group,
A is a divalent hydrocarbon group having an aliphatic ring, such as a cycloalkylene group
is there,
The diglycidyl ester represented by is preferably used.

That is, in the diglycidyl ester of the above formula (2), 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 crosslinked structure containing such an alicyclic structure results in suppression of swelling.
In particular, among the above diglycidyl esters, preferable 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.

  Crosslinking agents for such anionic polymers are preferably used in amounts of 150 parts by weight, in particular 10 to 40 parts by weight, per 100 parts by weight of anionic polymer.

Formation of a moisture trap layer (B);
In the water trap layer (B) described above, a coating composition in which a hygroscopic agent and, if necessary, a crosslinking agent are dissolved or dispersed in a predetermined solvent in a resin as a matrix is used. It is formed by applying on the (meth) acrylic-based coating (C) formed on the barrier layer (A1) and drying by heating to remove the solvent. Such heat drying is usually performed at a temperature of about 100 to 170 ° C. for a short time of 3 minutes or less, particularly about 0.25 to 1 minute, whereby, via the (meth) acrylic coating (C), It is possible to form a water trap layer (B) in close contact with the inorganic barrier layer (A1).

The water trap layer (B) and the inorganic barrier layer (A1) can be obtained by heating to a high temperature of 100 ° C. or more for a long time (eg, 1 hour or more) without using the (meth) acrylic coating (C) as a base. It is possible to firmly hold the adhesion of That is, to promote the condensation reaction of the reactive functional group present in the matrix resin or crosslinking agent of the water trap layer (B) and the silanol group (SiOH group) present on the surface of the inorganic barrier layer (A1) It is thought that the adhesion is increased by
However, such means requires long-time heating at high temperature, as described above, and the thermal deformation of the plastic film (A) to be the base of the inorganic barrier layer (A1), the water trap layer (B) The coating film itself may be cracked or the like, and the production rate is also greatly reduced. In order to avoid such a disadvantage, as described above, it is necessary to form the water trap layer (B) by heating at a temperature lower than 100 ° C. for a short time.

  Further, in the coating composition used for forming the water trap layer (B) as described above, the solvent is not particularly limited as long as it can be volatilized and removed by heating at a relatively low temperature, for example, methanol Use of alcoholic solvents such as ethanol, propyl alcohol and butanol, ketone solvents such as acetone and methyl ethyl ketone, mixed solvents of these solvents and water, or aromatic hydrocarbon solvents such as benzene, toluene and xylene However, when the silane compound is formulated as a crosslinking agent, it is desirable to use water or a mixed solvent containing water in order to accelerate the hydrolysis. Furthermore, when the water trap layer (B) containing an anionic polymer is formed, it is desirable that the pH be adjusted to be about 8 to 12 by addition of an alkali (for example, sodium hydroxide).

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
Such non-ionic polymers include polyvinyl alcohol, ethylene-propylene copolymers, saturated aliphatic hydrocarbon polymers such as polybutylene, styrene polymers such as styrene-butadiene copolymer, polyvinyl chloride, or These include various comonomers (for example, styrene-based monomers such as vinyl toluene, vinyl xylene, chlorostyrene, chloromethyl styrene, α-methylstyrene, α-halogenated styrene, α, β, β′-trihalogenated styrene, etc.) What copolymerized monoolefins, such as ethylene and butylene, conjugated diolefins, such as butadiene and isoprene, etc. can be mentioned.

  In the present invention, as the water trap layer (B) described above, one containing a cationic polymer as a matrix (film forming component) is particularly preferable. That is, those having such a cationic polymer require long-time heating at a high temperature of 100 ° C. or higher to secure particularly high adhesion, but in the present invention, (meth) acrylic-based materials described below By providing the coating (C) as a base, the water trap layer (B) firmly held in close contact can be formed without performing such high temperature and long time heating, which is an advantage of the present invention The reason is that you can make the most of

<(Meth) acrylic coating (C)>
Although briefly described above, in the present invention, a (meth) acrylic coating (C) is provided between the plastic film (A) and the water trap layer (B), and this (meth) acrylic coating A moisture trap layer (B) is formed with (C) as a base.

  The film-forming component of the (meth) acrylic coating (C) is a (meth) acrylic polymer having at least one functional group selected from an epoxy group, a silanol group and an isocyanate group, or a cured product thereof It exhibits high affinity to a matrix (for example, an ionic polymer) in the water trapping layer (B), and contributes to the improvement of adhesion to the water trapping layer (B).

The nonfunctional (meth) acrylic polymer having no functional group as described above is a (meth) acrylic monomer such as, but not limited to, (meth) acrylic acid or It is obtained by polymerizing a compound having a (meth) acrylic group such as (meth) acrylic acid ester. Examples of (meth) acrylic acid esters include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate and the like.
In addition, the (meth) acrylic polymer may be a copolymer of a (meth) acrylic monomer and another monomer, as long as the properties thereof are not impaired. Such other monomers include, but are not limited to, unsaturated carboxylic acids such as maleic acid, fumaric acid, itaconic acid or acid anhydrides, styrene, o-, m-, p-methylstyrene And styrene-based monomers such as α-methylstyrene and α-methyl-p-styrene; unsaturated nitrile monomers such as (meth) acrylonitrile; unsaturated group-containing silane monomers such as (meth) acrylsilane; Compounds having an unsaturated group copolymerizable with an acryl group are typical.

  Furthermore, the (meth) acrylic coating (C) exhibits high adhesion to the water trapping layer (B), and can effectively prevent the delamination of the water trapping layer (B).

  In the present invention, functional (meth) acrylic polymers having at least one functional group selected from an epoxy group, a silanol group and an isocyanate group can also be used. When the nonfunctional (meth) acrylic polymer described above is used, it is necessary to use a curing agent having the above-mentioned functional group when forming the coating (C). In the case of using an acrylic polymer, such a curing agent can be omitted.

The functional (meth) acrylic polymer described above is a monomer (functional group introduced) having the above-mentioned function and a functional group copolymerizable with the (meth) acrylic monomer together with the (meth) acrylic monomer described above Monomer) is used as a comonomer to obtain a copolymer.
As such a monomer for functional group introduction, although a monomer known per se can be used, one example thereof is as follows, although it is not limited thereto.
Epoxy group introduction monomer;
Glycidyl (meth) acrylate,
Glycidyl oxymethyl (meth) acrylate,
Glycidyl oxyethyl (meth) acrylate,
Glycidyl oxypropyl (meth) acrylate,
Glycidyl oxybutyl (meth) acrylate,
Polyethylene glycol glycidyl (meth) acrylate,
Polypropylene glycol glycidyl (meth) acrylate etc.
Monomers for introducing silanol groups;
Vinyltrimethoxysilane,
Vinyltriethoxysilane,
Vinyltrichlorosilane,
Vinyltriacetoxysilane,
Vinyltris (β-methoxyethoxy) silane,
γ-methacryloyloxypropyl trimethoxysilane,
γ-methacryloyloxypropyl tris (β-methoxyethoxy) silane and the like.
Monomer for introducing isocyanate group 2-isocyanatoethyl (meth) acrylate,
2- (2-isocyanatoethoxy) ethyl methacrylate and the like.
In addition, as a monomer for functional group introduction, the compound which can be used as a hardening agent mentioned later besides the thing illustrated above can also be used.

  In the present invention, the above nonfunctional or functional (meth) acrylic polymer may basically have a film-forming molecular weight, but preferably has a weight average molecular weight Mw of 20,000. The above, more preferably 30,000 or more, further preferably 50,000 or more. When a (meth) acrylic polymer having a low molecular weight is used, a crack or the like is easily generated when forming the (meth) acrylic coating (C).

[Formation of (meth) acrylic coating (C)]
In the present invention, in the case of using a (meth) acrylic polymer in which a specific functional group has been introduced in advance, a coating composition in which the above (meth) acrylic polymer is dissolved or dispersed in a solvent, A (meth) acrylic-based coating (C) can be formed by applying on the inorganic barrier layer (A1) and heating at a temperature of 100 ° C. or higher for baking.
When a nonfunctional (meth) acrylic polymer to which no functional group is introduced is used, a curing agent having an epoxy group, a silanol group or an isocyanate group is blended in the coating composition, By curing at the time of film formation, these functional groups can be introduced into the (meth) acrylic coating (C).

  In the present invention, as the (meth) acrylic polymer used for the coating composition, it can be used in the form of particles regardless of whether or not a functional group is introduced, (meth) acrylic It is preferable to form a (meth) acrylic coating (C) in which the polymer is uniformly distributed. The (meth) acrylic resin particles generally have an integrated particle diameter (D50) in terms of volume measured by a laser diffraction scattering method in the range of 0.02 to 3 μm, particularly about 0.03 to 1 μm.

As a solvent used for formation of coating composition, what is necessary is just what does not become high temperature heating for solvent volatilization unnecessarily, for example, the thing volatilized by heating about 100 degreeC, for example, water, alcohol type organic solvent, Dialkyl glycol ether solvents, ethylene glycol ether solvents, propylene glycol ether solvents, or mixed solvents of these with water, ester solvents, ketone solvents, ether solvents, hydrocarbon solvents, etc. are used. Ru.
These solvents are used in such an amount that the coating composition has a viscosity suitable for coating.

  Moreover, the following can be mentioned as a hardening | curing agent for introduce | transducing an epoxy group, a silanol group, or an isocyanate group in this coating composition.

For example, as a curing agent for introducing an epoxy group or a silanol group, a silane coupling agent is used.
Such silane coupling agents include, but are not limited to, methyltrimethoxysilane, methyltriethoxysilane, methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, vinyltrimethoxysilane, and vinyltrimethoxysilane, for example. Ethoxysilane, vinyltrichlorosilane, vinyltriacetoxysilane, vinyltris (β-methoxyethoxy) silane, γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropyltris (β-methoxyethoxy) silane, γ-chloropropyltrimethoxy Silane, γ-chloropropylmethyldimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β- (3,4-epoxycycle Hexyl) ethyltrimethoxysilane, N- phenyl--γ- aminopropyltrimethoxysilane, can be exemplified a hexamethyldisilazane, they may be used alone or in combination of two or more.
Among these silane coupling agents, glycidyl groups such as γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, among others. Alternatively, an epoxy group-containing silane coupling agent is preferable in terms of adhesion to the water trap layer (B).

  These silane coupling agents are generally used in an amount of 0.1 to 50 parts by weight, preferably 1 to 50 parts by weight, per 100 parts by weight of (meth) acrylic polymer (particularly (meth) acrylic resin particles) in the coating composition. The amount is about 30 parts by weight, more preferably 5 to 20 parts by weight.

Moreover, as a hardening agent for distributing an isocyanate group, polyisocyanate can be mentioned.
Examples of the polyisocyanate include diphenylmethane diisocyanate (MDI), tolylene diisocyanate (TDI), hexamethylene diisocyanate (HDI), metaxylylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, lysine isocyanate, isophorone diisocyanate (IPDI), and the like. Polynuclear condensates of isocyanate and the like can be mentioned, and these can be used alone or in combination of two or more.

  From the viewpoint of storage stability, the end of the polyisocyanate may be blocked with a blocking agent. Examples of such blocking agents include alcohols such as methanol, ethanol and lactic acid ester; phenol, salicylic acid ester and the like Phenolic hydroxyl group-containing compounds; amides such as ε-caprolactam and 2-pyrrolidone; oximes such as acetone oxime and methyl ethyl ketone oxime; active acetomethyl compounds such as methyl acetoacetate, ethyl acetoacetate, acetylacetone, dimethyl malonate and diethyl malonate; And the like, and these blocking agents may be used alone or in combination of two or more.

  These polyisocyanates are usually 1 to 50 parts by weight, preferably 5 to 40 parts by weight, per 100 parts by weight of (meth) acrylic polymer (particularly (meth) acrylic resin particles) in the coating composition. More preferably, it is blended in an amount of 10 to 30 parts by weight.

  In addition, it is also possible to use together the silane coupling agent and polyisocyanate which were mentioned above.

Furthermore, in the coating composition described above, various compounding agents are added as long as the adhesion between the (meth) acrylic coating (C) to be formed and the water trap layer (B) is not impaired. It is also good.
Examples of such compounding agents include thermoplastic resins such as polyolefin resins, polyester resins, polyamide resins, vinyl resins and polycarbonate resins, layered inorganic compounds, stabilizers (antioxidants, heat stabilizers, etc.) UV absorbers, etc.), plasticizers, antistatic agents, lubricants, antiblocking agents, colorants, fillers, crystal nucleating agents, etc. can be exemplified.

<Protective layer (D)>
In the present invention, the (meth) acrylic coating (C) described above is formed on the inorganic barrier layer (A1) as shown in FIG. Although formed, the present invention is not limited to such an embodiment, and for example, as shown in FIG. 3, a protective layer (D) is provided on the inorganic barrier layer (A1), and this protective layer A (meth) acrylic coating (C) can also be provided on (D).

  The protective layer (D) is for preventing peeling, scratching, breakage and the like of the inorganic barrier layer (A1) after film formation, and for example, under an accelerated test environment (under 85 ° C.-85% RH environment) The layer is not particularly limited as long as the barrier property of the barrier film in the above does not decrease, but in general, it is formed from two or more types of compounds in which component (D1) and component (D2) shown below are blended. Ru.

  Component (D1) is a water-soluble polymer, and examples thereof include polyvinyl alcohol, polyvinyl pyrrolidone, starch, methyl cellulose, carboxymethyl cellulose, sodium alginate and the like. In particular, polyvinyl alcohol is preferred.

  Component (D2) is at least one compound selected from the group consisting of organoalkoxysilanes or their hydrolysates, metal alkoxides or their hydrolysates, and phosphorus compounds.

The above organoalkoxysilanes can be prepared, for example, by the following formula (3):
R-Si (OR ') ₃ (3)
In the formula, R is an organic group,
R 'is an alkyl group,
Is represented by
As said organic group, the group which has an alkyl group or various functional groups (For example, (meth) acryloyl group, a vinyl group, an amino group, an epoxy group, an isocyanate group etc.) can be mentioned.
The alkyl group represented by R ′ is not particularly limited, but is generally a lower alkyl group having 4 or less carbon atoms (for example, a methyl group, an ethyl group, a propyl group and a butyl group).

  As such organoalkoxysilanes, for example, ethyltrimethoxysilane, (meth) acryloxyapropyltrimethoxysilane, vinyltrimethoxysilane, glycidoxytrimethoxysilane, glycidoxypropyltrimethoxysilane, epoxycyclohexylethyl Trimethoxysilane, isocyanate propyl trimethoxysilane, or its hydrolyzate is mentioned, These are used individually by 1 type or in combination of 2 or more types. Among these, glycidoxytrimethoxysilane and epoxycyclohexylethyltrimethoxysilane containing an epoxy group, and isocyanate propyltrimethoxysilane containing an isocyanate group are particularly preferable. These organosilanes are not limited to monomers, and depending on the structure, compounds such as dimers and trimers can also be used.

Moreover, said metal alkoxide is a following formula (4):
M (OR ') n (4)
In the formula, M is a metal atom,
R 'is an alkyl group as in the above formula (3),
n is an integer indicating the valence of the metal atom M,
It is a compound represented by
As such a metal alkoxide, tetraethoxysilane, tripropoxy aluminum etc. can be mentioned, for example, and such a metal alkoxide is also used individually by 1 type or in combination of 2 or more types.

The organoalkoxysilanes and metal alkoxides described above can also be used as component (D2) in the form of a hydrolyzate, respectively.
Such a hydrolyzate can be obtained by a known method using an acid or an alkali, and upon hydrolysis, a reaction catalyst such as a tin compound can also be used as necessary.

Furthermore, as a phosphorus compound, phosphoric acid or its salt is mentioned. Specifically, orthophosphoric acid, pyrophosphoric acid, metaphosphoric acid, or alkali metal salts or ammonium salts thereof; condensed phosphoric acids such as trimetaphosphoric acid, tetrametaphosphoric acid, hexametaphosphoric acid, ultrametaphosphoric acid, or alkali metal salts thereof Ammonium salts and the like can be mentioned. In addition, phosphate esters such as triphenyl phosphate can also be used.
These phosphorus compounds can also be used singly or in combination of two or more.

The component (D1) and the component (D2) described above are melt mixed so that the mass ratio (D1) / (D2) = 99/1 to 70/30, and this molten mixture is subjected to the surface of the inorganic barrier layer (A1) Is applied to form a protective layer (D).
The thickness of the protective layer (D) thus formed is generally in the range of 0.01 to 50 μm, preferably 0.1 to 2 μm.

  In the present invention, although the inorganic barrier layer (A1) is provided only on one surface of the plastic film (A) in the example of FIGS. 1 and 3, it goes without saying that the inorganic barrier layer is provided on both sides of the film (A). (A1) can also be formed, and furthermore, a (meth) acrylic coating (C) and a water trap layer (B) can also be formed on each of the inorganic barrier layers (A1) formed on both sides. .

The water-barrier laminate film 10 of the present invention having the above-described layer structure forms a water-trapping layer (B) according to the above-described procedure, and after releasing water from the water-trapping layer (B), the water-trapping layer The dry film is adhered to the surface of (B) and stored in a protected state, and the dry film is peeled off at the time of use.
In such a water trap layer (B), for example, a water trap layer (B) provided on another barrier film or another barrier film by dry lamination after forming a (meth) acrylic coating (C) Can also be laminated.

<Use>
The moisture barrier laminate film described above is extremely excellent in productivity because the adhesiveness of the moisture trap layer is secured without heat treatment at a high temperature for a long time.
Furthermore, since the cracking and peeling of the water trap layer are effectively prevented, the excellent water barrier property of the water trap layer is stably exhibited. Therefore, it can be suitably used as a film for sealing various electronic devices, for example, electronic circuits such as organic EL elements, solar cells, electronic paper and the like.

  The invention is illustrated by the following experimental example.

<Method of measuring molecular weight of (meth) acrylic polymer>
It measured in terms of polystyrene by gel permeation chromatography (GPC).
Detector: Shodex RI-101
Separation column: Shodex OHpak SB-806M HQ × 2
Eluent: 10 mmol / L LithiumBramide in DMF
Flow rate: 1.0 ml / min
Column temperature: 50 ° C

<Crack evaluation>
The presence or absence of cracks in the A4 size sample of the produced moisture barrier laminate film was visually evaluated. At this time, those with cracks were rated as x, and those without were rated as o.

<Adhesive strength>
A 100 μm-thick PET film was dry-laminated to the produced moisture barrier laminated film with an epoxy adhesive, and aging was performed at 50 ° C. for 3 days to cure the adhesive layer, to prepare a sample for T-type peeling test.
Laminated body under a measurement condition of peeling speed of 300 mm / min using a test piece of width 15 mm and length 200 mm (including non-adhered part 50 mm) by T-type peeling test in an atmosphere of 23 ° C. and 50% RH. The moisture-barrier laminate film-PET laminate strength (unit: N / 15 mm) was measured (n = 4).
At this time, 1 N / 15 mm or more was regarded as 〇, and less than 1 N / 15 mm as ×.

<Preparation of Water Trap Layer Coating Liquid (B1) Using Cationic Polymer>
As a cationic polymer, polyallylamine (manufactured by Nittobo Medical, PAA-15C, aqueous solution, solid content 15%) was diluted with water to a solid content of 5% by weight to obtain a polymer solution.
On the other hand, it melt | dissolved in water so that it might be 5 weight%, and the crosslinking agent solution was prepared, using (gamma)-glycidoxy propyl trimethoxysilane as a crosslinking agent.
Next, the polymer solution and the crosslinker solution are mixed so that 20 parts by weight of γ-glycidoxypropyltrimethoxysilane is contained with respect to 100 parts by weight of polyallylamine, and the mixed solution further contains, as a hygroscopic agent, A cross-linked product of sodium polyacrylate (Toyobo Co., Ltd., Tuftic HU-820E, water dispersion, solid content 13%) is added so as to be 420 parts by weight relative to polyallylamine so that the solid content is 5%. The reaction liquid was adjusted with water and stirred well to prepare a coating solution (B1) for a water trap layer.

<Preparation of Water Trap Layer Coating Liquid (B2) Using Anionic Polymer>
Polyacrylic acid (Nippon Pure Chemical Industries, AC-10LP) is used as an anionic polymer, and it is dissolved in water / acetone mixed solvent (80/20 by weight ratio) so that the solid content is 5% by weight, and hydroxylated Sodium was added to a polyacrylic acid neutralization ratio of 80% to obtain a polymer solution.
In this polymer solution, diglycidyl 1,2-cyclohexanedicarboxylate as a crosslinking agent is added to 20 parts by weight with respect to the partially neutralized polyacrylic acid, and then β- (3,4-) is used as an adhesive. Epoxycyclohexyl) ethyltrimethoxysilane is compounded to be 3 parts by weight with respect to the partially neutralized polyacrylic acid, and a granular hygroscopic agent (Toyobo Co., Ltd., Tough-tic HU-820E, water dispersion, solid content 13% ) To 431 parts by weight relative to the partially neutralized polyacrylic acid, and further adjusted with water / acetone mixed solvent (80/20 by weight ratio) so that the total solid content is 5% by weight After stirring well, a coating solution (B2) for a water trap layer was prepared.

<Preparation of Water Trap Layer Coating Liquid (B3) Using Nonionic Polymer>
A polyvinyl alcohol (manufactured by Kuraray, PVA 103) as a nonionic polymer was diluted with water to a solid content of 5% by weight to obtain a polymer solution. On the other hand, it melt | dissolved in water so that it might be 5 weight%, and the crosslinking agent solution was prepared, using (gamma)-glycidoxy propyl trimethoxysilane as a crosslinking agent. Next, the polymer solution and the crosslinker solution are mixed so that 20 parts by weight of γ-glycidoxypropyltrimethoxysilane is contained with respect to 100 parts by weight of polyallylamine, and the mixed solution further contains, as a hygroscopic agent, A cross-linked product of sodium polyacrylate (Toyobo Co., Ltd., Tuftic HU-820E, water dispersion, solid content 13%) is added so as to be 420 parts by weight relative to polyallylamine so that the solid content is 5%. The reaction liquid was adjusted with water and stirred well to prepare a coating solution (B3) for a water trap layer.

Example 1
A silanol group-containing acrylic polymer (Mw = 40,000) was used as a main ingredient, and this was diluted with a mixed solvent of water and 2-propanol to prepare an acrylic coating solution with a solid content of 20%.
Moreover, the commercially available barrier film (A letterpress printing, GL-RD, base material: PET (12 micrometers)) which has a protective layer (D) on a silicon oxide layer (inorganic barrier layer) was prepared. This protective layer (D) consists of polyvinyl alcohol and tetraethoxysilane.
On the protective layer (D) of this barrier film, the above-mentioned acrylic coating solution is applied by a bar coater, and heat treated under the conditions of a peak temperature of 100 ° C. and a peak temperature holding time of 3 minutes by an electric oven Acrylic coating (C) was obtained.
On the acrylic coating (C), the water trap layer coating solution (B1) using the above cationic polymer is coated by a bar coater, heat treated under conditions of peak temperature 100 ° C., peak temperature holding time 3 minutes, thickness A 4 μm water trap layer (B) was formed to obtain a water barrier laminated film 10.

Example 2
A non-functional acrylic polymer (Mw = 30,000) is used as a main agent, and 100 parts by weight of this main agent is mixed with 10 parts by weight of a silane coupling agent (3-glycidyloxypropyltrimethoxysilane) as a curing agent And diluted with toluene to prepare a 20% solids acrylic coating solution.
A moisture barrier laminate film 10 was obtained in the same manner as in Example 1 except that this acrylic coating solution was used.

Example 3
An acrylic coating solution was prepared in the same manner as in Example 2 except that the amount of curing agent per 100 parts by weight of the main agent was changed to 50 parts by weight.
A moisture barrier laminate film 10 was obtained in the same manner as in Example 1 except that this acrylic coating solution was used.

Example 4
A commercially available barrier film (Mitsubishi resin, Tech Barrier LX, base material: PET 12 μm) having a silicon oxide layer as an inorganic barrier layer and not provided with a protective layer (D) was prepared.
A moisture trap layer (B) having a thickness of 4 μm was formed on the inorganic barrier layer of the barrier film in the same manner as in Example 1 except that an acrylic coating solution was applied, to obtain a moisture barrier laminate film 10.

Example 5
A water barrier laminate film 10 was obtained in the same manner as in Example 1 except that a water trap layer (B) having a thickness of 4 μm was formed using a water trap layer coating solution (B2) using an anionic polymer.

Example 6
A moisture barrier laminate film 10 was obtained in the same manner as in Example 1, except that a moisture trap layer coating solution (B3) using a nonionic polymer was used to form a moisture trap layer (B) having a thickness of 4 μm. .

Example 7
In the same manner as in Example 1, an acrylic coating solution (C) containing a silanol group-containing acrylic polymer (Mw = 40,000) as the main component was used to coat the protective layer (D) of a commercial barrier film. And a water trap layer (B) having a cationic polymer thereon.
Then, the above-mentioned acrylic coating liquid is applied by a bar coater on the opposite surface (surface of the PET film) of the barrier film on which the acrylic coating (C) and the water trap layer (B) are formed as described above The resultant was heat-treated in an electric oven under conditions of a peak temperature of 100 ° C. and a peak temperature holding time of 3 minutes to obtain an acrylic coating (C1) of 0.5 μm.
Furthermore, the coating liquid (B1) for a water trap layer having a cationic polymer is applied by a bar coater on the above-mentioned acrylic coating (C1) formed on the opposite side, and the peak temperature is 100 ° C., the peak temperature Heat treatment was performed under the conditions of a holding time of 3 minutes to form a water trap layer (B) having a thickness of 4 μm, and a water barrier laminated film 10 having a water trap layer (B) on both sides was obtained.

Example 8
Acrylic resin particles (Toyochem, TOCRYL X-4402, average particle diameter: 157 μm) were prepared as main ingredients.
100 parts by weight of this main agent is mixed with 5 parts by weight of a silane coupling agent (3-glycidyl oxypropyl trimethoxysilane) as a curing agent, diluted with a mixed solvent of water and 2-propanol, and acrylic coated at 20% solids The solution was prepared.
A moisture barrier laminate film 10 was obtained in the same manner as in Example 1 except that the above-mentioned acrylic coating solution was used.

Example 9
An acrylic coating solution was prepared in the same manner as in Example 8 except that the amount of the curing agent was changed to 10 parts by weight based on 100 parts by weight of the main agent, and a moisture barrier laminate film 10 was prepared in the same manner as in Example 8 (Example 1). I got

Example 10
An acrylic coating solution was prepared in the same manner as in Example 8 except that the amount of the curing agent was changed to 15 parts by weight based on 100 parts by weight of the main agent, and a moisture barrier laminate film 10 was prepared in the same manner as in Example 8 (Example 1). I got

Example 11
An acrylic coating solution was prepared in the same manner as in Example 8 except that the amount of the curing agent was changed to 20 parts by weight based on 100 parts by weight of the main agent, and a moisture barrier laminate film 10 was prepared by the same method as in Example 8 (Example 1). I got

Example 12
An acrylic coating solution was prepared in the same manner as in Example 8 except that the amount of the curing agent was changed to 40 parts by weight based on 100 parts by weight of the main agent, and a moisture barrier laminate film 10 was prepared by the same method as in Example 8 (Example 1). I got

Example 13
Moisture barrier property was the same as in Example 8 (Example 1) except that the curing agent was changed to blocked isocyanate (Mitsui Chemical, XWB-F206 MEDG) and the amount of curing agent was 30 parts by weight with respect to 100 parts by weight of the main agent. A laminated film 10 was obtained.

Comparative Example 1
A polyester resin (Mw = 18000, Toyobo "Vylon GK 880") was diluted with methyl ethyl ketone (MEK) to prepare an anchor coating solution having a solid content of 20%.
A moisture barrier laminate film 10 was obtained in the same manner as in Example 1 except that this anchor coating solution was changed to an acrylic coating solution to form a base layer of the moisture trap layer (B).

Comparative Example 2
Coating solution (B1) for water trap layer having cationic polymer is applied on the protective layer (D) of the barrier film without forming acrylic coating (C) to form a water trap layer (B) with a thickness of 4 μm A moisture barrier laminate film 10 was obtained in the same manner as in Example 1 except that the film was formed.

Comparative Example 3
The commercially available barrier film which has a silicon oxide layer used also in Example 4 as an inorganic barrier layer, and is not provided with a protective layer (D) was prepared.
On the inorganic barrier layer of the above barrier film, in the same manner as in Comparative Example 2, a water trap layer (B) having a thickness of 4 μm having a cationic polymer was formed to obtain a water barrier laminated film 10.

Comparative Example 4
A moisture barrier laminate film 10 was obtained in the same manner as in Example 1 except that an acrylic coating solution was prepared using the non-functional acrylic polymer (Mw = 5,000) as a main ingredient.

Comparative Example 5
A non-functional acrylic polymer (Mw = 30,000) was used as a main agent, and this main agent was diluted with toluene to prepare an acrylic coating solution with a solid content of 20%, in the same manner as in Example 1 A moisture barrier laminate film 10 was obtained.

<Evaluation test>
The various properties of the moisture barrier laminate film 10 prepared above were measured by the method described above, and the results are shown in Table 1.

A: Plastic film A1: Inorganic barrier layer B: Water trap layer C: (Meth) acrylic coating D: Protective layer 10: Gas barrier laminate film

Claims (12)

In a moisture barrier laminate film comprising a plastic film (A) having an inorganic barrier layer (A1) on the surface thereof and a moisture trap layer (B),
A (meth) acrylic coating (C) is provided between the inorganic barrier layer (A1) and the water trapping layer (B), and the water trapping layer (B) comprises the (meth) acrylic coating (C) is formed as a base, and
The water-barrier laminate film, wherein the (meth) acrylic coating (C) contains at least one functional group selected from the group consisting of an epoxy group, a silanol group and an isocyanate group.   The moisture barrier laminate film according to claim 1, wherein the moisture trap layer (B) contains a hygroscopic polymer.   The water trap layer (B) has a structure in which a hygroscopic agent having a lower reaching humidity than that of the matrix is dispersed in a hygroscopic matrix of an ionic polymer. The moisture barrier laminated film as described above.   The moisture barrier laminate film according to claim 2 or 3, wherein the ionic polymer contained in the water trap layer (B) is a cationic polymer.   The moisture gas barrier laminate film according to any one of claims 1 to 4, wherein a protective layer (D) is provided between the inorganic barrier layer (A1) and the (meth) acrylic coating (C).   The protective layer (D) is at least one component (D2) selected from the group consisting of a water-soluble polymer (D1), an organoalkoxysilane or a hydrolyzate thereof, a metal alkoxide and a hydrolyzate thereof, and a phosphorus compound. The water gas barrier laminate film according to claim 5, which contains   The sealing material for electronic devices which consists of a moisture barrier laminated film in any one of Claims 1-6.   It comprises a coating composition in which a (meth) acrylic resin particle and a curing agent having at least one functional group selected from the group consisting of an epoxy group, a silanol group and an isocyanate group are dissolved or dispersed in a solvent. An (meth) acrylic coating composition for forming an underlayer of a water trap layer characterized by the following.   The coating composition according to claim 8, wherein the (meth) acrylic resin particles have a weight average molecular weight (Mw) of 20,000 or more.   The coating composition according to claim 8 or 9, wherein the (meth) acrylic resin particles have a particle size of 0.02 to 3 μm.   The coating composition according to any one of claims 8 to 10, wherein an isocyanate compound is contained as the curing agent in an amount of 1 to 50 parts by weight per 100 parts by weight of the (meth) acrylic resin particles.   The coating composition according to any one of claims 8 to 10, wherein a silane coupling agent is contained as the curing agent in an amount of 0.1 to 50 parts by weight per 100 parts by weight of the (meth) acrylic resin particles. .