JP2020157744A - Resin sheet with support - Google Patents

Abstract

To provide a resin sheet with a support for sealing, which can suppress damage of an organic EL device and deterioration of the organic EL device in the step of sealing, exhibits higher moisture shielding, and has high reliability.SOLUTION: A resin sheet with a support provided with a support, and a resin sheet provided on the support, in which the resin sheet has at least one hygroscopic layer formed from a hygroscopic resin composition and at least one low moisture permeable layer formed from a low moisture permeable resin composition, at least one of the low moisture permeable layers is provided on a side opposite to the support to the hygroscopic layer, the hygroscopic resin composition contains a hygroscopic filler, and the low moisture permeable resin composition contains a planar filler.SELECTED DRAWING: Figure 1

Description

The present invention relates to a resin sheet with a support, and is a resin sheet with a support suitable for sealing electronic elements, particularly light emitting elements such as organic EL (Electroluminescence) elements, optical semiconductors, and light receiving elements such as solar cells. Regarding.

The organic EL element is a light emitting element using an organic substance as a light emitting material, and has been in the limelight in recent years because it can obtain high-luminance light emission at a low voltage. However, the organic EL element is extremely vulnerable to moisture, and the light emitting material (light emitting layer) is altered by the moisture, resulting in a decrease in brightness or no light emission, or the interface between the electrode and the light emitting layer is peeled off due to the influence of moisture. , There is a problem that the metal is oxidized and the resistance is increased. Therefore, in order to block the inside of the device from the moisture in the outside air, for example, a sealing layer is formed by the resin composition so as to cover the entire surface of the light emitting layer formed on the substrate to seal the organic EL device. Is done.

As a resin composition suitable for sealing such an organic EL element, a resin composition containing a moisture absorbing filler is known. For example, Patent Document 1 describes a sealing resin composition containing a hygroscopic metal hydroxide and a support, and a sealing resin composition layer formed of the sealing resin composition. The sheet is disclosed. Further, Patent Document 2 describes sealing of an organic EL element including a moisture-absorbing resin composition layer containing a moisture-absorbing filler and a protective resin composition layer containing no moisture-absorbing filler or a small amount of the moisture-absorbing filler added as the resin composition layer. Suitable films are disclosed.

International Publication No. 2017/057708 International Publication No. 2011/016408

These resin sheets absorb moisture in the outside air and protect the organic EL element from moisture by a hygroscopic layer containing a hygroscopic filler, but the moisture captured by the moisture absorbing filler becomes the organic EL element with the passage of time. Since a new problem of reaching and causing deterioration has been found, it is not always sufficient for sealing a part such as an organic EL element that requires high moisture shielding property.

The present invention has been made in view of the above circumstances, and the problem to be solved is a resin sheet with a support having a hygroscopic layer, which is a support capable of exhibiting higher moisture shielding properties. It is to provide a resin sheet with a body.

As a result of diligent research to solve the above problems, the present inventors have conducted an organic EL element when the low moisture permeability layer is sealed in the resin sheet constituting the resin sheet with a support having a hygroscopic layer. It has been found that the above-mentioned problems can be solved by providing the moisture on the side of the portion to be shielded from water (that is, the side opposite to the support with respect to the hygroscopic layer), and the present invention has been completed. That is, the present invention includes those having the following characteristics.

[1] A resin sheet with a support including a support and a resin sheet provided on the support, wherein the resin sheet has at least one hygroscopic layer formed of a hygroscopic resin composition and low. It has at least one low moisture permeable layer formed by the moisture permeable resin composition, and at least one low moisture permeable layer is provided on the side opposite to the support with respect to the moisture absorbing layer, and the moisture absorbing resin composition. A resin sheet with a support containing a moisture-absorbing filler and a low-moisture-permeable resin composition containing a plate-shaped filler.
[2] The content of the hygroscopic filler in the hygroscopic resin composition is 10% by mass or more and 80% by mass or less when the non-volatile content of the hygroscopic resin composition is 100% by mass, according to [1]. Resin sheet with support.
[3] The content of the plate-like filler in the low-moisture-permeable resin composition is 10% by mass or more and 80% by mass or less when the non-volatile content of the low-moisture-permeable resin composition is 100% by mass, [1] or The resin sheet with a support according to [2].
[4] The resin sheet with a support according to any one of [1] to [3], wherein the hygroscopic filler is semi-baked hydrotalcite.
[5] The resin with a support according to any one of [1] to [4], wherein the plate-shaped filler is at least one selected from plate-shaped glass, unfired hydrotalcite, smectite, and synthetic phlogopite. Sheet.
[6] The resin sheet with a support according to any one of [1] to [5], wherein the plate-shaped filler has an average aspect ratio of 2 or more.
[7] The resin sheet with a support according to any one of [1] to [6], wherein the thickness of the resin sheet is 5 μm or more and 100 μm or less.
[8] The resin sheet with a support according to any one of [1] to [7], wherein the thickness of the hygroscopic layer is equal to or greater than the thickness of the low moisture permeable layer.
[9] The resin sheet with a support according to any one of [1] to [8], wherein the ratio of the thickness of the hygroscopic layer to the thickness of the low moisture permeable layer is 1.0 to 20.
[10] The resin sheet with a support according to any one of [1] to [9], wherein at least one low moisture permeable layer is provided on the side opposite to the support with respect to all the hygroscopic layers.
[11] The water vapor permeability of the resin sheet is not more than 10g / ^(m 2 · 24 hr) [1] support coated resin sheet according to any one of - [10].
[12] The resin sheet with a support according to any one of [1] to [11], wherein the hygroscopic resin composition and the low moisture permeable resin composition contain a thermosetting resin.
[13] The resin sheet with a support according to any one of [1] to [12], wherein the hygroscopic resin composition and the low moisture permeable resin composition contain an epoxy resin.
[14] The resin sheet with a support according to any one of [1] to [13], wherein the hygroscopic resin composition and the low moisture permeable resin composition contain a thermoplastic resin.
[15] The resin sheet with a support according to any one of [1] to [14], which is used for sealing an electronic device.
[16] The resin sheet with a support according to any one of [1] to [15], which is used for sealing an organic EL device.
[17] An electronic device sealed with the resin sheet with a support according to any one of [1] to [16].

According to the present invention, in a resin sheet with a support having a hygroscopic layer formed by a hygroscopic resin composition containing a hygroscopic filler, a resin sheet with a support capable of exhibiting higher moisture shielding properties can be provided. Can be done.

It is a schematic diagram which shows an example of the resin sheet in the resin sheet with a support of this invention.

The resin sheet with a support of the present invention includes a support and a resin sheet provided on the support, and the resin sheet includes a hygroscopic layer formed of a hygroscopic resin composition and a low moisture permeable resin. It has at least one low moisture permeable layer formed by the composition, and the at least one low moisture permeable layer is provided on the opposite side of the support from the moisture absorbing layer. In a typical aspect of the present invention, the hygroscopic resin composition comprises a hygroscopic filler, and the low moisture permeable resin composition comprises a plate-like filler.

<Hygroscopic layer>
The hygroscopic layer in the resin sheet with a support of the present invention is formed of the hygroscopic resin composition. In a typical aspect of the present invention, the hygroscopic resin composition comprises a hygroscopic filler.

The hygroscopic filler is not particularly limited as long as it is a hygroscopic filler. For example, calcium oxide, magnesium oxide, metal oxides such as calcined hydrotalcite, and layered metal water such as semi-firing hydrotalcite. Examples include oxides. As the hygroscopic filler, calcined hydrotalcite, semi-calcined hydrotalcite, and calcium oxide are preferable, and semi-calcined hydrotalcite is particularly preferable. Although the semi-baked hydrotalcite has excellent hygroscopicity, the problem of deterioration of the organic EL element due to the trapped moisture is also remarkable. However, in the present invention, the low moisture permeable layer suppresses the arrival of the trapped moisture to the organic EL element. Therefore, by fully utilizing the hygroscopicity of the semi-baked hydrotalcite, a resin sheet with a support, which is particularly preferable from the viewpoint of moisture shielding property, can be obtained. Only one of these hygroscopic fillers may be used alone, or two or more thereof may be used in combination. The hygroscopic filler in the present invention is a filler having a saturated water absorption rate of 1% by mass or more as defined below.

Unfired hydrotalcite is, for example, a metal hydroxide having a layered crystal structure typified by natural hydrotalcite _{(Mg 6 Al 2 (OH)} 16 CO 3 · 4H 2 O), for example, It consists of a basic skeleton layer [Mg _1-X Al _X (OH) ₂ ] ^{X +} and an intermediate layer [(CO ₃ ) _{X / 2} · mH ₂ O] ^X− . The uncalcined hydrotalcite in the present invention is a concept including hydrotalcite-like compounds such as synthetic hydrotalcite. Examples of the hydrotalcite-like compound include those represented by the following formulas (I) and (II).

^{_{[M 2+ 1-x M 3+}} x (OH) 2] x + · [(A n-) x / n · mH 2 O] x- (I)
^{(Wherein, M 2+} is ^Mg 2+, a divalent metal ion such as ^{Zn 2+, M 3+} represents a trivalent metal ion such as ^{Al 3+, Fe} 3+, ^{A n-} is _CO ³ 2-, Cl Represents n-valent anions such as ⁻ and NO ₃ ⁻ , where 0 <x <1, 0 ≦ m <1, and n is a positive number.)
Wherein ^{(I), M 2+} is preferably ^{Mg 2+, M 3+} is preferably ^{Al 3+, A n-is} preferably _CO ^{3 2-.}

^{_{M 2+ x Al 2 (OH)}} 2x + 6-nz (A n-) z · mH 2 O (II)
^{(Wherein, M 2+} is ^Mg 2+, a divalent metal ion such as ^{Zn 2+, A n-} is _CO ^{3 2-,} Cl ^-, represents an n-valent anion such as ^{NO 3-,} x is 2 or more Is a positive number, z is a positive number less than or equal to 2, m is a positive number, and n is a positive number.)
Wherein ^{(II), M 2+} is preferably ^{Mg 2+, A n-is} preferably _CO ^{3 2-.}

Semi-calcined hydrotalcite refers to a metal hydroxide having a layered crystal structure in which the amount of interlayer water is reduced or eliminated, which is obtained by calcining uncalcined hydrotalcite. The term "interlayer water" refers to "H ₂ O" described in the above-mentioned composition formulas of uncalcined natural hydrotalcite and hydrotalcite-like compounds, if it is described using a composition formula.

On the other hand, calcined hydrotalcite refers to a metal oxide having an amorphous structure obtained by calcining uncalcined hydrotalcite or semi-calcined hydrotalcite, in which not only interlayer water but also hydroxyl groups are eliminated by condensation dehydration.

Uncalcined hydrotalcite, semi-calcined hydrotalcite and calcined hydrotalcite can be distinguished by the saturated water absorption rate. The saturated water absorption rate of the semi-baked hydrotalcite is 1% by mass or more and less than 20% by mass. On the other hand, the saturated water absorption rate of uncalcined hydrotalcite is less than 1% by mass, and the saturated water absorption rate of calcined hydrotalcite is 20% by mass or more.

The "saturated water absorption rate" in the present invention means that 1.5 g of unfired hydrotalcite, semi-baked hydrotalcite or fired hydrotalcite is weighed with a balance, the initial mass is measured, and then the temperature is 60 under atmospheric pressure. The mass increase rate with respect to the initial mass when the product is allowed to stand in a small environmental tester (SH-222 manufactured by Espec Co., Ltd.) set at ° C. and a relative humidity of 90% for 200 hours.
Saturated water absorption rate (mass%)
= 100 × (mass after moisture absorption-initial mass) / initial mass (i)
Can be obtained at.

The saturated water absorption of the semi-baked hydrotalcite is preferably 3% by mass or more and less than 20% by mass, and more preferably 5% by mass or more and less than 20% by mass.

Further, uncalcined hydrotalcite, semi-calcined hydrotalcite and calcined hydrotalcite can be distinguished by the thermogravimetric reduction rate measured by thermogravimetric analysis. The thermogravimetric reduction rate of the semi-baked hydrotalcite at 280 ° C. is less than 15% by mass, and the thermogravimetric reduction rate at 380 ° C. is 12% by mass or more. On the other hand, the thermogravimetric reduction rate of uncalcined hydrotalcite at 280 ° C. is 15% by mass or more, and the thermogravimetric reduction rate of calcined hydrotalcite at 380 ° C. is less than 12% by mass.

For thermogravimetric analysis, 5 mg of hydrotalcite was weighed in an aluminum sample pan using TG / DTA EXSTAR6300 manufactured by Hitachi High-Tech Science, and the nitrogen flow rate was 200 mL / min in an open state without a lid. It can be carried out from 30 ° C. to 550 ° C. under the condition of a heating rate of 10 ° C./min. The thermogravimetric reduction rate is calculated by the following formula (ii):
Thermogravimetric reduction rate (mass%)
= 100 × (mass before heating-mass when a predetermined temperature is reached) / mass before heating (ii).

In addition, uncalcined hydrotalcite, semi-calcined hydrotalcite and calcined hydrotalcite can be distinguished by the peak and relative intensity ratio measured by powder X-ray diffraction. The semi-baked hydrotalcite shows a peak in which 2θ is split into two in the vicinity of 8 to 18 ° by powder X-ray diffraction, or a peak having a shoulder due to the combination of the two peaks, and the peak or shoulder appearing on the low angle side. The relative intensity ratio (low-angle side diffraction intensity / high-angle side diffraction intensity) of the diffraction intensity (= low-angle side diffraction intensity) and the diffraction intensity of the peak or shoulder appearing on the high-angle side (= high-angle side diffraction intensity) is 0.001. ~ 1,000. On the other hand, uncalcined hydrotalcite has only one peak near 8 to 18 °, or the relative intensity ratio of the diffraction intensity of the peak or shoulder appearing on the low angle side and the peak or shoulder appearing on the high angle side is in the above range. Be outside. The calcined hydrotalcite does not have a characteristic peak in the region of 8 ° to 18 °, but has a characteristic peak in 43 °. Powder X-ray diffraction measurement is performed by a powder X-ray diffractometer (PANalytical, Empyrena) with anti-cathode CuKα (1.5405 Å), voltage: 45 V, current: 40 mA, sampling width: 0.0260 °, scanning speed: 0. The measurement was performed under the conditions of .0657 ° / s and the measurement diffraction angle range (2θ): 5.0131 to 79.9711 °. The peak search uses the peak search function of the software attached to the diffractometer, and "minimum significance: 0.50, minimum peak tip: 0.01 °, maximum peak tip: 1.00 °, peak base width: 2". It can be performed under the condition of "0.00 °, method: minimum value of second derivative".

BET specific surface area of the hydrotalcite is preferably ^{1~250m 2 / g, 5~200m 2 /} g is more preferable. The BET specific surface area of hydrotalcite can be calculated by adsorbing nitrogen gas on the sample surface using a specific surface area measuring device (Macsorb HM Model 1210 Mountec) according to the BET method and using the BET multipoint method. ..

The average particle size of hydrotalcite is preferably 1 to 1,000 nm, more preferably 10 to 800 nm. The average particle size of the hydrotalcite is the median size of the particle size distribution when the particle size distribution is prepared on a volume basis by laser diffraction scattering type particle size distribution measurement (JIS Z 8825).

As the hydrotalcite, those surface-treated with a surface treatment agent can be used. As the surface treatment agent used for the surface treatment, for example, higher fatty acids, alkylsilanes, silane coupling agents and the like can be used, and among them, higher fatty acids and alkylsilanes are preferable. As the surface treatment agent, one kind or two or more kinds can be used.

Examples of the higher fatty acid include higher fatty acids having 18 or more carbon atoms such as stearic acid, montanic acid, myristic acid, and palmitic acid, and stearic acid is preferable. These can be used alone or in combination of two or more.

Examples of alkylsilanes include methyltrimethoxysilane, ethyltrimethoxysilane, hexyltrimethoxysilane, octyltrimethoxysilane, decyltrimethoxysilane, octadecyltrimethoxysilane, dimethyldimethoxysilane, octyltrimethoxysilane, and n-octadecyl. Examples thereof include dimethyl (3- (trimethoxysilyl) propyl) ammonium chloride. These can be used alone or in combination of two or more.

Examples of the silane coupling agent include 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-glycidyloxypropyl (dimethoxy) methylsilane and 2- (3,4-epoxycyclohexyl) ethyltrimethoxy. Epoxy silane coupling agents such as silane; mercapto silane coupling agents such as 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane and 11-mercaptoundecyltrimethoxysilane 3-Aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyldimethoxymethylsilane, N-phenyl-3-aminopropyltrimethoxysilane, N-methylaminopropyltrimethoxysilane, N- (2) Amino-based silane coupling agents such as −aminoethyl) -3-aminopropyltrimethoxysilane and N- (2-aminoethyl) -3-aminopropyldimethoxymethylsilane; ureido-based silanes such as 3-ureidopropyltriethoxysilane Coupling agents, vinyl-based silane coupling agents such as vinyltrimethoxysilane, vinyltriethoxysilane and vinylmethyldiethoxysilane; styryl-based silane coupling agents such as p-styryltrimethoxysilane; 3-acrylicoxypropyltrimethoxy Acrylic silane coupling agents such as silane and 3-methacryloxypropyltrimethoxysilane; isocyanate-based silane coupling agents such as 3-isocyanpropyltrimethoxysilane, bis (triethoxysilylpropyl) disulfide, bis (triethoxysilylpropyl) ) A sulfide-based silane coupling agent such as tetrasulfide; phenyltrimethoxysilane, methacryloxypropyltrimethoxysilane, imidazole silane, triazinesilane and the like can be mentioned. These can be used alone or in combination of two or more.

The surface treatment of hydrotalcite can be performed, for example, by adding and spraying a surface treatment agent while stirring and dispersing untreated hydrotalcite at room temperature in a mixer and stirring for 5 to 60 minutes. As the mixer, a known mixer can be used, and examples thereof include blenders such as V blenders, ribbon blenders and bubble cone blenders, mixers such as Henshell mixers and concrete mixers, ball mills and cutter mills. Further, when hydrotalcite is pulverized with a ball mill or the like, the above-mentioned higher fatty acid, alkylsilanes or silane coupling agent can be added to perform surface treatment. The amount of the surface treatment agent used varies depending on the type of hydrotalcite, the type of surface treatment agent, and the like, but is preferably 1 to 10 parts by mass with respect to 100 parts by mass of hydrotalcite that has not been surface-treated. In the present invention, surface-treated hydrotalcite is also included in the "hydrotalcite" in the present invention.

The content of the hygroscopic filler in the hygroscopic resin composition is not particularly limited as long as the effect of the present invention is exhibited, but it is preferable when the non-volatile content of the hygroscopic resin composition is 100% by mass. It is 10% by mass or more and 80% by mass or less, more preferably 15% by mass or more and 78% by mass or less, and even more preferably 20% by mass or more and 75% by mass or less. When the content of the hygroscopic filler is 10% by mass or more, the hygroscopic performance can be exhibited more effectively. Further, by setting the content of the hygroscopic filler to 80% by mass or less, the film-forming property at the time of film formation, the adhesive performance of the resin composition, the surface smoothness and the like can be further improved.

The hygroscopic resin composition in the present invention may contain a filler other than the above-mentioned hygroscopic filler as long as the effect of the present invention is not impaired. Examples of fillers other than the hygroscopic filler include silica, alumina, barium sulfate, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, boron nitride, aluminum borate, barium titanate, strontium titanate, and calcium titanate. , Inorganic fillers such as magnesium titanate, bismuth titanate, titanium oxide, zirconium oxide, barium zirconate, calcium zirconate, silicate, etc. .. The content of the filler other than the hygroscopic filler is preferably 50% by mass or less, more preferably 30% by mass or less, still more preferably 20% by mass or less, when the hygroscopic filler is 100% by mass. Even more preferably, it is 10% by mass or less.

The resin constituting the hygroscopic resin composition in the present invention is not particularly limited as long as the effects of the present invention are exhibited, and examples thereof include thermosetting resins, thermoplastic resins, and rubber-based resins.

Thermosetting resin The thermosetting resin is not particularly limited, and only one type may be used, or two or more types may be used in combination, but an epoxy resin is preferably used.

The epoxy resin can be used without limitation as long as it has two or more epoxy groups per molecule on average. Examples of the epoxy resin include bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, biphenyl type epoxy resin, biphenyl aralkyl type epoxy resin, naphthol type epoxy resin, naphthalene type epoxy resin, bisphenol F type epoxy resin, and phosphorus. Epoxy resin, bisphenol S type epoxy resin, aromatic glycidylamine type epoxy resin (for example, tetraglycidyl diaminodiphenylmethane, triglycidyl-p-aminophenol, diglycidyl toluidin, diglycidyl aniline, etc.), alicyclic epoxy resin, aliphatic Chain epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol A novolak type epoxy resin, epoxy resin with butadiene structure, diglycidyl etherified product of bisphenol, diglycidyl etherified product of naphthalenediol, diglycidyl etherified product of phenols Examples thereof include glycidyl etherified products, diglycidyl etherified products of alcohols, alkyl substituents, halides and hydrogenated products of these epoxy resins. Only one type of such epoxy resin may be used, or two or more types may be used in combination.

The epoxy equivalent of the epoxy resin is preferably 50 to 5,000, more preferably 50 to 3,000, even more preferably 80 to 2,000, still more preferably 100 to 1,500 from the viewpoint of reactivity and the like. is there. The "epoxy equivalent" is the number of grams (g / eq) of the resin containing an epoxy group equivalent to 1 gram, and is measured according to the method specified in JIS K 7236. The weight average molecular weight of the epoxy resin is preferably 5,000 or less.

Suitable epoxy resins include bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, biphenyl aralkyl type epoxy resin, naphthalene type epoxy resin, alicyclic epoxy resin, aliphatic chain epoxy resin and the like. Can be mentioned.

The epoxy resin may be either liquid or solid, and the liquid epoxy resin and the solid epoxy resin may be used in combination. Here, "liquid" and "solid" are states of the epoxy resin at room temperature (25 ° C.). From the viewpoint of coatability, processability, and adhesiveness, it is preferable that at least 10% by mass or more of the entire epoxy resin used is a liquid epoxy resin. From the viewpoint of kneadability with hydrotalcite and varnish viscosity, it is particularly preferable to use a liquid epoxy resin and a solid epoxy resin in combination. The mass ratio of the liquid epoxy resin to the solid epoxy resin (liquid epoxy resin: solid epoxy resin) is preferably 1: 2 to 1: 0, more preferably 1: 1.5 to 1: 0.1.

The content of the thermosetting resin in the hygroscopic resin composition is preferably 10 to 79.9% by mass, more preferably 20 to 70% by mass, when the non-volatile content of the hygroscopic resin composition is 100% by mass. , 30-65% by mass is more preferable.

The content of the epoxy resin in the hygroscopic resin composition is preferably 10 to 79.9% by mass, more preferably 20 to 70% by mass, and 30% by mass, when the non-volatile content of the hygroscopic resin composition is 100% by mass. ~ 65% by mass is more preferable.

When the hygroscopic resin composition contains a thermosetting resin, it usually contains a curing agent. The curing agent is not particularly limited as long as it has a function of curing the hygroscopic resin composition, but from the viewpoint of suppressing thermal deterioration of a light emitting element such as an organic EL element during the curing treatment of the hygroscopic resin composition, the curing agent is not particularly limited. It is preferable that the hygroscopic resin composition can be cured at a temperature of 140 ° C. or lower (preferably 120 ° C. or lower). As the curing agent, only one type may be used, or two or more types may be used in combination.

As the curing agent, an epoxy resin curing agent which is particularly preferable as a thermosetting resin will be exemplified. Examples of the curing agent include primary amines, secondary amines, tertiary amine-based curing agents, polyaminoamide-based curing agents, dicyandiamides, and organic acid dihydrazides. Among these, from the viewpoint of quick curing, amine adduct compounds (Amicure PN-23, Amicure MY-24, Amicure PN-D, Amicure MY-D, Amicure PN-H, Amicure MY-H, Amicure PN-31) , Amicure PN-40, Amicure PN-40J, etc. (all manufactured by Ajinomoto Fine-Techno), organic acid dihydrazide (Amicure VDH-J, Amicure UDH, Amicure LDH, etc. (all manufactured by Ajinomoto Fine-Techno)) and the like are preferable. ..

Further, as the curing agent in the present invention, the epoxy resin is melted in a temperature range of an ionic liquid (that is, 140 ° C. or lower (preferably 120 ° C. or lower)) capable of curing the epoxy resin at a temperature of 140 ° C. or lower (preferably 120 ° C. or lower). A salt that can be used and has a curing action of an epoxy resin) can also be used particularly preferably. It is desirable that the ionic liquid be used in a state of being uniformly dissolved in a thermosetting resin (particularly an epoxy resin). The ionic liquid has an advantage in improving the water blocking property of the cured product of the hygroscopic resin composition.

Examples of the cations constituting such an ionic liquid include ammonium cations such as imidazolium ion, piperidinium ion, pyrrolidinium ion, pyrazonium ion, guanidinium ion and pyridinium ion; tetraalkylphosphonium cation (for example, tetrabutylphosphonium ion, etc.). Phosphonium-based cations such as tributylhexylphosphonium ion); sulfonium-based cations such as triethylsulfonium ion and the like can be mentioned.

Examples of the anions constituting the ionic liquid include halide-based anions such as fluoride ions, chloride ions, bromide ions, and iodide ions; alkyl sulfate-based anions such as methanesulfonate ions; and trifluoromethanesulfonate ions. Fluorine-containing compound anions such as hexafluorophosphonate ion, trifluorotris (pentafluoroethyl) phosphonate ion, bis (trifluoromethanesulfonyl) imide ion, trifluoroacetate ion, tetrafluoroborate ion; phenol ion, 2-methoxy Phenolic anions such as phenol ion, 2,6-di-tert-butylphenol ion; acidic amino acid ion such as aspartate ion, glutamate ion; neutral amino acid ion such as glycine ion, alanine ion, phenylalanine ion; N-benzoylalanine N-acylamino acid ion represented by the following general formula (1) such as ion, N-acetylphenylalanine ion, N-acetylglycine ion; formate ion, acetate ion, decanoate ion, 2-pyrrolidone-5-carboxylic acid ion, Examples thereof include carboxylic acid-based anions such as α-lipoate ion, lactate ion, tartrate ion, horse urate ion, N-methyl horse urate ion, and benzoate ion.

(However, R is a linear or branched alkyl group having 1 to 5 carbon atoms, or a substituted or unsubstituted phenyl group, and X represents a side chain of an amino acid.)

Examples of the amino acid in the formula (1) include aspartic acid, glutamic acid, glycine, alanine, phenylalanine and the like, and glycine is preferable.

Among the above, the cation is preferably an ammonium-based cation or a phosphonium-based cation, and more preferably an imidazolium ion or a phosphonium ion. More specifically, the imidazolium ion is 1-ethyl-3-methylimidazolium ion, 1-butyl-3-methylimidazolium ion, 1-propyl-3-methylimidazolium ion and the like.

The anion is preferably a phenolic anion, an N-acylamino acid ion represented by the general formula (1) or a carboxylic acid anion, and more preferably an N-acylamino acid ion or a carboxylic acid anion.

Specific examples of the phenolic anion include 2,6-di-tert-butylphenol ion. Specific examples of the carboxylic acid-based anion include acetate ion, decanoate ion, 2-pyrrolidone-5-carboxylic acid ion, formate ion, α-lipoate ion, lactate ion, tartrate ion, horse urate ion, and N-. Methyl horseuric acid ion and the like can be mentioned, and among them, acetate ion, 2-pyrrolidone-5-carboxylic acid ion, formate ion, lactate ion, tartrate ion, horse urate ion and N-methyl horse urate ion are preferable, and acetate ion and N. -Methyl horseurate ion and formate ion are particularly preferable. Specific examples of the N-acylamino acid ion represented by the general formula (1) include N-benzoylalanine ion, N-acetylphenylalanine ion, aspartate ion, glycine ion, N-acetylglycine ion and the like. Of these, N-benzoylalanine ion, N-acetylphenylalanine ion, and N-acetylglycine ion are preferable, and N-acetylglycine ion is particularly preferable.

Specific ionic liquids include, for example, 1-butyl-3-methylimidazolium lactate, tetrabutylphosphonium-2-pyrrolidone-5-carboxylate, tetrabutylphosphonium acetate, tetrabutylphosphonium decanoate, and tetrabutylphosphonium tri. Fluoroacetate, tetrabutylphosphonium α-lipoate, tetrabutylphosphonium formate, tetrabutylphosphonium lactate, bis (tetrabutylphosphonium) tartrate, tetrabutylphosphonium horseurate, tetrabutylphosphonium salt of N-methyl horseurate, benzoyl-DL -Alanine tetrabutylphosphonium salt, N-acetylphenylalanine tetrabutylphosphonium salt, 2,6-di-tert-butylphenol tetrabutylphosphonium salt, L-aspartate monotetrabutylphosphonium salt, glycinetetrabutylphosphonium salt, N-acetylglycine Tetrabutylphosphonium salt, 1-ethyl-3-methylimidazolium lactate, 1-ethyl-3-methylimidazolium acetate, 1-ethyl-3-methylimidazolium formate, 1-ethyl-3-methylimidazolium horseurate Salts, 1-ethyl-3-methylimidazolium salt of N-methylhorseurate, bis (1-ethyl-3-methylimidazolium) salt of tartrate, N-acetylglycine 1-ethyl-3-methylimidazolium salt are preferable. N-Acetylglycine tetrabutylphosphonium salt, 1-ethyl-3-methylimidazolium acetate, 1-ethyl-3-methylimidazolium formate, horseuric acid 1-ethyl-3-methylimidazolium salt, N-methyl horseuric acid A 1-ethyl-3-methylimidazolium salt is particularly preferred.

As a method for synthesizing the above ionic liquid, NaBF ₄ , NaPF ₆ , CF ₃ SO are used as a precursor composed of a cation moiety such as alkylimidazolium, alkyl pyridinium, alkyl ammonium and alkyl sulfonium ion and an anion moiety containing halogen. ₃ Anion exchange method that reacts Na, LiN (SO ₂ CF ₃ ) _2, etc., an acid ester that reacts an amine-based substance with an acid ester to introduce an alkyl group, and the organic acid residue becomes a counter anion. There are, but are not limited to, a method and a neutralization method in which amines are neutralized with an organic acid to obtain a salt. In the neutralization method using anions, cations and solvents, it is possible to use equal amounts of anions and cations, distill off the solvent in the obtained reaction solution, and use it as it is, or further, an organic solvent (methanol, Toluene, ethyl acetate, acetone, etc.) may be added and concentrated.

The content of the curing agent in the hygroscopic resin composition is preferably 0.1 to 50% by mass, more preferably 0.5 to 40% by mass, when the non-volatile content of the hygroscopic resin composition is 100% by mass. , More preferably 1 to 30% by mass. If this content is less than 0.1% by mass, sufficient curability may not be obtained, and conversely, if this content is more than 50% by mass, the storage stability of the hygroscopic resin composition is impaired. May be When an ionic liquid is used as the curing agent for the epoxy resin, the content of the ionic liquid is 100 parts by mass of the epoxy resin (nonvolatile content) from the viewpoint of moisture blocking property of the cured product of the hygroscopic resin composition. On the other hand, it is preferably 0.1 to 20 parts by mass, and more preferably 1 to 15 parts by mass.

When the hygroscopic resin composition contains a thermosetting resin, it may contain a curing accelerator for the purpose of adjusting the curing time or the like. Examples of the curing accelerator include organic phosphine compounds, imidazole compounds, and amine adduct compounds (for example, epoxy adduct compounds obtained by stopping the addition reaction of tertiary amines to epoxy resins in the middle) and tertiary amine compounds. And so on. Specific examples of the organic phosphine compound include TPP, TPP-K, TPP-S, TPTP-S (manufactured by Hokuko Chemical Industry Co., Ltd.) and the like. Specific examples of the imidazole compound include Curesol 2MZ, 2E4MZ, C11Z, C11Z-CN, C11Z-CNS, C11Z-A, 2MZOK, 2MA-OK, 2PHZ (manufactured by Shikoku Chemicals Corporation) and the like. Specific examples of the amine adduct compound include Fujicure (manufactured by Fuji Kasei Kogyo Co., Ltd.). Specific examples of the tertiary amine compound include DBU (1,8-diazabicyclo [5.4.0] undec-7-ene), DBU 2-ethylhexanate, octylate, and other DBU-organic acid salts. , 2,4,6-Tris (dimethylaminomethyl) phenol (TAP), aromatic dimethylurea such as U-3512T (manufactured by San-Apro), aliphatic dimethylurea such as U-3503N (manufactured by San-Apro), etc. Be done. Of these, urea compounds are preferable from the viewpoint of moisture resistance, and aromatic dimethylurea is particularly preferably used. When a curing accelerator is used, its content is preferably 0.05 to 5% by mass, more preferably 0.1 to 5% by mass, when the non-volatile content of the hygroscopic resin composition is 100% by mass. is there. When this content is 0.05% by mass or more, the thermosetting time tends to be shortened, and when it is 5% by mass or less, the storage stability of the hygroscopic resin composition tends to be improved.

Thermoplastic resin or rubber resin Examples of the thermoplastic resin or rubber resin include polyolefin resin, polyester resin, polybutene resin, cycloolefin resin, phenoxy resin, polyvinyl acetal resin, polyimide resin, polyamideimide resin, and polyethersulfone resin. , Polysulfone resin, (meth) acrylic polymer and the like. Among these, polyolefin resins are preferable in terms of adhesiveness and adhesive wet heat resistance. Only one type of these thermoplastic resins or rubber-based resins may be used, or two or more types may be used in combination.

The content of the thermoplastic resin or rubber-based resin in the hygroscopic resin composition is preferably 15 to 85% by mass, more preferably 16 to 79% by mass, when the non-volatile content of the hygroscopic resin composition is 100% by mass. It is preferable, and 17 to 72% by mass is more preferable.

Adhesive-imparting agent The hygroscopic resin composition in the present invention may contain a tackifier for the purpose of further enhancing the adhesiveness. The tackifier is also called a tack fire, and for example, a terpene resin, a rosin resin, an alicyclic hydrocarbon resin, an aliphatic hydrocarbon resin, an aliphatic / aromatic copolymer resin, or an aromatic resin. Hydrocarbon resins, Kumaron-inden resins and the like can be mentioned. Two or more kinds of tackifiers may be used in combination. More preferable tackifiers include aliphatic / aromatic copolymer-based hydrocarbon resins, aromatic hydrocarbon resins, and kumaron-inden resins.

The content of the tackifier in the hygroscopic resin composition in the present invention is preferably 5 to 75% by mass, more preferably 6 to 69% by mass, when the non-volatile content of the hygroscopic resin composition is 100% by mass. , 8 to 63% by mass is more preferable.

Examples of commercially available tackifiers include Alcon P-90, Alcon P100, Alcon P115, Alcon P125, Pine Crystal ME-G, Pine Crystal ME-H, and Pine Crystal ME-G manufactured by Arakawa Chemical Industries, Ltd. JXTG Energy T-REZ RB093, T-REZ RC115, Neopolymer L90, Neopolymer 120, Neopolymer 140, T-REZ HA-105, Tosoh Petcol 120, Petrotac 90HS, Petrotac 100V, Novares -Novales C9 and Novales L manufactured by Lutgers, knit resin L-5 manufactured by Nikko Kagaku Co., Ltd., knit resin V-120S, knit resin G-90 and the like can be mentioned.

Diluent The hygroscopic resin composition in the present invention may contain a diluent in order to achieve an appropriate viscosity as a liquid hygroscopic resin composition. The viscosity of the diluent measured with an E-type viscometer under a temperature condition of 25 ° C. is preferably 0.1 to 5000 mPa · s, more preferably 0.1 to 2500 mPa · s, still more preferably 0.1 to 1000 mPa · s. s.

As the diluent, a reactive diluent is preferable. As the reactive diluent, a compound having one ethylenically unsaturated group in one molecule (hereinafter, may be abbreviated as "monofunctional ethylenically unsaturated compound") is preferable. The ethylenically unsaturated group is preferably a (meth) acryloyl group, and the reactive diluent is particularly preferably a (meth) acrylate having one (meth) acryloyl group in one molecule (hereinafter, "monofunctional (meth)"). It may be abbreviated as "acrylate").

Examples of the monofunctional (meth) acrylate used as a diluent include "ODA-N" (octyl / decyl acrylate, that is, a monofunctional acrylate having a long-chain alkyl group) manufactured by Daicel Ornex Co., Ltd., "EBECRYL 110". , "EBECRYL 1114" (ethoxylated phenylacrylate), "Light ester E" (ethyl methacrylate) manufactured by Kyoeisha Chemical Co., Ltd., "Light ester NB" (n-butyl methacrylate), "Light ester IB" (isobutyl methacrylate), "Light" "Ester TB" (t-butyl methacrylate), "light ester EH" (2-ethylhexyl methacrylate), "light ester ID" (isodecyl methacrylate), "light ester L" (n-lauryl methacrylate), "light ester S" (N-stearyl methacrylate), "light ester CH" (cyclohexyl methacrylate), "light ester THF (1000)" (tetrahydrofurfuryl methacrylate), "light ester BZ" (benzyl methacrylate), "light ester PO" (benzylphenoxy) Ethyl methacrylate), "Light ester IB-X" (isobornyl methacrylate), "Light ester HO-250" (2-hydroxyethyl methacrylate), "Light ester HOA" (2-hydroxyethyl acrylate), "Light ester G" (Glysidyl methacrylate), "light acrylate IAA" (isoamyl acrylate, that is, a monofunctional acrylate having a branched alkyl group), "light acrylate SA" (stearyl acrylate), "light acrylate EC-A" (ethoxy-diethylene glycol). Acrylate), "Light Acrylate EHDG-AT" (2-Ethylhexyl-Diglycol Acrylate), "Light Acrylate DPM-A" (methoxydipropylene Glycol Acrylate), "Light Acrylate IB-XA" (Isobornyl methacrylate, ie Monofunctional methacrylate having an alicyclic group), "Light acrylate PO-A" (phenoxyethyl acrylate, that is, monofunctional acrylate having an aromatic ring), "Light acrylate P2HA" (Phenoxydiethylene glycol acrylate), "Light acrylate" "P-200A" (phenoxy-polyethylene glycol acrylate), "light acrylic" Relate POB-A (m-phenoxybenzyl acrylate), "Light acrylate TFH-A" (Tetrahydrofurfuryl acrylate), "Light ester HOP-A (N)" (2-Hydroxypropyl acrylate), "HOA-MS ( N) ”(2-acryloyloxyethyl-succinic acid),“ epoxy ester M-600A ”(2-hydroxy-3-phenoxypropyl acrylate),“ IDAA ”(isodecyl acrylate) manufactured by Osaka Organic Chemical Industry Co., Ltd.,“ "Viscoat # 155" (cyclohexyl acrylate), "Viscoat # 160" (benzyl acrylate), "Viscoat # 150" (tetrahydrofurfuryl acrylate), "Viscoat # 190" (ethylcarbitol acrylate), "OXE-10" (3) -Ethyl-3-oxetanyl methyl acrylate, that is, an acrylate having an oxetane ring), "MEDOL-10" (2-methyl-2-ethyl-1,3-dioxolan-4-yl) methyl acrylate, that is, a dioxolan ring. Acrylate), "Aronix M-101A" (phenol EO modified acrylate) manufactured by Toa Synthetic Co., Ltd., "NK ester A-LEN-10" (ethoxylated o-phenylphenol acrylate) manufactured by Shin-Nakamura Chemical Industry Co., Ltd., "NK ester EH" -4E ”(ethylhexyl ethoxylated polyethylene glycol methacrylate),“ FA-511AS ”(dicyclopentenyl acrylate) manufactured by Hitachi Chemical Co., Ltd.,“ FA-512AS ”(dicyclopentenyloxyethyl acrylate),“ FA-513AS ”(dicyclo) Pentanyl acrylate), Alchema "SR217NS" (4-Tert-butylcyclohexanol acrylate), "SR420NS" (3,3,5-trimethylcyclohexanol acrylate), "SR531" (cyclic trimethylpropanformal acrylate) , "CD421" (3,3,5-trimethylcyclohexanol methacrylate), "CD535" (dicyclopentadienyl methacrylate), "VEEA" manufactured by Nippon Catalyst Co., Ltd. (2- (2-vinyloxyethoxy) ethyl acrylate) , "VEEM" (2- (2-vinyloxyethoxy) ethyl methacrylate) and the like. The term "octyl / decyl acrylate" means a mixture of octyl acrylate and decyl acrylate.

As the monofunctional (meth) acrylate used as a diluent, monofunctional methacrylate having an alicyclic structure is particularly preferable. The alicyclic structure is synonymous with the above. Examples of commercially available monofunctional (meth) acrylates having an alicyclic structure include "Light Ester IB-X" (isobornyl methacrylate) and "Light Acrylate IB-XA" manufactured by Kyoeisha Chemical Co., Ltd., which have a Bornan ring structure. Isobornyl methacrylate), Kyoeisha Chemical Co., Ltd. "Light Ester CH" (cyclohexyl methacrylate), Osaka Organic Chemical Industry Co., Ltd. "Viscoat # 155" (cyclohexyl acrylate), Alchema "SR217NS" (4-Tert) -Butylcyclohexanol acrylate), "SR420NS" (3,3,5-trimethylcyclohexanol acrylate), "CD421" (3,3,5-trimethylcyclohexanol methacrylate), "CD535" (dicyclopentadienyl methacrylate) , "FA-511AS" (dicyclopentenyl acrylate), "FA-512AS" (dicyclopentenyloxyethyl acrylate), "FA-513AS" (dicyclopentenyl acrylate), Alchema manufactured by Hitachi Chemical Co., Ltd. having a dicyclo ring structure. "CD535" (dicyclopentadienyl methacrylate) manufactured by Nippon Catalyst Co., Ltd., "VEEA" (2- (2-vinyloxyethoxy) ethyl acrylate) manufactured by Nippon Catalyst Co., Ltd., "VEEM" (2- (2-vinyloxyethoxy) methacrylate) ) Ethyl) and the like.

When a diluent is used, the content thereof is preferably 2% by mass or more, more preferably 5% by mass or more, still more preferably 10% by mass or more when the non-volatile content of the hygroscopic resin composition is 100% by mass. It is preferably 60% by mass or less, more preferably 55% by mass or less, and further preferably 50% by mass or less.

Silane Coupling Agent Examples of the silane coupling agent include 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-glycidyloxypropyl (dimethoxy) methylsilane and 2- (3,4-epoxycyclohexyl). ) Epoxy silane coupling agents such as ethyltrimethoxysilane; mercaptos such as 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane and 11-mercaptoundecyltrimethoxysilane Silane coupling agent; 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyldimethoxymethylsilane, N-phenyl-3-aminopropyltrimethoxysilane, N-methylaminopropyltrimethoxysilane, Amino-based silane coupling agents such as N- (2-aminoethyl) -3-aminopropyltrimethoxysilane and N- (2-aminoethyl) -3-aminopropyldimethoxymethylsilane; 3-ureidopropyltriethoxysilane and the like. Ureid-based silane coupling agent; vinyl-based silane coupling agent such as vinyltrimethoxysilane, vinyltriethoxysilane and vinylmethyldiethoxysilane; styryl-based silane coupling agent such as p-styryltrimethoxysilane; 3-acrylic An acrylate-based silane coupling agent such as oxypropyltrimethoxysilane and 3-methacryloxypropyltrimethoxysilane; an isocyanate-based silane coupling agent such as 3-isocyanoxidetrimethoxysilane; bis (triethoxysilylpropyl) disulfide, bis ( Triethoxysilylpropyl) A sulfide-based silane coupling agent such as tetrasulfide; phenyltrimethoxysilane, metharoxypropyltrimethoxysilane, imidazolesilane, triazinesilane and the like can be mentioned. Of these, an acrylate-based silane coupling agent is preferable. Only one kind of these silane coupling agents may be used, or two or more kinds thereof may be used in combination.

Commercially available products of silane coupling agents include, for example, "KBM-502", "KBM-503", "KBE-502", "KBE-503", "KBM-5103", and "KBM-5803" manufactured by Shin-Etsu Chemical Co., Ltd. , Etc. can be mentioned.

When a silane coupling agent is used, the content thereof is preferably 0.10 to 5.00% by mass, more preferably 0.25 to 3 when the non-volatile content of the hygroscopic resin composition is 100% by mass. It is 0.000% by mass, more preferably 0.30 to 2.00% by mass.

Other components The hygroscopic resin composition in the present invention may contain other components different from the above-mentioned components as long as the effects are not impaired. For example, thickeners such as Orben and Benton; silicone-based, fluorine-based, and polymer-based defoaming agents or leveling agents; adhesion-imparting agents such as triazole compounds, thiazole compounds, triazine compounds, and porphyrin compounds; Can be done.

Further, the hygroscopic layer in the resin sheet with a support of the present invention has a multilayer structure composed of a plurality of hygroscopic layers having different configurations (for example, different types of hygroscopic fillers, different contents of hygroscopic fillers, etc.). There may be.

<Low moisture permeability layer>
The low moisture permeable layer in the resin sheet with a support of the present invention is formed by the low moisture permeable resin composition. In a typical aspect of the present invention, the low moisture permeable resin composition comprises a plate-like filler.

The plate-shaped filler is plate-shaped and is not particularly limited as long as the effects of the present invention are exhibited, but the plate-shaped filler in the present invention does not include a hygroscopic filler. That is, the plate-shaped filler in the present invention is a plate-shaped filler having a saturated water absorption rate of less than 1% by mass. Examples of the plate-shaped filler include plate-shaped glass (A glass, C glass, E glass, etc.), uncalcined hydrotalcite, layered silicate mineral, and the like. Examples of the layered silicate mineral include kaolinite, halloysite, talc, smectite, mica and the like. Among mica, synthetic phlogopite is preferable from the viewpoint of improving transparency. As the plate-shaped filler, plate-shaped glass, unfired hydrotalcite, smectite and synthetic phlogopite are preferable because they have a high aspect ratio, exhibit low moisture permeability, and are excellent in transparency. Only one kind of these plate-shaped fillers may be used alone, or two or more kinds thereof may be used in combination.

The content of the plate-like filler in the low-moisture-permeable resin composition is not particularly limited as long as the effects of the present invention are exhibited, but when the non-volatile content of the low-moisture-permeable resin composition is 100% by mass, It is preferably 10% by mass or more and 80% by mass or less, and more preferably 30% or more and 70% by mass or less. By setting the content of the plate-shaped filler to 10% by mass or more, the effect of low moisture permeability can be more effectively exhibited. Further, by setting the content of the plate-shaped filler to 80% by mass or less, it is possible to further improve the film-forming property at the time of film formation, the adhesive performance of the resin composition, the surface smoothness, and the like.

The plate-shaped filler has an average aspect ratio (average particle size / average thickness) of preferably 2 or more, and more preferably 5 or more. By setting the average aspect ratio to 2 or more, low moisture permeability can be exhibited more effectively.

The average thickness of the plate-like filler is preferably 0.01 to 20 μm, more preferably 0.05 to 10 μm.

The average thickness of the plate-like filler is measured by the following method.
It is determined by measuring the thickness of each of 100 particles using a scanning electron microscope (SEM) and averaging the measured values. In this case, individual particles may be observed and measured with a scanning electron microscope, or a filler (particle group) may be filled in a resin and molded, the molded body may be broken, and the fracture surface thereof shall be observed. You may measure. In any of the measuring methods, the sample table of the scanning electron microscope is adjusted by the sample table fine movement device so that the cross section (thickness surface) of the particles is perpendicular to the irradiation electron beam axis of the scanning electron microscope.

The average particle size of the plate-shaped filler is preferably 0.05 μm or more, more preferably 0.1 μm or more, and further preferably 2 μm or more. Further, from the viewpoint of transparency, 200 μm or less is preferable, 150 μm or less is more preferable, and 100 μm or less is further preferable.

The average particle size of the plate-shaped filler can be measured by a laser diffraction / scattering method based on the Mie scattering theory. Specifically, it can be measured by creating a particle size distribution of the filler on a volume basis with a laser diffraction type particle size distribution measuring device and using the median diameter as the average particle size. As the measurement sample, a filler dispersed in water by ultrasonic waves can be preferably used. As the laser diffraction / scattering type particle size distribution measuring device, LA-500 manufactured by HORIBA, Ltd. or the like can be used.

The low moisture-permeable resin composition in the present invention may contain a filler other than the above-mentioned plate-shaped filler as long as the effect of the present invention is not impaired. The content of the filler other than the plate-shaped filler is preferably 50% by mass or less, more preferably 30% by mass or less, still more preferably 20% by mass or less, when the plate-shaped filler is 100% by mass. Even more preferably, it is 10% by mass or less.

The resin constituting the low moisture permeability resin composition in the present invention is not particularly limited as long as the effects of the present invention are exhibited, and examples thereof include thermosetting resins, thermoplastic resins, and rubber-based resins. .. The thermosetting resin, the thermoplastic resin, and the rubber-based resin are as described above for the hygroscopic layer. Further, the low moisture-permeable resin composition in the present invention may contain each component described for the above-mentioned hygroscopic layer.

Further, the low moisture permeable layer in the resin sheet with a support of the present invention has a different configuration (for example, different types of plate-shaped fillers, different contents of plate-shaped fillers, different average aspect ratios of plate-shaped fillers, etc. ) It may be a multilayer structure composed of a plurality of low moisture permeable layers.

<Resin sheet>
The resin sheet in the resin sheet with a support of the present invention has at least one hygroscopic layer and at least one low moisture permeable layer described above. The resin sheet has at least one low moisture permeable layer on the side opposite to the support with respect to the hygroscopic layer. When the resin sheet has such a structure, the movement of moisture trapped in the hygroscopic layer is hindered by the low moisture permeable layer, and as a result, the resin sheet with a support capable of exhibiting higher moisture shielding property can be obtained. It is presumed that it will be obtained.

The thickness of the resin sheet is not particularly limited as long as the effects of the present invention are exhibited, but is preferably 5 μm or more and 100 μm or less, and more preferably 10 μm or more and 80 μm or less. When the thickness of the resin sheet is 5 μm or more, the film-forming property of the film, the adhesive performance of the resin composition, and the like can be further improved. Further, when it is 100 μm or less, the contact area of the side surface of the resin sheet with the outside air is also reduced, and the invasion of moisture can be suppressed more efficiently.

The thickness of the hygroscopic layer is not particularly limited as long as the effect of the present invention is exhibited, but is preferably 2.5 μm or more and 95 μm or less, and more preferably 5 μm or more and 50 μm or less.
The thickness of the low moisture permeable layer is not particularly limited as long as the effects of the present invention are exhibited, but is preferably 0.25 μm or more and 50 μm or less, and more preferably 2.5 μm or more and 50 μm or less.

Further, in the resin sheet, the thickness of the hygroscopic layer is preferably equal to or larger than the thickness of the low moisture permeable layer, and for example, the ratio of the thickness of the hygroscopic layer to the thickness of the low moisture permeable layer is preferably 1. It is 0 to 20, more preferably 1.5 to 15. By setting the above ratio to 1.0 or more (that is, by making the hygroscopic layer thicker than the low moisture permeable layer), the hygroscopic performance can be exhibited more effectively, and by setting it to 20 or less. The low moisture permeability of the low moisture permeability layer can be more effectively exhibited.

Water vapor permeability of the resin sheet in the support with a resin sheet of the present invention, 10g / (m 2 · ²⁴ hr) or less is preferably. Water vapor transmission rate is more preferably not more than 5g / ^(m 2 · 24 hours). The water vapor transmittance of the resin sheet can be determined by an infrared sensor method according to JIS K7129B in an atmosphere of a temperature of 40 ° C. and a relative humidity of 90%. Examples of the water vapor transmittance measuring device by the infrared sensor method according to JIS K7129B include a water vapor transmittance measuring device (PERMATRAN-W 3/34) manufactured by MOCON.

The resin sheet in the resin sheet with a support of the present invention has at least one hygroscopic layer and at least one low moisture permeable layer. At least one low moisture permeable layer is provided on the opposite side of the support from the hygroscopic layer. From the viewpoint of exhibiting higher moisture shielding property, it is preferable that at least one low moisture permeable layer is provided on the side opposite to the support with respect to all the hygroscopic layers. Further, the resin sheet in the present invention has one or more arbitrary layers (for example, an arbitrary resin composition layer) other than the hygroscopic layer and the low moisture permeable layer at an arbitrary position within the range in which the effect of the present invention is exhibited. You may have it in. Further, the resin sheet with a support of the present invention may have a cover film on the surface of the resin sheet opposite to the support side. The layer structure of the resin sheet with a support of the present invention includes, for example, the following aspects.
(1) Support + Hygroscopic layer + Low moisture permeability layer + Cover film (2) Support + Low moisture permeability layer + Hygroscopic layer + Low moisture permeability layer + Cover film (3) Support + Hygroscopic layer + Low Moisture-permeable layer + hygroscopic layer + low-moisture-permeable layer + cover film (4) Support + hygroscopic layer + low-moisture-permeable layer + hygroscopic layer + cover film Parts that require high moisture shielding properties such as organic EL elements When used for sealing or the like, the cover film is peeled off and applied to the sealing portion or the like. In the above layer structure (4), the moisture trapped in the hygroscopic layer on the support side is suppressed by the low moisture permeable layer to move to the portion requiring moisture shielding, but the moisture absorption on the cover film side. Since the water trapped in the sex layer can move without being suppressed, at least one low moisture permeable layer supports all the hygroscopic layers as in the layer structures (1) to (3). It is preferable to have a layer structure provided on the opposite side to the above.

<Resin sheet with support>
The resin sheet with a support of the present invention includes a support and a resin sheet provided on the support as described above.

Examples of the support include polyolefins such as polyethylene and polypropylene (PP), polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), polycarbonate (PC), polyimide (PI), cycloolefin polymer (COP), and the like. Examples thereof include plastic films such as polyvinyl chloride. Only one type of plastic film may be used, or two or more types may be used in combination. The support is preferably a PET film, a PEN film or a COP film, and more preferably a PET film.

In order to improve the moisture resistance of the resin sheet, a plastic film having a barrier layer may be used as a support. The barrier layer and the hygroscopic layer of the resin sheet may be in contact with each other, and the barrier layer and the hygroscopic layer of the resin sheet may not be in contact with each other (that is, for example, they may come into contact with the hygroscopic layer of the resin sheet. A barrier layer may be formed on the surface of the support opposite to the surface of the support). Examples of the barrier layer include nitrides such as silicon nitride, oxides such as aluminum oxide, stainless steel foils, and metal foils such as aluminum foils. The barrier layer may have a multi-layer structure of two or more layers. Examples of the plastic film of the plastic film having a barrier layer include films of polyethylene terephthalate, polyethylene naphthalate, polycarbonate, cycloolefin polymer and the like. The plastic film may have a multi-layer structure of two or more layers. A commercially available product may be used as the plastic film having the barrier layer. Examples of commercially available polyethylene terephthalate films with aluminum foil include "Al (1N30) with PET" manufactured by Tokai Toyo Aluminum Sales Co., Ltd. and "AL3025 with PET" manufactured by Fukuda Metal Co., Ltd.

For example, when the resin sheet with a support of the present invention is used for a display, a polarizing plate or the like may be used as the support. Further, the support may be composed of a plurality of layers having different functions such as a plastic film having a barrier layer and a polarizing plate. For example, a plastic film having a barrier layer and a polarizing plate bonded together with an adhesive such as an optical adhesive sheet (OCA) may be used as a support. In this case, the resin sheet with a support has a structure in which a plastic film having a barrier layer comes into contact with the resin sheet.

The support may be subjected to a mold release treatment, a mat treatment, a corona treatment, or the like with a silicone resin-based mold release agent, an alkyd resin-based mold release agent, a fluororesin-based mold release agent, or the like. The thickness of the support is not particularly limited. From the viewpoint of handleability and the like, the lower limit of the thickness of the support is preferably 10 μm, more preferably 20 μm, and the upper limit thereof is preferably 200 μm, more preferably 125 μm. The preferred range of support thickness (ie, preferred combination of upper and lower limits) is (i) 10-200 μm, (ii) 20-200 μm, (iii) 10-125 μm, and (iv) 20-125 μm.

The resin sheet with a support of the present invention may have a cover film on the side opposite to the support side of the resin sheet. Examples of such a cover film include those similar to the plastic film of the support. The cover film is preferably a PET film, a PEN film, a PP film or a COP film, more preferably a PET film, a PEN film or a COP film, and even more preferably a PET film. The cover film may be subjected to a mold release treatment, a mat treatment, a corona treatment, or the like with a silicone resin-based mold release agent, an alkyd resin-based mold release agent, a fluororesin-based mold release agent, or the like. The cover film may have a multi-layer structure of two or more layers. The thickness of the cover film is not particularly limited. From the viewpoint of handleability and drying of the resin sheet, the lower limit of the thickness of the cover film is preferably 10 μm, more preferably 20 μm, and the upper limit thereof is preferably 200 μm, more preferably 125 μm. The preferred range of cover film thickness (ie, preferred combination of upper and lower limits) is (i) 10-200 μm, (ii) 20-200 μm, (iii) 10-125 μm, and (iv) 20-125 μm.

<Electronic device>
The electronic device in which the electronic element is sealed with the resin sheet with a support of the present invention can be manufactured, for example, by laminating the resin sheet with a support of the present invention on the electronic element on a substrate.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited by the following examples, and is appropriately modified to the extent that it can be adapted to the above and the following objectives. Of course, it is possible to carry out, and all of them are included in the technical scope of the present invention.
In addition, "%" in the amount described below means "mass%" unless otherwise specified.

<Manufacturing example 1>
Varnishes having the compounding ratios shown in Table 1 below were prepared by the following procedure. A cyclohexane ring-containing saturated hydrocarbon resin (tacking agent; Alcon P125) dissolved in swazole so as to have a solid content of 60%, and maleic anhydride-modified liquid polybutene (HV-300M, manufactured by Nisseki Mitsubishi Corporation), Polybutene (HV-1900, manufactured by Nisseki Mitsubishi Corporation) and semi-baked hydrocarbonite (hygroscopic filler; DHT-4C, manufactured by Kyowa Chemical Co., Ltd.) were dispersed in three rolls to obtain a mixture. In the obtained mixture, a glycidyl methacrylate-modified polypropylene-polybutene copolymer (T-YP341 (manufactured by Starlight PMC), swazole solution, solid content 20%), an anionic polymerization type curing agent (TAP, manufactured by Kayaku Akzo) and Toluene was blended and the obtained mixture was uniformly dispersed with a high-speed rotary mixer to obtain a varnish of a hygroscopic resin composition.

<Manufacturing example 2>
Varnishes having the compounding ratios shown in Table 1 below were prepared by the following procedure. Cyclohexane ring-containing saturated hydrocarbon resin (tacking agent; Archon P125) dissolved in swazole so as to have a solid content of 60%, and maleic anhydride-modified liquid polybutene (HV-300M, manufactured by Nisseki Mitsubishi), Polybutene (HV-1900, manufactured by Nippon Oil Mitsubishi Corporation) and synthetic fluorine phlogopite (plate-like filler; PDM-5B, manufactured by Topy Industries, Ltd.) were dispersed in three rolls to obtain a mixture. In the obtained mixture, a glycidyl methacrylate-modified polypropylene-polybutene copolymer (T-YP341 (manufactured by Starlight PMC), swazole solution, solid content 20%), an anionic polymerization type curing agent (TAP, manufactured by Kayaku Akzo) and Toluene was blended and the obtained mixture was uniformly dispersed with a high-speed rotary mixer to obtain a varnish having a low moisture permeability resin composition.

<Manufacturing example 3>
Varnishes having the compounding ratios shown in Table 1 below were prepared by the following procedure. Cyclohexane ring-containing saturated hydrocarbon resin (tacking agent; Archon P125) dissolved in swazole so as to have a solid content of 60%, maleic anhydride-modified liquid polybutene (HV-300M, manufactured by Seiko PMC), polybutene. (HV-1900, manufactured by Seiko PMC Corporation) and a plate-shaped glass filler (FTD010-F01, manufactured by Nippon Sheet Glass Co., Ltd.) were dispersed in three rolls to obtain a mixture. In the obtained mixture, a glycidyl methacrylate-modified polypropylene-polybutene copolymer (T-YP341 (manufactured by Starlight PMC), swazole solution, solid content 20%), an anionic polymerization type curing agent (TAP, manufactured by Kayaku Akzo) and Toluene was blended and the obtained mixture was uniformly dispersed with a high-speed rotary mixer to obtain a varnish having a low moisture permeability resin composition.

<Manufacturing example 4>
Varnishes having the compounding ratios shown in Table 1 below were prepared by the following procedure. Cyclohexane ring-containing saturated hydrocarbon resin (tacking agent; Archon P125) dissolved in swazole so as to have a solid content of 60%, maleic anhydride-modified liquid polybutene (HV-300M, manufactured by Seiko PMC), polybutene. (HV-1900, manufactured by Seiko PMC Corporation) and smectite (plate-like filler; smecton SAN, manufactured by Kunimine Industries, Ltd.) were dispersed in three rolls to obtain a mixture. In the obtained mixture, a glycidyl methacrylate-modified polypropylene-polybutene copolymer (T-YP341 (manufactured by Starlight PMC), swazole solution, solid content 20%), an anionic polymerization type curing agent (TAP, manufactured by Kayaku Akzo) and Toluene was blended and the obtained mixture was uniformly dispersed with a high-speed rotary mixer to obtain a varnish having a low moisture permeability resin composition.

<Manufacturing example 5>
Varnishes having the compounding ratios shown in Table 1 below were prepared by the following procedure. Cyclohexane ring-containing saturated hydrocarbon resin (tacking agent; Archon P125) dissolved in swazole so as to have a solid content of 60%, maleic anhydride-modified liquid polybutene (HV-300M, manufactured by Seikou PMC), polybutene. (HV-1900, manufactured by Starlight PMC), glycidyl methacrylate-modified polypropylene-polybutene copolymer (T-YP341 (manufactured by Starlight PMC), swazole solution, solid content 20%), anionic polymerization type curing agent (TAP, chemical agent) Axo) and toluene were blended, and the obtained mixture was uniformly dispersed with a high-speed rotary mixer to obtain a varnish of a resin composition.

<Example 1>
The varnish obtained in Production Example 1 is uniformly applied by a die coater on the mold release surface of the PET film "SP3000" (PET: 35 μm: trade name manufactured by Toyo Cloth Co., Ltd.) treated with a silicone-based mold release agent. A hygroscopic layer having a thickness of 25 μm was provided by applying and heating at 130 ° C. for 60 minutes.
The varnish obtained in Production Example 2 is uniformly applied by a die coater on the release-treated surface of the PET film "SP4020" (PET: 50 μm: trade name manufactured by Toyo Cloth Co., Ltd.) treated with a silicone-based mold release agent. A low moisture permeable layer having a thickness of 15 μm was provided by applying and heating at 130 ° C. for 60 minutes.
The hygroscopic layer and the low moisture permeable layer were laminated using a batch type vacuum laminator (manufactured by Nichigo Morton, V-160) to obtain a resin sheet with a support. The laminating conditions were a temperature of 80 ° C., a reduced pressure time of 30 seconds, and then a pressure of 0.3 MPa for 30 seconds.

<Example 2>
In Example 1, a resin sheet with a support was obtained in the same manner except that the thickness of the low moisture permeability layer was set to 25 μm.

<Example 3>
In Example 1, a resin sheet with a support was obtained in the same manner except that the thickness of the hygroscopic layer was 35 μm and the thickness of the low moisture permeable layer was 25 μm.

<Example 4>
In Example 1, a resin sheet with a support was obtained in the same manner except that a low moisture permeability layer was obtained by using the varnish obtained in Production Example 3 instead of the varnish obtained in Production Example 2.

<Example 5>
In Example 1, a resin sheet with a support was obtained in the same manner except that a low moisture permeability layer was obtained by using the varnish obtained in Production Example 4 instead of the varnish obtained in Production Example 2.

<Comparative example 1>
The varnish obtained in Production Example 1 is uniformly applied by a die coater on the release-treated surface of the PET film "SP3000" (PET: 35 μm: trade name manufactured by Toyo Cloth Co., Ltd.) treated with a silicone-based mold release agent. The film was applied and heated at 130 ° C. for 60 minutes to obtain a resin sheet with a support having only a hygroscopic layer having a thickness of 25 μm.

<Comparative example 2>
The varnish obtained in Production Example 2 is uniformly applied by a die coater on the release-treated surface of the PET film "SP4020" (PET: 50 μm: trade name manufactured by Toyo Cloth Co., Ltd.) treated with a silicone-based mold release agent. The film was applied and heated at 130 ° C. for 60 minutes to obtain a resin sheet with a support having only a low moisture permeability layer having a thickness of 25 μm.

<Comparative example 3>
In Example 1, a resin sheet with a support was obtained in the same manner except that a low moisture permeability layer was obtained by using the varnish obtained in Production Example 5 instead of the varnish obtained in Production Example 2.

<Device reliability test (emission area reduction rate)>
Using an organic EL element, the sealing property (barrier property) of the resin sheet against moisture intrusion from the frame was evaluated. Specifically, first, an organic EL element (organic film thickness: 110 nm, Al cathode thickness: 100 nm) is formed on a glass substrate with indium tin oxide (ITO) (manufactured by Geomatec) so that the light emitting area is 4 mm ^2. did.
Next, the PET film on the hygroscopic layer side of the resin sheet with support (length: 25 mm, width: 15 mm) produced in Examples and Comparative Examples was peeled off, and a batch type vacuum laminator (Nichigo) was placed on the hygroscopic layer. Aluminum foil / PET composite film "AL1N30 with PET" (aluminum foil: 30 μm, PET: 25 μm: trade name manufactured by Tokai Toyo Aluminum Sales Co., Ltd.) is laminated as a support using Morton Co., Ltd., V-160). A resin sheet with a support was obtained. The laminating conditions were a temperature of 80 ° C., a reduced pressure time of 30 seconds, and then a pressure of 0.3 MPa for 30 seconds. The PET film on the low moisture permeability layer side of the resin sheet with a support is peeled off, and the low moisture permeability layer is applied to the substrate (width: 25 mm, length: 25 mm) having an organic EL element (light emitting area of about 4 mmφ) on the organic EL element side. Then, under a nitrogen atmosphere, a roll laminator (manufactured by Fujipla, LPD2325, roll material: rubber), roll temperature: 90 ° C., roll speed: 360 mm / min, roll pressure: 0.2 MPa, resin with support. The sheets were laminated to obtain an organic EL device in which the organic EL element was sealed with a resin sheet with a support.
A voltage was applied to the sealed organic EL element, and the initial light emitting area before storage in a constant humidity and constant temperature bath was measured. The organic EL device was then stored in a constant humidity and constant temperature bath set at a temperature of 85 ° C. and a relative humidity of 85%. 100 hours after storage, the organic EL device was taken out from the constant humidity and constant temperature bath, a voltage was applied to the organic EL element, and the light emitting area after storage was measured.
As an index for comparing the sealing property (barrier property), the residual light emitting area ratio is calculated by the following formula:
Emission area reduction rate (%) = 100 x (dark spot area) / (initial emission area)
It was calculated from and evaluated according to the following criteria. The results are shown in Table 2.
(Standard for emission area reduction rate)
Those with a light emitting area reduction rate of 10% or less ○
Those with a light emitting area reduction rate of 10% or more and less than 30% are △
Those with a light emitting area reduction rate of 30% or more ×

<Ca sealing performance measurement>
Using calcium, the sealing property (barrier property) of the resin sheet against moisture intrusion from the frame and the vertical direction was evaluated. A 50 mm × 50 mm square of non-alkali glass was washed with boiling isopropeel alcohol for 5 minutes and dried at 150 ° C. for 30 minutes or more. After cleaning, UV ozone cleaning was performed. Calcium (purity 99.8%) was vapor-deposited (thickness 200 nm) using the glass and a mask having a distance of 2 mm from the end. The PET film on the hygroscopic layer side of the resin sheet with a support produced in Examples and Comparative Examples was peeled off, and this hygroscopic layer was used as a PET film "Lumirror 38 R80" (PET: 35 μm: trade name manufactured by Toray Industries, Inc.). By laminating, another resin sheet with a support was obtained. The PET film on the low moisture permeability layer side of the obtained resin sheet with a support was peeled off, and the low moisture permeability layer was put into calcium in a glove box using a thermal laminator (Lamipacker DAiSY A4 (LPD2325) manufactured by Fujipla). Was bonded to non-alkali glass vapor-deposited to obtain a sample for evaluation. The evaluation sample was stored in an environment of 25 ° C. and a relative humidity of 40%, and the calcium state was visually observed 24 hours later.
Those in which calcium can be visually confirmed are evaluated as ◯, and those in which calcium adsorbs water to become calcium hydroxide and becomes transparent and cannot be visually confirmed are evaluated as x. The results are shown in Table 2.

<Water vapor permeability test method>
The PET film on the hygroscopic layer side of the resin sheet with a support produced in Examples and Comparative Examples was peeled off, and a batch type vacuum laminator (manufactured by Nichigo Morton, V-160) was used on the hygroscopic layer. As a support, a PET film "Lumirror 38 R80" (PET: 35 μm: trade name manufactured by Toray Industries, Inc.) was laminated to obtain another resin sheet with a support. The laminating conditions were a temperature of 80 ° C., a reduced pressure time of 30 seconds, and then a pressure of 0.3 MPa for 30 seconds.
With respect to the obtained resin sheet with a support, the water vapor transmittance of the resin sheet portion was determined by an infrared sensor method according to JIS K7129B. Water vapor permeability (g ^{/ m} 2 · 24 hours), the water vapor transmission rate measurement device (MOCON (MOCON) Co., PERMATRAN-W 3/34) using a temperature of 40 ° C., a relative humidity of 90% Measured in.
The water vapor permeability of the resin sheet is calculated by the following formula 1 / P = 1 / P1 + 1 / P2
Calculated from.
P: water vapor permeability of the support with a resin sheet P1: water vapor permeability of the resin sheet P2: 35μmPET film water vapor transmission rate of the (support) (calculated as 15g ^{/ m} 2 · 24 hours)
With respect to the resin sheet portion of the resin sheet with a support produced in Examples and Comparative Examples having different film thicknesses, the film thickness was converted to 50 μm by the following formula and compared.
P3 = P1 * X1 / 50
P3: Water vapor transmittance of the resin sheet alone X1: Film thickness of the resin sheet alone

From the results in Table 2, it can be seen that the resin sheets with supports of Examples 1 to 5 showed good results in the Ca sealing performance measurement and exhibited higher moisture shielding properties. Further, the organic EL element sealed by using the resin sheet with the support of Examples 1 to 5 exhibits high moisture shielding property, so that the light emitting area reduction rate after 100 hours is low and the device reliability is improved. You can see that it is doing.

According to the present invention, it is possible to provide a resin sheet with a support for sealing, which can exhibit higher moisture shielding properties and improve the reliability of the organic EL element device.

1 Hygroscopic layer 2 Low moisture permeability layer

Claims (17)

A resin sheet with a support including a support and a resin sheet provided on the support, wherein the resin sheet has at least one hygroscopic layer and a low moisture permeable resin formed of a hygroscopic resin composition. It has at least one low moisture permeable layer formed by the composition, and at least one low moisture permeable layer is provided on the side opposite to the support with respect to the hygroscopic layer, and the hygroscopic resin composition absorbs moisture. A resin sheet with a support containing a sex filler and the low moisture permeable resin composition containing a plate-shaped filler. The support according to claim 1, wherein the content of the hygroscopic filler in the hygroscopic resin composition is 10% by mass or more and 80% by mass or less when the non-volatile content of the hygroscopic resin composition is 100% by mass. Resin sheet. The first or second claim, wherein the content of the plate-like filler in the low moisture-permeable resin composition is 10% by mass or more and 80% by mass or less when the non-volatile content of the low moisture-permeable resin composition is 100% by mass. Resin sheet with support. The resin sheet with a support according to any one of claims 1 to 3, wherein the hygroscopic filler is semi-baked hydrotalcite. The resin sheet with a support according to any one of claims 1 to 4, wherein the plate-shaped filler is at least one selected from plate-shaped glass, unfired hydrotalcite, smectite, and synthetic phlogopite. The resin sheet with a support according to any one of claims 1 to 5, wherein the plate-shaped filler has an average aspect ratio of 2 or more. The resin sheet with a support according to any one of claims 1 to 6, wherein the thickness of the resin sheet is 5 μm or more and 100 μm. The resin sheet with a support according to any one of claims 1 to 7, wherein the thickness of the hygroscopic layer is equal to or greater than the thickness of the low moisture permeable layer. The resin sheet with a support according to any one of claims 1 to 8, wherein the ratio of the thickness of the hygroscopic layer to the thickness of the low moisture permeable layer is 1.0 to 20. The resin sheet with a support according to any one of claims 1 to 9, wherein at least one low moisture permeability layer is provided on the side opposite to the support for all the hygroscopic layers. Support coated resin sheet according to any one of claims 1 to 10, the water vapor permeability of the resin sheet is not more than 10g / ^(m 2 · 24 hours). The resin sheet with a support according to any one of claims 1 to 11, wherein the hygroscopic resin composition and the low moisture permeable resin composition contain a thermosetting resin. The resin sheet with a support according to any one of claims 1 to 12, wherein the hygroscopic resin composition and the low moisture permeable resin composition contain an epoxy resin. The resin sheet with a support according to any one of claims 1 to 13, wherein the hygroscopic resin composition and the low moisture permeable resin composition contain a thermoplastic resin. The resin sheet with a support according to any one of claims 1 to 14, which is used for sealing an electronic device. The resin sheet with a support according to any one of claims 1 to 15, which is used for sealing an organic EL device. An electronic device sealed with a resin sheet with a support according to any one of claims 1 to 16.