JP6287289B2 - Gas barrier laminate - Google Patents

Description

  The present invention relates to a gas barrier laminate in which an inorganic barrier layer and a moisture trap layer (moisture absorbing layer) are formed on a plastic substrate, and more specifically, such a gas barrier laminate and the laminate. The present invention relates to a coating composition used for forming a moisture trap layer.

  As a means for improving the characteristics of various plastic substrates, particularly gas barrier properties, it is known to form an inorganic barrier layer made of silicon oxide or the like on the surface of a plastic substrate by vapor deposition (Patent Document 1). ).

  By the way, in various electronic devices that have been developed and put to practical use in recent years, such as organic electroluminescence (organic EL), solar cells, touch panels, electronic papers, etc. A high moisture barrier property is required for a plastic substrate such as a film for sealing the substrate or the circuit board. Since the formation of the inorganic barrier layer described above cannot meet such a high demand for moisture barrier properties, various proposals for improving the moisture barrier properties have been made.

For example, in Patent Document 2, an inorganic barrier layer is formed on the surface of a plastic substrate, and a sealing layer in which nanoparticles such as metal oxide and carbon nanotubes are dispersed as a hygroscopic agent is provided on the inorganic barrier layer. Gas barrier laminates have been proposed.
Patent Document 3 proposes a gas barrier laminate (film) in which an inorganic barrier layer, an organic layer, and a water catching layer are formed on a base film, and the water catching layer has a hygroscopic polymer (film). Specifically, it is disclosed that it is formed from a polyamide) or is formed by dispersing a hygroscopic material such as silica gel or aluminum oxide in a polymer binder such as an electron beam or an ultraviolet curable resin.
Further, Patent Document 4 includes a gas barrier film layer and a moisture absorption layer formed by vapor deposition on the surface of a plastic substrate, and the moisture absorption layer contains alkylene oxide, acrylate nanoparticles, or an organometallic complex. A gas barrier laminate has been proposed.

However, even in the gas barrier laminate proposed in these Patent Documents 2 to 4, it is difficult to obtain a high moisture barrier property. For example, the water vapor permeability is 10 ⁻⁶ g / m ^{2 with} respect to moisture. In order to obtain a super-barrier property that is equal to or less than / day, it is necessary to have a layer structure in which many layers for moisture absorption (a moisture absorption layer or a sealing layer) exist, and as a result, There is a problem that labor is required for forming a multilayer structure, resulting in a decrease in productivity, and further improvement in moisture barrier properties is required. In addition, the moisture absorption layer (moisture absorption layer or sealing layer) swells due to moisture absorption, and there is a drawback in that it lacks dimensional stability.

JP 2000-255579 A JP 2010-511267 A JP 2009-90633 A JP 2011-131395 A

Accordingly, an object of the present invention is to provide a gas barrier laminate having a super barrier property against moisture with a small layer structure.
Another object of the present invention is to provide a gas barrier laminate in which swelling due to moisture absorption is effectively suppressed and dimensional stability is excellent.
Still another object of the present invention is to provide a coating composition suitably used for forming a moisture trap layer in the gas barrier laminate.

According to the present invention, a gas barrier laminate in which an inorganic barrier layer and a moisture trap layer are formed in this order on a plastic substrate, the moisture trap layer being formed from an anionic polymer (a). In addition, the matrix has a cross-linked structure introduced therein, and a particulate moisture absorbent (b) having a moisture absorption property in which the ultimate humidity is lower than that of the matrix is dispersed .
The particulate hygroscopic agent (b) is blended in an amount of 50 to 1300 parts by weight per 100 parts by weight of the anionic polymer (a).
The anionic polymer (a) is at least one anion of methacrylic acid, acrylic acid, maleic anhydride, α-halogenated vinyl sulfonic acid, styrene sulfonic acid, vinyl sulfonic acid, vinyl phosphoric acid and salts of these monomers. A homopolymer of a functional monomer or a copolymer with another copolymerizable monomer, or a partially neutralized product of these polymers by alkali treatment,
The particulate moisture absorbent (b) is an inorganic moisture absorbent selected from zeolite, alumina, activated carbon, montmorillonite, silica gel, calcium oxide and magnesium sulfate, or (meth) acrylic acid, maleic anhydride, vinyl halide sulfonic acid An anionic polymer which is a homopolymer of at least one anionic monomer of styrene sulfonic acid, vinyl sulfonic acid, vinyl phosphoric acid and salts of these monomers or a copolymer with other monomers, and A gas barrier laminate is provided which is an organic moisture absorbent selected from a crosslinked product of a partially neutralized product .

In the gas barrier laminate of the present invention, the following modes can be suitably employed.
(1) A siloxane structure is introduced into the matrix, and an alicyclic structure is included in the crosslinked structure.
(2) The crosslinked structure is introduced by a crosslinking reaction between the anionic group and the epoxy group of the anionic polymer, and the siloxane structure is introduced by a reaction between the anionic polymer and a silane compound. about.
(3) The moisture trap layer is blended with an adhesive (c) having a functional group reactive to the matrix into which the cross-linked structure is introduced and the surface of the inorganic barrier layer, A siloxane structure is introduced by the reaction between the adhesive and the matrix.
(4) The adhesive (c) is a compound having an alicyclic epoxy group and an alkoxysilyl group.
(5) The granular hygroscopic agent (b) is a crosslinked product of a monovalent metal salt of poly (meth) acrylic acid.
(6) The inorganic barrier layer is an inorganic oxide film formed by a CVD method.
(7) The moisture trap layer and the inorganic barrier layer are adjacent to each other.

According to the present invention, at least the anionic polymer (a), the particulate hygroscopic agent (b) having a hygroscopic property in which the ultimate humidity is lower than that of the anionic polymer (a), the crosslinking agent and the adhesive agent are used as the solvent. Dissolved or dispersed ,
The particulate hygroscopic agent (b) is blended in an amount of 50 to 1300 parts by weight per 100 parts by weight of the anionic polymer (a).
The anionic polymer (a) is at least one anion of methacrylic acid, acrylic acid, maleic anhydride, α-halogenated vinyl sulfonic acid, styrene sulfonic acid, vinyl sulfonic acid, vinyl phosphoric acid and salts of these monomers. A homopolymer of a functional monomer or a copolymer with another copolymerizable monomer, or a partially neutralized product of these polymers by alkali treatment,
The particulate moisture absorbent (b) is an inorganic moisture absorbent selected from zeolite, alumina, activated carbon, montmorillonite, silica gel, calcium oxide and magnesium sulfate, or (meth) acrylic acid, maleic anhydride, vinyl halide sulfonic acid An anionic polymer which is a homopolymer of at least one anionic monomer of styrene sulfonic acid, vinyl sulfonic acid, vinyl phosphoric acid and salts of these monomers or a copolymer with other monomers, and A coating composition is provided which is an organic moisture absorbent selected from a crosslinked product of a partially neutralized product .

The coating composition of the present invention is suitably used for forming the moisture trap layer of the gas barrier laminate, and for example, the following embodiments are suitable.
(1) the anionic polymer (a) 100 parts by weight of per previous SL crosslinking agent is 1 to 50 parts by weight, and that the adhesion agent is blended in an amount of 0.1 to 10 parts by weight.
(2) The particulate hygroscopic agent (b) is a cross-linked product of a monovalent metal salt of poly (meth) acrylic acid.
(3) The crosslinking agent is represented by the following formula (1):
G-O (C = O) -A- (C = O) OG (1)
Where G is a glycidyl group;
A is a divalent hydrocarbon group having an aliphatic ring,
It is a diglycidyl ester represented by
(4) The adhesive agent has the following formula (2):
X-SiR ¹ _n (OR ² ) _3-n (2)
In the formula, X is an organic group having an epoxy group,
R ¹ and R ² are each a methyl group, an ethyl group, or isopropyl.
And
n is 0, 1, or 2;
A silane compound represented by

In the present invention, the moisture trap layer can trap moisture even in an extremely low humidity atmosphere, traps moisture at a rate sufficiently faster than the rate at which moisture permeates the inorganic barrier layer, and traps moisture throughout the layer. Therefore, it does not leak outside. Thus, the gas barrier layered product of the present invention, the plastic substrate and the inorganic barrier layer and significantly high water barrier property with only three layers of the moisture trapping layer, such as an organic electroluminescence applicable to (organic EL) panel 10 ^- A moisture permeability of ⁶ g / m ² / day or less is also possible. Moreover, since the moisture supplemented by the matrix is taken into the hygroscopic agent (b), swelling of the moisture trap layer due to moisture absorption is also effectively suppressed, and therefore, the dimensional stability is also excellent.

  As described above, the gas barrier laminate of the present invention exhibits a remarkably high barrier property against moisture and is excellent in dimensional stability, and thus is useful as a substrate or a sealing layer for various electronic devices.

Explanatory drawing for demonstrating the principle about the gas-barrier laminated body of this invention. The schematic sectional drawing which shows the layer structure of the gas-barrier laminated body of this invention. 1 is a schematic cross-sectional view showing a layer structure of a laminate laminate produced in Example 1. FIG. FIG. 10 is a schematic cross-sectional view showing a layer structure of a laminate laminate produced in Example 12. FIG. 6 is a schematic cross-sectional view showing a layer structure of a laminate laminate produced in Comparative Example 6. The figure for demonstrating how to obtain | require a moisture absorption speed | velocity in an application experiment example. The figure which shows the relationship between temperature and relative humidity (attainment humidity) in an application experiment example.

<Principle of the present invention>
Referring to FIG. 1 showing the principle of moisture trapping in the moisture trap layer in the gas barrier laminate of the present invention, the moisture trap layer has many hydrophilic groups (COONa groups and COOH groups in FIG. 1). A matrix is formed by the anionic polymer (a), and the particulate moisture absorbent (b) is dispersed in the matrix (see FIG. 1A).

  In such a laminate, a trace amount of water that has passed through the plastic substrate (not shown in FIG. 1) and the inorganic barrier layer is captured by the moisture trap layer and absorbed by the matrix (FIG. 1B). reference). Since the matrix itself exhibits high hygroscopicity, moisture is captured and absorbed without leakage.

By the way, when the moisture is merely absorbed by the matrix, the interval between the polymer molecules forming the matrix is widened by the penetration of moisture, and as a result, the moisture trap layer swells. Further, the absorbed moisture is easily released due to environmental changes such as temperature rise.
However, in the present invention, the moisture absorbed in the matrix is further trapped by the particulate hygroscopic agent having a higher hygroscopicity (that is, lower ultimate humidity) than the matrix (see FIG. 1C). . For this reason, not only is the swelling caused by the absorbed water molecules effectively suppressed, but the water molecules are confined in the moisture trap layer, and as a result, the release of moisture from the moisture trap layer is also effectively prevented. It becomes. As described above, the moisture trap layer has a dual function of capturing and confining moisture as well as having a high moisture absorption capacity. Therefore, the moisture trap layer can capture moisture even in an extremely low humidity atmosphere as described later. In addition, the moisture is trapped at a rate sufficiently higher than the rate of permeation through the inorganic barrier layer and is not leaked to the outside in order to trap moisture in the entire layer. As a result, with only three layers of a plastic substrate, an inorganic barrier layer, and a moisture trap layer, a significantly high moisture barrier property, for example, 10 ⁻⁶ g / m ² / day or less applicable to an organic electroluminescence (organic EL) panel It is also possible to have a water permeability of.
In addition, as can be understood from FIG. 1, since the crosslinked structure is introduced into the matrix, the intermolecular expansion of the ionic polymer due to the penetration of moisture is suppressed, and the swelling due to the absorption of moisture is more effective. It is suppressed.
It will be described later that the moisture trap layer of the present invention can capture moisture even in an atmosphere of extremely low humidity, and can capture at a rate sufficiently faster than the rate at which moisture permeates the inorganic barrier layer. It is shown by applied experiments.

<Layer structure of gas barrier laminate>
Referring to FIG. 2 which shows a schematic cross section of the gas barrier laminate of the present invention having the moisture trap layer described above, this laminate as a whole is denoted by 10 on the surface of the plastic substrate 1 and the plastic substrate 1. The inorganic barrier layer 3 is formed and a moisture trap layer 5 is formed on the inorganic barrier layer 3.

<Plastic substrate 1>
In the present invention, the plastic of the plastic substrate 1 may be formed from a known thermoplastic or thermosetting resin.

Examples of such resins include, but are not limited to, low density polyethylene, high density polyethylene, polypropylene, poly 1-butene, poly 4-methyl-1-pentene or ethylene, propylene, 1- Random or block copolymers such as butene, 4-methyl-1-pentene, etc., polyolefins such as cyclic olefin copolymers, ethylene / vinyl acetate copolymers, ethylene / vinyl alcohol copolymers, Ethylene / vinyl compound copolymer such as ethylene / vinyl chloride copolymer, polystyrene, styrene resin such as acrylonitrile / styrene copolymer, ABS, α-methylstyrene / styrene copolymer, polyvinyl chloride, polyvinylidene chloride , Vinyl chloride / vinylidene chloride copolymer, polyacrylic Polyvinyl compounds such as methyl phosphate and polymethyl methacrylate, polyamides such as nylon 6, nylon 6-6, nylon 6-10, nylon 11 and nylon 12, polyethylene terephthalate (PET), polybutylene terephthalate, polyethylene naphthalate (PEN) ) And other thermoplastic polyesters, polycarbonate, polyphenylene oxide, polyimide resin, polyamideimide resin, polyetherimide resin, fluororesin, allyl resin, polyurethane resin, cellulose resin, polysulfone resin, polyethersulfone resin, ketone Resin, amino resin, biodegradable resin such as polylactic acid, etc. can be exemplified, and further, blends thereof, those resins modified by copolymerization as appropriate, or multilayer structure It may have.
In particular, in applications where transparency is required, polyester resins such as PET and PEN are suitable among the above, and polycarbonates and polyimide resins are preferable in applications where heat resistance is also required.
Of course, the above-mentioned various resins may contain a resin compounding agent known per se, for example, an antioxidant or a lubricant.

In addition, the form of the plastic substrate 1 is not particularly limited as long as the barrier property against moisture is sufficiently exhibited, and may have an appropriate form according to the application. The most common case is in the form of a film or sheet.
Furthermore, the thickness and the like are set in an appropriate range depending on characteristics (for example, flexibility, flexibility, strength, etc.) according to the application.

  Such a plastic substrate 1 is formed by known molding means such as injection or co-injection molding, extrusion or co-extrusion molding, film or sheet molding, compression moldability, and cast polymerization depending on the form and type of plastic. Can be molded.

<Inorganic barrier layer 3>
The inorganic barrier layer formed on the plastic substrate 1 is an inorganic vapor deposition film formed by physical vapor deposition represented by sputtering, vacuum vapor deposition, ion plating, etc., chemical vapor deposition represented by plasma CVD, etc. Although it is a film formed of various metals or metal oxides, in particular, it is uniformly formed even on a surface having irregularities, and it is dense and secures high adhesion to the plastic substrate 1 and has an excellent barrier. In view of exhibiting the properties, it is preferably a deposited film formed by plasma CVD.

In the vapor deposition film formed by plasma CVD, a plastic substrate 1 on which an inorganic barrier layer is to be formed is placed in a plasma processing chamber maintained at a predetermined vacuum degree, and a gas (reaction gas) of a metal or a compound containing the metal to form the film. And a plasma processing chamber in which an oxidizing gas (usually oxygen or NOx gas) is shielded by a metal wall and decompressed to a predetermined degree of vacuum using a gas supply pipe together with a carrier gas such as argon or helium as appropriate. In this state, a glow discharge is generated by a microwave electric field or a high-frequency electric field, plasma is generated by the electric energy, and a decomposition reaction product of the compound is deposited on the surface of the plastic substrate 1 to form a film. Can be obtained.
In the case of using a microwave electric field, film formation is performed by irradiating a microwave into the plasma processing chamber using a waveguide or the like. In the case of using a high-frequency electric field, a pair of plastic substrates 1 in the plasma processing chamber are attached. Films are formed by placing them between the electrodes and applying a high frequency electric field to the electrodes.

  The reaction gas is generally an organometallic compound from the viewpoint that a film having a flexible region containing a carbon component on the surface of a plastic substrate and a region having a high degree of oxidation and excellent barrier properties can be formed thereon. For example, it is preferable to use a gas such as an organoaluminum compound such as trialkylaluminum, an organic titanium compound, an organozirconium compound, or an organosilicon compound. Organosilicon compounds are most preferred because they can be formed well.

  Examples of such organosilicon compounds include hexamethyldisilane, vinyltrimethylsilane, methylsilane, dimethylsilane, trimethylsilane, diethylsilane, propylsilane, phenylsilane, methyltriethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane. , Tetramethoxysilane, tetraethoxysilane, phenyltrimethoxysilane, methyltrimethoxysilane, methyltriethoxysilane and other organic silane compounds, octamethylcyclotetrasiloxane, 1,1,3,3-tetramethyldisiloxane, hexamethyl Organic siloxane compounds such as disiloxane are used. Besides these, aminosilane, silazane and the like can also be used.

  In addition, the organometallic compound mentioned above can be used individually or in combination of 2 or more types.

  In the present invention, when forming a film by plasma CVD using the reaction gas and oxidizing gas of the organometallic compound as described above, the glow discharge output (for example, microwave or high frequency output) is lowered and the film is formed at a low output. After starting, it is preferable to perform film formation by plasma reaction at high output.

That is, organic groups (CH ₃ , CH _2, etc.) contained in the molecule of the organometallic compound are usually volatilized as CO ₂ , but at low output, some of them are not decomposed to CO ₂ , and plastic It is deposited on the surface of the substrate 1 and contained in the film. On the other hand, as the output is increased, the organic group is decomposed to CO ₂ . Therefore, by increasing the output, it becomes possible to reduce the C content in the film and form a film having a high degree of oxidation of the metal contained in the organometallic compound. However, a film having a high degree of oxidation of metal has a very high barrier property against a gas such as oxygen, but it has poor flexibility and is insufficient in adhesion to the plastic substrate 1, whereas the degree of oxidation of the metal is low. A low film with a high organic component content does not have sufficient gas barrier properties, but is highly flexible and exhibits high adhesion to the plastic substrate 1.

  As can be understood from the above description, in the present invention, an organometallic compound is used as a reaction gas, and film formation is performed at a low output in the initial stage of film formation by plasma CVD, and then the output is increased. As a result, a highly adhesive region containing a large amount of an organic component (carbon) is formed in a portion in contact with the surface of the plastic substrate 1, and a region having a high degree of metal oxidation and a high gas barrier property is formed thereon. It becomes.

  Therefore, the inorganic barrier layer 3 in the gas barrier laminate 10 according to the present invention has a metal (M) oxidation degree of x (x = O / M atomic ratio) in order to ensure excellent gas barrier properties. It is preferable to include a high oxidation degree region having an oxidation degree x of 1.5 to 2.0. In addition, on the lower side of the high oxidation degree region (the side in contact with the surface of the plastic substrate 1), the carbon (C) concentration is based on the three element standards of metal (M), oxygen (O), and carbon (C). An organic region of 20 element% or more is preferably formed. Further, silicon (Si) is most preferable as the metal (M).

The high oxidation degree region in the inorganic barrier layer 3 is preferably present at a ratio of 60% or more of the total thickness of the inorganic barrier layer 3, and the organic region is 5% of the total thickness of the inorganic barrier layer 3. It is preferably formed on the surface and contact side of the plastic substrate 1 with a thickness of about 40%.
Further, the overall thickness of the inorganic barrier layer 3 varies depending on the use of the gas barrier laminate 10 and the required level of gas barrier properties, but in general, the thickness is such that the characteristics of the plastic substrate 1 are not impaired. It should be a 4 to 500 nm thin film.

The glow discharge output when the inorganic barrier layer 3 is formed by plasma CVD in the organic region or the high oxidation region described above is slightly different between the case of using microwaves and the case of using high frequencies. For example, in the case of microwaves, the organic region is formed with a low output of about 30 to 100 W, and in the high oxidation region, the film is formed with a high output of 90 W or more. In the case of high frequency, the organic region is formed with a low output of about 20 to 80 W, and in the high oxidation region, the film is formed with a high output of 100 W or more.
The film formation time may be set so that the thickness of each region is within the above-described range.

<Moisture trap layer 5>
The gas barrier laminate 10 of the present invention includes a moisture trap layer 5 on the inorganic barrier layer 3. The moisture trap layer 5 has a hygroscopic matrix formed from an anionic polymer (a). The matrix has a structure in which the particulate moisture absorbent (b) having a lower reach humidity than the matrix is dispersed in the matrix.
That is, by forming the moisture trap layer 5 having such a dispersion structure on the inorganic barrier layer 3, as described above, a remarkably high super-barrier property against moisture can be obtained.

Hygroscopic matrix (anionic polymer (a));
In the present invention, the anionic polymer (a) used for forming the hygroscopic matrix 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, and the like. It is a polymer having in its molecule an acidic base whose group is partially neutralized. The anionic polymer having such a functional group can form a hygroscopic matrix because the functional group captures water by hydrogen bonding.
The amount of anionic functional group in the anionic polymer (a) varies depending on the type of the functional group, but generally, the water absorption rate of the formed hygroscopic matrix (JIS K-7209-1984) is 80% RH and 30% humidity. The amount may be 20% or more, particularly 30% to 45% in the atmosphere of ° C.

Examples of the anionic polymer (a) having the above functional group include carboxylic acid monomers such as methacrylic acid, acrylic acid, and maleic anhydride; α-halogenated vinyl sulfonic acid, styrene sulfonic acid, and vinyl. A sulfonic acid monomer such as sulfonic acid; a phosphonic acid monomer such as vinyl phosphoric acid; and salts of these monomers; Those obtained by polymerization or copolymerization with other possible monomers and, if necessary, partial neutralization by alkali treatment are used.
Examples of other copolymerizable monomers include, but are not limited to, styrene, vinyl toluene, vinyl xylene, α-methyl styrene, vinyl naphthalene, α-halogenated styrenes, acrylonitrile, acrolein. , Methyl vinyl ketone, vinyl biphenyl and the like.

  Further, instead of using the anionic monomer, an ester of the anionic monomer or a monomer having a functional group capable of introducing an anionic functional group, such as styrene, vinyl toluene, vinyl, etc. Xylene, α-methylstyrene, vinylnaphthalene, α-halogenated styrenes, etc. are used, and after the polymerization, treatments such as hydrolysis, sulfonation, chlorosulfonation, and phosphoniumation are performed to obtain an anionic polymer (a). You can also.

  In the present invention, a suitable anionic polymer (a) is poly (meth) acrylic acid and a partially neutralized product thereof (for example, a part thereof is a Na salt).

The polymerization for forming the anionic polymer (a) described above is generally carried out by radical polymerization by heating using a polymerization initiator.
The polymerization initiator is not particularly limited, but octanoyl peroxide, lauroyl peroxide, t-butylperoxy-2-ethylhexanoate, benzoyl peroxide, t-butylperoxyisobutyrate, t-butylperoxide. Organic peroxides such as oxylaurate, t-hexyl peroxybenzoate, and di-t-butyl peroxide are typical, and in general, the above-mentioned anionic monomer (or a single amount capable of introducing an anionic group) Body) It is used in an amount of about 0.1 to 20 parts by weight, particularly about 0.5 to 10 parts by weight per 100 parts by weight.

  An anionic polymer (a) is obtained by carrying out the polymerization as described above, but when a monomer capable of introducing an anionic functional group is used, hydrolysis, sulfonation, An anionic group introduction treatment such as chlorosulfonation or phosphoniumation may be performed.

In the present invention, a crosslinked structure is introduced into the hygroscopic matrix formed using the anionic polymer (a) described above, thereby further improving the moisture barrier property and further improving the dimensional stability. Improvement has been brought.
That is, in the case of an anionic polymer, unlike a cationic polymer, it is only supplemented with water by hydrogen bonding, so that a crosslinked structure is required to obtain sufficient hygroscopicity. In particular, it is preferable to form a network structure of a space suitable for moisture absorption in the matrix. By forming a hydrophobic site such as an alicyclic structure in the network structure, the moisture absorption effect of the hydrophilic site can be further enhanced. Furthermore, since a cross-linked structure is introduced into the hygroscopic matrix, when the matrix absorbs water, the molecules of the anionic polymer (a) are constrained to each other by cross-linking, and volume change due to swelling (water absorption) is suppressed. Will be.

The cross-linked structure is introduced by blending a cross-linking agent in the coating composition for forming the moisture trap layer 5. The crosslinking agent used here will be described later.
In addition, it forms by anionic polymer (a) by mix | blending and polymerizing polyfunctional monomers, such as divinylbenzene, in the polymerizable monomer composition for forming the anionic polymer (a) mentioned above. Although it is possible to introduce a crosslinked structure into the matrix, in this case, it becomes difficult to form the moisture trap layer 5 using the coating composition containing the anionic polymer (a) ( Such as a uniform dispersibility of the coating composition and a decrease in coating properties), which is less desirable.

Granular hygroscopic agent (b);
In the present invention, the particulate moisture absorbent (b) is dispersed in the moisture trap layer 5 having the above-described anionic polymer (a) as a matrix (hygroscopic matrix). This hygroscopic agent has an extremely high moisture absorption performance because it has a lower ultimate humidity than the anionic polymer (a) forming the hygroscopic matrix. That is, in the moisture trap layer 5, a hygroscopic agent having a higher hygroscopic property than the matrix is dispersed, so that the moisture absorbed in the hygroscopic matrix is immediately captured by the hygroscopic agent and absorbed. The trapped moisture is effectively trapped in the matrix.
As a result, in the present invention, the release of moisture trapped in the moisture trap layer 5 is effectively suppressed, and the moisture absorption ability can be effectively exhibited even in an extremely low humidity atmosphere, and moisture absorption is also achieved. The swelling of the hygroscopic matrix due to is also effectively suppressed.

  As the above highly hygroscopic particulate hygroscopic agent (b), on the condition that the ultimate humidity is lower than that of the anionic polymer (a), for example, as shown in the examples described later, the humidity is 80%. Those having an ultimate humidity of 6% or less under environmental conditions of RH and temperature of 30 ° C. are preferably used. That is, when the moisture reach of the hygroscopic agent is higher than that of the anionic polymer (a), the moisture absorbed in the hygroscopic matrix is not sufficiently confined, and the release of moisture is likely to occur. I can't expect improvement. Further, even when the ultimate humidity is lower than that of the anionic polymer (a), if the ultimate humidity measured under the above conditions is higher than the above range, for example, moisture trapping in a low humidity atmosphere becomes insufficient, There is a possibility that the moisture barrier property cannot be fully exhibited.

The particulate hygroscopic agent (b) as described above generally has a water absorption rate of 50% or more (JIS K-7209-1984) in an atmosphere of 80% humidity and 30 ° C., and is inorganic and organic. There is something.
Examples of inorganic hygroscopic agents include clay minerals such as zeolite, alumina, activated carbon, and montmorillonite, silica gel, calcium oxide, and magnesium sulfate.
Examples of the organic hygroscopic agent include a crosslinked product of an anionic polymer or a partially neutralized product thereof. 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 phosphones. Listed are those obtained by polymerizing or copolymerizing at least one of an anionic monomer represented by an acid monomer (such as vinyl phosphoric acid) and salts of these monomers with other monomers. be able to. In particular, in applications where transparency is required, organic moisture absorbents are effective. For example, fine particles of a crosslinked product of a monovalent metal salt of poly (meth) acrylic acid such as crosslinked poly (meth) acrylic acid Na and crosslinked poly (meth) acrylic acid K are typical organic moisture absorbents.

In the present invention, next to the specific surface area is large, preferably the particle size is small hygroscopic agent from the viewpoint of showing a high moisture absorption (e.g., average primary particle diameter D ₅₀ at reduced volume as measured by a laser diffraction scattering method 100nm or less In particular, an organic polymer hygroscopic agent having a small particle size is most suitable.
In other words, the organic polymer hygroscopic agent has a very good dispersibility in the matrix of the anionic polymer (a) and can be dispersed uniformly, as well as emulsion polymerization and suspension as a polymerization method for producing this. By adopting turbid polymerization or the like, the particle shape can be made into a fine and uniform spherical shape, and by blending this to some extent, extremely high transparency can be secured. . Such transparency is presumably because fine and spherical hygroscopic particles are distributed in the vicinity of the interface between the moisture trap layer and the adjacent layer (for example, an inorganic barrier layer), and light scattering at this interface. This is considered to be suppressed. In particular, ensuring the transparency is a great advantage when the gas barrier laminate 10 is used for a substrate such as an organic EL panel or a sealing layer.
In addition, in the organic fine moisture absorbent, the above-mentioned reached humidity is remarkably low, and not only shows high hygroscopicity, but also volume change due to swelling can be extremely reduced by cross-linking, and therefore, while suppressing the volume change, It is most suitable for reducing the humidity to the place where the environmental atmosphere is completely dry or near dry.
As such organic hygroscopic fine particles, for example, crosslinked polyacrylic acid Na fine particles (average particle diameter of about 70 nm) in the form of a colloidal dispersion (pH = 10.4), Tufic HU-820E from Toyobo Co., Ltd. It is commercially available under the trade name.

Other suitable organic hygroscopic agents include fine particles made of a crosslinked polymer having a potassium salt type carboxyl group in which 80% or more of the carboxyl groups are neutralized with a potassium salt. Since this potassium salt type hygroscopic agent does not release the absorbed water even at high temperatures, it is excellent in hygroscopicity at high temperatures.
Such a crosslinked polymer having a potassium salt type carboxyl group is obtained by homopolymerization of a potassium salt monomer of a carboxyl group-containing vinyl monomer such as (i) (meth) acrylic acid or maleic acid, or these 2 polymers. A method of polymerizing by copolymerization of more than one species, or copolymerization of other monomers copolymerizable with these monomers, (ii) a method of obtaining a polymer having a carboxyl group and then converting to a potassium salt type , (Iii) a method of introducing a carboxyl group by chemical modification and changing it to a potassium salt type, or (iv) a method of carrying out the methods (i) to (iii) by graft polymerization. It is preferable to prepare by a method of introducing a carboxyl group into the polymer by the hydrolysis treatment of iii) and then changing to a potassium salt type by ion exchange.

Monomers having a cyano group such as acrylonitrile and methacrylonitrile that can be used in a method using hydrolysis treatment include monomers having a cyano group; acrylic acid, methacrylic acid, maleic acid, itaconic acid And derivatives such as vinyl propionic acid.
The other monomer copolymerizable with the above monomer is not particularly limited, but glycidyl methacrylate, N-methylol acrylamide, hydroxyethyl methacrylate, triallyl isocyanurate, triallyl cyanurate, divinylbenzene, ethylene glycol Examples thereof include crosslinkable vinyl compounds such as di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, and methylenebisacrylamide.
Moreover, it is preferable to contain a sulfonic acid group and / or a salt type sulfonic acid group as polar groups other than a potassium salt type carboxyl group. As a monomer having such a sulfonic acid (salt) group, vinyl sulfonic acid ( Salt), (meth) allylsulfonic acid (salt), styrenesulfonic acid (salt), 4-sulfobutyl (meth) acrylate and salts thereof, methallyloxybenzenesulfonic acid (salt), allyloxybenzenesulfonic acid (salt), Examples include 2-acrylamido-2-methylpropanesulfonic acid (salt), 2-sulfoethyl (meth) acrylate, and the like. The sulfonic acid (salt) group-containing monomer can be introduced by a method of copolymerizing with the above monomer, a method of introducing a sulfonic acid (salt) group to the polymer terminal by an initiator or a chain transfer agent, and the like.
Specifically, there is a method of hydrolyzing a cross-linked copolymer containing a monomer capable of obtaining a carboxyl group by hydrolysis and divinylbenzene as a monomer composition using potassium hydroxide. Alternatively, after conversion to a carboxylic acid group, it has a potassium salt type carboxyl group prepared by ion exchange by acting a solution containing a large amount of potassium ions such as an aqueous potassium hydroxide solution or an aqueous potassium chloride solution or an ion exchange resin. A crosslinked polymer can be suitably used as a hygroscopic agent.

  In the present invention, the particulate hygroscopic agent (b) as described above sufficiently exhibits its characteristics, effectively suppresses the moisture barrier property and effectively suppresses the dimensional change due to swelling, and at the same time, for example, the inorganic barrier layer 3 shows. From the viewpoint of ensuring a moisture barrier property higher than the barrier property over a long period of time, it is 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 (a) in the moisture trap layer 5. Preferably, the amount is more preferably 150 to 1200 parts by weight.

<Formation of moisture trap layer 5 (coating composition)>
The moisture trap layer 5 having a matrix (hygroscopic matrix) formed of the anionic polymer (a) described above and in which the particulate hygroscopic agent (b) is dispersed comprises the anionic polymer (a), granular It is formed by using a coating composition in which a hygroscopic agent (b), a crosslinking agent and an adhesion agent are dissolved or dispersed in a solvent, applying the composition, and drying to remove the solvent.

  In such a coating composition, the anionic polymer (a) and the particulate hygroscopic agent (b) are used in the aforementioned quantitative ratio. That is, with respect to 100 parts by weight of the anionic polymer (a), the granular hygroscopic agent (b) is used in a coating composition in an amount of 50 parts by weight or more, particularly 100 to 1300 parts by weight, further 150 to 1200 parts by weight. It is blended in the product.

  The crosslinking agent blended in the coating composition is for introducing a crosslinked structure into the hygroscopic matrix of the anionic polymer (a) described above. As described above, the mechanical strength can be ensured without lowering the moisture absorption capacity, and at the same time, swelling (increase in volume) due to moisture absorption can be suppressed and dimensional stability can be improved.

As the cross-linking agent, for example, a compound having two or more cross-linkable functional groups (for example, epoxy groups) capable of reacting with the ionic group of the anionic polymer (a) can be used. The following formula (1):
G-O (C = O) -A- (C = O) OG (1)
Where G is a glycidyl group;
A is a divalent hydrocarbon group having an aliphatic ring, for example, a cycloalkylene group.
The diglycidyl ester represented by these is suitable.

That is, in the diglycidyl ester of the above formula (1), an epoxy group reacts with an anionic group, and a crosslinked structure including an alicyclic structure with a divalent group A is formed in the matrix.
By such a crosslinked structure containing an alicyclic structure, the molecules of the anionic polymer (a) are constrained and swelling is suppressed. In particular, from the viewpoint that a network structure of a space suitable for moisture absorption can be formed, the aliphatic ring contained in the divalent organic group A is particularly preferably a cyclohexane ring, and more preferably two ester groups are included. It is a diglycidyl ester represented by the following formula (1-1) formed at a position adjacent to the cyclohexane ring.

That is, the diglycidyl ester of the formula (1-1) is effective because it introduces an alicyclic structure into the crosslinked structure.
In the present invention, the above-mentioned crosslinking agent is desirably used in an amount of 1 to 50 parts by weight, particularly 10 to 40 parts by weight, per 100 parts by weight of the anionic polymer (a). If the amount of the crosslinking agent used is too large, the mechanical strength becomes brittle and handling properties are impaired, and there is a possibility that an effective pot life cannot be ensured because the viscosity increases quickly when made into a paint. In connection with this, there exists a possibility that the tolerance (for example, mechanical strength) when exposed to a severe environment (for example, under high humidity) cannot be secured.

In the present invention, the coating composition for forming the moisture trap layer 5 is blended with an adhesive for improving the adhesion between the moisture trap layer 5 and the inorganic barrier layer 3.
Such an adhesive has a functional group that is reactive with the surface of the inorganic barrier layer 3 and the matrix of the anionic polymer (a). For example, the adhesive has an epoxy group and an alkoxysilyl group, and more specifically. In the following formula (2):
X-SiR ¹ _n (OR ² ) _3-n (2)
In the formula, X is an organic group having an epoxy group,
R ¹ and R ² are each a methyl group, an ethyl group, or isopropyl.
And
n is 0, 1, or 2;
Is preferably used.

That is, silanol groups (SiOH groups) generated by hydrolysis of alkoxysilyl groups are distributed on the surface of the inorganic barrier layer 3 (M is a metal element that forms the inorganic barrier layer, for example, Si) and In order to perform dehydration condensation, a siloxane structure is introduced into the matrix, and the adhesion agent (silane compound) is closely bonded to the surface of the inorganic barrier layer 3 by the siloxane bond. Moreover, an epoxy group reacts (esterifies) with the acidic group (for example, COOH) and its salt (for example, COONa) which anionic polymer (a) has, and couple | bonds. Therefore, this adhesive also binds to the matrix of the moisture trap layer 5. Thus, such an adhesive improves the adhesion between the inorganic barrier layer 3 and the moisture trap layer 5 and improves the bonding strength. As a result, peeling of the moisture trap layer 5 and the like are effectively prevented for a long time. As a result, a high moisture barrier property is maintained.
In particular, when the inorganic barrier layer 3 is a deposited film formed by plasma CVD of an organosilicon compound, SiOH groups are distributed on the surface, and the moisture trap layer 5 (matrix) and the inorganic barrier layer 3 are between them. It is easy to form a siloxane bond, and its adhesion improving effect is extremely large.

  Among the silane compounds of the above formula (2), those having a plurality of alkoxysilyl groups (wherein n in the formula (2) is 0 or 1), such as γ-glycidoxypropyltrimethoxysilane and γ-glycol. Sidoxypropylmethyldimethoxysilane is preferred. In addition, those in which the epoxy group is an alicyclic epoxy group such as an epoxycyclohexyl group, for example, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and the like are most suitable as the adhesive.

  In the present invention, the above-mentioned adhesion agent sufficiently exerts its characteristics without impairing the above-described moisture barrier property, so that 0.1% per 100 parts by weight of the anionic polymer (a) in the moisture trap layer 5. It is preferably present in an amount of 1 to 10 parts by weight, in particular 1 to 8 parts by weight.

The solvent used in the coating composition containing the various components described above is not particularly limited as long as it can be volatilized and removed by heating at a relatively low temperature. For example, alcohols such as methanol, ethanol, propyl alcohol, and butanol An organic solvent, a ketone solvent such as acetone and methyl ethyl ketone, a mixed solvent of these solvents and water, or an aromatic hydrocarbon solvent such as water, benzene, toluene, and xylene can be used.
In particular, when a silane compound having an alkoxysilyl group is used as an adhesive as in the compound of formula (2) described above, it is preferable to use a solvent containing at least water. This is because the hydrolysis of the alkoxysilyl group is promoted and the function as a cross-linking agent or an adhesion agent is enhanced.

  Furthermore, an alkali (for example, sodium hydroxide) can be added to the coating composition for forming the moisture trap layer 5 described above for pH adjustment. Addition of such an alkali is effective in promoting dehydration condensation between the silanol group generated from the silane compound used as an adhesive and the MOH group on the surface of the inorganic barrier layer 3, and has a pH of 8 for example. It is preferable to add alkali so as to be about 12 or so.

The above-mentioned solvent is used in such an amount that the coating composition has a viscosity suitable for coating. However, for adjusting the viscosity of the coating composition or the water absorption rate of the formed hygroscopic matrix is in an appropriate range. Therefore, the nonionic polymer can be blended in an appropriate amount.
Examples of such nonionic polymers include polyvinyl alcohol, ethylene-propylene copolymers, saturated aliphatic hydrocarbon polymers such as polybutylene, styrene polymers such as styrene-butadiene copolymers, polyvinyl chloride, or These include various comonomers (for example, styrene monomers such as vinyl toluene, vinyl xylene, chlorostyrene, chloromethyl styrene, α-methyl styrene, α-halogenated styrene, α, β, β'-trihalogenated styrene, And monoolefins such as ethylene and butylene, and conjugated diolefins such as butadiene and isoprene).

  In the present invention, the above-described coating composition is applied to the surface of the inorganic barrier layer 3, for example, and the solvent is removed by heating for several seconds to several minutes, depending on the ability of the oven at a temperature of about 80 to 160 ° C. Furthermore, a cross-linking structure is introduced into the matrix of the anionic polymer (a) by the reaction between the cross-linking agent and the anionic polymer, and the adhesive (silane compound) is converted into the cationic polymer (a) or the inorganic barrier layer 3. It reacts with the MOH on the surface of the film, and high adhesion is maintained between the moisture trap layer 5 and the inorganic barrier layer 3.

The thickness of the moisture trap layer 5 described above is not particularly limited, and can be set to an appropriate thickness according to its use and the required level of moisture barrier. In general, in order to maintain high water vapor permeability over a long period of time, it varies depending on the amount of the particulate moisture absorbent to be blended, but usually has a thickness of at least 1 μm or more, particularly about 2 to 20 μm. Is sufficient.
That is, in the present invention, since the moisture trap layer 5 has a dual function of moisture absorption and confinement, only one moisture trap layer 5 having an appropriate thickness is formed on the inorganic barrier layer 3. Thus, the super barrier property as described above can be exhibited against moisture. Therefore, in the present invention, a high barrier property can be obtained by reducing the number of layers, which is extremely advantageous in terms of productivity and production cost.

<Other layers>
In the present invention, it is not necessary to provide a special layer on the moisture trap layer 5 described above, but a known layer that can be formed in this type of gas barrier laminate as long as the advantages of the present invention are not impaired. It is also possible to provide.
For example, a water-repellent layer, for example, an olefin-based resin layer, can be provided in order to reliably prevent moisture from being released from the moisture trap layer 5 and to avoid a decrease in electrical insulation due to moisture release.
In order to further improve the barrier property against oxygen, an oxygen barrier layer made of an ethylene vinyl alcohol copolymer or an aromatic polyamide can be provided, or an oxygen absorbing layer containing a transition metal such as iron or cobalt can be provided. It is also possible to provide it.
Further, in order to ensure adhesion between each layer as described above and the moisture trap layer 5, an adhesive resin layer made of an olefin resin graft-modified with an unsaturated carboxylic acid anhydride such as maleic anhydride is provided. It is also possible.
Each layer described above can be easily formed by a known means such as coextrusion or coating.

<Application>
The gas barrier laminate 10 of the present invention is remarkably excellent in moisture barrier properties, and is suitably used as a film for sealing various electronic devices, for example, electronic circuits such as organic EL elements, solar cells, and electronic paper. Further, when a plastic film substrate 1 having excellent transparency such as PET, PEN, polycarbonate, polyimide resin or the like is used, a transparent electrode is formed thereon, and An organic EL light-emitting element having a light-emitting layer or the like, or a photovoltaic element of a solar cell can also be formed.

The excellent performance of the gas barrier laminate of the present invention will be described by the following experimental examples.
Examples 1 to 8 and Examples 10 to 14 are included in the scope of the present invention, but Example 9 is a reference example not belonging to the scope of the present invention.

<Evaluation of ultimate humidity>
After drying at 140 ° C. for 1 hour, in a 30 ° C. 80% RH atmosphere, a moisture impervious steel foil laminated cup having an internal volume of 85 cm ³ , 0.5 g of a measurement object and a wireless thermohygrometer (High Glocron: KN Laboratories) was put, and the container mouth was heat sealed with an aluminum foil laminated film lid. Thereafter, the temperature was elapsed at 30 ° C. and 80% RH, and the relative humidity inside the container one day later was defined as the ultimate humidity.

<Measurement of moisture permeability (g / m ² / day)>
Prepared in accordance with ASTM-F1249, measured using a moisture permeation measuring device ("Permatran-W" manufactured by Modern Control Co., Ltd.) under the conditions of a temperature of 40 ° C and a relative humidity of 90%. Those less than m ² / day were marked with ◯, and those with 0.01 or more were marked with x.

<Haze measurement>
In accordance with JIS K7361-1, SM color computer (manufactured by Suga Test Instruments Co., Ltd., SM-4) was used to measure haze.

<Adhesion strength>
In order to ensure the strength of the film against the tensile test, 7 μm thick aluminum foil is dry laminated on both sides of the laminate laminate of the sample via a 4 μm thick urethane adhesive to cure the adhesive layer. Aging was performed at 50 ° C. for 3 days to prepare a sample for a T-type peel test.
The T-type peel test sample was cut into 100 mm × 15 mm strips, and a T-type peel test was performed with a tensile tester at a pulling speed of 300 mm / min (N = 3). The average strength at this time is defined as adhesion strength, those with 2 (N / 15 mm) or more, ◯, those with 1 (N / 15 mm) or more and less than 2 (N / 15 mm), and those with less than 1 (N / 15 mm). The thing was set as x.

<Preparation of an inorganic barrier layer-coated polyethylene terephthalate (PET) film>
A silicon oxide inorganic barrier layer 3 was formed on one side of a 12 μm thick biaxially stretched PET film using a plasma CVD apparatus. The film forming conditions are shown below.
A high frequency output power source having a frequency of 27.12 MHz and a maximum output of 2 kW, a matching box, a metal cylindrical plasma processing chamber having a diameter of 300 mm and a height of 450 mm, and a CVD apparatus having an oil rotary vacuum pump for evacuating the processing chamber were used. A plastic substrate is placed on parallel plates in the processing chamber. After introducing 3 sccm of hexamethyldisiloxane and 45 sccm of oxygen, a high frequency is oscillated at a power of 50 W by a high frequency oscillator to form a film for 2 seconds to form an adhesion layer. did. Next, a high frequency was oscillated with an output of 300 W by a high frequency oscillator, and a film was formed for 15 seconds to form a barrier layer. The obtained inorganic barrier layer-coated PET film has a water vapor transmission rate of 0.1 g / m ² / day measured in an atmosphere of 90% humidity and 40 ° C. temperature.

<Example 1>
Polyacrylic acid (manufactured by Nippon Pure Chemical Co., Ltd., AC-10LP) is used as the anionic polymer, dissolved in a water / acetone mixed solvent (weight ratio 80/20) so that the solid content is 5% by weight, and hydroxylated. Sodium was added so that the neutralization rate of polyacrylic acid would be 80% to obtain a polymer solution.
In this polymer solution, diglycidyl 1,2-cyclohexanedicarboxylate as a crosslinking agent was blended so as to be 20 parts by weight with respect to the partially neutralized polyacrylic acid, and then β- (3,4- (Epoxycyclohexyl) ethyltrimethoxysilane is blended so as to be 3 parts by weight with respect to the polyacrylic acid partial neutralized product, and further, a crosslinked product of polyacrylic acid Na as a granular moisture absorbent (Toyobo, Tufic HU-820E Water dispersion, solid content 13%, average particle size D ₅₀ : 70 nm) is blended so as to be 431 parts by weight with respect to the partially neutralized polyacrylic acid, and the total solid content becomes 5% by weight. The mixture was adjusted with a mixed solvent of water / acetone (80/20 by weight) and stirred well to prepare a coating solution.

  The coating liquid obtained above was applied onto the vapor deposition surface 3 of the previously prepared inorganic barrier layer-coated PET film by 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 moisture trap layer 5 having a thickness of 4 μm, whereby a coating film 10 was obtained.

  Next, in the glove box adjusted to a nitrogen concentration of 99.95% or more, the inorganic barrier layer-coated PET film is formed on the coating layer of the coating film 10 via the urethane adhesive layer 6 having a thickness of 4 μm. In order to cure the adhesive resin layer so that the vapor deposition surface 3 is on the inside, and to cure the adhesive resin layer so as not to absorb moisture, aging is performed under vacuum at 50 ° C. for 3 days, and the laminate structure having a layer structure as shown in FIG. Body 11 was obtained.

<Example 2>
In Example 1, a laminate laminate was obtained in the same manner as in Example 1 except that the particulate hygroscopic agent was blended so as to be 50 parts by weight with respect to the partially neutralized polyacrylic acid.

<Example 3>
In Example 1, a laminated laminate was obtained in the same manner as in Example 1 except that the particulate hygroscopic agent was blended so as to be 1300 parts by weight with respect to the partially neutralized polyacrylic acid.

<Example 4>
In Example 1, 1 glyceryl diglycidyl 1,2-cyclohexanedicarboxylate, which is a cross-linking agent, was blended in an amount of 1 part by weight with respect to the polyacrylic acid partial neutralized product. A sample laminate was obtained in the same manner as in Example 1 except that the amount was 364 parts by weight with respect to the product.

<Example 5>
In Example 1, 1,2-cyclohexanedicarboxylate diglycidyl as a cross-linking agent was blended so as to be 50 parts by weight with respect to the polyacrylic acid partial neutralized product, and the particulate hygroscopic agent was partially neutralized with polyacrylic acid. A sample laminate was obtained in the same manner as in Example 1 except that the amount was 536 parts by weight based on the product.

<Example 6>
In Example 1, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, which is an adhesion agent, was blended so as to be 0.3 parts by weight with respect to the polyacrylic acid partial neutralized product, and further, particulate moisture absorption A laminate laminate of the sample was obtained in the same manner as in Example 1 except that the agent was blended so as to be 422 parts by weight with respect to the partially neutralized polyacrylic acid.

<Example 7>
In Example 1, the adhesion agent β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane was blended so as to be 10 parts by weight with respect to the polyacrylic acid partial neutralized product. A sample laminate laminate was obtained in the same manner as in Example 1 except that the amount was 455 parts by weight with respect to the partially neutralized polyacrylic acid.

<Example 8>
In Example 1, the neutralization rate of the partially neutralized polyacrylic acid was 10%, and β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane as an adhesive was not blended. A laminated laminate was obtained in the same manner as in Example 1 except that the mixture was mixed with the partially neutralized polyacrylic acid so as to be 150 parts by weight.

<Example 9>
In Example 1, polyvinyl alcohol (Kuraray, Kuraray K polymer KM-118) imparted with anionic property was used as the anionic polymer, and β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane as an adhesive was The sample was mixed in the same manner as in Example 1 except that it was blended so as to be 8 parts by weight with respect to KM-118 and further blended so that the particulate moisture absorbent was 640 parts by weight relative to KM-118. A laminate laminate was obtained.

<Example 10>
In Example 1, the neutralization rate of the polyacrylic acid partial neutralized product was set to 50%, ethylene glycol diglycidyl ether was used as a crosslinking agent, and the heat treatment temperature was set to 160 ° C. A laminate laminate was obtained by this method.

<Example 11>
In Example 1, γ-glycidoxypropyltrimethoxysilane was blended as an adhesive so as to be 5 parts by weight with respect to the polyacrylic acid partial neutralized product, and the particulate moisture absorbent was contained in the polyacrylic acid part. A laminated laminate was obtained in the same manner as in Example 1 except that the amount was 438 parts by weight with respect to the Japanese product.

<Example 12>
In Example 1, a biaxially stretched nylon film 7 having a thickness of 15 μm was dry-laminated on the vapor deposition surface 3 of the PET film coated with an inorganic barrier layer via a urethane adhesive layer 6 having a thickness of 4 μm, and the nylon film A laminate laminate 12 having a layer structure as shown in FIG. 4 was obtained in the same manner as in Example 1 except that the moisture trap layer 5 was formed on the substrate 7.

<Example 13>
In Example 1, instead of the inorganic barrier layer-coated PET film, a vapor-deposited PET film (Mitsubishi Resin, Tech Barrier Type T) formed by a commercially available PVD method was used. A sample laminate was obtained.

<Example 14>
An ion exchange resin (Amberlite 200CT, manufactured by Organo) was used to convert the Na salt-type carboxyl group of the crosslinked polyacrylic acid Na (HU-820E) into an H-type carboxyl group, and then a 1N aqueous solution of potassium hydroxide. Was used to obtain a crosslinked product of polyacrylic acid K having a potassium salt type carboxyl group (water dispersion, solid content 10%, average particle diameter D ₅₀ : 70 nm, neutralization rate 80%).
A laminate laminate of the sample was obtained in the same manner as in Example 1 except that the cross-linked product of polyacrylic acid K was used as the hygroscopic agent.

<Comparative Example 1>
In Example 1, a sample laminate was obtained in the same manner as in Example 1 except that the hygroscopic agent and the crosslinking agent were not blended.

<Comparative example 2>
In Example 1, a sample laminate was obtained in the same manner as in Example 1 except that no hygroscopic agent was blended.

<Comparative Example 3>
In Example 1, laminate lamination was performed in the same manner as in Example 1 except that the crosslinking agent was not blended and that the particulate moisture absorbent was mixed so as to be 361 parts by weight with respect to the partially neutralized polyacrylic acid. Got the body.

<Comparative Example 4>
In Example 1, a laminate laminate of a sample was obtained in the same manner as in Example 1 except that polyvinyl alcohol (manufactured by Kuraray, PVA103) was used as the anionic polymer.

<Comparative Example 5>
In Example 1, a cross-linked product of polyacrylic acid Na having an average particle size of 900 nm (Toyobo, Tuftic HU-700E, aqueous dispersion, solid content 20%, average particle size D ₅₀ : 900 nm) is used as the granular hygroscopic agent. A sample laminate laminate was obtained in the same manner as in Example 1 except that the moisture absorbent was blended so as to be 431 parts by weight with respect to the polyacrylic acid neutralized product.

<Comparative Example 6>
As a hygroscopic agent, a crosslinked product of polyacrylic acid Na having an average particle size of 4 μm (Toyobo, Tuftic HU-720SF, powder, average particle size: 4 μm) is 43 parts by weight with respect to LDPE (Tosoh, LUMITAC08L55A) And blended at 150 ° C. with a twin-screw kneading extruder, and wound using two 12 μm thick PET films and a laminator so that the thickness of the moisture trap layer 5 is 20 μm between the PET films. Both surfaces of the moisture trap layer 6 were protected with a PET film. Inorganic used in Example 1 by peeling the PET film in a glove box adjusted to a nitrogen concentration of 99.95% or more, and via a 4 μm-thick urethane adhesive layer 6 on both sides of the sample. A barrier layer-coated PET film is dry-laminated so that the deposition surface 3 is on the inside, and the adhesive resin layer is cured so as not to absorb moisture, so that it is aged at 50 ° C. for 3 days, and has a layer structure as shown in FIG. A laminate 13 was obtained.

<Evaluation test>
About the laminated laminate of the sample produced above, various characteristics were measured by the method described above, and the results are shown in Tables 1 and 2.
In addition, in the term of adhesiveness in Table 2, it is assumed that the separation interface is not less than the value except for the vapor trapping surface of the moisture trap layer and the inorganic barrier layer-coated PET (Note 1).

<Application experiment example>
To 100 parts by weight of an anionic polymer (partially neutralized with polyacrylic acid, sodium hydroxide. Partial neutralization rate: 80%), 420 parts by weight of a hygroscopic agent (Toughtic HU820E) and a crosslinking agent ( 0.5 g of a composition containing 20 parts by weight of 1,2-cyclohexanedicarboxylic acid diglycidyl) and 3 parts by weight of an adhesive (2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane) at 140 ° C. for 1 hour After drying, the weight was measured and left for 5 minutes in an atmosphere of temperature 30 ° C. and humidity 20-40% RH, and the weight was measured again. The moisture absorption rate at each humidity of the moisture trap layer was calculated from the obtained weight increase, and the moisture absorption rate in an extremely low humidity atmosphere was obtained by extrapolation. (See Figure 6)

The moisture absorption rate in the extremely low humidity atmosphere of the moisture trap layer determined from extrapolation is 10 ⁻⁴ g / m ² / min, and the humidity of the inorganic barrier layer-coated PET film used in Example 1 is 90% RH. The water vapor transmission rate in an atmosphere at a temperature of 40 ° C. is 0.1 g / m ² / day, that is, 10 ⁻⁵ g / m ² / min. Therefore, the moisture trap layer of the present invention has a moisture content even in an extremely low humidity atmosphere. This makes it possible to capture water at a rate sufficiently higher than the rate at which moisture permeates the inorganic barrier layer.

In order to prove the trapping of trapped moisture from the matrix into the hygroscopic agent, the following experiment was conducted. After 0.5 g of the measurement object was dried at 140 ° C. for 1 hour, in a 30 ° C. 80% RH atmosphere, a moisture-impermeable steel foil laminated cup having an internal volume of 85 cm ³ was placed in a wireless thermohygrometer (High Glocron). : Made by KN Laboratories), the container mouth was heat-sealed with an aluminum foil laminated film lid, and left for 1 day. Then, it was left to stand for 3 hours at each temperature of −20, 5, 22, 30, and 40 ° C., and the relative humidity inside the container at that time was defined as the ultimate humidity at each temperature.

  FIG. 7 shows the ultimate humidity at each temperature of an anionic polymer (polyacrylic acid partially neutralized product, partial neutralization rate: 80%), a hygroscopic agent (Toughtic HU820E), and a 1: 1 mixture of an anionic polymer and a hygroscopic agent. Indicates. While the anionic polymer increased the humidity in the container as the temperature increased, the moisture absorbent, a mixture of the anionic polymer and the hygroscopic agent was able to reduce the humidity in the container to a completely dry state. Since the mixture showed a hygroscopic performance equivalent to that of the hygroscopic agent alone, the moisture absorbed by the cationic polymer is not released to the outside air even when the temperature rises, and has a higher hygroscopicity (that is, reached). It is suggested that it is further trapped by the hygroscopic agent (low humidity).

1: Plastic base material 3: Inorganic barrier layer 5: Moisture trap layer 6: Urethane adhesive layer 7: Biaxially stretched nylon film
10, 11, 12, 13: Gas barrier laminate

Claims (13)

A gas barrier laminate in which an inorganic barrier layer and a moisture trap layer are formed in this order on a plastic substrate, the moisture trap layer comprising a matrix formed from an anionic polymer (a), and In the matrix, a crosslinked structure is introduced, and a particulate hygroscopic agent (b) having a hygroscopic property in which the humidity reached is lower than that of the matrix is dispersed ,
The particulate hygroscopic agent (b) is blended in an amount of 50 to 1300 parts by weight per 100 parts by weight of the anionic polymer (a).
The anionic polymer (a) is at least one anion of methacrylic acid, acrylic acid, maleic anhydride, α-halogenated vinyl sulfonic acid, styrene sulfonic acid, vinyl sulfonic acid, vinyl phosphoric acid and salts of these monomers. A homopolymer of a functional monomer or a copolymer with another copolymerizable monomer, or a partially neutralized product of these polymers by alkali treatment,
The particulate moisture absorbent (b) is an inorganic moisture absorbent selected from zeolite, alumina, activated carbon, montmorillonite, silica gel, calcium oxide and magnesium sulfate, or (meth) acrylic acid, maleic anhydride, vinyl halide sulfonic acid An anionic polymer which is a homopolymer of at least one anionic monomer of styrene sulfonic acid, vinyl sulfonic acid, vinyl phosphoric acid and salts of these monomers or a copolymer with other monomers, and A gas barrier laminate comprising an organic moisture absorbent selected from a partially neutralized crosslinked product .   The gas barrier laminate according to claim 1, wherein a siloxane structure is introduced into the matrix, and an alicyclic structure is included in the crosslinked structure.   The cross-linked structure is introduced by a cross-linking reaction between an anionic group of the anionic polymer and an epoxy group, and the siloxane structure is introduced by a reaction of the anionic polymer and a silane compound. A gas barrier laminate as described in 1.   The moisture trap layer is blended with an adhesive (c) having a functional group reactive to the matrix into which the crosslinked structure is introduced and the surface of the inorganic barrier layer, and the siloxane structure is The gas barrier laminate according to claim 3, wherein the gas barrier laminate is introduced by a reaction between the adhesive and the matrix.   The gas barrier laminate according to claim 4, wherein the adhesive (c) is a compound having an alicyclic epoxy group and an alkoxysilyl group.   The gas barrier laminate according to any one of claims 1 to 5, wherein the particulate moisture absorbent (b) is a crosslinked product of a monovalent metal salt of poly (meth) acrylic acid.   The gas barrier laminate according to any one of claims 1 to 6, wherein the inorganic barrier layer is an inorganic oxide film formed by a CVD method.   The gas barrier laminate according to any one of claims 1 to 7, wherein the moisture trap layer and the inorganic barrier layer are adjacent to each other. At least an anionic polymer (a), a particulate hygroscopic agent (b) having a hygroscopic property in which the humidity reached is lower than that of the anionic polymer (a), a crosslinking agent and an adhesive agent are dissolved or dispersed in a solvent ,
The particulate hygroscopic agent (b) is blended in an amount of 50 to 1300 parts by weight per 100 parts by weight of the anionic polymer (a).
The anionic polymer (a) is at least one anion of methacrylic acid, acrylic acid, maleic anhydride, α-halogenated vinyl sulfonic acid, styrene sulfonic acid, vinyl sulfonic acid, vinyl phosphoric acid and salts of these monomers. A homopolymer of a functional monomer or a copolymer with another copolymerizable monomer, or a partially neutralized product of these polymers by alkali treatment,
The particulate moisture absorbent (b) is an inorganic moisture absorbent selected from zeolite, alumina, activated carbon, montmorillonite, silica gel, calcium oxide and magnesium sulfate, or (meth) acrylic acid, maleic anhydride, vinyl halide sulfonic acid An anionic polymer which is a homopolymer of at least one anionic monomer of styrene sulfonic acid, vinyl sulfonic acid, vinyl phosphoric acid and salts of these monomers or a copolymer with other monomers, and A coating composition comprising an organic moisture absorbent selected from a crosslinked product of a partially neutralized product. The anionic polymer (a) 100 parts by weight of per previous SL crosslinking agent is 1 to 50 parts by weight, and the coating composition according to claim 9, wherein the adhesion agent is blended in an amount of 0.1 to 10 parts by weight object.   The coating composition according to claim 9 or 10, wherein the particulate hygroscopic agent (b) is a crosslinked product of a monovalent metal salt of poly (meth) acrylic acid. The crosslinking agent is represented by the following formula (1):
G-O (C = O) -A- (C = O) OG (1)
Where G is a glycidyl group;
A is a divalent hydrocarbon group having an aliphatic ring,
The coating composition according to claim 9, which is a diglycidyl ester represented by: The adhesive agent has the following formula (2):
X-SiR ¹ _n (OR ² ) _3-n (2)
In the formula, X is an organic group having an epoxy group,
R ¹ and R ² are each a methyl group, an ethyl group, or isopropyl.
And
n is 0, 1, or 2;
The coating composition according to claim 9, which is a silane compound represented by the formula:

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